DE1595267A1 - Process for curing epoxy resins - Google Patents

Description

^ un hardener;

i-'Ür this. ". nr« ^ aun'g. wiru aie £ ris-ri v = iv u «r correcliena.-n oritisciiiiii t'.jcentanmeldung! ir. 17? ~ 5 v? ^m . ^ c. ^ prix 19l ^ claims.

jie experience. oetril "i '" D a Veri'äiircn Sim Häi-ven of epoxy resins, and inöDesonieren a Veruuren surr. Hardening of ipoxiclharaen vern> ixtels r

üas hardening of ^ poxiaiiarsen 'vernivteis. ^ ciyami-iüarzen- iet

b insuesonuere oekanrii, "äarcxi Kenüenaation von vaciiien with-" Cne ^ en ja er Tri "? eren iangket-iger, sätiigiier ^ ettsäu.-s, which emerge from na-üiiriica α et: · üexeD unu Latvians will win, ernalx -i »: ö .-- x ;. ^r arr.i-ii-r-ie _x anaavenia. The hardening capacity of this rcly.t -._ uö ^ angs, from eier An ^ anl -er encstänainen Arcino groups in the? VCxe -: ix oo. ^ s sense "Attempts undertaken -wer α en, üiu ^ jIscüs acids / how they are -synthetically obtained, 2" ür atad "-! Creation of iOIyamiden by means of reaction with xOlyaiicyier.poiyaainen to be used ■ • Examples of such acids sina adipic acid, ' Sitaric Acid and Similar Acids ".

Bie with such saturated syntnexisciien, dibasic Acids with -Polyakkylenpolyaminen .emailer..en Heaktionsprodukte However, they are not completely satisfied when sex-denied niohü by an occasional -ärsav.3 of the dioasic acids

009810/163 $ _ _k .

modified by a monobasic acid, aind the. Reaction products Driichige i-eststoff'e, which are unsuitable for the application together with jipoxy resins even if a modification takes place in the manner described, nina the reaction products often not homogeneous, cloudy αηα mediate in the hardened epoxy resin ssn-Lecnte properties. According to the invention, one obtains an improved synthetic resin - kind of by using a xyanide as a hardening agent, which contains free primary and secondary amino groups, which are obtained by reacting a cyclo-ene or poly-olyajucylene polymer or a mixture of an amino acid or the like Lactam of an amino acid in the presence of a basic caroonic acid i ^ ergeei.ellt wirj. The iOIyar.ide 'neraen obtained in this way are more appropriately modified by adding, in addition to the diDi-tisciieri acid, a proportion of a monocaroonic acid or other acids.

According to the invention, improved hardenable masses 2. :: Proposal are baked, the mixtures of .ipoxian arsenic in the manner defined below and as a hardening agent contain a mixture that is obtained by unseening an amino acid with an alkylenepxyamine in the presence of a diose Ciirbonsäqrra is produced.

The A! R: inosary can have the formula HH ₆ (CE ₂ ) COQH, in aer η amounts to 1 to 12, or the jforsiel HH ₂ -Il-JuOH Desitzen, in which R is a divalent hydrocarbon residue, which is aliphatic, aromatic or alicyellic. can be, and the amino group can be in any position in the x-chain or the ring. In the Aipnatic pail Ii 1 ois 12 may have carbon soxoffat-otae. The amino acid icaan Gegeoerjenfa. xs having a branched Straktur, from de _s r strength Amänosäuren aogeleitete lactams are in the same "ίβΐε _{e; üfet;}

009810/1638 ⁵ "

BM) ORIGINAL

Suitable liquid basic acids include dibasic, saturated aliphaticν Γ-auren o - '. er dibasieche iiromaiiscne acids or cycioaliphatic acids »To the Aibasic aliphatic

: Acids gertci-en those aer ^ Prrmex HOOG (GH ₂ ) COOH, in which s are on C oaev 1 to 12 beiäuit. Suitable aromatic acids include isophthalic and terepuithic acids. The acids can be used in ι. r- from function rushing descendants, such as z.xi. Esters with MonohyurcxyaxkOhoXen are used that are less than 5

.Have carbon atoms.

