CS271381B1 - Accelerator of epoxy groups reaction with epoxy resins' aliphatic polyamines - Google Patents

Abstract

The solution applies to the field of epoxy resins and their raw materials. A technical problem is solved of how to use bothersome waste that arises during non-standard conditions of the continuous condensation of acetone with a surplus of phenol, or that forms, as accelerators of the reaction of epoxy groups with aliphatic polyamines of epoxy resins, the refining residuum during the refining of diane. This residuum is brought in the reactive epoxy composition in the form of a liquid mixture in the modified dianil epoxy resin with the medium molecular weight 440 to 750 modified by reactive and/or non-reactive dissolvents and/or in the form of liquid mixtures in these dissolvents.

Description

The invention relates to the use of a mixture of mono-, di- and triphenols which is formed under non-standard conditions of continuous acetone condensation with a molar excess of phenol or forms a refining residue in dianium refining as epoxy group accelerators β aliphatic polyamines of epoxy resins. modifier itself.

In the continuous condensation of acetone with phenol at a molar ratio of 1: 6 to 10 with a cation exchanger catalytic effect, the reaction temperature, molar ratio, reactor flow rate and catalyst age influence the production process. The liquid product is thermo-labile and sensitive to oxygen. When starting production after technological and non-technological interruptions, the first parts are usually dark colored and chemically inconsistent. The presence of up to 30 by-products, by-product products such as dian isomers, tri-nuclear phenol derivative BPX, isopropenylphenol and its dimer, monofunctional codimer, isopropylphenol, cresol-acetone condensation products, resin phenolic polycondensates etc. are considered. epoxy resins or polycarbonates, these substances need to be removed as they deteriorate the quality of the produced epoxides and polycarbonates. No analytical procedures have yet been developed to determine the full composition of condensates and the mechanism of all reactions has not been known. The condensate does not always have the same composition. It usually becomes a waste and environmental problem.

The refining of dian is usually by crystallization of dian from various solvent systems or by crystallization of the dian-phenol adduct or by high-vacuum distillation. Refining residues concentrate the undesirable substances in dian for the preparation of epoxy resins. According to the prior art, refining residues find little use as a raw material for the production of isopropenylphenol. They are predominantly disposed of by incineration, as no other more efficient use is known. Condensation with epichlorohydrin to epoxy resins leads to hardly reproducible and high-viscosity resins of dark color.

We have now found that the discussed phenol mixture having a phenolic hydroxyl content of 0.70 to 0.93 mol / 100 g, preferably 0.85 to 0.87 mol / 100 g, falling off under non-standard conditions of continuous acetone condensation with an excess of phenol or forming a refining residue in the refining of diane, dissolves well in epoxide resins with an average molecular weight of 440-750, modified with reactive and / or non-reactive solvents of epoxy resins, and accelerates the reaction of epoxy groups with 8 aliphatic polyamines, adducts and modifications thereof. This makes it possible to use mixtures of mono-, di- and triphenols as accelerators for the reaction of epoxy groups with aliphatic polyamines of epoxy resins introduced into the system by the modifier or by the modifier itself.

The mixtures under discussion form a semi-solid to solid resinous substance that smells of phenol and has a softening point of 30 to 60 ° 0 (ring-ball method). The content of phenolic substances is from 90 to 99% by weight. It contains about 30 phenolic substances. The pp * -isomer of dian (about 50 to 90%), the o, p'- and o, o'-isomers of the dian (about 1 to 15%) predominate, and a number of by-products such as codimer, BPX, phenol, creaol , isopropylphenol, isopropenylphenol and its dimer. It is preferably processed as a melt, dissolved with stirring in unmodified and modified epoxy resins, in modifiers or aliphatic polyamines, and their adducts and modifiers. ⁴ ·

Reactive and non-reactive modifiers are aliphatic epoxy resins and glycidyl ethers, glycidyl esters, both lamina and glycidylsulfones, unsaturated carboxylic acid esters such as maleates and acrylates, phthalates, polyglycols, xylene, benzyl alcohol, styrene and the like. *

Aliphatic polyamines whose reaction with the epoxy group is accelerated can be used.

mentioning diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tri-, methylhexamethylenediamine, their adducts, for example with allyl glycidyl ether and modifications. PoCS 271381 B1 uses ee in an amount corresponding to 90 to 150% of the theory with respect to the epoxy group content. When alpha, beta-unsaturated carboxylic acid esters are used as internal plasticizers, the amount of amine must be increased by a proportion corresponding to the double bond content.

