DE1495233A1 - Process for the production of synthetic resins based on polyepoxides - Google Patents

Description

CONSORTIUM HL / R t UK I KOCHtMIsCH Ir INMWSlRlh C / rnl.M

1495233 Munich, May 21, 1962 Int. Hr.ι Co 6210 IX / Pat.Abt. / Dr.Rs. / Κθ

Method stubbornly manufacturing τοη synthetic resins based Clay polyepoxides

Eb is known, synthetic hares based on τοη polyepoxides duroh Hardening τοη epoxy compounds with addition τοη metal fluoroborates to produce. Due to their great reactivity, the Metal fluoroborates are difficult to handle in practice. Part begins the hardening reaction already during the use of the catalyst, so that a homogeneous mixing and subsequent deformation not possible, in some cases the rapid reaction sequence is shown below local overheating and carbonization of the resin «trots existing strong demand for rapid hardeners for ^ poxyde the metal fluoroborates have therefore hardly found any broader technical application.

There was now a method for producing τοη synthetic resins duroh Hardening τοη epoxy compounds, optionally in the presence τοη Sriureanhydrides and / or poly oils with metal fluoroborates found, in which the metal fluoroborates in combination with organic compounds and / or Friedel-Craft's catalysts and / or Phosphoric acid esters can be used.

In this way it is possible to produce epoxides without external heat input harden, whereby the abovementioned parts do not occur.

According to the invention in combination with the metal fluoroborates The substances used delay the beginning of the hardening reaction to a greater or lesser extent, and pictures at the same time delay its course, without however, the properties of the harass have an unfavorable influence

According to their effect, they can be regarded as inhibitors.

According to the process according to the invention, epoxy compounds such as Olyoidylather τοη polyphenols and polyalcohols, further epoxydt of unsaturated fatty oils, terpenes such as Dipenteniiepoxyd and

'i Il 1 Ö / iötS 4 BAD OFUGINAL

Κ / Γ I UK I IUK HhMISlHh INPUMRIt- C / inl-l I

hardened. With a special gate part, they can cure cyclic epoxy compounds such as dicyclopentadiene and deseen derivatives, so 3 ₍ 4> £ poxydio,>'olopentadlen «9 * glycolyl ether _v dicyolopentadiene diepoxide. 6-iasthylcyolohexylmethyl-3 »4-epoxye-methyloyolohexanecarboxylate, Ylnylcyclohexendiepoxyd etc ·

The epoxies can be carboxylic acids, carboxylic acid anhydrides such as Maleic anhydride, phthalic anhydride, Diisoootylbernstelns'iureanhydrld etc. can be added. Furthermore, phenols and poly oils, such as methylpentnndlole, trimethylolpropane, hexanetriol, nthylhexanetriol, Polyether glycols and / or nitrogen compounds are used will. Also solvents or reactive thinners can be used will. Furthermore, fillers, e.g. silicon dioxide, aluminum oxide, Polyvinyl chloride can be used

All metal fluoroborates are in particular those of zinc, tin and antimony suitable. You can in amounts of 0.1-5 wt. ^, Based on depending on the finished mixture. Preferred If a range of 0.5-3 >> · It is about general Clues, the amount of fluoroborates used depends on the one hand in each case on the reactivity of the epoxies and other components of the mixture as well as on the type of anhydride or Polyol. This also applies to the inhibitors that are used in combination be used with the metal fluoroborates

Al · organotin compounds are preferably used with the general formula R, SnX, in which R is alkyl, aryl or aralkyl groups and 1 is a radical such as alkoxy, carboxyl, halogen, hydroxyl or OSnR.

Particularly suitable are, for example, compounds such as tributylsin oleate or hexyl butyl distannoxane, but other organotin compounds such as triphenylsinnoloride, dibutylsin diethylhexoate or tetrabutyliaa can generally be used in amounts of 0.1-5% by weight of the organotin compounds, based on the total weight to be set up. Besondsrs_ suitable er-SShelat si "range from 0 _t 5 - 3 *. BATH ORIGINAL

909810/0784 " ³ "

IUR IrUKTROCHI-MISCHI- INPWS I RII t / mbH

-'- U95233

All Friedel-Craft'a catalysts are Yoraugawelae, the halides the 4th and 5th main group dte pearlescent systems, in particular Zlnntctraohlorid or Antimonypentaohlorld suitable. Of these additions suffice la general eohon manganese ron 0.01 - 0.5 jC

Ale Phoaphoraäureeator alnd beaoadara lower allyl esters of Phoeihoric acid "la β · Β · Trinthylphosphet suitable" Ea can also use Diphenylkreeylphosphat, on the other hand Tricresylphosphat almost ineffective. Dleae Eater «earth in quantities τοη 0.1 - 10 96» roraugawaiaa In 2 - 6 % elngeaetst «

When dividing the hardening mixture, the general procedure is to ground the inhibitors homogeneously into the epoxy, optionally mixed with anhydrides or poly oils, then ground the metal fluoroborates either immediately afterwards or react later. The Vermleohung now takes place without difficulty because the mixture a certain duroh the type and amount represents augeaetsten inhibitors related regulier * bare Since brauoht, make up 41 Härtungereaktion elnaetct · In some iat 9 »AUOH mOglloh, metal fluoride borates and other compounding ingredients gleiohaeltlg einsuarbeiten gemeinesa.

