DE1418700A1 - New epoxy compounds and methods of making them - Google Patents

Description

Dr. F. Zumstein - Dr. E. AssmcB " Dr. R. Koenigsberger Dipl. Phys. R. Holzhauer Pa! Entanv »öi» ·

2, Bräuhaussfrefo »4 / ffl

New documents

P 14 IS 700 »9 Case 4341/1 + 2 / E

GIBA ASEIEBSESBULSGRASE, Basel (Switzerland)

their manufacture

imd expire to

The invention relates to new epoxy compounds and processes for their production.

GE-Ic ...

I f

-GH

-OH

CH

n-I

ar.

80 980 1/0431

New documents (Article 7, Section 1, Paragraph 2, No. I Safe3 of the Amendment Act of 4 September 1967)

• C - CH ₂ - O-

CH> -.CH 1 ^ CH-

Γ fh

-CH j CH

■ GH ..

Jn-I

(D

wherein R, and R "are methyl groups or, preferably, hydrogen atoms and η stands for an integer with a value of 1 or 2.

The monoepoxides of the formula (I) / ti = ij which still contain a C =C double bond in the cyclopentene ring are light-colored liquids with low viscosity at room temperature which are valuable active thinners for epoxy resins.

The diepoxides of the formula (1) / n-2 ^ Jslna are practically colorless resins which are viscous at room temperature, which with the usual hardeners for epoxy resins turn into infusible resins. allow very valuable technical properties to cure.

The inventive epoxy compounds of the formula (I) can be obtained by putting main in a .connection of the, # * Formulaί

CH _A

I 8

CH - C - CIU-O-

-CH

CH

-CH CH

(II)

wherein R. and R _{2 have} the same meaning as In 'formula (I). and shark means a halogen atom such as chlorine or bromine in

9801/0431

14187Ö0

In any order, the halohydrin group is converted into the corresponding 2-epoxy group by treatment with dehydrohalogenating agents and, if appropriate, the C * G double bond in the cyclopentene ring by treatment with epoxidizing agents. * ·. epoxidized. ,. ^:

• As dehydrohalogenlerende Mittet fürdie conversion of the halohydrin to an epoxy group are in particular _x

special strong alkalis, ζ .B * potassium hydroxide or sodium hydroxide " As an epoxidizing agent for the possibly durd to *

. »Ι

leading epoxidation of the C = C double bond in the cyclopentene ring is preferably used organic peracids such as peracetic acid, perbenzoic acid, peradipic acid, monoperphthalic acid, etc. It can be used as epoxidizing. Agents also use hypochlorous acid, with HOCl being added to the double bond in a first stage, and the epoxy group being formed in a second stage under the action of HCl-releasing agents, e.g. strong alkalis. ■ _-'- ■

The starting materials of the formula (II) are easily accessible » by either

1. a monohalohydrin of the formula CH ₂ OH "- CRg * ■ CHR, Γ °«

^ SaI = halogen atom, e.g. bromine or chlorine / on dicyciophene-tadiene in Presence of an acidic catalyst or a Lewis acid, v7ie Sulfuric acid or boron 1-uoride ·. or B <->? fluoride complexes, attaches.

ο ^ Lr J UI {· J ϊ + OI

or by using ιman

2ο an epihalohydrin of the formula

CH ₂ HaI - CR ₀ -CHR ₁

condensed with dihydrodicyclopentadien-'S-ol «,. '■

As _{Monochlorhydrinß}} which as starting materials in the *

Method (1) can serve selenium the ot ^ methylglycerin-ot-mono-]

chlorohydrin, ß-methylglycerin-tf-monochlorhydrin, glycerin-ß- j

monochlorohydrin, glycerin-tf ~ bromohydrin and in particular ',. |

Glycerin-oc -'- called monochlorohydrin. Mixtures'.,! [

such monochlorohydrins, such as _o the technical mixture I. ~: "<_ \

vonGlycerin-ß-monochlorhydrln "nd glycerin-ct-monochlorhydfln r \ j be used ,," ... ■

Used as epihalohydrins, dis in process (2) be epichlorohydrin and especially epichlorohydrin called" .

