CS252771B1 - Reaction products of higher saturated and / or unsaturated carboxylic acids with polytopic amines - Google Patents

Abstract

The purpose of the solution is products of higher saturated and/or unsaturated carboxylic acids with polytopic amines with better utility properties. The purpose was achieved by reaction products containing 75 to 99% by weight of activated quaternary coppex (polyimine with various end groups) of the structural formula R.COOH3N+./(CH2)m-NH/n.(CH2)m. . NHj.OOC.R, R.C00H3N+■/(CH2)m-NH/n.(CH2)m-NH2 and R.C00HjN+./(CH^-NH^.00C.R/ . . (CH„) .NHÍ.OOC.R , where m =2 to 6, n - 0 to 8 and R = C, to C2a alkylalkenyl, alkanedienyl, alkantrienyl) and 1 to 25 wt. % of compounds of amide character of the structural formula R.CONH./CCHj -NH/ .(CH„) .NHOC.R zrn n Zrn and H2N./(CH2)m.NH/n·(CH2)m.NHOC.R, where m = 2 to 6, n = 0 to 8 and R = C, to alkyl (alkenyl, alkanedienyl, alkantrienyl) and possibly unreacted starting materials and side reaction products. The reaction products can be dissolved in up to 65% by weight of ethyl alcohol.

Description

The invention relates to reaction products of higher saturated and / or unsaturated carboxylic acids with polytopic amines.

The reaction products of higher saturated and / or unsaturated carboxylic acids with polytopic amines find an important place in the production of bituminous mixtures, asphalt dispersions, tar paper, bituminous materials, etc.

Currently, imidazole-type products are used to improve the adhesive properties of resins to aggregates, particularly acidic. Imidazole-type products used to improve the physical-mechanical properties of bituminous mixtures are produced in Czechoslovakia due to the high exchange rate of raw materials and energy consumption of production to a limited extent. Some are imported from the capitalist countries under the trademarks Serfax-AK Servo-Delden (The Netherlands), Redioote E 11 - Armor Hess (UK) and Stabiram EM - Auby-Proohinor (France). The products imported from the KS states are foreign exchange demanding and are imported in the form of dilute solutions, which increases the demands on storage space and increased dosage. These imidazole-type products hitherto used have a number of disadvantages and drawbacks. Among the most demanding shortcomings is the fact that finished products change their Theological properties shortly after production, thereby losing their quality.

252 771 and their effect is reduced. They are difficult to process because they must be heated before use. Another consequent disadvantage is their harmfulness to health and the unpleasant odor of imidazole-type products, not only during their manufacture but also during further processing, especially after heating.

Imidazole-type products cannot be used for the preparation of penetration asphalt lacquers with a softening point above 105 ° 0 as they lose their penetration ability and activity under long-term thermal stress.

The disadvantages of the current state are eliminated by the products of higher saturated and / or unsaturated carboxylic acids with the polytopic amines according to the invention, containing up to 99 wt. activated quaternary ammonium complex of higher carboxylic acids with polytopic amines (polyimines with different end groups) of structural formula

R.COOH ./(CH ₃ N ⁺ _{2) m} -W _{n. (CH2) m} + .IJH. OOC.R,

C00H R ₃ N ^+. / (CH ₂ ) _m -W _n . (CH ₂ ) _m . NH ₂ a

R.COOH ./(CH ₃ N ⁺ ₂₎ -NHj.OOC.R _m / _{n. (CH2) m} ^ .OOC.R .NH wherein m = 2-6, n = 0-8 and R = % C 8 -C 14 alkyl (alkenyl, alkanedienyl, alkanetrienyl) and up to 25 wt. amide compounds of the structural formula

R.COHN./( CH ₂ ) _m -W _n (OT ₂ ) _m

H ₂ N./(CH ₂ ) _m -NH / _n . (CH ₂ ) _m. NHOC.R, where ms 2 to 6, n = 0 to 8 and R = C 8 to ^C 24 alkyl (alkenyl, alkanedienyl, alkanetrienyl) ) and optionally unreacted feedstocks and by-product products.

The reaction products can be dissolved in up to 65% by weight of ethyl alcohol.

The advantages of the reaction products according to the invention reside in their improved utility properties. They can be prepared in a wide concentration range according to the needs of processors and are significantly less demanding in terms of currency compared to existing domestic and imidazole-based products. They have a higher ability to increase the adhesion of bitumen to aggregates, even wet and acidic. Manufactured products

The toxicological tests have shown that the reaction products of the present invention are less harmful to health and are not associated with an unpleasant odor as imidazole-type substances.

