DE1245369B - Process for the preparation of addition products containing epoxy groups - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN ^ W ^ S PATENT OFFICE

EDITORIAL

Ifat CL:

C07d

D c 03/02. *

German KL: 12 o-:

Number: 1245 369

File number: F48065IVb / 12o

Filing date. December 31, 1965

Opened on: July 27, 1967

The invention relates to a method of manufacture of additive products containing epoxy groups from glycidic esters of cycloahiphatic carboxylic acids and aliphatic or cycloahiphatic polyvalent ones Alcohols

It is known by reacting hydroxyl compounds reaction products with terminal hydroxyl or epoxy groups with epoxy compounds manufacture (see German patent specification 974 567)

It is also known, low molecular weight sulfone salts or sulfur-containing compounds with Epihalohydrins react to form sulfonium salts can be used as catalysts for the addition of epihalohydrins to polyhydric phenols Formation of the corresponding S-chloro - ^ - hydroxylpropylather to be used (see Belgian patent specification 654 482)

The present invention now relates to a process for the preparation of addition products containing epoxide groups using an epoxide equivalence greater than 1 by reacting polyvalent organic hydroxyl compounds with epoxide compounds which contain more than one epoxide group per molecule, in the presence of a catalyst at temperatures from 100 to 200 ^° C , optionally in a solvent, characterized in that polyhydric aliphatic and / or cycloaliphatic alcohols and di- and poly-2,3-epoxypropyl esters of polyhydric cycloahphatic carboxylic acids, 1.1 to 4 epoxy equivalents of the carboxylic acid ester being used for one hydroxyl group of the polyhydric alcohols in the presence of low molecular weight aliphatic thioathem of the general formula

Rj ö ls.2

worm R ₁ and R _{8 can represent} a) C ₁ - to C _J2 -alkyls, b) co-hydroxyalkyls, c) epoxypropyl groups

It was surprising that the process according to the invention leads to epoxidgrappen-containing soluble addition products in a simple reaction and good yields, since it is known that alcoholic hydroxyl groups, in particular secondary or highly hindered, only in the presence of strongly acidic or basic catalysts or without catalysts at high temperatures and able to react smoothly with an epoxide group under pressure. Furthermore, it was surprising that under the conditions of the process according to the invention, no transesterification takes place with cleavage of the epoxide group
containing addition products

Applicant

Paint factories Bayer Aktiengesellschaft,

Leverkusen

Named as inventor:

Dr Manfred Blazejak, Düsseldorf;

Dr. Josef Haydn,

Dr Rolf Kubens, Leverkusen

acid diglycidester with 0.5 mol of hydroquinone or 4,4-dihydroxydiphenyl-dimethyhnethane with the addition of 0.025 g of 2-hydroxyethyl-ethyl sulfide to 100 ⁰ C, then a strong exothermic reaction occurs em, with the

"5 temperature of the reaction mixture to about 220 ⁰ C rises After cooling, one obtains an insoluble in organic solvents resin could be detected in the no epoxide An advantage of the inventive method harbors gut, that the polymerization of the epoxy group is pushed back and colorless to schwachgelbhchgefarbte Soluble addition products are obtained without volatile by-products. It has also been shown that the products produced by the process of the invention show hardly any color changes even at higher temperatures and, as finished paint films, tend less to chalk than the usual epoxy resins, the aromatic ones, after conversion with conventional hard materials Ring systems contain or have greater stability against UV radiation and weather influences

Polyvalent as di- or poly-2,3-epoxypropyl ester Cyclophatic carboxylic acids are those which differ from cycloiphatic di- or polycarboxylic acids with 7 to 12 carbon atoms, preferably 8 to 9 carbon atoms, derive Examples which may be mentioned. Hexahydrophthalic acid diglycidester, methylhexahydrophthalic acid diglycidester, Hexahydroterephthalic acid diglycidester, hexahydroisophthalic acid diglycidester, tetrahydrophthalic acid diglycidester, 3,6-endomethylene hydrophthalic acid diglycidate, camphor saurediglycidester, norcamphersaurediglycidester,

709 61

3 4

kahydronaphthalenedicarboxylic acid - diglycidate, which may be mentioned as catalysts, for example

Poly-2,3-epoxypropyl ester hydrogenated benzene and diethyl sulfide, / 7-hydroxyethyl ethyl sulfide, / S-hydroxy

Benzol tetracarboxylic acids, the di-2,3-epoxypropyl ester propyl ethyl sulfide, eo-hydroxy-tetramethylene-ethyl sulfide

of esterification products from 2 χ moles protruding fid, thiodiglycol

of cyclic dicarboxylic acids with χ moles of a two- 5 Preferably, aliphatic thioethers are used with

valuable aliphatic or cycloaliphatic hy- not too large alkyl groups, especially with un-

hydroxyl compound ¹ , as described below, branched Cj to C ₅ alkyl radicals or oxyalkyl

suid Mixtures of the named di- or poly- residues are also used to prevent the

Glycidester can be used to avoid catalytic activity

Preferably Hexahydrophthalsauredigly- io The catalysts are used in amounts of 0.001 to

cidester, methylhexahydrophthalic acid diglyodester, 1 percent by weight, based on glycidester, preferably

