CS255318B1 - Branched amino amide resins - Google Patents

Abstract

The solution describes resins of the structural formula RlCONH—Rs OH I NCH2CHCH2—MZ RzCONH—Rs OH R5—HNCOR3 I Z ■CH2CHCH2N R5-HNCOR4 where Rl, R2, R3 and R4 represent an alkyl radical with 6 to 22 carbon atoms or 8-heptodecenyl, Rs an alkylene radical with 2 or 3 carbon atoms, M a radical epoxy) dian-based resins. The adducts are suitable for the surface treatment of glass fibers, especially in the form of salts with water-soluble acids.

Description

255313

The invention relates to branched amino amide resins and their salts with water-soluble acids suitable for treating glass fibers.

Transparent laminates based on glass fibers and unsaturated polyester resins are always in the focus of research, mainly because their quality, ie increased light transmission, is influenced by many factors of Bo-lo found that even when evaluating the refractory and glass fiber index it is practically impossible to prepare a transparent laminate. The development of transparent laminates is closely linked to the development of glass fiber surface treatments. On the other hand, the coating of glass fibers does not have a negative effect on the transparency, but at the same time they must give them the properties which allow their textile processing. wherein the necessary condition for their properties is to be good compatible with the polyester resins and at the same time impart the necessary textile properties to the fibers. Significant application to the glass fiber refinement has been found in epoxy resin and amine based adducts and polyadditives, especially dian based. While the alkanolamine and / or aliphatic polyamine adducts (Nos. AO No. 204 407,204 408, 210,307) are used in their application to the glass fiber coating, good textile properties are obtained, but the glass is thus prepared. fibers cannot be used as reinforcement of unsaturated polyester, but mainly as reinforcement of epoxy resins. Since the epoxy-based amine adducts impart good textile properties to the fibers, their synthesis was smooth so that they could be used for glass fibers used as reinforcement of unsaturated polyester resins. In the application research, we have found that the properties of the invention have these properties. By using them for the surface treatment of glass fibers, not only good textile properties are immobilized, but at the same time they can be used to produce transparent laminates.

The invention relates to branched amino amide resins of the general formula

RiCONH — Rs OH \ t NOH2CHCH2 — M—

Z R2CONH-R5 OH R5-HNCOR3

IZ

R5 — HNCOR4 where it is

R 1, R 2, R 3, R 4 is an alkyl radical having 6 to 22 carbon atoms or 8-heptadecenyl,

R 5 is an alkylene radical having 2 or 3 carbon atoms, the moiety having a structure

n is 0 to 4, and salts thereof with water-soluble acids. For the preparation of resins, the amidamido base of the monomeric fatty acids adiethylenetriamine or dipropylenetriamine, prepared by amidation at a molar ratio of fatty acid: polyamine of 2: 1 at 150-200 ° C, are used. Fatty acids are used either singly but more often in mixtures such as fatty acids isolated from various oils and fats. The (2,2-bis) -4-hydroxyphenyl-propane dioxide-based epoxy resins used are usually prepared by the alkaline condensation of epichlorohydrin with dian and their structure can be represented by the general formula 255318 V2 / i

O CHo cw5

OH

AND

OCH2CHCH2

Ch3

O -? -? - OCH-C? O? O

Industrial products of epoxy resins are of the utmost importance, and apart from the basic component, they contain a number of polymorphists, the costly isolation of pure products, which can be accomplished by molecular distillation and crystallization. In the preparation of the heat, it is advantageous to add a dianu-based epoxy nutrient to the melt of the amine amide heated to 60 DEG to 180 DEG C. and to terminate the reaction after the epoxide groups have reacted. If desired, the synthesis can be carried out in an organic diluent environment, with water-soluble alcohols and ether-cocks being the most important. The preparation of the salts of water-soluble acids, whether mineral or organic, can be accomplished by simply mixing the resin with the acid either immediately after completion of the synthesis or before application thereof to form emulsions or resin solutions. Table 1 in water. The advantage of this process is the ease of availability of raw materials, which are commonly commercially available and easy to plant, so that their production is also feasible in businesses that are not directly involved in chemical production.

