Modifier for increasing elasticity and strength of epoxide compounds for anhydride hardening

FIELD: chemistry.

SUBSTANCE: modifier selected from oligooxypropylenediols with molecular weight from 400 to 5003, oligooxyethylenediols with molecular weight from 400 to 5003, mixtures thereof with molecular weight from 400 to 5003. The modifier is added in amount of 10-15 wt %. Epoxide compounds have relative elongation from 12.5 to 20% with retention or improvement of strength characteristics.

EFFECT: high elasticity and strength of compounds.

2 cl, 1 tbl, 13 ex

 

The invention relates to polymeric compositions based on epoxy binder anhydrite curing, which can be used as adhesives, coatings, impregnating compositions, adhesives for composite materials, produced mainly by the method of wet wound.

Known epoxy binder for fiberglass, including epoxygenase resin, hardener - isomethyltetrahydrophthalic anhydride, a curing catalyst is 2,4,6-Tris(dimethylamino-methyl)phenol and modifier - plasticizer ADOS [Patent RU NO. 21456177, C08L 63/02. Epoxy binder for fiberglass. Publ. 20.02.2000]. The disadvantages of this binder are low elongation at tensile, high brittleness in the cured state, the presence of a modifier toxic volatile substances.

The closest in technical essence is epoxy binder for composite materials (taken as a prototype), including epoxygenase resin (40-53%), hardener - isomethyltetrahydrophthalic anhydride (32-42%), curing catalyst is 2,4,6-Tris(dimethylaminomethyl)phenol (0,7-1,5%) and plasticizer polyurethane brand Plaster rcof-0203" (5-18%) [Patent RU NO. 21607527, C08L 63/02. Epoxy binder for composite materials. Publ. 20.12.2000].

The disadvantages of epoxy resins such composition are low from oxytelinae elongation tensile (up 6%) and as a consequence, the low elasticity of the cured material, the need to dissolve the solid rubbery thermoplastic polyurethane "Plaster" dioctylphthalate, which complicates the manufacturing process of the composition.

An object of the invention is the creation of an epoxy composition, providing a significant increase in relative elongation while maintaining the strength properties of the hardened materials under tension, thus eliminating their tendency to tremino-education and ensure solidity.

To solve this problem is proposed modifier to improve the elasticity and strength of epoxy composites anhydrite curing, which is chosen from the series consisting of oligoamenorrhea with a molecular mass (MM) 400 to 5003 and oligoastrocytoma with a molecular weight of from 400 to 5003, their mixtures with molecular weight from 400 to 5003.

The modifier is added to the epoxy composition anhydrite curing in the amount of 10-15 wt.%.

The lower limit of molecular weight oligoastrocytoma, oligoastrocytoma or their mixtures selected because it is the minimum MM industrial output in Russia at the moment, finished products (Laprol) and compounds with lower MM were not considered in this decision as inaccessible in production volume. Silicenium MM modifier increases the viscosity of the composition and hampered its processing. In this regard, the use as a modifier lapola with MM more 5003 impractical.

The optimal quantity of modifier in epoxy compositions were determined experimentally (see table).

Improved deformation properties of polymeric compositions, including the specified modifier, due to the fact that during curing of the composition of the oligomeric link modifier fits into the chain of a polymeric material and due to structural plasticization increases the elasticity of the material.

Laprol widely known and used in the production of various types of polyurethanes. It is also known the use of Laprol as a component of brake fluid. However, the identified sources of information about their use as modifiers in epoxy compositions anhydrite curing. Thus, the proposed solution meets the criteria of the invention of "novelty" and "inventive step".

The inventive modifier has a low viscosity and a good combination with the other components of the epoxy composition, which is a temporary plasticizer at low temperatures. This allows to reduce the viscosity and increase the viability of the binder at the stage of processing.

