DE2012914A1 - Process for the preparation of addition products - Google Patents

Description

20129H

Dft. ALFRIf) SOW PN

PAJE N TA N WA VT

- 8 MPNCHEN 22 Wli3ENMAYEBSTHASSE 49/1 TELEFON iDBII) 226187

PF |. AUFBEQ SßHPN ■ 8 MPNGHEN 22 · WIDENMAYEflSTRASSE 49/1

2. u. Η & h

OZ 369

INVSNXA Aß for research and patent exploitation v Zurich / Switzerland Process for the division of addition products

The present invention relates to a process for the preparation of addition products. a

Ea was found to be addition products that act as hardeners are suitable for epoxy resins and correspond to formula I.

can divide by adding an N-alkyl lactarn of the formula II

j (II)

84.1 / tpd

BATH ORIGINAL

or a Graaieeli of such IJ-alkyl lactams with a polyamine the formula III

(III)

or mixtures of such polyamines are reacted at temperatures above 20O ⁰ O and optionally under pressure, at least 1 mol of polyamine of formula III being used per hol converted N-alkyllactam of formula II, and wherein

η is an integer from _{5-11, R 1 is} a lower alkylreat and

H _{2 is} a divalent aliphatic, cycloaliphatic or aromatic hydrocarbon radical which can be interrupted by ether, shioether and / or secondary or tertiary amino bridges.

It is known (DHP 837 539 and DAS 1 124 688) that lactam amines which are not substituted on the nitrogen atom can attach in the described Visiss. However, \ mv questionable whether this reaction would be to the H-subatituierten lactams transferred de * m of these compounds knows you, that they not only "reactionsträger but are thermodynamically more stable than the unsubstituted lactams. So runs example the saponification of N-methylcaprolactam 20 times slower than that of the oaprolactam itself (N. Ogata, Bull.ehem.Soc. Japan 32, 813 095S) * Ohem.Abstr. 54, 12987e , (1960), and the polymerization equilibrium of the Methyloaprolaotamsi is known to be completely on the monomer side (RGP Cubbon, Ifekromolekulare Chem. 80, 44 (1964), a sign that N-alkyllactams are very stable towards unalkylated lactams. It is known that caprolactam can be used

BATH ORIGINAL 009841/1810

polymerize easily, which was previously not possible with N-alkylcaprolactam.,

In fact, the reaction of the N-alky! Lactams with.!; polyvalent amines under the conditions welcbe for the \ m "substituted lactams are recommended (200 - ί ^ Ό ° ϋ) me, so no interest to the technical evaluation of sales are generated very slowly. At temperatures of 250-30O ⁰ O, however, the addition of polyvalent amines to N-alkyllactams proceeds smoothly and with technically useful speeds. Since the duration of the systems is usually exceeded at this temperature, the reactions are preferably carried out in autoclaves. Temperature rsn-; About 300 ⁰ C Bind generally return less advantageous because then often unwanted Zersetsungoreaktiorien .eintreten "Bs goes without saying that the treatment organicc3 \ ^ r" substances at such high Temperatureniz. .Abwesenheit of atmospheric oxygen carried must, and the β vo therefore the autoclave: c of the reaction either evacuated or purged with an inert gas, advantageously nitrogen, the H ~ Alkyllactrju8 of formula II can sB .dusrcJi Uriso; ρλ ·· _γ, τ of the lactams with a Alkylieriingsmit-irca .!?!, Ijai.epicliivroinc dialkyl, we get: - In dön v; ölcarra HolverliöliniK rl · ¹ lactam and the polyvalent Acin eir> £ 3se r -i; vierder- \ ma the - * i which sales Jaan the reaction to proceed Ι3β8 ^·:;? _Γ depends Oer or> on the extent to ee ssuläsBi ;, dasss the göbrlldete of formula I contain high molecular weight Hebenprodiü'te findungsgemäse products obtained vrelcne fas "& u borrowed consist of compounds of formula I" ie which ent to no lifting products hold, are preserved, wsxm mars ensures that (on the side of the resolution) at least one _r advantageously three, ^{unreacted 1} diamine molecules pi'o Hclek'll converted lactam are present. XJies'Icann'thisachieved'v& r

0Ö98A1 / 1810 BAD ORIGINAL

denotes that 1 mol of an N-Alkyllaetaras in the presence of 4 mol a diamine rolletäncU.g reacted ifird, or by that Equimolar amounts of the N ~ alkylle, otam and dßö Biaiains "up to au a conversion of # 25. The mutual Molar ratio of output connection and degree of conversion the reaction also depend on ßelbetverotäxirllich by the Bigennohaften al), wolohe bestowed on the end product will roll.