According to method (l), mixtures of d- and ß-monohalohydrin ether§ in process (2) · one obtains the oMonohalohydrin ether In practically quantitative yield »

In the method according to the invention, one can use the desired = if there is also an undecomposed mixture of isomers, which in the process (3.) accrues treat with dehydrohalogenerating agents, but only the proportion of cc-monochlorohydrin ether in the epoxyalkyl ether will be converted »

Ci r es η r \ λ Ι π / -j «c- υ υ ^) UI, - U / + <j ι

141870C

In the event that is subsequently carried out Epoxidation of the C = C double bond will be in the latter case as by-products - also monoepoxide compounds of the molded ice

al

R, -CH H-

-CH

CH-

3H

I «fs

-gh \ ci:

CH

educated. Furthermore, in the case of the optional treatment with epoxidizing agents, in addition to the diepoxides as a result of side reactions, completely or only partially hydrolyzed epoxides can be formed at the same time, ie compounds in which the epoxide groups of the diepoxide of the formula (!) Are wholly or partly to hydroxyl groups !. have been saponified. It has been found that the presence of such by-products generally has a beneficial effect on the technical properties of the hardened diepoxides, therefore recommends

it is generally not necessary to isolate the pure diepoxides from the reaction mixture.

About the exact chemical constitution of the starting material. compounds of the formula (II) originally prevailed a few «■ o uncertainty (cf. the American patent lift 'No, ^' 375» 768, ^ where the production of the unsaturated monochlorohydrin ethers des

σ Dihydrpdlcyclopentaaiens is first described). Since has been proven by exact investigations that these ethers have the structure given in formula {11}, whereby

also the 8-position of the chlorohydrin radical in the Dihydrodlcyclopentadiengerüat "is most likely (see American, patent No.2

- β

As mentioned above, the diepoxy compounds according to the invention react with the usual hardeners for epoxy compounds. They can therefore be crosslinked or cured in the same way as other polyfunctional epoxy compounds or epoxy resins by adding such hardeners. Basic or, in particular, acidic compounds are suitable as hardeners of this type. Amines or amides, such as aliphatic and aromatic primary, secondary and tertiary amines, e.g. mono-, di- and tributylamines, p-phenylenediamine, bis, p-aminophenyl-pmethane, ethylenediamine, N, N = diethyl-ethylenediamine, have proven to be suitable , Tetra ^ öxyäthyljdiäthylenetriamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, piperazine, guanidine and guanidine derivatives, such as phenyldiguanldln, diphenylguanidine, dicyandiamide, aniline-formaldehyde, polymers of amine-formaldehyde,. those made from aliphatic polyamines and di <- or tx'imerized, unsaturated fatty acids, isocyanates, isothiocyanates, polyvalent phenols, for example resorcinol, hydroquinone, quinone, phenolaldehyde resins, oil-modified phenolaldehyde resins. Reaction products of aluminum alkonolates Ozv / "-phcnoXaten with tautomerically reacting compounds of the acetoacetic ester type, Friedel-Crafts catalysts, eg AlCl ,, SbCl ,, SnCl ₁ ^, FeCl ,, ZnClp, BF .. and their 'complexes with organic compounds;} Phosphoric acid.

309301 / OA31

Polybasic carboxylic acids and their anhydrides, ζ-B, are preferably used as hardeners. Phthalic anhydride, Methylendomethylene tetrahydrophthalic anhydride or endomethylene tetrahydrophthalic anhydride or their mixtures5 maleic or succinic anhydride, where appropriate nor accelerators, such as tertiary amines, also advantageously added polyhydroxyl compounds, such as hexanetriol.

