SU834035A1 - Epoxy composition - Google Patents

Description

This invention relates to the preparation of low flammability polymer composites based on epoxy oligomers and llorocyclophosphazenes, suitable for use as bonding for glass glass, adhesive and flow compounds, adhesives. Polymer composites with low flammability are known on the basis of epoxy resins and phosphazenes used as prepolymers of chlorophosphazenes with epoxy compounds fll of adhesives of pnpofosfazenes with hexametpium phosphoramide 1.21. The COMPOSITION is closest to the one proposed; containing epoxy oligomer and chlorocyclophosphazenes of the general formula (PMCt.) and the amount of 1-66% 66% wt.% 2. The polymeric compositions after chevedvarngrelnoe prepolymerisadii heated in one absence of catalytic acid without it "hardened at 902 ° C in one of the presence of catalytic acid or without it. Main feature The main advantage of the known composition is to carry out a php polymerisation of an epoxy oligomer with chlorophosphazenes, which makes it possible to chemically bind chlorophosphazene to epoxibination and retain in the composition of the polymeric composition chlorine fect reducing flammability 1FI administered in phosphazenes epoxides. The disadvantages of the known composition are that when used for the preparation of combustibles, chloroclophosphazenes of the general formula (PYSe2) and where AND 3.4, in the process of heating the composition from and above, continuous sublimation of cyclophosphazene and after curing in the composition remains only the mass distribution. including non-flammable additives. In addition, the material obtained after curing is characterized by a reduced cross-sectional v 1 performance. These disadvantages drastically reduce the positive effect of the prepromerization of shsh using chlorocyclophosphate, while it is known that cyclic phosphazes 1 is a very valuable addition to polymers. BoaroH chlor-chlorophosphazene, for example, hexachloro-chloroslotrifosphaene, leads to the destruction of the initial composition, complicates the design of the technological process of the composition and promotes the formation of pores in the cured product. The purpose of the invention is to prevent the sublimation of chlorasshosphosphazene from the polymer composition of the polymer to its processing and shyness in hardened state. The goal is achieved by introducing into the composition of a polymer composition, including an epoxy oligomer, chlorocyclo phosphazene and a catalyst for curing helogen containing alcohol or phenol 1FI, the following ratio of mass components, including:. Epoxy Oligomer 7O-93 Chlorocyclophosphazene 3-2O Halogen-containing alcohol or phenol4-10 Curing catalyst 5-10 The use of halogen-containing alcohols or phenols in the composition of the polymer composition at the stage of prepolymerization and curing prevents the formation of chlorocyclophosphazene from the mixture due to the intermolecular composition of the compound and interconnection and curing at the expense of intermolecular composition and curing. including partial replacement of chlorine by cyclophosphazene and, by changing the structure of the approved epoxide, provides an increase in cohesive strength. To obtain a new polymer composition with reduced flammability, epoxy oligomers of various types and grades are used, for example, Diane grades (grades, ED-16, etc.), chlorine-containing (EHD-grades, etc.), resorcinate (RZS-3 grades). ) etc. Chlorine-containing and fluorinated alcohols, as well as chlorinated and brominated phenols, which are produced by domestic pharmaceuticals, are used as halogen-containing alcohol and phenols. Chlorosine chlorophosphazenes of the general formula) ii, where n 3.4, were obtained by a known method under laboratory conditions. As a curing catalyst, hardeners of the main type are used, for example, triethanolamine titanate (TEAT -1), produced by domestic industry. The polymer compositions obtained, Sch), are homogeneous transparent liquids with a viscosity of 30–40 Pa with, depending on the type of epoxy resin, stable during storage for 1 month. Cured materials are non-meltable transparent substances with an insoluble portion content of 95-99%. The compositions for the physicomechanical properties of polymer compositions are presented in Tables 1 and 2, respectively. Example. Take 35 masses. including epoxy oligomer brand RES-3 with a content of epoxy groups of 32.25% mixed with 1O masses. including chlorocyclophosphazene formula (PNCRj). and 5 masses. hours 2, 4, 6-trichlorophenol and for the purpose of carrying out the prepolymerization 1 phi is stirred for 10 hours. The resulting composition is combined after cooling with 5 masses. h. TEAT-1 and pour into the mold. Curing is carried out according to the mode: 9 ° C - 2 h, - 1 Oh, - 10 h. During the heat treatment of the composition, the sublimation of chlorocyclo phosphazene is not observed, the weight of the sample does not change and a solid transparent material is obtained. PRI mme R 2. Take 4O masses. including epoxy oligomer brand RES-3 with the content of epoxy groups of 32.25% is mixed with 7.5 wt. including chlorocyclophosphazene formula (PNCta): and 2.5 mass. h. 1,1,3-trihydrotetrafigor 1 propanol and extract 10) and 9O2 for. 4 with stirring to prepolymerize. After cooling, the composition is mixed with 5 g of TEAT-1 to obtain a homogeneous mass and poured into a mold for curing according to the regime: - 2 hours, - 15 hours, hours. During the period of prepolymerization and curing, no sublimation of chlorocyclo phosphazene occurs. The weight of the cured sample is equal to the weight of the original polymer composition. Froze Take 93 masses. including poxide oligomer brand RES-3 content of Epox 32, 25% shift from 4 mass. including Y-bromophenol 3 mass. including chlorocyclophosphazene of the formula and stirred in the reactor for 10 hours at 9 ° C. The obtained 1-faraway homogeneous mass is cooled, 5 ml of oil is added to it. h. TEAT-1 and poured into a mold for curing. After discharge at 90 ° C for