The invention is further illustrated by the following examples. Example 1

100 g of amine-base amine and diethylenetriamine amine having an initial number of 86 mg of KKOH / g were added to the flask with a stirrer and thermometer and heated to 130 ° C. With stirring, the epoxy resin with varying degrees of polyaddition was gradually added and the batch was maintained at the indicated temperature for 2.5 h. The amounts of various epoxy resins and the properties of the prepared adducts shown in Table 1. epoxy resin weight (degree of polyaddition -, (g) n) melting point amine number (° C) (mg KOH / g) 0.1 30.0 0.5 38.0 1.9 71.2 4.0 118.6 35 - 3860 - 62 67 62 50 39 Example 2 For the preparation of the adduct, an amino-amide resin based on a technical mixture of fatty acids with the composition shown in Table 2 of adlethylenetriamine with an amine number of 86 mgKOH / g was used.

Table 2 Fatty acid (%) weight stear 52,4 palmit 42,3 lauric 1,9 arach. 0,7 capryl 0,1 pentadecane 0,3 heptadecane 1,7 capric 0,3 unidentified 0,3

To 100 g of amine, 30 g of epoxy resin was added at a temperature of 120 DEG C., and 0.1 g of the resin was maintained at 2 DEG C. for 2 hours and 65 mg of KOH / g. 10 g of acetic acid was added to the adduct melt and after homogenization the resin was diluted with water to a dry weight of 15% to give a dilutable thiotropic composition Example 3: Amine amide used as a technical fatty acid blend of Table 3 was used to prepare the resin. and diethylenetriamine amine 110 mg COD / g.To either 1 fatty acid 3% lauric 50.8 myrist 13.8 palmitic 11.6 capric 8 1 caprylic 7.8 oil 3.7 stearic 1.2 unidentified 3.0 To 100 g of amine, 96 g of epoxy resin based on dia = 1.9 was added at 130 ° C for 3 h. The prepared resin had a melting point of 48-50 ° C. and amine number 56 mg KOH / g. Example 4 An amine was used to prepare the resin oamide provides fatty acids with the composition of Table 2 and dipropylenetriamine with an amine atom of 82 mg KOH / g. To 100 g of amidamidamide at 140 ° C, 113 g of epoxide resin was added at 4.0 ° to which was maintained for 3 h. The prepared resin had a melting point of 56 to 58 ° C and an amine number of 36 mg of KOH / g. To 100 g of adduct prepared according to Example 1 with an amine number of 67 mg KOH / g was added 8 g of acetic acid at 50 [deg.] C. and the batch was diluted with water to a dry matter content of 25% by weight. A glass fiber strand composed of 200 elephant fibers having an average thickness of 15 microns was adjusted by the composition of Table 4.

Table 4 Raw material (%) Masses ammonium amide resin (25%) 5.0 3-methacryloxypropyltrime toxysilane 0.2 acetic acid 0.1 lithium chloride 0.2 oxyethylated nonylphenol 0.1 water 94.4

The glass fiber was treated in the same manner using a polyvinyl acetate dispersion instead of an amine amide. The treated fibers were dried at 120 degrees Celsius for 6 hours and used to produce unsaturated polyester resin laminates. When using amine-modified com- pounds, laminate delivery of 85 to 90% is achieved in the second case, 70 to 75%.

Claims (1)

255318 18 SUBJECT Branched, amine-amide resins of the general formula RiCONH-R5 OHNCH2CHCH2-M-Z RzCONH-R5 OH R5-HNCOR3 I / -CH2CHCH2N carbon or 8-heptadecenyl, R 5 is an alkylene radical having 2 or 3 carbon atoms, the moiety of the structure is: Cf; OH 1 OCH.CHCH. A ~ & Cř-L ζ ~~ χ I J r -, O _./θ\..f VCj and CHa n are 0 to 4 and their salts with water-soluble acids.