The term "hardening", as used here, means the conversion of the above epoxy compounds to insoluble and infusible resins. The present invention therefore also relates to hardenable mixtures which contain the diepoxides of the formula (I) according to the invention and also hardeners for epoxy resins, such as preferably.Dl · = odei * polycarboxylic acid anhydrides. The curable mixtures according to the invention can also advantageously contain a proportion of the corresponding diepoxides, the epoxy groups of which, however, are wholly or partially saponified to hydroxyl groups, and / or polyhydroxyl compounds such as hexanetriol, furthermore, as active thinners, monoepoxides such as, for example, cresyl glycol or those described above Monoepoxides of the formulas (l) or (lll) _f contained

Other polyepoxides, such as ZcB, can also be added to the curable epoxy compounds. Mono- or polyglycidyl ethers of mono- or PoJLyalkohoien such as butyl "1,4-Bufcandiol or glycerol, or esters of mono- or

.Λ - ^ / ·, _ri Λ, '■■) / -j'

Polyphenols, such as resorcinol, bis £? -Oxypheny3J? Dimethylmethane or condensation products of aldehydes with phenols (novolaks) 5 furthermore polyglycidyl esters of polycarboxylic acids, such as phthalic acid, and also aminopolyepoxides, such as are obtained, for example tfurch dehydrohalogenation of reaction products from EpI-. : halohydrins and primary or secondary amines, such as n-butylamine, aniline or 4, ^ «- di ^ monomethylamino7diphenylmethane.

The properties of such known polyepoxides can also through the addition of monoepoxides of the formula (I) be modified as active thinners in valuable catfish.

The epoxy compounds or their mixtures with hardeners and optionally other epoxy resins can be used before Hardening in any phase with fillers, plasticizers, coloring substances etc. are added. As stretch and Fillers can, for example, asphalt, bitumen, glass fibers, mica, quartz powder, cellulose, kaolin, finely divided silica (AEROSIL) or metal powder can be used.

The mixtures of the diepoxide compounds according to the invention and hardeners can be used in the unfilled or filled state, as well as in solution or emulsion, as textile auxiliaries, Laminating resins, varnishes, paints, dipping resins, casting resins, Brushes, fillers and fillers, adhesives and the like or serve to produce such agents. The new resins are particularly valuable as insulation compounds for the Electrical industry.

:: o 1 ΌΛ3 \

In the examples below, parts mean parts by weight, percentages mean percentages by weight? da3 ratio the parts by weight to the parts by volume is the same as the kilogram to the liter? the temperatures are in degrees Celsius specified.

Example 1.

ι ·

1. Addition of ot-monochlorohydrin to dicyclopentadienes

324 parts of dicyclopentadlene are mixed with parts of oc-monochlorohydrin and 5 parts by volume of a solution of BF in diethyl ether. The mixture is slowly heated to 75 ° 5 and an exothermic reaction takes place, which lasts 1 hour, but the temperature is maintained during this time and then at 70-75 ° for 2 hours. It is then allowed to cool, 6 parts of anhydrous sodium carbonate are added and finally the reaction mixture is subjected to fractional distillation under reduced pressure (0.12-0.15 mm Hg).

30 ° / 0.15 mm ζ 5 parts dicyclopentadiene 75 ° / 0.12 mm g 301 "glycerin-a-monochlorohydrin 130 ° / 0.15 mm s 431" adduct (a)

111 ". Residue.

The yield is $ 82 of theory, based on cc-monochlorohydrin. '

A second approach focused on the separation of Addition product (a) and residue varies

8 0 9 0 0 1/0 / ♦ 3- ι

ίο -

put crude product is hereinafter ala addition product (b) designated.

2. Epoxidation "

Mix 2 ^ 3 parts of the addition products (a) or (b), 600 parts by volume of benzene, 206 parts of peracetic acid ( ¹ U ^ Ig) and 12 parts of sodium acetate. It enters an exothermic reaction that lasts 3 hours ι keeping during this time the temperature at 30 ~ 32 °, stirred for a further 1 hour, the solution is washed then 2 times with 200 volumes of water and then distilled everything from benzene. There remain 264 parts of epoxidized addition product (a ¹ ) or / _t (b ¹ ) ·

Third Dehydrochlorinationo

26 ² parts each of the epoxidation products (a ^v ) or (b * 5) are treated with 135 parts of 30 oily aqueous NaOH for 1 hour at 50 ° The benzene layer is separated off, the lower aqueous layer is washed out twice with 50 volumes of benzene each time. The combined benzene solutions are concentrated and 220 parts of viscous, colorless epoxy resin (A) or (B) with an epoxy content of 6.25 or 6.25 are obtained. 6.2 epoxy equivalents per kg ο