After the desired conversion has been reached, the unreacted must Starting products can be divided off then without v / eiteree in a new approach, if necessary in the Kre.lKprozossB, to be reinstated. The end product "remains boi this distillation aXa Rttckstancl jsurücl?:.

The eriiaü ^ ngßgc.Jiiißse urasetsimg polyvalent amines with N ~ alkyllactarr ^ nv / ei ts gogejaUbsr of the condensation of 6? "" ea yes 5.Ώ CISN msitsteii cases! the 6J H AlkylamJ.nocarbonsäuren ihrerßßitß äux-oh Yersoiijyig de ?: N Alkyllaotame be made I »a lactams due aor present invention, the N-alkyl ~ directly ndLt the polyvalent Amiiiön uiogeraetsst can be the saponification and the subsequent, often expensive, isolation and purification of the O -H-alkyl'minocarboxylic acids

On the other hand, various i ^ H-alkylaminocarboxylic acids, such as, for example, d19 OF-alkylamino caproic acids, "only lead to moderate yields in the condensation with polyvalent amines because they sometimes convert back into the H-alkyllactams with intramolecular elimination of water.

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In these cases, the H-alkyllactams formed as by-products are isolated by distillation , then saponified again to give the CJ-N-alkyl aminocarboxylic acids and add them to a new condensation. But it goes without saying that such a procedure would be very time-consuming. When according to d @ in such Pällen r present OF INVENTION dung starting directly from the M ~ alkyl lactams, there remains in the worst case, only the Umsats on a value determined by the equilibrium position Wert.beschränkt * The distilled after the reaction H ~ A135grllactam-Araingemisch may g However , they can be used again immediately, if necessary in the cycle.

Example- I ₁

254 g (2 mol) of K-methyleaprolaotain, vaaA 31 β g. (2 mol) 2,2,4-iiriiaethylhexamethylenediainine are refluxed for 17 hours under the purest argon atmosphere, with a boiling temperature of 226-229 ⁰ G. Then, at 0.2 'Sforr, the unset ΪΓ-methylcaprolactam and diaraine are distilled off, the temperature in the loosening bladder being allowed to rise to 130 °. 55 g of a colorless, viscous oil remain as residue. Conversion: 9 ₉ 6% on F-Hethylcaprolaotam bs ^ ogsB.

Belapial 2

254 g (2 moles) of methylcaprolactaffi and 316 g (2 moles) of 2 ₀ 2,4 ~ 2 riffi8thylhe3caiaethylniamine are heated together in an autoclave that has been flushed with nitrogen at 260 ° C for 12 hours, laughs the cooling v / i2? d the unreacted material, xfle described under Example 1, distilled off. 114 g of it ^ lT-MethylamXnocapr acid-ir '- (6- »aiainotrimethylhe3cyl) ~ a! Iiid in 3? Orm oines are added as residue. yellow-

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lichon Ö "Jn received, ümsata: 20 fi (based on H-Methy 1-caprolaotam).

Kf? the procedure is as described in Example 2, with the difference that the autoclave is heated ^{to 300 ° C. for 6 hours.} Ifech of distillation then drops 185 g of the product & a. Revenue: $ 32.5 (based on IT methylcaprolactam).

Example 4

100 g &IM'Iethylo prolao-FCAM (0.788 mol) and 498 g (3.15 mol) i'rimeo'l'.yl ^ exametliylexidiarflin v / analog ground Beispifäl heated during 2 hours in an autoclave fi suf 28O ⁰ C. Ansohliessend the excess Diamia and the unchanged Metnyllactam a "bil &> is 3tilliert where rfeise 44> s aminoamide al" HUckstand arfallen ia üblioher 'sales. 19.6 55 (lied to the

211 g (1 mol) of JET-ethyllaurinlactam and 3 '"6 g -" 2 mol) 2,2,4- i'rimothylhexainetfcylendi.aiain v / erden sueaiamen heated under nitrogen for 4 hours to 30O ⁰ C. Ultimately this is not urasssetste Ifeteriai distilled off at 0.2 forr _s where at the end the sample in the bladder is degassed to 182 ⁰ O. 320 g of the CJ-N-MethylaiaiaolEurinsS.ure-H '' - {β-arainotriinathylhexyl) remain as carbon. , / 'arms but immediately 86.5 fi is -am3.ös as a yellowish viscous oil which partially krietallißiert at Raumtomperatur at sohviacheia Srv clear. Umsatzt (based on the N-Methyllaurinlactam). H-Methyllaurinlaotarn can be prepared by methylation of Laurinlßctam by known Methods are made.

