DE1495452A1 - Process for accelerating the reaction of epoxy compounds with compounds containing -OH -, - SH -, - COOH groups or carboxylic acid anhydride groups - Google Patents

Description

Troiadorf, May 22nd, 1963

H95452

DYMAMIT HOBEL AKTIENGESELLSCHAFT
Troiadorf / District Cologne

Process to accelerate the implementation of τοη epoxy compounds with -OH -, -SH -, -COOH - groups or carboxylic acid anhydride groups containing compounds.

The present invention relates to a method sur Accelerated implementation τοη mono- and / or polyepoxides old Compounds containing -OH and / or -SH groups and / or carboxyl groups or carboxylic acid anhydride groups

It is known that mono- or polyepoxides can be reacted with monohydric or polyhydric alcohols, phenols or compounds containing -SH groups, as well as organic acids and their anhydrides. The reaction of an epoxy group, for example with an alcoholic hydroxyl group, proceeds extremely slowly in the absence of a suitable acidic or basic catalyst. Phenols also only react slowly with epoxides if the reaction is not controlled by special catalysts from the group of acids or bases or quaternary ammonium salts. but must usually also be carried out at higher temperatures. The reaction of acids or their anhydrides with epoxides generally proceeds only at temperatures above 100 ⁰ C in most cases even only above 150 ⁰ C at a sufficiently for teohniaohe requirements speed. Al

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Acceleration for this reaction, "" poor acid hardening in the chemistry of the epoxy resin has played a great part so far numerous accelerators have become known, such as s.B. tertiary amines, quaternary ammonium salts, alcohols, phosphines, arsines, Stibine and BF, compounds.

In the case of the mentioned reactions of the epoxides with the listed reaction partners, the technical implementation is sub part slow response time affects, if not completely; questioned · Haoh "Methods of Organic Chemistry" (Houben-Weyl) Vol. 14 · 2nd part, p. 506 (4th edition [1963)) Bind therefore, despite the large number of polyhydric alcohols available, these are used as curing components for epoxy resins has remained practically of no importance to this day because of their low reactivity), however, they are occasionally used for Production of τοη modified epoxy resins used

It has now been found, surprisingly, that the reaction of mono or polyepoxides with alcohols, phenols or other compounds containing acidic OH groups, meroaptans, acids and acid anhydrides can be accelerated considerably if salts of hydrothodic acid are added to the mixture of reaction partners. The salts of hydrofluoric acid can be salts with inorganic as well as organic cations. Complex compounds of such salts have also proven to be suitable accelerators. Examples of such compounds include1 IH.SCM, MaSCH ₉ KSCM, Mg (SCM) ₂ , Ca (SCI) ₂ , Zn (SCI) ₂ , Mn (SCM) ₂ , aniline.HSCI, guanidine.H3CI, Cd (SCM) ₂ .4 IH ₅ , 2 K 3CI. i (CE ₂ ) ₆ tE ^ , Zn (SCl) _2. (pyridine) ₂ , -

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Mn (C ₅ H ₅ I) _2. (SCM) ₂ , [(MHg) ₂ C SJ ₃ .K SCM »owl · their compounds containing kriatallwaaeer or Kriatall solvents ·

The amount of the added rhodanide can vary depending on the reactivity the reaction participants can be varied over a wide range Ea have aioh accelerator quantities τοη 0.01 bia 10 Gewiohtsprosent, Yorsttgaweiae τοη 6.1 to 4 percent by weight, sucked on daa Epoxydhar «, ala sufficiently proven

You can accelerate Rhodanide the mixture of Epoxydrerbimdung and -OH and / or -SH groups and / or carboxyl groups, bsw. Compounds containing carboxylic acid anhydride groups In substances, as a dispersion or as a solution in a solvent which does not influence the reaction · You can also use one of the reaction components be solved. The rhodan compound can also correspond to the reaction can only be denied at a higher tea temperature.