The epoxy resin [λ] consists mainly of a diepoxy bleaching of the formula

“AD ORIGWAL

80SG0 1/043 1

CH

CH,

CH ^ -CH-CH _n -O-CH

V ^2/2
x Ο ⁷

■ OH

_f CH CH

CH ^ '· CH ^

Example 2,

100 parts of each of the epoxy resins α and B prepared according to Example 1 are fused with 71 parts or 68.8 parts of phthalic anhydride as curing agent at 120 °, 0.75 equivalents of anhydride groups being used for every 1 equivalent of epoxy groups of the resins.

The mixtures are cured in an aluminum mold ^ö (40 χ χ 10 140 mm) 2h hours at l40. The properties of the hardened cast bodies can be seen from the following table

Fpu .; _: ". resin Impact bending
strength
cmkg / cm ² Bend
strength
kg / rmn ^ Heat resistant
digköit for
Martens DIN
⁰ C ίι
Via ase up
after b days at
20 ⁰ C A.
B. 6.5
12.8 8.2
8.8
! 130
145 0.28

_eA 0

Example 3

. '"■' - .- '" ■ The epoxy resin A described in Example 1 can also

be prepared in the following way: Io condensation of epichlorohydrin with 8-0xy-dihydrodi-

cyclopentadiene «Πι ·· 'ι |

The mixture is heated 300 parts of 8-oxy-dihydrodicyclopentadiene f to 75 °. Adds 2 parts BF, "etherate of $ 40 to 203 parts of epichlorohydrin, and then leaves within 20 minutes dropwise ₀

The reaction starts immediately with considerable evolution of heat and by cooling at 80 = 85 ° held after completion of the dropping of the epichlorohydrin the Wäimeentwicklung stops "and stirring under heat for another 20 minutes at 80 ° to ₀ at this time can be in ileaktionsgemisch no free Epichlorohydrin more regrowth ₀ This gives 505 parts of a dark-colored viscous liquid _p which is mainly composed of the compound of the formula t

| ^H 2 <f 2

CH

CIoCH ₂ -OH-CH ₂ -O-OH | Jig ^ ^ F & OH \ _si ~ «

8CS GQ I / O / * 3 ι

I I! '

consists ο used instead of. BF _ * »etherate an equal amount of SnCl. as a catalyst, the same product _{or the like is obtained with otherwise analogous reaction compounds}

■ ι '\

2ο epoxidation of chlorohydrin _{or similar}

503 parts of the chlorohydrin described above with 1,360 parts by volume of benzene and 25 parts added latriumaoetat, with good stirring and under a moderate cooling is allowed now 464 ropes of a ¹ 36 _o l # lgen Peressigsäurolösung in Essigsäur © within 30 minutes dropwise, while maintaining a temperature from 33 35 ° o One hour after the addition of peracetic acid, the heat development ceases and the temperature begins to drop. »are consumed acetic acid _o You now dio aqueous phase is separated, di © Bönzolschicht washed three times with 450 parts by volume of water, then while simultaneously neutralizing remaining acetic xraa dor once with 200 cc of water ₉ which 35 Toilo 30 $ NaOH includes _c schliösslich again With 250 parts by volume of water, the benzene and any water still present are then placed in a partial vacuum evaporated _p and at the end the last residue of volatile constituents at 0 ^ 2 mm Quock-

80-9 00 1/0 A3 1

■ '- 14

Silver column and "an internal temperature up to 80 ° removed

This gives 485 units of epoxidized chlorohydrin of the formula

, CH

F ₂ 01, CH ₀ -QH-CH ₀ -O-CH

CH ₂

in the form of a yellow liquid and with an eposyd content of 3 _r 58 aeq _o / kg, which corresponds to 87 ^ 5 ^ dor theory _o