Comparison of application properties - adhesion properties of resins to aggregates, especially acidic and wet, showed that with the same dosage of active substance of existing domestic and foreign preparations from KS compared to reaction products according to the invention, reaction products according to the invention have especially when applied resins acid wet aggregate up to 20% higher activity than existing imidazole-type domestic or foreign products. The evaluation was carried out by the methodology according to ČSN 65 7089 - Determination of adhesion of asphalt products to aggregates from 1982. The influence of additives was assessed in percentage of uncovered aggregate surface.

The products according to the invention can also be used for the preparation of penetration bituminous varnishes with a softening point above 105 ° C, since they are not subject to thermal changes and thermal stress in the desired temperature range and do not lose their penetration ability and activity.

Example 1

9% wt. % palmitic acid, 31 wt. oleic acid, 20 wt. % linoleic acid and 40 wt. Linolenic acid with dipropylene triamine contain a network

75% wt. quaternary ammonium complex (polyimine)

R.COOH ./(CH ₃ N ⁺ _{2) m} -NH / _{n. (CH2) m} ^ .NH. OOC.R,

R.COOH ./(CH ₃ N ⁺ _{2) m-HH} / _n. (CH ₂

R.C00H ./(CH ₃ N ⁺ ₂₎ -NHj.000.R _m / _{n. (CH2) m} ^ .NH. % OOC.R and 25 wt. amide compounds

R.C0HN./(CH _{2) m} -NH / _{n. (CH2) m} and .NH0C.R

H ₂ N./( CH ₂ ) _m -NH / _n (CH ₂ ) _m -NHCO.R, wherein m »3, η« 1 and R «alkyl (alkenyl, alkanedienyl, alkanetrienyl) corresponding to the reacting carboxylic acids.

The consistency of the product measured at the outlet cup with an opening S4 at ° C is 60 s.

252 771

Procaato uncovered aggregate surface determined by the test according to the methodology ČSN 65 7089 Sine for dolomitic limestone Tunežice (SSR) and asphalt A-80 with the addition of 0.1 wt. % of the reaction product according to the invention 100%, with an addition of 0.1% by weight. of Redicote E 11 (UK) was 98% and only 80% without addition.

Example 2

The reaction product of the reaction mixture of 50 wt. % behenic acid, 30 wt. % oleic acid and 20 wt. % linoleic acid with ethylenediamine, liquefied by addition of 2 wt. ethyl alcohol, containing:

95% wt. quaternary ammonium complex (polyimine)

R.C00H ./(C3H ₃ N ⁺ _{2) m} -NH / _{I1. (CH2) m} + .IÍH .OOC.R,

R.C00H ./(CH ₃ N ⁺ ₂₎ NI ^ _m. (CH ₂ ) _m. NH ₂ a

R.COOH ₃ N ⁺ ./(CH ₂ .00C.R / _n · (0¾) _ffl .00C, R and 5% by weight of amide compounds R.CONH./CCHgJ^NH/jj (CH ₂ ) _m .NH0C.R a

H ₂ N./(CH ₂ ) _m -NH / _n (CH ₂ ) _m -NHOC.R, where m »2, n = 0 and R is alkyl (alkenyl, alkanedienyl) corresponding to the reacting carboxylic acids.

The consistency of the product measured at 20 ° C is 40 s.

The percentage of uncovered aggregate surface determined by the test according to the methodology of ČSN 65 7089 is for the biotitic granodiori Litice nad Orlicí and asphalt A-80 with the addition of 0.5% by weight. % of the reaction product according to the invention 100%, with an addition Θ, 8% by weight of the reaction product; of Redicote E 11 (UK) 100% and without additive 40%.

Example 3

The reaction product of the reaction of stearic acid with tripropylenetetraamine liquified by the addition of 50 wt. ethyl alcohol containing:

98% quart emího ammonium complex (a polyimine) ₃ N ⁺ R.C00H ./(CH _{2) m} -] 3 H / _{N. (2} 0H) _m ^ .NH. OOC.R

R.C00H ₃ N ⁺ ./(CH ₂ ) _m -HH / _n · (CH ₂ ) _B. NH ₂

252 771

R.C00H ./(CH ₃ H ⁺ _{2) m} HH ^ 00C.R / _{a. (CH2) m} .00C.R and 2% by weight of the amide compounds of character ·

(CH ₂ ) _m -NH / _n (0 ') _m

H ₂ N./(CH ₂ ) _m -HH / _n . (CH ₂ ) _m .HCO 3 R, where m = 3, n = 2 and R = CH ₃ (CH ₂ ) jg— ·

The consistency of the product measured at 20 ° C is 20 s.