From the large number of Kpoxydrerbindungen, which with alcohols, Phenols, Meroaptaaen, acids and acid anhydrides are used can be mentioned as the most important) The epoxies from mono- or polyunsaturated hydrocarbons (ethylene, Propylene, batylene, butadiene, cyolohexene, vinyloyolohexene, dioyolopentadiene, cyolododeoatriene, polybutadiene, styrene), lalogenous epoxies such as s.B. Bpiohlorhydrin, Spoxyether der simple alcohols (methyl, ethyl, butyl, 2-ethylhexyl, Dodecyl glycol ether), epoxy ether of polyhydric alcohols (ethylene, propylene, butyl glycol ?, polyglycols, thiodoglycols, Glycerine, pentaerythritol, sorbitol), acetals of the olycidal

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" ⁴ " U95A52

dehyds, Spoxyäther on and polyvalent phenol · (glycidyl ethers of phenol, cresol, resorcinol ^"f hydroquinone, 4? 4 -Dioxydiphenya, 4,4'-I) ioxydiphenylmethan, 4,4'-dioxydiphenylpropane, 4.4 ^I -Dioxydiphenyl" sulfone and their oxyethyl ether, phenol-formaldehyde condensation products), N-containing epoxies (KjN-Mglycidylaniline, KjN ^ -Mmethyl-diglycidyl ^^ '- diaminodiphenylmethane) and epoxides, which are obtained from unsaturated carboxylic acids, other acidic compounds (cyanuric acid) by conventional methods or their derivatives are available.

From the group of alcohols whose conversion can be accelerated with epoxy-containing compounds, mono- and polyvalent aliphatic, cycloaliphatic, fatty aromatic or aromatic alcohols, preferably single primary or secondary hydroxyl groups, may be mentioned. Examples of such monohydric alcohols are the simple saturated or unsaturated fatty alcohols with a straight or branched carbon chain, for cycloaliphatic alcohols cyolopentanol, cyclohexanol and their substitution products, for aromatic alcohols bensyl alcohol, phenylethyl alcohol, as an example of a fatty aromatic or polyhydric alcohol, and also partially with monohydric aromatic phenols Etherified polyalcohols such as the phenyl ethers of glycols, glycerol (2,2-bis-Mfl-oxy-ethoxy) -phenyl) -propane, 2,2-bis- (4- (fl _t Ϊ dioxy-propoxy) -phenyl) propane. Examples of polyhydric alcohols are ethylene glycol, propylene glycol, butylene glycol, hexanediols, higher glycols which can be obtained, for example, by hydrogenation τοη dicarboxylic acids, xylylene glycol, hexahydroxylylene glycol, 1,4-cyclohexanedicQ «glycerine, diglycerine, and higher polyethylglycerine, triglycerine Trimethylolpropane, pentaerythritol, di-pentaerythritol, pentite,

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Hexites and mono-, di- and polysaccharides, which can optionally be partially etherified or esterified. Belong here also polyglycols, which are formed, for example, by polymerization or copolymerization of olefin oxides and which both low molecular weight products such as diethylene glycol and triethylene glycol and the like, as well as higher molecular weight products.

Also polyvinyl alcohol, partially acylated polyvinyl alcohol, polyallyl alcohol and the copolymers of allyl alcohol with other unsaturated compounds or partially or completely saponified polymers of vinylidene carbonate can be implemented with epoxies.

The group of polyhydric alcohols should also include compounds which additionally contain ester groups, such as esters of oxyacids with monohydric or polyhydric alcohols, e.g. Tartaric acid esters, castor oil or polyester, which were formed from polycarboxylic acids and an excess of polyols are. Also alcohols containing sulfur or nitrogen, such as thiodiethylene glycol, Ν, Ν-diethylethanolamine, triethanolamine, Mono- and polymethylol compounds, which, for example, by reacting compounds containing amino groups with Formaldehyde is formed, such as methylolureas, methylolmelamines can advantageously be calibrated according to the method according to the present invention Implement the invention.

Half-acetals with one or more OH groups can also be reacted with epoxides according to the present process. To lift the hemiacetals of the aldehydes can also be the dihydrates of polymeric formaldehyde and other polymeric aldehydes described in Way to be implemented with epoxies.

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suitable eJnd. 209810/1713

From the group of phenols mono- and polyvalent ones are mentioned Phenols such as phenol, cresol, resorcinol, hydroquinone, 4,4'-dioxybiphenyl, 4,4 Dioxydiphenylaethane, 4,4'-Dioxydiphenylpropane, 4,4 * -Dioxydiphenylsulfon, phenolic alcohols and products, which through acidic or alkaline condensation of aldehydes with phenols and are known as resols or novolaks are known.