3o dehydrochlorination (1 && epox.yjli ^ -t ^ n Chlorhydrina

475 iaile of the chlorine _{opoxidized under 2 0}

Hydrina been with 524 5Joil © n 30 ₉ 2 $ LGEV UaOH for 90 minutes at 55 ° liräftig stirred _o are then added 1000 parts by volume of benzene to _a cool abg filtered off from the precipitated salt and the aqueous phase is separated from ₀ The Bonzolschicht is in partial. Vacuum from the solvent and then at Or2 mrn mercury and. 105 internal temperature freed from the last residues of volatile components o One obtains 405 ropes of the epoxidized glycidyl ether3 (epoxy resin A) of the form

. ·. ■ · · ■ 8AD

80930 1/0431

-CH- CH * - O

in the form of a dark brown liquid, which 7.44 Aeq ₀ epoxy / kg
boBitztp which 82 "5 # corresponds to the theory _o The product contains \
no more saponifiable chlorine *,

If the order of operations 2 and 3 is reversed » a ₀ h _o "

one dehydrates first and then epoxidizes »this is how *

one to the same end product ». |

. If one dehydrochlorinated without epoxidizing; then \

one the corresponding? adön glycidyl ether _p which use as ί

can find active thinner and wirdo described below \

Example 4

Dehydration of the chlorine hydride obtained in Example 3>, Paragraph 1 , -

250 parts of that described in Example 5 under 1 " ,
unsaturated chlorinated hydrochloride for 75 minutes with 2 <'; -
Partial of NaOH of 30 _P 2 ^c / o to 58 ° veri "ühr-i; o Then one adds
500 parts by volume ücnaol z \ x _s cools down _c sucks the excreted
Table salt and separates the '.fäoariga phase from _o Dia * 3onsolschiclit

^] / ^Λ λ 3

is washed with 100 parts by volume of water and then freed from benzene in a partial vacuum. Finally, the last remaining solvent is removed at 0-5 mm of mercury and an internal temperature of 100 °. This gives 200 parts of glycidic ether of the formula · ■■■. '· ·· ■. ■■' ■ ■. '■ ■. ·· -: / ': ■'

OH - CH ₂ -O-OH

r. : ■■

in the form of a light brown mobile liquid with a Bpoxide content. of 3.82 Aeq * / kg,. ·.

BATH ^ - ^

803001/0 U 31

Example 5. '. · ■ - '"· ..

Sample 1 is a cycloaliphatic epoxy compound of the formula

CH C \ ^ ^ CH - CH ^N CH

\ l I II / '

CH CH ₂ CH ₂ CH

with an epoxide content of 6.08 epoxide equivalents / kg (obtained by epoxidation of the acetal produced from ^ ~ tetrahydrobenzaldehyde and 1,1 = »bis ^ oxymethyl ^ cyclohexene-3 with peracetic acid) and for sample 2 a mixture consisting of 80 parts of the above cycloaliphatic diepoxides and 20 parts of the unsaturated glycidyl ether described in Example 4 with an eicoxide content of 3 _P 8 epoxy equivalents / kg used as hardening agents in both samples O ₉ 65 equivalents of phthalic anhydride per equivalent of Bpoxide groups at 120-125 °

The casting resin mixtures obtained in this way are cast in aluminum molds (40 × 10 × 140 mm) _{at approx. 0 120 ° and cured for 24 hours at 140 °} greatly reduced ₉ and the properties of the hardened cast bodies are improved ^

BATHROOM size

809001/043 1

rehearse viscosity Impact bending Bend Heat bestlin « des Hui ^ ea * ■ '& o strength strength di ^ nity according to Resin mixture
at 23 ° in cP " cmkg / cni kg / mm * Martens DIN 1 > .200 »000
\. ■ 4.3 4 ₀ 0 158 2 47,000 5.6
'■! 5.4 184 i ,,.
J:.

Example 6.