The polyamines used for the production of the polyamides have the jjOrriex HK ₂ (h * NH-) "H ¹ KH ₂ , in which R * is an alkylene radical and r sieji aui * 0 or 1 to 6. Such amines can be used as such" or used as a mixture *

'The amino acid of the Lactaris is added to the reaction mixture in a _s . _: Molar ratio of dibasic acid from 0.25: 1 to 5: 1 added. : set. ■.

Monocarboxylic acids can be used to control aerodynamic acids should be replaced by this, preferably in one equivalent '-fenge. Suitable monocarboxylic acids include those ax made of naturally occurring oils or fats, such as Coconut ox acids, ieinseed oleic acids, safflower oleic acids, falloic acids or .C ^ isic acid are derived. JSs can also aromatic !! cn ο carboxylic acids are used. JSs is preferred that the acids used have an iodine number greater than 60. These can also be in the form of simple newcomers, as in the 3? all of the dicarboxylic acids are used "

The production of the polyamide can be carried out conveniently by heating the iteaktionsteilfiehnier to 130 ° to 300 ⁰ G, and • vprzugE- example under exclusion of air or oxygen

became. 0 09810/1638 - 4- '-

BATH ORIGINAL

Polyamides suitable for the purposes of the invention can be represented by the following general formula; H ₂ N (K ¹ NH) It ¹ NHuG (OH ₂ ) UO (NHRCO) NH (E ¹ NH) K * NH0üE _a , where r and s are numbers of the values defined above and χ is one or greater. Ä and R ¹ are divalent radicals in the manner indicated above and H ₂ is a monovalent alkyl, alkenyl or aryl radical.

This formula shows the products according to the invention, for example, and is not an exclusive definition.

The curing of an epoxy resin which is a polyamide according to the invention has been added * runs spontaneously, but can polyamides according to the invention have a considerable range of amine numbers, and this latter function is used in the reaction rate of the polyamiüe to a considerable extent and the epoxy resins and thus the ones required for hardening Period of time determined. For the most part, however, they are in the The polyamides described are able to produce epoxy resins within a short period of time at normal temperatures to harden. Some polyamides or epoxies can be heated to elevated temperatures for the purpose of curing within a Require a reasonable amount of time, and where appropriate Temperatures up to 25ü ° C can be used. Not only the composition of the polyamide resin is important, but also the amount in use. It is iib - Borrowed 20 to 100 parts by weight of polyamide to apply to 100 parts by weight of resin. The amount of a given polyamide to be used in any given epoxy resin depends on both the content of epoxy groups in the resin as well as the amine number of the Polyamides.

009810/163 _BADOR .G1NAL

Under epoxy resins are to be understood those Harae- which

an average of more than one lipoxide group = 0-0- per Molecule have ο

The polyepoxide compound can be a saturated or unsaturated lipidic, cycloaliphatic, aromatic or heterocyclic compound and optionally substituted by halogens, hydroxyl or ether radicals. The polyepoxide can also be a monomer or polymer, examples of epoxy resins that can be used are the ethoxylin resins ¹¹ which are polyhydroxyphenol or alcohol derived products: which has spoxy groups which, by means of reaction of a polyhydroxyphenol or alcohol, such as hydroquinone, resorcinol, glycerin , or condensation products of paneols with ketones, such as bis (4-hydroxyphenyl) -2.2-propane with iupicnlorohydrin. The formula of such resins can be given as follows: i

OH ₂ -OH-OH ₂ (0O ₆ H ₄ O (OIiJ) _a ö ₆ H ₄ 00H _a CH (OH) -OH ₂ LOC ₆ H ₄ C (OH ₃ ) _a C ₆ H ₄ -

OGH ₂ -CHGH ₈ ■ - ,; ■■■ '· "

in which G ₆ H _{4 is} a phenylene group uiad η a value from 0 to about 7 _tt Such resins are commercially available under. The trademarks "Epikote" and "Araldite" are known.