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Example 6

, 292 g (2 moles) of triethylenetetramine and 2! 54 g (2 mol) IT Methyloaprolactam as described in Example 2 for 9 hours at 280 ⁰ C reacted and worked up with 323 ,, dee corresponding ArainoamidB in Fona g of clear, yellow and viscous oil can be obtained. Uinsata; 59 » $ 2 (based on N-methylcaprolaetaine used).

example 7th \

254 g (2 mol) N-Methylcaprolactarn and 244 g (2 moles} hexamethylenediamine \ tferden after Übllclian method choosing 9 hours at 280 ⁰ C are reacted together. After distillation of the unreacted starting compounds are erhSlt 173 g N-Methylaminooapronsäure-N ' - (6-aminohexy 1) ~ amide as Hticisa tand "The product is partially crystalline at hemi-perature. Um ~ Bate: 34.7 $>

example 8th

! (? _P 0 J 7 moles)! 113 (0.57 mol) of N-Äthylcaprinlactam 90 and ₁ 5 g of 2,2 ^ 4- Crime thy lhexame thy diamine are susammen under Sticke toi "in the autoclave for 9 hours at 280 ⁰ C heated After distilling off the% of unchanged starting products are 152 g of N-Äthylanjinocaprinsaurö IP (6-amino-trinethyIhexyl) amide in sales.:. $ 74.8>.

211 g (1MoI) H-Methyllaurinlactam and 158 g (1 Hol) 2 _? 2 _? 4- Irime thy lhexame thylenediamine are refluxed for 4 1/2 hours under pure stargone . The boiling temperature rises from 258 to 261 ⁰ C. Then, below 0.3 Stora?

009841/1810 ORIGINAL BATHROOM

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the unreacted starting products are distilled off, with the surapi temperature is increased to 182 ° C. After the used material has been added, the distillate is transferred to a new one Try reinstalled. As a residue, 73.4 g of N-Methy Xaminolaur ins äure ~ N'- · (ß-aminotrimethylhescyl) -amide in in the form of a semi-solid mass that liquefies when heated slightly. Sales: 20 # (based on N-Hethyllaurinlaotarn).

ORfGJN _AL

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Claims (5)

Sponsorship claims 1., process for the production of Addltioasproduktea ,. the ale Hardeners are suitable for epoxy resin © and correspond to Foraael I, ₂ ) _n characterized in that one H-AXkyIlsetarn a®r
lOrmel II or a mixture of such N-AliqrXlaetame with eisaai Pslyamiu of formula III or mixtures of such polyamines free Semperatmrssi Ufcgr 20O ° ö and optionally uinsetat under pressure, with converted per mole N-alkyllaotam of the formula II at least 1 mol of polyaraine the EOrmel III is v / ends, imd where η a number from 5 - Vl ₉ _ E ^ measured a lower alkyl radical Eg © inen divalent aliphatic, oyaloaXi- * Phatic or aromatic hydrocarbon radical, which can be subdivided by ether- ₉ Shioltthar- Kml / cd © r secondary or tertiary AmiBolbrtiekeri, "mean * 009841/1810 BADORiGlNAL 20129U - ίο - 2. Method naoii claim 1, dachu'ch germinated that one N-Hethylcaprolactam or N-Methyllaurinlactam or mixtures these compounds are used. 3. The method according to claim 1 and 2, characterized in that maa use a polyamide of Pormel III ·: which except the two primary amino groups has no other groups that react with epoxy resins. 4. The method according to claim 3, characterized in that one _{uses hexamethylene diamine, 2.2 f} 4-iÜA ^> .imothylhoxaniQthylen3.1amJ.7i or mixtures of these polyamines. 5. The method according to claim 1 - A, characterized in that the reaction at 2 temperatures av / ischen 250 and 300 ⁰ O, optionally in an autoclave and in the absence of I »mf tsausrstoff, is carried out. BATH ORIGINAL 009841/1810