CS232282B1 - Polyaminic adduct compositions - Google Patents

Abstract

The invention relates to the field of synthetic resins. The technical problem of preparing solvent-free liquid hardeners for tough epoxy binders is solved. The essence of the invention is a composition consisting of mixtures of polyene polyamides, adducts of polyene polyamides with acrylates and adducts of polyene polyamines with epoxy resins. The invention can be used in all areas where the application of epoxies with curing temperatures up to about 80° C is considered.

Description

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The invention relates to a composition of polyamine adducts based on epoxy resins, acrylic esters and polyamides.

Addition products resulting from the reaction between polyemines and epoxy resins or acrylic esters find use in a variety of industries, particularly as curing components of apoxy or polyisocyanate resins. Polyamine-acrylate adducts are used only rarely because they cause an irregular structure of the polymer network, resulting in poor mechanical properties of the cured composition.

In contrast, adducts of epoxides with polyamines allow the formation of a relatively uniform network structure, but they need to be processed and used either in the form of solutions in flowing solvents or in excess polyamines. Usually, 50 to 70% adduct solutions in polyamines are used which, after curing the mass, have increased thermal stability, relatively good tensile and compressive strength values, but low impact strength and high brittleness values.

We have now found a composition of polyamine adducts, providing a balanced structure of screens of cured compositions that are tough and have very good mechanical properties.

The composition according to the invention consists of 5 to 20 parts by weight of aliphatic polyenpolyamines having an average molecular weight of 103 to 350, an amine number of 800 to 1630 gig KOH / g e - an equivalent weight of 20 to 50; 0 to 30 parts of an adduct having an average molecular weight of 230 to 600, an amine number of 500 to 700 mg KOH / g and an average equivalent weight of 57 to 100, obtainable by reacting one mole of polyenpolyamines with one mole of acrylic esters; and from 60 to 85 parts of an adduct having an average molecular weight of 546 to 1300, an amine number of 430 to 800 mg KOH / g and an equivalent weight of 60 to 108, obtainable by reacting one molar part of epoxide resin with an average molecular weight of 340 to 600 with two molar parts polyenpolyamines.

The composition according to the invention may also contain from 1 to 15% by weight. % phthalic, citric, esters of fatty acids, triphenylphostite and the like. In cases where an increased curing rate is desired, or curing is carried out at temperatures below 15 ° C, it is appropriate to add 0.5 to 5 wt. % phenolic accelerators, especially cresol, xylenol, salicylates and the like.

The composition of the invention has good miscibility and compatibility with conventional types of epoxy and polyisocyanate resins, and typically has a viscosity of less than 20,000 mPe.s / 25 ° C.

Preferably, use! polyenpolyamines derived from ethylenediemine or propylenediamine. in particular diethyltriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tatrapropylenepentamine, mixtures thereof, technical distillation slices, technical fractions or distillation residues containing said polyolefin polyamines.

Of the acrylic esters, n-butyl acrylate, isobutyl acrylate, non-oxyacrylate, n-octylacrylate, ethylexyl acrylate, lauryl acrylate, benzyl alkoxylate, methylbenzyl acrylate, or mixtures of these acrylates in technical grade are preferably used.

Of the epoxy resins, palm epoxy resins are preferably used, but it is also possible to use epoxy resins based on flsphenol F or resorcinol.

'and

Typically, liquid low molecular weight epoxy resins are used for curing, and the amount of composition necessary to fully cure 100 g of epoxide is calculated by the formula:

ϊ, χ H U, where E represents the epoxy content found in the epoxide (mol / 100 g)

H is the equivalent weight of the composition,

M is the amount of composition in g required to

Curing is usually performed to the extent necessary to use curing accelerators.

curing 100 g of epoxide.

to 80 ° C, at lower ambient temperatures is

He did

Mix 5 wt. parts by weight of tetrsetylenepentamine (molecular weight 189.3, amine number 1482 mg KOH / g, equivalent weight 27.04), 30 wt. 65 parts by weight of n-butyl acrylate adduct (1: 1 molar ratio, mean molecular weight 231, amine number 729 mg KOH / g, equivalent weight 57.7) and 65 wt. parts of an adduct formed by reacting 1 mole of bis- / glycidylether / diene with 2 moles of tetreetylsnpentamine (mean m61, mass 719, amine number 789 mg KOH / g).

The composition is homogenized at 60 ° C and then cooled to room temperature. It has a viscosity of 2,450 mPa · s / 25 ° C, an average molecular weight of 546, an amine number of 799 mg KOH / g, an average functionality of 9.35, and an average equivalent weight of 58.15.

100 g low molecular weight epoxy resin with average molecular weight 378 epoxy group content e (E ₁₎ 0.526 mol / 100 g is mixed at room temperature with 30.6 g * composition * thoroughly homogenized and allowed to stand 5 days. The cured mass has a tensile strength of 49.1 MPa, a tensile strength of 9%, an impact strength of 19.8 kJ / m @ 2.