Other types of epoxy resins include the following: The Glyeidyläther of ITovolakharzen _t vermiTteIs the condensation of an aldehyde with a phenol obtained werddn, such as by. Condensation of formaldehyde with bis (4-hydroxyph, enyl) -2.2-propane _{or the like}

Another group of epoxy-containing products consists in the epoxidized, polyethylene-unsaturated hydrocarbons, such as epoxidized 2,2 ^ bis (2-cyclohexenyl) propane »epoxidized

4-Tinyloyclohexen and epoxidized «bimers of Oyolopenta- OG98T0 / 1g3§

; ■■ SAD ORIGINAL ■ --6-

- b -

It can eoenfails polyepoxides's formula

GH ₂ -OHGH ₂ U (OH ₂ ) OGH ₈ -OH-GH ₂ throw in the y one

Count with an average value of 2 ois 4 aarsteUfc.

The curable Ma sea invention are particularly for the manufacture of "OberflächenUderzügen, castings, .tfußüodenoelägen, precious FiDerglasschicntkörpem or Kiepstoffen. The genärtete Prociukte prepared by curing the epoxy resins with the novel polyamides, have excellent flexibility and resistance to acids and alkalis una improved Resistance to solvents. Furthermore, the compatibility of the polyamides according to the invention with the iipoxy resins is excellent. Conventional solvent systems can be used for the preparation of coating or other materials for areas of application where it is necessary or advisable to use solvents, e.g. when a solid epoxy resin is used -KLe polyamide products are soluble in the solvent systems commonly used for dissolving epoxy resins in the manufacture of coating and other compositions The following are further explained, for example, where parts and percentages are on a weight basis:

example 1

There are acids 1098 parts of adipic acid, 6321 ropes safflower Pett ~, 1695 parts Caporlactarn and 3861 ropes Diäthylentriamiö at 220 ⁰ C for 1 hour at normal pressure and further 3 hours under reduced pressure to form a klardurchsicJiti · gen *, amber liquid with an amine number of implemented ,, The Polyamxdprodukt leads with an addition on a liquid Epoxidjaaxa jDit an ^ epoxy equivalent of 175-210

■ '■. ■■ -. - -. '■ ■ - -.7 ■ - ■

BATH ORIGINAL

that from bis (4-hydroxypitienyl) 2.2-propane by means of keaiction with epichlorohydrin in a ratio of 70 parts of polyamide ■ feu. 100 parts of resin have been produced, within one hour at 50 ⁰ G to a hardener. At room temperature, the epoxy-polyamide mixture kicks in within 24 hours,

Example 2

There are 292.5 parts of adipic acid, - 1052.5 parts of safflower oil fatty acids, 282.5 parts of Capröla0tam and 516 parts of diethylenetriamine at 220 ° 0 l / 2 hours under normal pressure and then 1 hour at reduced pressure with Ausöiiden a pale yellow liquid miτ . an amine number of 197 implemented. When added, the polyamide product leads to a liquid epoxy resin with an epoxy equivalent of 175-210, which is made from bis - ^ - hydroxyphenyl ^ · 2-propane by means of keä & ion with epichlorohydrin hea? in a ratio of 80 parts of the folyamide to 100 parts of resin is.t, within 45 minutes at 50 ⁰ O to a hardening * At room temperature, the epoxy resin-polyamide mixture hardens within 24 hours.

Example 3

There are 292.5 parts of adipic acid, 927 »5 parts safflower oil fatty acids, 5.65 parts Gaprolactam and 516 cords diethylenetriamine at 220 ⁰ C l / for 2 hour at" Hormaldruck and 1 hour at reduced pressure to form a schwaohgelben liquid with an amine number of 197. The polyamide product, when added, leads to a liquid epoxy resin with a epoxy equivalent of 175-210, which is produced from bis (4-hydroxyphenyl (2.2-propane by means of reaction with epilhydrin in a ratio of 80 parts of polyamide to 100 parts of resin has been hardened within 40 minutes at 50 ° 0. At room temperature, the epoxy resin-polyamide mixture cures within 24 hours. 009810/1631 ^{BAD 0} ^ OlNAl " ⁸ "

_ 8 - loao ^ ö /

Example 4

There are 219.3 i'eile adipic acid, 843 parts Saf flor oil · - fatty acids, 339 parts of a rigid Gaprolactam and 438 'feile Triäthyientetramin at 220 ⁰ C for 8 hours under forming reacted amber-colored paste having an amine number of 199!. When added, the polyamide product leads to a liquid epoxy resin with an epoxy equivalence of 175-10, which is obtained from bis (4-hydroxyphenyljl2 _[ , £ i-proyain by reacting with epicialoriaydrin in a ratio of 80 parts polyaraia to iO Parts of the heart have been obtained to harden within 97 minutes at 50 ° 0. At room temperature, the epoxy resin-polyamide mixture hardens within 36 hours.