The method of manufacture of epoxy compositions with the proposed modifications is a PR

In the compositions of epoxy composites with the use of the proposed modifier in addition to the widespread epoxygenase resin ED-20 can be used other epoxygenase resin (for example, ED-16, or ED-22), halogenated epoxygenase resin (e.g., UE-631), and epoxy resin other chemical nature, including having more than two epoxy groups in one molecule (for example, the condensation product of epichlorohydrin with p-aminophenols - resin pack-610 or epoxydodecane resin pack-643) and others, as well as mixtures thereof.

As a hardener, along with the most common isomethyltetrahydrophthalic anhydride can be used, and other anhydrides and polyanhydrides.

As catalysts for curing except 2,4,6-Tris(dimethyl-aminomethyl)phenol can be selected from imidazole and its derivatives - vinylimidazole, 1-Mei, the 2-phenylimidazole, 2-ethyl-4-methyl-imidazole, and their adducts with epoxy resins.

In a reactor equipped with a stirrer and connected to a vacuum pump, alternately loaded epoxy resin, anhydrous curing agent, curing catalyst and modifier. The mixture is stirred for 10 minutes with simultaneous vacuum at a temperature of 20-25°C and at a residual pressure of 10-15 kPa, and then poured into metal molds and utverjdayut at a temperature of 120-150°C in those who tell 2-3 hours.

Physico-mechanical characteristics of solidified samples tensile strength σpMPa and the elongation of the sample under tension, ε % is determined according to GOST 270-75.

To study the properties of compositions with the proposed modifier and determine the optimal number of his compositions, experiments were carried out with the addition of the modifier with different MM and with different weight ratio of the components. Tensile strength and elongation of solidified samples tensile was determined on a tensile testing machine R-50 at test speeds of 100 mm/min

Example 1. The composition was made using the above method in the following ratio, wt.%:

epoxy resin ED-20 - 48

isomethyltetrahydrophthalic anhydride (IMTFE) - 39

2,4,6-Tris(dimethylaminomethyl)phenol (yn-606/2) - 0,5

modifier with 400 MM - 12,5

Examples 2-5. The song was produced analogously to example 1 with the modifier with different MM, respectively, 502, 1052, 2002, 5003 ceteris paribus.

Examples 6, 7. Compositions were made with the modifier with MM 1052 added in amounts, respectively, 8 and 20 wt.% (outside of the proposed intervals).

Examples 8, 9. Compositions were made with the modifier with MM 1052 added in amounts, respectively, 10 and 15 wt.% (on the borders claimed in which Ermolov).

Examples 10-12. The song was produced analogously to examples 1-5 with modifier with 1052 MM, but with the use of other resins (EDMS, UE-643) or 2-ethyl-4-Mei as a catalyst under otherwise equal conditions.

Example 13. The composition of the prototype (average data specified in the description of the patent No. 2160752).

The results of the experiments presented in the table.

As can be seen from the table, epoxy compositions with the proposed modifier in the claimed limits of the ratios of the components have a relative elongation of 12.5 to 20% with the same or a slight increase in strength properties.

Epoxy compositions with the proposed modifier was tested as a binder in the manufacture of GRP pipes with a diameter of 500, length 3000, thickness of 5 mm After manufacturing GRP pipes were subjected to hydraulic pressure to 100 ATM. During the test tubes were kept tightness in the entire pressure range, with no leaks and cracks. Safety factor for the achieved pressure was 4.5.

Epoxy compositions with the proposed modifier were tested as part organoplastic based fibers Armos and Rusar. Organoplastic after the adhesive had a breaking load 1500-1770 MPa.