Example 2

It mixes and homogenizes 20 wt. parts by weight of tetropropylenepentamine (amine number 1143 mg KOH / g), 10 wt. parts of an adduct of 1 mole of lauryl acrylate (240) with 1 mole of tetrapropylenepentamine (245 g), the mole of which is 1 mol. the mass is 485, the amine number is 578 and the equivalent weight is 80.83; 70 wt. parts of an adduct of 1 mole epoxy resin palm (with a molecular weight cut of 598) with 2 moles of tetrspropylenepentemine (491), a mean mol. weight 1 089, an amine number of 515 mg KOH / g and an equivalent weight of 90.75.

The homogeneous composition has a viscosity of 7,050 mPaa / 25 ° C, an average molecular weight of 860, an amine number of 555 mg KOH / g, a mean functionality of 10.4, and an average equivalent weight of 82.7.

100 g of epoxy resin of E. 0.526 o-cresol, at 10 to 12 ° C. After 7 days, the ¹ µ cured mass has a tensile strength of 52.7 MPa, a drawing strength of 12%, an impact strength of 22.1 kJ / m.

Example 3

The composition of: 5 wt. parts of diethylenetriamine (amine number 1630 mg KOH / g); 10 wt. parts of adduct 1 mol. % of ethylhexyl kralate (184 g) and 1 mol. a portion of dipropylene triamine (131.2 g) having an average molecular weight of 315, an amine number of 534 mg KOH / g, and an equivalent weight of 78.85; 85 wt. parts of the adduct prepared by the reaction of 1 mol. % of an epoxy resin having an average molecular weight of 555 with 2 mol. parts of triethylenetetramine (292 g) having an average molecular weight of 847, an amine number of 530 mg KOH / g and an equivalent weight of 84.70.

The homogeneous composition has a viscosity of 15,830 mPa.e / 25 ° C, an amine number of 585 mg KOH / g, an average molecular weight of 757, an average equivalent weight of 80.91, and an average functionality of 9.15. 100 g of a low molecular weight epoxy resin of 0.526 mol / 100 g is mixed with 42.5 g of the composition and cured at 60 ° C for 48 hours. The mass obtained has a tensile strength of 55.1 MPa, an elongation of 8% and an impact strength of 15.7 kJ / m @ 2.

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Example

Mixes aa and thoroughly homogenizes: 10 wt. parts of the distillation residue from the aminolysis of dichloropropane, composed of:

85.0% tetrapsopylenepentamine,

5.3 X tripropylenetheramine,

1,6 X dipropylenetetramine,

8,1 X sum 3 neident. substances having an amine number of 1,148 mg KOH and an average molecular weight of 236, an average equivalent weight of 35.03;

wt. parts of adduct 1 mole of hansyl acrylate (162 g) with 1 mole dest. aminolysis residue (236 g), with a mean mol. weight 398, amine salt 681 mg KOH / g, and medium equiv. mass 69.22;

wt. parts of an adduct of 1 mole of bla- (glycidylether / dian) (340 g) with 2 moles of diethylenetrlemine (206) having an average molecular weight of 546, an amine of 616 mg KOH / g and an average equiv. mass 68.25;

wt. parts of dibutyl phthalate.

t

After shomogenization and e, a composition having a viscosity of 3 168 mFa.s / 25 ° C, an average molecular weight of 458, an amine of 644 mg KOH / g, an average equivalent weight of 60.95 is obtained. 100 g * of molybdenum epoxy resin > 0.526 mol / 100 g is mixed with 32.1 g of the composition and allowed to cure at room temperature. After 7 days, the cured mass has a tensile strength of 48.1 KPa, a ductile 16X and an impact strength of 46.1 kJ / m ² .

SUBJECT OF THE INVENTION

Claims (3)

The composition of the polyamine adducts, characterized in that it consists of 1 wt 5 to 20 parts of polyenpolyamines having an average molecular weight of 103 to 350, an amine number of 350, an amine number of 800 to 1,630 mg KOH / g, and an average equivalent weight of 20 to 50, 10 to 30 parts of an adduct having an average molecular weight of 230 to 600, an amine number of 500 to 600 730 mg KDH / g and an equivalent weight of 57 to 100 resulting from the reaction of 1 mole of polyenpolyamines with 1 mole of acrylic esters, 60 to 85 parts of an adduct having an average molecular weight of 546 to 1300, an amine strength of 430/800 mg and an equivalent weight of 60 to 108 resulting from the reaction of 1 molar part of epoxy resin of 340 to 600 molar molecular weight with two molar parts of polyenpolyamines. Severography, n. P., MOST Price 2,40 Kčs