The percentage of uncovered aggregate surface determined by the test according to the methodology of ČSN 65 7089 is for amphibolic-biotithioc Silica. dio rit Mrač and asphalt A-80 with 1% wt. % of the reaction product according to the invention 100%, with an addition of 1% by weight; of Serfax AK (The Netherlands) 95%, without additive 60%.

Example 4

The reaction product of the reaction of rioinoleic acid with diethylenetriamine liquefied by the addition of 10 wt. ethyl alcohol containing:

80 wt. quaternary ammonium complex (polyimine)

R.C00H ./(CH ₃ H ⁺ _{2) m-HH} / _{I1. (CH2) m} ^ .NH. OOC.R,

R.C00H ./(CH ₃ N ⁺ _{2) m} -NH / _{n. (CH2) m} .HH ₂

R.000H ./(CH ₃ H ⁺ _{2) m} -NH +. 00C.R / _n . (CH ₂ ) _m . HH ^. % OOC.R and 20 wt. amide compounds

R.C0HH./(CH _{2) m} -NH / _{n. (CH2) m} and .NH0C.R

H ₂ N./.(CH ₂ ) _m -NH / _n . (CH ₂ ) _m .NHCO.R, where m = 2, η. = 1 and R = CH ₃ (CH ₂ ) ₅ -JH-CH ₂ .CH = CH- (CH ₂ ) ₇ OH

The consistency of the product measured at the outlet cup S4 at 20 ° C is 30 s.

Percentage of uncovered aggregate surface determined by test according to CSN 65 7089 Sine for olivine basalt agglomerate

Spruce and asphalt A-80 with 0.1% wt. % of the reaction product according to the invention 100%, with the addition of 0.2 wt. Redicote

E 11 (UK) 100% and no additive 60%.

β

Example 5;

The reaction product of the reaction mixture of 20 wt. % stearic acid and 80 wt. oleic acid with tetraethylenepentaarain, liquefied by the addition of 65 wt. ethyl alcohol containing:

86% wt. quaternary ammonium complex (polyimine)

R.COOH ₃ Ni / (CHP _m -W _{I1. (CH2) m} + .NH. OOC.R,

R.000H ./(CH ₃ N ⁺ _{2) m} -NH / _{n. (CH2) m} .NH ₂

R.OOOH ₃ N ^{+. ((} CH ₂ ) _m -NH ₂ . OOC.R / _n . (0¾) _m . NH +. % and 14 wt. amide compounds

R.C0NH./(CH _{2) m} -NH / _{n. (CH2) m} and .NH0C.R

H _? N./( CH ₂ ) _m -NH / _n (CH ₂ ) _m NHOC · R, where m - 2, n = 3 and R = CH ₃ pH ₂ - ₁₆ - respectively. CH ₃ CCH ₂ ) ₇ .CH = CH.CCH ₂ ) _? -.

The consistency of the product measured at 20 ° C is 20 s.

The percentage of unoccupied aggregate surface determined by the test according to the methodology of ČSN 65 7089 is for natrolitic alkaline trachyl Mariánská skála and asphalt A-80 with the addition of 1% by weight. % of the reaction product according to the invention 100%, with an addition of 1% by weight; of Redicote E 11 (UK) 95% and without additive 40%.

Example 6

The reaction product of oleic acid with di-ethylenetriamine containing:

78% wt. quaternary ammonium complex (polyimine)

R.C00H ./(CH ₃ N ⁺ _{2) m} -NH / _{n. (CH2) m.} NH +. OOC.R,

R. OOOH ₃ N ⁺ . / (CH ₂ ) _m -W _n . _{(CH2) m} .HH ₂

R.COOH ₃ N ^{+. ((} CH ₂ ) _m -NH ₂ . OOC.R / _n . (CH ₂ ) _m . NH +. % OOC.R and 22 wt. amide compounds

R.CONH./(CH _{2) m} -NH / _{n. (CH2) m} and .NHOC.R

H ₂ N./(CH ₂₎ -NH _ffi / _{n. (CH2) m} .NHOC.R wherein m = 2, n = 1 and R = CH ₃ (CH _{2) 7} CH = CH _{(CH2) 7} -.

The consistency of the product measured at the outlet cup with the opening S4 at ° C is 55 s.

Percentage of uncovered aggregate surface as determined by test according to

252 771 of the methodology ČSN 65 7089 for dolomitic limestone Tunežice (SSR) and asphalt A-80 with the addition of 0.1 wt. % of the reaction product according to the invention 100%, with an addition of 0.3 wt. of Serfax AK (The Netherlands) 100% and without additive 80%.