To the OH-group-containing compounds in the sense of the gate-lying Invention also include organic compounds whose OH groups contain a silky residue of water. As an example of such Compounds are especially called cyanuric acid

From the group of mercapto compounds, the implementation of which ait Bpoxides can be accelerated by rhodanides, are the called simple mercaptans, thiophenols and polyacroaptans " Also polysulfides containing several mercapto groups, which are available as liquid Thiokol types LP 2, 3t β, 32, 38 from the Thiokol company ta trade, are suitable for the invention

As acids, whose implementation ait Kpexyden according to the invention & fi · » This is possible, be aliphatic, oyoloaliphatic, ar- attach · or heterocyclic mono- and polycarboxylic acids called. Cyclic acid anhydrides are suitable as acid anhydrides ▼ · & aliphatic, aromatic or heterocyclic Carboxylic acids As particularly suitable anhydrides, sioh dl al · Amhjdridaärter common products like maleic «succinic anhydride, Oednepjlbuccinic anhydride, phthaiic anhydride, Tetra- or hexahydrophthalic anhydride, trimellithedron Pyroaellitic anhydride, itaconic anhydride, Hezaehloroendoaethylenetetrahydrophthalic anhydride and their substituents

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tion products as well as the sienna adducts from unsaturated acids and react dianes with epoxy compounds »preferably» it polyepoxides »in the presence of τοη rhodanides. Can be equally beneficial also eaters with free carboxyl groups or anhydride groups, such as eaters as well as 1 mol of glycol and 2 mol of triaellitic anhydride or pyromellitic anhydride can be used · In analogous Weiae can Acid aaide alt free carboxyl groups or Anhydride groups used for the implementation of old Spoxyden will·

Maoh dea foolish procedures can auoh Geaiaehe τοη connections aua several of the mentioned classes of substance with epoxy, preferred »it polyepoxides are implemented» woduroh products old very special technological properties can be obtained.

The compounds mentioned can also be used with KpoxydTerbiadangen in atoeohioaetrical addition ala auoh la under- or Be applied everywhere.

According to the method according to the present invention, the Implementation dea Epoxyda ait one of the named partners be carried out at the same temperature "which was previously normal without the addition of the new accelerator" in theeaea However, it is the case that etching takes less time completed. However, the implementation can also be done according to the invention The procedure is ready to be carried out at a considerably lower temperature »ala ea without acceleration aöglioh let.

The naoh dea process prepared in accordance with the present invention Uaaetzungaprodukte τοη monoepoxides can ala valuable intermediate products on the production of pharmaceuticals »textile auxiliaries, Pesticides, plastic products

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- · ■ - H95452

and intermediate products are widely used

Mixtures of polyepoxides with the reaction partners mentioned and the new accelerators can be used as sons hardening casting resins, Coating compounds, Laok resins, molding compounds, sealing materials and adhesives are used, depending on the intended use Fillers »Pigments and plasticizers can be added.

The shortening of the reaction times or the lowering of the reaction temperatures for the implementation of clay epoxies or polyepoxides with the reactants mentioned by the new catalysts can be seen from the examples below

example 1

100 g of a diglycidyl ether de · 2,2-bis- (4-oxyphenyl) -propane · with an epoxy value of 0.53 (AM Paquin, EpoxydTerbindungen und Epoxydharze (1958) p. 754 »Epoxydwert - Epoxydäquiralent / 100 g) were with 24 g of 2,2-di * ethylolbutanol- (3) in the presence of 1 g clay Kaliumrhodaaid at 120 ⁰ C in 30 minutes cured to a solid Blook. A batch without potassium rhodanide was cured accordingly for about 43 hours.

Example 2

100 g of a diglycidyl ether of 2,2-bis (4-oxyphenyl) propane with an epoxy value τοη 0.53 were with 24 g of 1,1,1-trinethylolpropane in the presence of τοη 1 g of potassium rhodanide at 120 ° C in 35 minutes hardened. The hardening time of a corresponding approach without potassium rhodanide was about 72 hours.

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Beiapjel 3

100 g 1η β siglyoidyl ether of 2,2-Bie- (4-oxyphenyl) propane sit «in ·« Spoxydwert of 0.20 were sit 24 g 1,1,1-trinethylolpropa » in the presence τοη 1 g Kaliunrhodanid al · accelerator l> «i Hardened at 120 ° C. The hardening time was 10 minutes. Without XaIiunrhodanid it took about 70 hours to cure.

Example 4

100 g of a "diglyoidyl ether de · 2 _t 2-bis- (4-oxyphenyl) -propane ■ with an epoxy value τοη 0.53" will be a "geniach of 18 g 1,1,1-trimethylolpropane and 25 g polyethylene glycol (nittlere · Molekulargewieht 400) in the presence of 1 g τοη Kaliuarhodanid in 28 minutes at 120 ⁰ C cured. Am Tergleieheansats without Kalittnxhodanid was not completely hardened after 72 hours,

At »game 5

100 g of a diglyoidyl ether de 2,2-bis (4-oxyphenyl) propane with an epoxy value τοη 0.59 were bit 45 C 2,2-bis (4-oxyphenyl) propane and 10 g triethylene glycol in the presence of 1 g τοη Natriunrhodanid at 120 ⁰ C ungesetst. The hardening time was 3 minutes.

