DE1745322A1 - Production of imidazoline-containing polyamidoamines - Google Patents

Description

- WALTER NlELSCH St 5. Fob, J ₃₆ /

Closes,; -. *. Ρ "." «!, 1C914

^{Ferniüf: 6529707} File: 2088

REICHHOLD CHEMIE AKTIENGESELLSCHAFT Hamburg 70, Iversstrasse 57

Production of imidazoline-containing polyamidoamines

From patent literature (see British patent specification 803 517) is the production of certain polyamidoamines known. These known products are condensation products of one or more polyamines with a copolymerization product from styrene or hydrocarbon-substituted styrene and dehydrate riftzinus oil fatty acids.

It has now been found ₃ that significantly improved products are obtained if copolymers of conjugated unsaturated fatty acids or their esters and ethylenically unsaturated aromatic compounds such as styrene, ct-methylstyrene, vinyl toluene, divinylbenzene, which are generally produced that to the conjugated unsaturated fatty acids or fatty acid esters heated to temperatures of 150 to 250 ° C., preferably 180 to 210 ° C., while stirring and passing inert gas, for example nitrogen, over a longer period of about 5 to 30 hours, preferably 18 to 20 hours, 0.5 to 3, preferably 1 to 2 moles of the ethylenically unsaturated aromatic compound or mixture of compounds is continuously added and for a few more hours at these temperatures for complete conversion, with approximately equinolar amounts of ethylcenediamine and / or its homologues such as diethylenetriamine, Tr iäthylentetramln and / or Tet.r-aäthylenpentamin by heating at 200 ° C to polyamido converts min connections and then by further heating to temperatures between 220 and 350 ° C, preferably 300 ° C and optionally by applying a vacuum to support the water

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cleavage for the purpose of ring closure to the imidazoline derivative accordingly the equation:

- CONH. CHp. MHR ₂

N - CH

R - C ¹ ^ ι + H ₀ O, where R _{1 is} the remainder of the * \!

N - CH ₀ copolymerized fatty acid

^R 2

and R ₀ = H or - (CH ₂ .CH ₃ NH) _n H with η = 0 - 4,

lets react.

Suitable conjugated unsaturated fatty acids for producing the copolymers are dehydrated castor oil fatty acids, isomerized linseed oil fatty acids, isomerized soybean oil fatty acids, and wood oil fatty acids or their methyl or ethyl esters. Those conjugated unsaturated fatty acids or their esters can be used which contain 10 to 2k carbon atoms. Examples of suitable ethylenically unsaturated compounds for preparing the copolymers are: styrene, α-methylstyrene, divinylbenzene and vinyltoluene.

The following polyamines can be used for the preparation of the polyamino amides: diethylenetriamine, xthylenediamine, triethylenetetramine and / or tetraäthylenpentatnin. The copolymerization products can be obtained by heating the conjugated fatty acids, for example dehydrating castor oil fatty acid with styrene, α-methylstyrene, vinyltoluene or divinylbenzene, preferably in the presence of a polymerization catalyst which forms free radicals. Preferably, organic peroxide as a catalyst, such as di-tertiary-butyl peroxide, Benzoylporoxid, 2, ⁱ i-di-chlorobenzoyl peroxide, p-chlorobenzoyl peroxide, diacetyl peroxide, lauryl peroxide, succinyl peroxide, tert. Buty! Hydroperoxide, cumene hydroperoxide, cyclo-

; ^; - 3 - ^ ₀ ORIGINAL

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hexanone peroxide, methyl isobutyl kotone peroxide and / or pinane hydroperoxide used, if necessary in conjunction with non-metallic reducing polymerization inhibitors, consisting of an alky! mercaptan with 6 to 12 carbon atoms, preferably laury! mercaptan. the Polyamidoamines themselves are produced by heating one or more polyamines at elevated temperatures with the (^ polymerization products.

The imidazoline-containing polyamidoamines can be used are used as stabilizers for polyacetals and especially as curing agents for epoxy resins.

According to the process according to the invention, imidazoline groups are obtained Polyamidoamines, which are lighter in color and lower in viscosity differentiate between imidazoline-free products. In addition, these new products are particularly suitable as hardeners for epoxy resins, since the epoxy resins hardened with them significantly improve their physical properties Experienced.

The following examples explain the process for preparing the new imidazoline-containing polyamidoamines.

Manufacture; of the copolymer A

2850 seconds of dehydrated castor oil fatty acid (commercially available as dedico fatty acid, conjuene content: 30 to 50%) are heated to 190 ° C. in a flask equipped with a reflux condenser, dropping funnel, stirrer and thermometer. Within ion 20 hours. Allowed to a mixture of 520 £ styrene, 3 β lauryl mercaptan and 1.5 £ di-tert-butyl peroxide is added dropwise uniformly. The reaction mixture is then kept at dleser temperature for a further 10 hours and left to cool. A copolymer is obtained with an acid number of 162.4 and a viscosity of 204 cP, measuring at 2 ^t 5 ° 0, when the

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Copolymers with n-butanol do not show any signs of clouding.

Example l

805 g of the copolymer A _3, 297 g of diethylenetriamine and 0.3 ml of 1 # silicone defoamer in toluene are heated to the reflux temperature of about 150 in a flask equipped with a stirrer, thermometer and reflux condenser under an Np atmosphere in 1.5 to 2 hours ° G and heated to reflux for 1.5 hours. A distillation receiver is now attached to the flask, heated _{to 300 ° C. in about 2 3 5 hours with the introduction of N 2} and continuous distillation of water and excess amine. Once this temperature has been reached, the reaction mixture is left in a vacuum without further heating Cool down to 200 ° C for approx. 20 to 30 minutes. At this temperature, the vacuum is released by means of N ₃ , the mixture is allowed to cool down to 100 ° C. and the batch is filtered. Diethylenetriamine is determined titrimetrically in the aqueous distillate. An imidazoline-containing polyamidoamine with an amine number of 24 ^ 1 and a viscosity of 7 ^ 6 cP at 25 ° C. is obtained.