Table
Formulations of the compositions of examples and properties of the hardened fiberglass
# exampleName ingredientsContent, wt.%Ultimate tensile strength, MPaElongation at elongation, %
1ED-20486020
IMTFE39
UE-606/20,5
Modifier MM 40012,5
2ED-20485617
IMTFE39
UE-606/20,5
Modifier 502 MM12,5
3ED-2048 6020
IMTFE39
UE-606/20,5
Modifier MM 105212,5
4ED-2048of 57.513
IMTFE39
UE-606/20,5
Modifier MM 200212,5
5ED-20485514
IMTFE39
UE-606/20,5
Modifier MM 500312,5
6ED-20a 50.5498
IMTFE41
UE-606/2 0,5
Modifier MM 10528
7ED-20444515
IMTFE35,5
UE-606/20,5
Modifier MM 105220
8ED-20505215
IMTFE39,5
UE-606/20,5
Modifier MM 105210
9ED-20475317
IMTFE37,5
UE-606/20,5
Modifier MM 105215
10The EDMS 485814
IMTFE39
UE-606/20,5
Modifier MM 105212,5
11Resin pack-643485913
IMTFE39
UE-606/20,5
Modifier MM 105212,5
12ED-20485613
IMTFE39
2-ethyl-4-Mei0,5
12,5
Modifier MM 1052
13 (prototype)ED-2052545,6
THEM the GFA 30
UE-606/21,0
The modifier "Plaster rcof-0203"17

1. Modifier to improve the elasticity and strength of epoxy composites anhydrite curing, which is chosen from the series consisting of oligoamenorrhea with a molecular weight of from 400 to 5003, oligoastrocytoma with a molecular weight of from 400 to 5003, their mixtures with molecular weight from 400 to 5003.

2. The modifier according to claim 1 is added to the epoxy composition anhydrite curing in the amount of 10-15 wt.%.



 

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FIELD: chemistry.

SUBSTANCE: epoxide compound contains at least one epoxydiane resin or mixture thereof with other resins, an anhydride hardener and a hardening catalyst - an organic cation of a quaternary ammonium salt immobilised by a layered aluminium silicate of the montmorillonite group, where the said organic cation has the formula:

, where R1, R2 and R3 are aliphatic hydrocarbon radicals, at least one of them containing 8-20 carbon toms, and the rest having not more than two carbon atoms, R4-H, CH3, C2H5, benzyl, A is the skeleton of the montmorillonite plate.

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1 cl, 2 tbl

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24 cl, 2 ex, 3 tbl

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1 tbl, 10 ex

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5 cl, 4 dwg, 1 tbl, 9 ex

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2 tbl, 1 ex

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2 cl, 2 ex, 2 tbl

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26 cl, 1 ex, 1 tbl, 2 dwg

FIELD: chemistry.

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21 cl, 2 ex, 3 tbl

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2 cl, 9 dwg, 2 tbl, 1 ex

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2 tbl, 7 ex

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3 cl, 13 ex, 1 tbl, 1 dwg

FIELD: transport.

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7 cl, 1 dwg, 1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: band made from crude fabric can be used as an auxiliary layer, cushion layer and reinforcement base in the carcass of a tyre. The band is made by saturating crude mini-fabric, which contains several separate strands, with a solvent based adhesive. The adhesive, which contains a solvent and an elastomer composition, is dried such that, most of the solvent evaporates. The elastomer composition remains, covering the fabric and forming a band that way.

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12 cl, 7 dwg

FIELD: chemistry.

SUBSTANCE: stabilising composition for resistant to atmospheric impacts halogen-containing thermoplastic resins, and polymer composition based on halogen-containing thermoplastic resins, containing said stabilising composition, which includes stabilising calcium compound representing calcium hydroxide and/or calcium oxide, whose surface can probably be modified, or calcium salt of organic carboxylic acid, or mixture of two or more such compounds at least one dye or pigment or their mixture, dye or pigment giving halogen-containing thermoplastic resin colour parameters L≤95, a=0 ± >1 or b=0 ± >1, or a=0 ± >1 and b=0 ± >1, and at least one isocyanurate, which has hydroxyl groups, content of β-diketone, or β-diketone salts, or their mixtures in stabilising composition constituting less than 0.1 wt % of all stabilising composition. Polymer compositions are obtained by mixing said ingredients and are used for manufacturing formed products.

EFFECT: obtaining coloured polymer compositions resistant to atmospheric impacts.