1. Addition of β-methyl-glycerol-ct-monochlorhydrln to Picyclo ?. pentadels. . | ".

A mixture of 33 parts of cyclopentadiene and 31 parts of 1-chloro-2-methyl-2,3-dioxypropane is heated to 85 °. Then 0.2 part of H ₂ SO ₁ ^ (98 # Lg) is added, a slight increase in temperature being observed. The mixture is kept at 85-90 ° for 6 hours and then 0.5 parts of Na ₀ CO- are added. The unreacted products are distilled under high vacuum, 7 parts of which at 34 ° below 0.2 mm Hg and 8 parts Parts of it pass below 0.2 mm Hg at 60 °. This leaves 48 parts of the chlorohydrin of the formula:

^ CH,

OH,

I ^- CH ₉ j

CH-

CH

-CH

ClCH ₀ -C - CH ₀ - 0 - CH

² I ²

OH

in the form of a viscous, dark liquid.

BATH

80 930 1/0431

2. Epoxidation.

47 parts of the above-described chlorohydrin are in '

I * ■ -

^Γ 150 parts of benzene dissolved. 3 parts of sodium acetate are added and warmed up to 55 °. Thereafter, 36 parts of peracetic acid (42.9%) were added and the temperature was maintained for 2

Maintained at approx. 35 ° for hours * The product is now washed

4 times old 40 parts of water. The last wash will be with 1.5 parts of NaOH (30%) neutralized. Subsequently, nan concentrated first under partial vacuum and then at 0.2 mm Hg up to 110 °. There are 35 parts of an orange-colored oil get »which has an epoxy content of 3.08 epoxy equivalents / kg having.

3 «Dehydrochlorination of the epoxidized Chlorhydrina. \

33 * 5 parts of the described under 2 are stirred epoxidized product with 163 parts of NaOH (30.2 lg) for 1 hour * Then 100 parts by volume of benzene are added and separates off the aqueous layer, which is then washed twice with 10 parts by volume of benzene. The 3 benzene layers if they are united, they are first concentrated under partial Vacuum and then below 0.2 ram Hg to 110 °. 27 parts of a viscous, dark resin are obtained which have an epoxy content of 5.4 epoxy equivalents / kg and mainly

G j C 3 G 1/0 / ♦ 3 ι

; ■ / * ■

■! ■ i '-'- l. .til ti - ..: - - ·

■ y <λ

20 -

from the diepoxyd of the formula

W P- ■■■■■ '■'

■ i · '··' "*;. =] ί: -
** _> - r * * "A 'f. ■'" ./;V • ■■ • ■■ i-r,: t '-
■ ': ■ *' ■, - ■ -_: ■ · '■■ ■ '*.' · -. - ■ · .- "'- · *. · · "■ '*: - ·. .. 's'- "' .V

BATH ORIGINAL

809001/043

Claims (1)

Claims Ι «, epoxy compounds of the formula Tbsp CH -GH CHT ^ CH "OH-vj .CH "' vo3? i'A fl · 'V & .cl H «Mötbylgruppe.iJ. oäer YorssiJigB hydrogen atoms Ibede'aten and ώ. for an integer worth 1 or;?. aur Heretelln: ag 'iron ": a thereby getosBia ^ eiciiiiel; _r that ubh. tu, elo.er ^ e the 3pQr HO-HaI- t! ί CH
i
Hj-CH j ^'s kang -CH M ^GH 2 I .. Il r ° Ί CH ϊί, 'Ui-Vi B ₀ o'blge Bedeattm ^ iaabaii und Hai e;!.: a .H as Ohlor iMer Brom' means _s I.ö. oelieMger order the abjcfi ".ogriuppö by treating aixt deliydronalogeniören ttöAü -αϊ dj.e enta ^ iceoaende 1 _a 2 - =» E'pos: ygrp.pi> ® ül-erftlhri; HAD ORtGiWAL COPY 8 09001 / 0Λ31 New documents (Art. 7 11 Paragraph 2 No. 1 Sofr 3 of the Amendment Act of 4 September 1967) 141870C and, if necessary, the C ^ G double bond in the cyclopentene ring is epoxidized by treatment with epoxidizing agents * 3ο method according to claim 2, characterized in that one the monochlorohydrin group into the corresponding by treatment with strong alkalis as dehydrohalogenating agents 1,2-epoxyalkyl group transferred «, 4. The method according to claim 2 or 3, characterized in that the GsC double bond in the cyclopentene ring is treated epoxidized with organic peracids » 90 0 1/0 481