Example 7

10% wt. % caprylic acid, 10 wt. % capric acid, 50 wt. lauric acid, 20 wt. % myristic acid and 10 wt. % palmitic acid with a 50 wt. % of ethylenediamine and 50 wt. % diethylenetriamine liquefied by the addition of 5 wt. Ethanol contains:

72 wt. quaternary ammonium complex (polyimine)

R.000H ./(CH ₃ N ⁺ _{2) R} HH / _{n. (CH2) m} NH + · · OOC.R,

R.000H ./(CH ⁺ ₃ H _{2) m} -líH / _{n. (CH2) m.} NHg a

(CH ₂ ) _m -HH? 100C.R / _n (CH ₂ ) _m . % OOC.R and 28 wt. amide compounds

R.CO H./(CH _{2) m} HH / _{n. (CH2) m} and .HHOC.R

H, ₂ H, / _{(CH2) m-HH} / _{n. (CH2) m} .NH0C.R wherein m "2 n" 0 respectively. 1 and R alkyl belonging to the respective carboxylic acid.

The consistency of the product measured at the outlet cup with an S4 opening at 20 ° C is 45 s ·

The percentage of uncovered aggregate surface determined by the test in accordance with the methodology of ČSN 65 7089 is for the biotithiocitic granodiorite Litioe nad Orlicí and asphalt A-80 with the addition of 0.2% by weight. % of the reaction product according to the invention 100%, with the addition of 0.2 wt. of Serfax AK (The Netherlands) 90% and without additive 40%.

Example 8

The reaction product of the mixture was 50 wt. oleic acid, 35 wt. % palmitic acid and 15 wt. % stearic acid with a 5 wt. % ethylenediamine, 92 wt. % diethylenetriamine and 3 wt. % triethylenetetramine liquefied by the addition of 20 wt. % ethanol containing: 92 wt. quaternary ammonium complex (polyimine)

R.COOH ₃ N ^{+. ((} CH ₂ ) _m -NH / _n . (CH2Cl2HiTj. OOC.R.

R.COOH ./(CH ₃ N ⁺ _{2) m} -NH / _{n. (CH2) m} .NH ₂

R. GOOH ₃ N ⁺ . (CH ₂ ) _m -NH ₂ OOC.R / _n (CH ₃ ) _m NH ₃ ⁺ .

252 771

% OOC.R and 8 wt. amide compounds

R.CONH./(CH _{2) m} -NH / _n. (CH) _m .NHOC.RH N./(CH _{2 2) m} HH / _n. (CHG) .NHOC.R _m wherein m = 2, ns O ^ resp. L _R R = alkyl (alkenyl) belonging to the corresponding reactive carboxylic acid.

The consistency of the product measured at 20 ° C is 35 s.

The percentage of uncovered aggregate surface determined by the test according to the methodology of ČSN 65 7089 is agglomerate of olive basalt Smrčí and asphalt A-80 with the addition of 1% by weight. % of the reaction product according to the invention 100%, with the addition of 1 wt. of Redicote E 11 (Great White) 95% and without additive 60%.

Example 9

The reaction product of the reaction of stearic acid with a mixture of 20 wt.% Ethylenediamine, 60 wt. % diethylenetriamine and 20 wt. % lentriamine dipropy liquefied by addition of 6 wt. ethanol contain cis

95% wt. quaternary ammonium complex (polyimine)

and 5 wt. amide compounds

R.C0NH./(CH _{2) m} -NH / _{n. (CH2) m} and .NH0C.R

H ₂ N./( CH ₂ ) _m -NH / _n (CH ₂ ) _m . 3, η «Ο, τββρ. l, and R «CH ₃ (CH ₂ > 16“) ·

The consistency of the product measured by the outlet cup with the opening S4 at ° C is 30 s.

Percentage of uncovered aggregate surface determined by the test according to the methodology ČSN 65 7089 for natrolitic alkaline trachyt Marián ká skála and asphalt A-80 with the addition of 0.6 wt. of the reaction product

252,771 according to the invention is 100%, and 0.8% by weight of the additive. of Formulation E 11 (UK) 100%, with no additive 40%.