The Haramlechungen can ale Oiefl- and Laminierharie, adhesives, Ubarcttga and impregnating benUtat "ground" your "Auehärtung can at lormaltemperatur In Polyeeter- or Polyearbonatformen be -vorgenommen _v" obel überrasohenderweiee occurs in most cases, no Terklebung ₉ but a müheloaaa unmolding mOglloh let "Ea laaeen aleh ao without any formal effort to make any copies of the matrices at normal temperature, even the hardening can be grounded" if required, even at higher temperatures. "

example 1

100 parts of 3,4-epoxydioyolopentadienyl-9-glyoidyl ether were mixed with 25.7 parts of maleic anhydride, 25 parts of 3-methylpentanediol-2,4 and 2.7 parts of tributylsinnoleate with stirring completely clear, nladarrlakoaen liquid that

909810/0764

CONSORHUM FOR ELECTROCMEMICAL INDUSTRY C / nibH

U95233

• in · stand side τοπ had several questions, 1.25 were for sale · Zinc fluoroborate lugeeetat. Haoh 90 min · I started the dead body heat up, laoh 15 StA * storage was the lead hardness d bo obtained clear colorless test specimen 2 H,;

The comparison procedure was carried out under similar conditions, however worked without Slnnorganylsuaats * Dl · Xleehung was eohon after 14 min »hot over 180 ° and had turned a deep brown τ · r,

Example 2

100 SeUe 3,4 * EpoiydieyQlOuentadienyl ~ 9-gly6id] rlether, 37,5 Τ · 11β Xalneic anhydride and .5 part 3-methylpentane <5iol-2,4 was " ■ with 3.1 files Tribernyleinclaurat rermleoht, 29 min · naoh tueata ▼ on 1 «25 file zinc fluoroborate calibrate the mixture 150 °. After an hour there was a clear, hard echwaeh yellow oufi plate developed.

example 3

There was a rental of 100 pelts 3,4 »Epoxyöioyolepentadienyl- > -Glyeidylether with 37.5 pelts, aleic acid anchors and 25 files > ~ Mtthylp * ntan <5iol ~ 2,4 «with each disregarded binary amounts (0 | 2J §ew »> C 21nn) yerrüArt. The table shows the difference the hardship and the rough rehearsals for the tereehieden iinerer * »Indungen naeh Susati ven 1.25 files left fluoroborate *

share inside ». to 100 VI · Epoxya

Start of hardening near

Max f emp,

hardness

AU * -

It min

1.17 fl · Dibeniylsinnohlorld 1.10 fl. FetrabtttylBinn 1.87 fl · dibutylmine dichloride

f1.43 fl. »ibu

I - hexoa

9098

10

30 «in 18 nin

23 min

1Ο / Ο7 6

14 * ISO * 180 *

141 ¹

BAbOFUQINAL

eprsdej dkl

5 1

9 M 5 H.

Brown

CONSORMUM FOR fclfcK I ROCHtMISCHF INDWSl'Rlfc C / mbM

H95233

Part · Zirurrerb. to 100 teaspoons of epoxy

Start there
Hardening after

Max «Temp.

Hard·

If 1.25 tsp. IriphenyXeinnohiorid | g 1.88 tsp. tributyltin oleate

O.94 TX * hexabutyl dietannoxane

24 »in
2 h

19O ¹
110 *

12Q ¹

5 H.

j 5H

I 5 H

CO O (ft »Ο»

σ>

After the finished mixture has been stored for 2 days, Tor Zutati The fluoroboratee aeigte various samples, dl · under Zueats τοπ 2i! Imr «rbinding« n were established, beteer · Sig «naohaft« nt lnsb · - • onder «1» reference to dl · discoloration d * a Hare ···

A miaohung τοη 100 parts 3 »4-FpoxydloyoXopentadl» iqrX «9-> stthyX-glyrtdyimer, 33 parts of maleic anhydride, 7.6 parts of triethylolpropaa and 2.64 parts of tributylin oleate leads 6 minutes to Zu- ■ ata tob 0.56 parts 2 inn fluor boron at eur hardening without heat supply. The temperature rose to 110 °, whereby a clear colorless outer body of the BXeietifth hardness H was obtained