15 cl, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to concentrate of additives for polyolefin processing. The concentrate contains polybutylene-1, polypropylene and from 5% to 6% of one or more additives. The concentrates compound a product, which can be added to various polyolefin for adding additives. Colored polypropylene fiber is prepared by mixing polyolefin with concentrate containing pigments with further moulding. The concentrates are used for volume coloring of polyolefines.

EFFECT: precisely, invention simplifies coloring stage during extrusion of polypropylene fibers.

8 cl, 2 tbl, 1 dwg

FIELD: chemistry.

SUBSTANCE: present invention relates to the rubber industry, particularly to oil resistant rubber composition with good operational characteristics. The rubber composition is based on butadiene-nitrile rubber mixed with, wt.pts, 1.8-2.0 tetramethylthiuram disulphide, 1.4-1.6 hexachloro-n-xylol, 0.9-1.1 N-phenyl- N1-isopropyl-n-phenylenediamine and 1.0-2.0 oligomer of 2,2,4tetramethyl-1,2 dihydroquinoline, 0.9-1.1 antifatigue agent and heat stabiliser of dioctylamine(4-phenylaminophenyl) thiophosphonic acid ("Б"-26) with technical carbon, sulphur and target additives.

EFFECT: increased tear resistance and improved physical and mechanical properties of the rubber.

3 tbl

FIELD: chemistry.

SUBSTANCE: present invention relates to the technology of obtaining rubber, particularly to hydrogenated or non-hydrogenated nitrile rubber, to the method of obtaining it, to a polymer composite material, to the method of obtaining it and method of making moulded objects. Hydrogenated or non-hydrogenated rubber is obtained, with molecular weight Mw between 20000 and 250000, Mooney viscosity -ML 1+4 at 100°C between 1 and 50 and polydispersity index of not more than 2.5. The polymer composite material contains not less than one hydrogenated or non-hydrogenated nitrile rubber, not less than one filler and not less than one crosslinking agent. Without adding coolefin, the nitrile rubber is subjected to metathesis in the presence of Grubbs's catalyst in an inert solvent.

EFFECT: obtaining hydrogenated or non-hydrogenated nitrile rubber with low molecular weight and narrower molecular weight distribution.

13 cl, 4 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention can be applied in tire production and rubber industries for obtainment of cured stock with long-term resistance to thermal oxidation and ozone ageing. Cured rubber mix includes natural or synthetic rubber, curing substances, curing boosters and activation agents, fillers and other additives, and composition age resistor in amount of 0.5-2.0 weight parts per 100 weight parts of rubber, including colloid silicic acid as powder carrier and liquid alloy of age resistors obtained at 70-90°C and containing N-isopropyl-N-phenyl-n-phenylenediamine - 21-22.5 and ε-caprolactam - 11-14. Additionally age resistor alloy includes 2,2,4-trimethyl-1,2-dihydroquinolin polymer - 10.0-11.5, stearic acid - 10.0-11.5, protection wax - 24.0-25.5.

EFFECT: enhanced resistance of cured stock to thermal oxidation and ozone.

6 tbl, 2 ex

FIELD: phenoplast production, in particular casting composition for technical applications.

SUBSTANCE: claimed casting composition included (mass %): novolac phenol-formaldehyde resin 47-49.3; wood powder 28.4-29.5; urotropine 7.1-7.4; kaolin 3.2-3.4; burnt magnesia 0.7-0.9; nigrosine 1.4-1.5; talk 3.7-3.9; naphthalene 1.9-2; stearin 0.2-0.4; calcium stearate 0.4-0.6; polyethylene wax 0.5-0.7; phosphoric acid triphenyl ester 1-5. Composition of present invention has increased destructive torque stress and decreased viscosity coefficient at 120°C and shear velocity gradient of 15 l/s.

EFFECT: composition with increased destructive torque stress and decreased viscosity coefficient.

4 ex, 1 tbl

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