Example 1

The phenol mixture had an approximate composition in% by weight: phenol 1, p-p'-dian 87, op * dian 3, BPX 2, isopropenylphenol 6 dimers and sum of isopropyl and isopropenyl phenol 1, phenolic group content 0.169 mol / 100 G·

The following table compares the effect of the amount of phenol mixture (M) in the resin on the viscosity (V) of the epoxy resin (80 wt%, palm 5 epoxy resins 519 + 20 wt% dibutyl maleate) on the reaction rate (R) with equimolar amount by tyentent of lamin (to epoxy groups in resin 1 double bonds in maleate) expressed as an increase in temperature of 170 g of reactive epoxy composition after start of homogenization, relative gelation time of tensile test specimens (G), tensile strength (T) values and ductility (t) at 23 ° C after 28 days of free storage in the laboratory and to T ^ values, t ^ after thermo-oxidative aging for 4 days at 125 ° C, including weight loss (µ ^) in%:

M in R G T t ^T 4 ^f 4 ^ú 4 % wt. mPa.e / 25 ° C ° C / min MPa % MPa % % wt. 0 1 500 16/5 1 40 11 28 6 6.05 5 2 600 17/3 0.6 42 10 26 5 6.32 10 3 550 15/2 0.3 41 8 22nd 4 6.61

Example 2

The phenol mixture had approximately a composition in% by weight: phenol 0.1, p, p * -dian 76, ο.ρ'-dian 10, BPX 5, isopropenyl phenol 6 dimers and the sum of isopropyl and isopropenyl phenol 3, phenolic group content 0.864 mol / 100 g.

Dissolve 4,4 g of phenol mixture in 120 g of a 80% solution of an average molecular weight of 579 epoxy resin in dibutyl phthalate and then add 44,4 g of diethylenetrlamine at 23 ° C. The reactive epoxy composition shall be homogenized after 15 minutes. at the start of homogenization, the temperature of the composition is 32 ° C. When carried out in the absence of phenol mixture, the temperature is only 30 ° C. 5 MPa and 73% ·

Example 3

The phenol mixture had approximately a composition by weight. %: phenol 4, p, p'-dian 78, o, p'-dian 5, BPX 3, isopropenylphenol dimers 7 and the sum of isopropyl and isopropenylphenols 3, phenolic group content 0.869 mol / 100 g.

5 g of phenol mixture are dissolved in 20 g of dibutyl phthalate. Then, 76 g of an average molecular weight of 519 epoxy resin is added. At 23 ° C, the reactive epoxy composition is homogenized. After 3 minutes from the start of homogenization, the temperature of the composition is 41 ° C. After 28 days, a tensile strength of 46 MPa and an elongation of 8% were found.

Claims (1)

Use of a mixture of mono-, di- and triphenolates containing phenolic hydroxyl groups 0.70 to 0.93 mol / 100 g, preferably 0.85 and 0.87 mol / 100 g, falling off under abnormal conditions of continuous o-oetone condensation with an excess of phenol or forming a refinery residue in the raffinol dianu as epoxide group 8 accelerators epoxy resins, reactive epoxy vnáěený into the composition as a solution in a mixture of palm modified epoxy resin with an average molecular Weight _{f M} NESS 440-750, modified by reactive and / or nonreactive of a solvent, or as a solution in a mixture těohto rospouětědlsoh,