At «piele 6-11

In the following examples, were respectively 100 g · a Digly- • idyläthers de · 2 _t 2-bis (4-oxyphenyl) propanes nit a "Bpoxydwert τοη 0.53 in the presence of 1 g τοη Kaliunrhodanid at 120 C ■ it the indicated Folyolgeaisohen unetxted and the hardening times beatiant "

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- 1β -

Η95452

fieiapiel 12th
+ 14 g polyol ; Hardship
, (in minutes) 6th 14th
+ 8 g 1,1,1-trimethylol
propane
g diethylene glycol 7th 7th 18th
+ 10 g 1,1,1-trimethylol
propane
g triethylene glycol 8th 8th 18th g 2,2-dimethylol
butanol- (3)
g triethylene glycol 3 9 + 100 g 2,2-dinethylol 3 68
+ 15 g polyethylene glycol
(middle mole
weight 6000) 10 13th g castor oil
g triethylene glycol 3 11 g dimerized fat 27

alcohol (OH-Equiral "at 200)

+ 12 f 2,2-diethylol- ()

()
+ 10g triethylene glycol

Β · 1 »ρ1 · Χ 12

2 g of phthalimide were xuaaamwi t with 1 g of potassium thiocyanate ia "Ims G" miaoh au x 6.5 g 1 ₁ 1,1-Trim · thylolpropan and 7 g of triethylene Clykol at 120 * g * C * luh. This was Lösuag · a diglycidyl de · 2.2-Bia (4-eiyphenyl) propane · sit an "epoxy value 0.53 tob cured at 120 C ^e. The hardness time is 8 minutes ». Without potassium rhodamide, the hardening of the same approach took 6 days under the same conditions.

13th

In 21 g of pimelic acid, 0.5 g of potassium ^{thiocyanate was added at 150 ° C.}

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Solute and "with this solution 50 g" of a diglyeidyl ether de · 2,2-Bie- (4-oxyphenyl) -propane cured with an epoxy value τοη 0.53. Me cure time was 7 minutes versus 3 hours without potassium uarhodanide. The hardness side of the same mixture at 100 ⁰ C was 3.5 hours with Kaliuarhodanid, but 5 days without Kaliuarhodanitsueats.

Example U

50 g of 2,2-Diglyoidyläthers of bending (4-oxyphenyl) propanes ■ it an epoxy value το "were 0.53» it 50 g Hexahydrephthaleäureanhydrid ⁹ at 130 C in the presence of 0.5 g of tob Kaliuarhodanid cured in 25 minutes. Cure took 6 hours without potassium uarhodanide.

Example 15

50 g of a diglyoidyl ether dos 2,2-Bie- (4-oxyphenyl) propane With an epoxy value of τοη 0.53, a mixture was made up from 5 g of hexahydrophthalic anhydride and 11 g of 1,1,1-triaethylelpropane in the presence τοη 0.5 g Kaliuarhodanid at I30 C in

Cured for 9 minutes. She has been since the lease version j

without calluarhodanidsusats was 3 days.

Example 16

50 g of a diglycidyl ether of 2,2-Bie- (4-oxyphenyl) -propane ait an epoxy value τοη 0.53 were old 34.5 g of di- (ß-oxyethyl) terephthalate and 0.5 Kaliuarhodanid at 120 ⁰ C in Cured for 15 minutes. The hardening time of the Tergleiahsansatses without Kaliuarhodanid was 180 minutes.

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U95A52

Example 17

1.5 β HexaaethjlolinelaBin and 0.5 β Kaliuarhodanid were dissolved at 140 ⁰ C in 11 g 1,1,1-Triaethylolpropane and with this solution 50 g of a diglycidyl ether of 2,2-bis- (4-oxyphenyl) -propane · ait hardened to a Bpoxide value of 0.53. The hardening time is 7 minutes compared to a hardening time τοη 3 days without Kaiiuarhodanidsusatβ

Example 18

100 g of a siglyoid ether of 2,2-bia- (4-oxyphenyl) -propane with a Kpoxydwert τοη 0.53 were hardened with 27 β triethanolaain in the presence of 1 g of potassium urohodanide in 20 minutes.