5 h and 1 fi 120 ° C for 2 h h, solid yellow yellow samples are obtained.

PRI me R 4. Take 9O masses. including epoxy resin marks ED-20 with an epoxy content of 21.65% mixed with 15 mass, including chlorine mixture of cyclophosphazene of the formula (PNCKj) 5 mass. including 1D, 3-trihydrotetrafluoropropane n is stirred at

for 1O h. The mass is cooled, 1O mass is added. Part of TEAT-1 is mixed until a homogeneous composition is obtained, poured into the formula for obtaining otverdny and maintained at 9CP-5 and 155C -15 hours. Solid transparent thermofixed samples are obtained.

PRI me R 5 (known). Take 40 of the masses. including epoxy resin brand RES-3 is mixed with 10 wt.h. chloroiclofosfazenum fmpiles (PMCv, g) h and gradually heated to, at that temperature, 10 hours, and then introduced into the composition of 1O mass. h. TEAT-1. The resulting composition is poured into a mold and cured according to the regime: 125 ° C - 4 hours, - 18 hours. During the heat treatment, chlorocyclophosphazene is sublimated from the mixture at a mass of 7 wt. H, so that about 30% of the initial cyclophosphazene remains in the composition. Dark colored slightly transparent samples are obtained after curing.

With the introduction of chlorocyclophosphazene into the composition of the polymer composition and halogen containing alcohol or phenol in an amount exceeding the upper limits, a sharp decrease in the physicomechanical properties of the cured material and the appearance of porosity are observed. Minimum

the value of chlorocyclophosphazene and a halogen-containing alcohol or phenol is necessary and sufficient for technologically to obtain a polymeric composition of reduced combustibility.

Thus, from the above data it can be seen that the proposed composition of the polymer composition allows to improve the design of the technological process of preparation of the composition, preventing the sublimation of chlorine cyclo-phosphazene from the mixture.

In the past, physico-mechanical tests (Table 2) show that the proposed polymer composition in a hardened state has broken fracture elongation when stretched (up to 1O5 MPa) while maintaining a low degree of Gfuschiness, high heat resistance, relative elongation and destructive heat. compression.

This combination of the properties of cast compositions makes new materials promising for their use as binders in various polymer compositions for adhesives (adhesives, potting compounds, fiberglass plastics) that can be found in shipbuilding, aviation and space technology.

Table

 Take the epoxy oligrmer brand ED-20

Indicators

145.0 145.0 138.0 132, O

105, O 91, O 92.7 72.5 6.3 7.5 7.0 6.65 210 210223 228 98.5 98.2 99.1 99, O

O, O6 0.07 0.06 O, 06 5677

Samoza- Samoza- Samoza- Samozatuhanye fading, fading, fading f or m izbreteni. An epoxy composition comprising a 35 epoxy oligometer, chlorocyclophosphazene and a curing catalyst, which is because with the aim of eliminating the sublimation of chlorocyclophosphazene from the polymer composition during its processing and increasing its strength in a hardened composition of hsp, the composition additionally contains halogen-containing alcohol or phenol with the following ratio of components, masses, including: Epoxy oligomer 7О-93 Chlorocyclo-phosphase N; 3- 0 Halogen-containing alcohol or phenol 4-1О Catalyst fromVertification 5-1O Sources of information that are relevant to the 1 st examination 1. US patent N93939738, cl. 74-859, published, 1976. 2. US Patent No. 3641193, cl. 260-83О, published. 1975 (prototype)

Claims (1)

Claim An epoxy composition including a ₃₅ epoxy oligometer, chlorocyclophosphazene and a curing catalyst is distinguished by the fact that, in order to prevent sublimation of chlorocyclophosphazene from the polymer composition during its processing and to increase its strength in the cured state, the composition additionally contains a halogen-containing alcohol or phenol in the following ratio of components, mass. hours: Epoxy Oligomer70-Θ3 Chlorocyclophosphazene; 3-20 Halogenated alcohol or phenol 4-10 Curing Catalyst 5-10