Example 10

9% wt. % palmitic acid, 31 wt. oleic acid, 20 wt. % linoleic acid and 40 wt. % linolenic acid with a mixture of 50 wt. % diethylenetriarain and 50 wt. % dipropylene triamine liquefied by the addition of 40 wt. ethyl alcohol containing:

82% wt. quaternary ammonium complex (polyimine)

R.C00H ./(0H ₃ N ⁺ _{2) m} -NH / _{n. (CH2) m} ^ .NH. OOC.R,

R.C00H ./(CH ₃ ⁺ R _{2) m} -NH / _{n. (CH2) m} .NH ₂

R.C00H ./(CH ₃ N ⁺ _{2) m} -NH ₂ .00C.R / _{n. (CH2) m.} NH +. OOC.R and 18% wt. amide compounds

R.OONH./(GH _{2) m} -NH / _{n. (CH2) m} and .lIHOC.R

H ₂ N./( CH ₂ ) _m -NH / _n . (CH ₂ ) _m . NHOC.R where m = 2 is res. 3, n = 1 and R = alkyl (alkenyl, alkanedienyl, alkanetrienyl) belonging to the respective carboxylic acid.

The consistency of the product measured by the outlet cup with an opening S4 at 20 ° C is 40 e.

The percentage of uncovered aggregate surface determined by the test according to the methodology of ČSN 65 7089 is for the biotithiocyte granodiorite Litice nad Orlicí and asphalt A-80 with the addition of 0.2% by weight. % of the reaction product according to the invention 100%, with the addition of 0.2 wt. of Redicote E 11 (UK) 95% and without additive 40%.

Example 11

The reaction product of the reaction mixture of 50 wt. palmitic acid and 50 wt.%, oleic acid with a mixture of 90 wt. dipropylenetriamine,

5 wt.% Hexa (isopentylene) heptaamine and 3 wt. % octabutylene nonaarain and 2 wt. % propylenediamine liquefied by the addition of 20 wt. ethyl alcohol containing:

80 wt. quaternary ammonium complex (polyimine)

R.C00H ./(0H ₃ N ⁺ _{2) m} -NH / _{n »(CH2) m} + HH. 00C. R,

R.COOH ./(CH ₃ N ⁺ _{2) m-HH} / _{n. (CH2) m} .NH ₂

- IQ 252,771

R.COOH ₃ N ⁺ ./(CH2)m-NH^. 00C.R / n. ( ^GH 2) _m · HH 3 · OOC. R and 20% of the compounds of an amidiac nature

R.CONH./(CH _{2) m} HH / _{n. (CH2) m} .NHOC. R a

H ₂ N./(CH ₂ (CH ₂ ) _m . NHOG. R, where m ~ 3> 4, or · 5, n · 0, 1, 5, or ^ 7 and R ® CH ₃ (0H ₂ > 14 - respectively CH ₃ (CH ₂ ) ₇ .CH = CH (CH ₂ ) ₇ -.

The consistency of the product measured at 20 ° C is 30 s.

The percentage of uncovered aggregate surface determined by the test according to the methodology of ČSN 65 7089 is for the agglomerate of olivine basalt Smrčí and asphalt A-80 with the addition of 0.1% by weight. % of the reaction product according to the invention 100%, with the addition of 0.2 wt. of Redioote E 11 (UK) 100% and no additive 60%.

Claims (3)

P S E DM Sl OF THE INVENTION 232 771 1. Reaction products of higher saturated and / or unsaturated carboxylic acids with polytopic amines characterized in that they consist by weight of: 75 to 99% of activated quaternary ammonium complex of higher carboxylic acids with polytopic amines (polyimines with different end groups) of structural formula R. COOH ₃ N @ ⁺ . / (CHg) _m -W _n . (CH 2) _m · NH + .000.R, R.COOH ₃ N ⁺ .Z (CH ₂ ) _m -SH / _n . (CH ₂ ) _m. NH ₂ and R.COOH ₃ N ^{+. (} CH ₂ ) _m -NH ⁺ . OOC.R / _n · (CH ₂ ) _m .NH + .OOC.R, wherein m = 2 to 6, n? 0 to 8, and R? To C 8 -C 8 alkyl, alkenyl, alkanedienyl, alkanetrienyl and 1 to 25% of the compounds the amidic character of the structural pattern R.CONH./(CH _{2) m} -NH / _{n. (CH2) m} and .NnOC.R H ₂ N./(CH ₂ ) _m -NH / _n . (CH ₂ ) _m .NHOC.R wherein m 2 to 6, n 0 to 8 and R 8 to C 8-6 alkyl, alkenyl, alkanedienyl, alkanetrienyl and possibly unreacted feedstocks and by-product products · Reaction products according to claim 1, characterized in that they are dissolved in up to 65% by weight of ethyl alcohol. Printed by Moravian printing works, center. 11 100, People's Militia Class 3, Olomouc Price: 2,40 Kčs