Example 5

There are rigid 157.8 parts of adipic acid, 843 parts safflower oil fatty acids, 244 »2 parts Caprolactarn and 438 parts of triethylenetetramine at 22O ⁰ C for 8 hours under forming a reacted amoerfarbenen paste having a Amiszahl of 227th The polyamide product leads when added to a liquid epoxy resin with a spoxy equivalent of 175-210, which has been obtained from bis (4-hydroxyphej3yl) 2,2-propane by reaction with epichlorohydrin in a ratio of 70 parts of polyamide to 100 parts of resin, to one Hardening at 50 ° 0 within 1 hour. At room temperature the G-emisch hardens within 48 hours =

Example 6

It werdiö 219.3 parts of adipic acid, 98.5 parts safflower Pettsäuren, 282.5 parts Oaprolactarn and 774 parts Diäthylentetramin at 22O ⁰ G l / 2 hour at normal pressure and then for 1 hour at reduced pressure to form a liquid having a valid Amia number of 318 converted .. The polyamide product

009810/1631 - 9 -

. BATH ORIGINAL

runs with an addition on a liquid epoxy resin with a spoxy equivalent of 175-210, which has been produced from bis (4-hydroxyp] aenyl j 2,2-propate by means of addition with epichlorohydrin in a ratio of 70% polyamide to IuO l'exen resin , innerhalD of 22 minutes at 5O ⁰ O to a hardening "üei cures Hardly temperature the Epoxiaaarz-rolyarnidgemisch innerhalu 24 hour s _o

The proportions of the iOlyaraid products to the epoxy resins in the above examples illustrate the performance of the j / oty araid products and are typical, but not definitive to watch. ■.

Examples 1, 2, 3, 6 and 4.5 illustrate the effects quantitative modifications of the translation participants. To the Extent for the modification of the chemical nature of the participation participants To show, the following variants have been carried out successfully.

Example 7

There are 294.5 ropes safflower oil fatty acid, 65.8 parts of adipic acid, 66.8 'feile α-alanine and 193.4 parts iiiäthylentriamin 45 minutes at 22O ⁰ C at atmospheric pressure and then for a further 45 - ■ minutes at reduced pressure to Forming a slightly dark red liquid with an amine number of 306 implemented. The curing of the epoxy resins takes place under the conditions given in the above examples.

Example 8

589 parts of safflower oil fatty acids, 131.5 parts of Aüipin-

• go acid, 205.7 parts of anthranilic acid and 386.8 parts of diethylene triamine ° for 1 hour at 22O ⁰ O at atmospheric pressure and then 45 Minu-J ^ th at Terringertem pressure to form a flaky

GD amber-colored liquid with an amine number of 261 implemented. The epoxy resins cure satisfactorily. - 10 -

BATHROOM OP

Example 9 .

There are 1,178 "venal Saffioröl fatty acids, 299 ropes terephthalic acid, 339 parts Gaprolactam and 773 '6 parts Diäthyientriamin! Hour at 220 ⁰ G at normal pressure and then for 40 minutes at reduced pressure to Ausoiiden a clear acioerfarbenen liquid with a Aminzanl of 268 implemented. Jas epoxy resins harden under the usual conditions.

Example 10

About 120 parts of 2-Aexayj.nexanansäure, 73 parts of adipic acid, 113 parts of Oaprolaetara and 116.4 parts of diethylenetriarain 30 minutes at 22U ⁰ O at normal pressure and then 1.5 hours under reduced pressure with formation of a kJß Drigen green liquid with an amine number implemented by 247 ^. 3ieseloe £ ur.rt for an effective hardening of the epoxy resins under the usual conditions.

There are numerous other participants in the reaction innernaio des The range of molar proportions used in the above examples has been found to be one polyamides with satisfactory hardening properties receives. These include the following: Instead of the dicarboxylic acids according to the examples, Ibis step: oxalic acid, dietary oxalate, shark acid, succinic acid, and azelaic acids, diethyl malonate and diethyl adipate, isophthalic acid, Tetrahydrophthalic acid.