Comparison 1

For comparison, a polyamidoamine was produced with the same starting materials without carrying out the conversion to the imidazoline.

805 g of the copolymer A, 297 g of diethylenetriamine and 0.3 ml of a liquid silicone defoamer in toluene - as described in Example 1 - under an N ^ atmosphere brought to the reflux temperature and refluxed for 1.5 hours. Then you heat with switching on c-inqp distillation system at 200 ° C for approx. 1 hour and holds at this temperature until the acid number is <^ 3. It is then allowed to cool to 100.degree. C. and the residue is filtered. In the aqueous distillate, diethylone triamine is titrated

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certainly. A polyamide-amine with an amine number of 304 and a viscosity of 1,550 cP at 25 ° C. is obtained.

From the product according to the invention and the comparison substance and a liquid epoxy resin based on bisphenol A and epichlorohydrin, which has an epoxide equivalent weight (E-VaI) of 190 and a viscosity of 9,750 cP at 25 ° C 10 mm thick plates in the specified mixing ratio were poured into a plate mold in such a way that that the bubble-free mixture is first 24 hours at room temperature and then another 2 hours at 100.degree have been cured.

Table 1

test Mixture of 190 g
Epoxy resin (E-VaI 190)
and 130 g of resin
example 1 Groaning from
190 ζ epoxy
resin (E-VaI 190)
and 130 grams of resin
after comparison 1 Limit bend
tension
(DIN 53 452)
Deflection
(DIN 53 452)
Impact resistant
speed
(DIN 53 453) 1,200 (Kp / cm ² )
1.0 (cm)
20 (cp. Cm)
<om ² ) 850 (Kp / cm ² )
1.5 (om)
15.5 (bp cm)
(cm ² J

Production of the copolymer B

2120 g of dehydrated castor oil fatty acid (al3 dedico fatty acid on the market, $ 50 conjuene content) are in one with Reflux condenser, dropping funnel> The flask fitted with a stirrer and thermometer is heated to 190 ° C. Within 20 hours a mixture of 790 g of styrene and 2.3 ml of lauryl mercaptan is left

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and drop 2, j5 ml of di-tert-butyl peroxide evenly. The reaction mixture is then held for a further 10 hours at this temperature and then allowed to cool. A copolymer with an acid number of 14o is obtained and a viscosity of 812 cP, measured at 25 ° C. This product can also be mixed with n-butanol without causing turbidity.

Example 2t

According to the information in Example 1, 800 g of the copolymer B, 226 g of diethylenetriamine and 0.3 ml L ^ iger silicone defoamer an imidazoline-containing polyamidoamine produced with an amine number of 190 and a viscosity of 1022 cP at 25 ° C.

Comparison 2t

According to the information in Comparison 1, 800 g of copolymer B were converted into 226 g of diethylenetriamine and 0.3 ml Liquid silicone defoamer produced a polyamidoamine with an amine number of 19I and a viscosity of 1,480 cP at 25 ° C.

From these products and a liquid epoxy resin based on bisphenol A and epichlorohydrin, which has an epoxy equivalent weight of 190 and a viscosity of 9 »750 cP at 25 ° C, 10 mm thick plates in the specified mixing ratio were poured into a plate mold in the manner that the mixtures are first 24 hours at room temperature and then another 2 hours at 100 ° C have been cured.

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- 7th
Table 2

Test: Mixture of 190 g
Epoxy resin (E-VaI I90)
and 130 grams of resin
according to example 2 Mixture of 190 g
Epoxy resin (E-VaI
190) and 130 g of resin
after comparison 2 Limit bend
tension
(DIN 53 4525
Deflection
(DIN 53 452)
Impact resistant
speed
(DIN 53 453) II30 (Kp / cm ² )
1.5 (cm)
34.0 (bp cm)
2)
cm ' 900 (Kp / cm ² )
1.4 (cm)
27.5 (IP.cm)
(2)
^x cm '

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Claims (1)

DR. IV / WkV4 w «Akto: 208β PATENT CLAIMS 1. Process for the preparation of imidazoline-containing polyamidoamine resins from copolymers of conjugated unsaturated fatty acids and / or fatty acid esters with ethylenically unsaturated aromatic compounds, rfie e.g. styrene, α-methylstyrene, vinyltoluene and / or Divinylbenzene and xthylenediamine and / or its homologues such as diethylenetriamine, triethylenetetramine and / or Tetraethylene pentamine, characterized in that one a) the copolymers with stirring and passing over Inert gas at temperatures of 150 to 250 C, preferably 180 to 210 ° C, in such a way that that by heating the conjugated unsaturated fatty acids or fatty acid esters in a longer Period of about 5 to 30 hours, preferably 18 to 20 hours, with continuous addition of Polymerization catalysts, preferably peroxides, and the ethylenically unsaturated compounds or Compound mixtures in amounts totaling 0.5 to 3 moles, preferably 1 to 2 moles per fatty acid or fatty acid ester, converted, then to completion the reaction continues to heat up, and b) the copolymers obtained with approximately equimolar Amounts of Diarainen by heating up to 200 ° C to the pole; mldoaaiin implements, and c) the polyamidoaroin resins obtained at temperatures between 220 to 350 ° C, preferably 300 ° C, if under vacuum systems, heated. 209819/1032