Example 19

Ia a three-necked flask was 550 g of a diglycidyl ether de * 2,2-bis (4-oxycphenyl) propane has an epoxy value τοη 0.53 and a glycol according to the following table at 140 ° C in Ig-Ataoaphäre with stirring in the presence of τοη 3.5 β NH, SCI uageaetst.

Glykelkoaponeates amount used EpoxyJrert naoh
Uasetsung without IH.SCI Tersuohs "
duration ait HH ₄ SCV 0.43 4.5 h Biäthjlenglykol 53 C 0.24 0.42 5.5 h Triethylene glycol 75 κ 0.22 0.4 5.5 h Tetraethylene glycol 97 g 0.21 0.31 6.0 h Polyethylene glycol
(MO 400) 200 g 0.18

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-.13 -

Example 20

Of the following components, a clearcoat was prepared and spread on sheet iron You · painted panels were cured in air Torge Dries and Lackfil "at 150 ⁰ C in a drying oven" When! "Ackhars was a Siglyeidyläther of 2,2-bending _v 4- oxyphenyl) propane with an epoxy value of 0.2.
Lickansats

Lacquer component A 1 CSS FGHIK

Α-Σ

Siglyoldyl ether trinethylolpropane Diethylene glycol, triethylene glycol, polyethylene glycol (MO 200)

92

88 6

83.5

189.5 j 90.5 | 92

(83

"(MS 400)

- i'l-

9.5 I 5 I -

4.5! -

mm
ί - ί 11 i Wed - - be, 5 ! 1 1 ¹ I ¹

Corresponding approach * · each without KSCI

(Information in Gewiohtaprosent)

The Laeke were adjusted with a thinner (the Zusansensetsungi 20 parts of ethyl ethyl ketene, 20 parts of methyl butyl ketone, 20 parts of ethylene glycol and 50 parts of toluene) to a harmonic content of τοη 40 £.

They samples A bie I were cured after 15 'at 150 ⁰ C and selgten excellent Filneigeneohaften. The corresponding Laoke (K. -) without KSCI were not hardened even after an hour.

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! •! Game 21

TO g Pheaylelyeldäther "Ad 54 g of bemsyl alcohol are in Qegemvart tob 1 f KaUumrhedeaid with stirring at 12O ⁰ C" ad la starirnten Ζ · 1 day "

Terettoheda »he
(in the hour) fipoxydwert O 0.550 1 0.170 2 0.0? 4 2.5 0.046 3 0.059 3.5 0.014 4 * 5 0.000

In the eimea glelemem Ame & ts «jedoeh emme Beeehleumigiuiff der Keaktiem durek Keliumrhodmmid ₍ was meek 5 hours moeh germ iemahae dee Bfeiqrdvertee f« etsmstellem.

Case 22

TMX Ieretellmmg EIMEA linear Polyeetere eue Bpoxyd ornd Säareembydrid »it Smedamid the catalyst prior to 74 Phthalsäureamkydrld 9 (1/2 mole) umter Kührem mmd heating at 100 ⁰ C in 116 g m-Prepylfflyoidyltther (1 mol) dissolved. 0.5% potassium rhodamide was added to the beam, stirred at 100 ° C. in order to monitor the decrease in the anhydride during analysis.

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BATH ORIGINAL

Time (in hours) Unsat *

anhydride

0.5 2? 6

1.5 41.3 *

3 84.0 *

4 97.5 #

5 99.0 *

U95452

laoh abortion 4m üfeeraohüaaigaa Glyoi4yläth «r« ar holds aan feataa plaatiaahaa Hars, daa βehr gata Löaliahkaitaaiganaehaftan having.

The invention is aalbatrarständlioh not only on the beaohriabanan executionaBaiapiala basohränkt. Sa laaaaqfaiah rialaahr ■ annigfaoha make modifications without aan see rom Waaaa removed from the invention «

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BATH ORIGINAL

Claims (1)

Pntemt & mapraoht Verfahr «* nr lesehlmLmlgaaf dar UasetBttmg ▼ · ■ Ipoxydem ■ it Y« r »i» dmac * B _t veleh · Hydrexyl- «md /« d »r Mercapto ·« ad / vdcx * Cariwaylgrepp · «m & d /« d «r CariMimaäureaabjrdrldcrapplavMacwa contains · β ₉ dadmr «hg« lc «uuitlehnet, since · Baa dl« 9aa «ts» a4 [la wart tone 3 «1χ · η of the Rhodaawas« «r * toffaäur · dmrehf leads. Dr Ka / Ma. BAD ORiGSHAL 209810/1713