The monocarboxylic acids according to Examples 1 to 1 are replaced by: methyl esters of saffloric acids, fatty acids from soybeans _T sunflower, linseed and tall oils, acetic acid, caprylic acid, stearic acid and technical oleic acids, benzoic acid.

009810/1630 - ii-

BATH

The caprolactam and α-alanine of Examples 1-10 are replaced by: glycine, β-alanine, γ-aminobuxyric acid, ε-aminocaproic acid, 2- pyrrolidones

Instead of diethylenetriamine and trietnylenetetramine step: mixtures of diethyl triamine and triethylenetetramine, Hexamethylenediamine ".

To illustrate the superior properties of the invention Polyaraid products compared to those used in have been prepared in a similar manner, but without using the amino acid »which is the inventive feature the following results are reported.

A product prepared from 292.5 parts of adipic acid, 521.5 ropes of safflower oil fatty acids, 516 parts of triethylenetetramine in a manner similar to the examples; represents a cloudy, yellow liquid with an A «« eh ± amine number of 197 _c

Manufactured from this product (ale product A) denotes hardened Resins are compared to hardened resins made from the products obtained by means of Examples-2 and 3 are obtained have been. These comparisons can be found in the following table +

BATH ORIGINAL

- 12 -

009810/1638

Product amine epoxy resin product

number with epoxy parts by weight

equivalent to Ie 175-210 parts by weight.

Resistant to hardening, dissolution, heat, bending

data weight 70 aDsorbed warping strength

within 3 days unstem-

Jüntauchen temperature methyl indu- tu-tri after ätiiylstrielketon les

Ethanol

oi chlorine ASTM

ethy- I) 648-5b len

nacn rens b

ASTM 5ü ° C Ü7 90-56T min.

kg /

cm*

a 191 ίου

Atap. 2 197

Example 3 197

80

80 80 2 h at
60 ° ΰ
1 h at
lüO ° Ö

- dito -

- dito -

15.0

6.09
6.72

5.8

13.8 11.82

4.62 6.06 5.43 3.78 3.56 3.71

42.5 577

44.5 777 44.5 942

m § ο

€ 0

crt

σ>

These results show that the solvent resistance, flexural strength and HartungsgesohviindigkeiT; of the hardened epoxy resin Throw significantly improved when the hardener one is polyamide according to the invention.

- BAD ORIGINAL

nil -14 -

Claims (6)

1. Process for hardening ipoxidharaen, durcxi marked, that a product is used as hardening agent) the one Polyamide contains the free primary and alkaline amino groups has and by linaeizen a PolyalicyjLenpoiya-rins with a Amino acid or the lactam of an amino acid in the presence of an aiDaic üaruonsäure nerves is divided. 2. The method according to claim 1, characterized gekennzeicnnet that the Hardener with the epoxy resin in an amount of 20 to 100 parts by weight per 100 liew.l'eiien epoxy resin is mixed. 3. The method according Anaprucn 1 or 2, characterized gekenazelcnnet, daf curing at a temperature is carried out up to 250 ⁰ U. 4. The method according to any one of the preceding claims, characterized in that a curing agent is used which is derived from an amino acid of the ü'ormel M ₈ -H-UOOH, in the H an aliphatic reads with 1 to 12 carbon atoms aromatic keet or an aiicyeic heat let. 5. Verfahret) according to claim 4 »characterized in that the curing agent is used which is derived from a polyalkylenepolyamine of the formula NH ₃ (E'NH ^ R ¹ NH ₈ , in which R» is an alkylene radical and r 0 or a number of 1 to 6 is. 6. The method according to claims 4 and 5 $ characterized in that a curing agent is used, which consists of a _o aliphatic dicarboxylic acid with 2 to 14 carbon atoms or Φ isophthalic acid or terephthalic acid with a monocarboxylic acid, -α derived from aliphatic or aromatic acid. ο - * 7 · Method according to one of the preceding claims, characterized w characterized in that the yäärtmittel by heating the Umsetzuijgsteilnehmer is made to 130 to 32O ° G. '- -' ■ 'BATH