BeiapieX ft

A rental rom 100 parts 3 _f 4- ^ polyoyolohβIyl »βthyl-3,4-ep« xycyelehe \ aaoarboneäuree »ter _t 29 parts maleic anhydride, 6.7 parts tri« »thylolpropane and 2.32 feiXea tributylinoxeate leads to« seil Zueats τοη 0 .43 file zinc fluoroborate after 1} min. Without any further hardening of the oil, which was heated to 160 °. The clear, eohwaoh yellow guiibody like a lead pencil hardness το »2 H on ♦

Sv a Hiaohung τοη 100 feiXen 3,4-Ep © xydicyeXopentadienyi-9- «Lyoidyl ether, 37.5 parts maleic anhydride and 2 $ parts 3« MethylpentanedieX-2,4 was 0.69 Telle-AntimoaAentaohXorid in

CONSORTIUM FUR tUK I ROCHEMISCHE INDUSI RlE GnibH

5 parts of Diaethyldlglykol dissolved sugesetst. Sine 3td after Zuaats of 1.25 parts of zinc fluoroborate set in the hardening reaction, with eioh the mixture heated to 80 °.

In the VerbleiohsverBUoh the same word was used, but no antinone pentahloride as an inhibitor sugesetst · 30 min * naoh Addition of zinc fluoroborate started the strongly exothermic hardening, where you can see the specimen heated to over 180 ° and very dark « shower discolored ». _

Its mixture of 100 parts of 3,4-epoxydieyolopentadlenyl-9-glyoidyinther, 37 # 5 parts of maleic anhydride, 25 parts of 5-methylpentuvene-2,4 1 1/2 atd began with 6.2 parts of triethyl phosphate. neoh addition «of 1.25 parts of zinc fluoroborate duroheheharden · The clear, colorless Guu bodies had a pencil hardness after 24 hours by H.

Example 6

The mixture of 100 parts 3,4- "Rpoxydioyolopentadienyl-9-glycidylether, 37 _t 5 parts maleic anhydride, 25 parts 3-methylpentandloX · 2.4 was mixed with 0.25 part antimony pentachloride, dissolved in 2.5 parts triethy1phosphate * 30 min After the addition of 1.25 parts of zinc fluoroborate, dissolved in 6.2 parts of triethylphoephate, the hardening reaction began, with the body heating up to 130 °. The clear yellow sample had a pencil hardness of 2 H *

example 9

A mixture of 100 parts of 3t4-epoxydieyolopentadienyl-9-glyoidyl ether, 15.6 parts of hexeinic anhydride and 33 parts of di-o-octenylsuccinic anhydride was mixed with 1.25 parts of zinc fluoroborate dissolved in 6.2 parts of triethyl phosphate. laugh 30 XIn. the hardening process began. The "chwaoh yellow clear Guilplatte of 4 to strength had naoh 24 hours, a pencil hardness of 5 H.

Example 10 909810 / 076A

A solution of 100 parts 3 »4 ~ lpoxydioyolopeiitadlenyl ~ 9-glyoidyl · - ether old 37.5 parts maleic anhydride and 8 parts dimethyl

i ^^ UEKmOCHEMISCMb INDUS I RIt C / nibH

• ⁷ "H95233

butanol was treated with _t Q 6 parts of zinc fluoroborate, dissolved in 6.2 fei-1 · η TriMthylphoBphat mixed. laugh 15 Hin. the hardening reaction started «The clear eohwaoh yelled (Jußplatte like« after an hour · a lead pencil hardness · τοη 5 R ·

BtlBPlel 11 ■ '·: · ■■■ ■■ - ■ ^: ■ ■, - ^; . -. . ■. ■ · ■■

With a mixture of 100 parts of Jfi-epoxydioyolopentadienyl-9-glyoidyl ether, 37 _{tons of} 5 parts of malelene acid anhydride, 50 parts of a polyether glycol «1t of the trade aaaen Ilax Triol 240 and 4» 5 parts of tributylin oleate began 2 $ Hinη ·tnaohfluorate the hardening. After 24 hours, the clear elaetlsone Ouöplatte showed a hardness of H euf.

10/07

Claims (1)

IUM IUK MIKIROi! MMJs (Ji! INDUS mi (/i.iMI Claim Claim 1 Process eur production of synthetic resins based on polyepoxides duroh hardening τοη epoxy compounds, optionally in the presence of acid anhydrides and / or polyols with metal fluoroborates, daduroh characterized _f that the metal fluoroborates in combination rushes organosin compounds and / or Friedel-Craft ^f α-catalysts and / or phosphoric acid meters uses «earth» Claim 2 Method according to claim 1, characterized by that in combination with metal fluoroborates organotin compounds of the general formula R.SnX in the R alkyl «aryl or aralkyl groups and X is a radical hydroxyl, carboxyl, halide, Alkoxy1 or OSnR, mean Claim 3 Method according to claim 1, characterized by that in combination with metal fluoroborates Antiiaonpentachlorid or tin tetrachloride can be used Claim 4 Method according to claim 1, daduroh recognized n · t, daii in combination with metal fluoroborates alkyl phosphates how triethyl phosphate can be used 909810/0764