3,6-endomethylenetetrahydrophthalic acid diglycidester, in amounts of 0.01 to 0.4 percent by weight,

and 3,6-endomethylene hexahydrophthalic acid diglycide- used

ester used The implementation of the reactants according to the

The preparation of the invention & ACCORDANCE to use- 15 reclining invention is carried out at temperatures from the di- or Polyglycidester follows a opposite from 80 to 200 ° C, preferably at 130 to 18O ⁰ C, gege own proposal the hereinafter di- obtained and appropriate, m nitrogen atmosphere this case, is as polyglycidyl esters contain a residual chlorine content of methods that initially at temperatures less than 1.1%, it is readily possible for the working of 80 to 13O ⁰ C until the Haupterfindungsgemaße method distilled products single 20 quantity of hydroxyl groups attached and to prepare which are completely colorless and chlorine-free and after closing the reaction at 130 to 180 ° C. to the end of the reaction according to the invention is practically colorless

If desired, the reaction can be carried out in solution Ais polyhydric, in particular dihydric alcohols, such as toluene, xylene, Cympl, anisole, dichloro are aliphatic with 2 to 18 carbon atoms, preferably 25 benzene or mixtures thereof, with 4 to 6 carbon atoms, which can be branched. 3, l ^ -Dimethyl-lS-propanediol, 1,3-butanediol, alcohols are chosen so that on a hydroxyl-butanediol-lAPentanediol-lShexanediol-ljo ^. ^^ Tn-30 group of alcohols at least 1.1 epoxypropyfmethylpentanediol -1,3,3 methyl-5-ethyl-heptanediol-2,4, groups are omitted, while for the application to octadecanediol-1,12, diethylene glycol, tnathyleneglycol the lacquer, coating and adhesive sector to octaethylene glycol Kol, Dipropylejiglykol to Hexapro addition products, in which on a hydroxylpylene glycol (ie Veratherungsprodukte from Pro- group 1.1 to 2.0 epoxypropyl groups used pyleneglycol-1,2), butenediol-1,4, glycerine, Tnmethylol- 35 were, especially are suitable, are suitable for the propane, hexantanol-1,2,6, pentaerythritol It can be used as laminating resins, casting resins, stabilizers, mixtures of the aforementioned aliphatic generators, especially the products in which on 1 Hyg hydroxyl group 2.0 to 4 epoxy groups are used, and cycloahiphatic alcohols can be used
40 Those made by the process of the invention

Preferably, aliphatic saturated glycols are products that are obtained in quantitative yield

with only primary hydroxyl groups with 4 to 6 carbon atoms, are in aster line due to their epoxide content

men or their mixtures used, then characterized by the molecular weight, the

Among polyvalent, aliphatic and cycloah chlorine content, the color number, the viscosity or the

In this document, phatic alcohols are referred to as Aiko softening point.

hole understood with a maximum of 4 hydroxyl groups. All of the epoxy equivalents can be from about 200 to about

polyhydric alcohols contain, in addition to C-, O-, 3000, the molecular weights about 400 to about

Η atoms nuclei of different types of atoms 4000 The products represent colorless to yellowish resins

As polyvalent, especially divalent cyclo- with chlorine contents of 0 to 0.8%

Aiphatic alcohols are used for the invention. The di- and polyglycidic esters of the invention

Measures processes those with 5 to 19 carbon atoms, before processes can easily be carried out with other mono-,

preferably with 6 to 15 carbon atoms, or their mixed di- or polyglycidic esters of cycloaphatics

For example, there may be mentioned cyclocarboxylic acids, with cycloahiphatic mono- or

pentanediols, cyclohexanediols, cyclohexanediols, polyepoxides ^ which by peroxidation from olefinic

2,2,4-tetramethylcyclobutanediol-1,3,4,4'-dihydroxy-55 unsaturated compounds can be obtained

dicyclohexylmethane, 4,4'-dihydroxydicyclohexyldime or with mono- or polyepoxides based on one

thylmethane, 4,4'-dihydroxydicyclohexyl, the hydrogenated or polyhydric alcohols or phenols, from

th reaction products of 1 mol of a diphenol, aliphatic or aromatic mono- or diamines

with 6 to 15 carbon atoms mixed with 2 moles of ethylene oxide or sulfonamides or of cyanuric acid

for the method according to the invention, the hy- 60 will be

third products from reaction products of Since the products according to the invention only ah-

2 mol of a diphenol with 6 to 15 carbon atoms and phatic or cycloaliphatic atom groups

1 mole of a «, co'-dichloroalkyl ether such as 2,2'-dichloro, they have a high stability against UV exposure

Diet ether, 4,4'-dichlorodibutyl ether suitable radiation and the effects of the weather on you

Have a special interest. Cyclohexanediol-1,4 65 easily into crosslinked products by common hardeners

and 4,4'-dihydroxydicyclohexyl-dimethylmethane, bis-overpassed. If necessary, the inventive

oxathylated 4,4'-dihydraxydicyclohexyl-dimethylmeas products in combination with dyes,

than pigments, fillers, glass fibers, tars, pitches,

5 6

The encryption used Crackruclcstanden Also 16O ⁰ C under nitrogen heated After cooling

Esterification with drying fatty acids is readily available in the analysis data of the addition product

possible determined

The products according to the invention epoxy equivalent 373, molecular weight 588, 584, Farbais casting resins, impregnating and lambing resins, soft number 3, chlorine 0.26, viscosity 15,700 cF / 60 ° C. are used
Makers, stabilizers for chlorine-containing polymers,

for the production of paint films, coatings, example 6

Primers, molding compounds, binders, grouts 625 weight point (2.2 mol) hexahydrophthalic acid

casting compounds, etc. diglycidic ester, 240 weight points (1 mole) 4,4'-dihydro-

For example ¹⁰ dicyclohexyl dimethyl methane, 104 weight point

(1 mol) 2,2-dimethyl-propanediol-l _> 3 and 0.4 Ge

100 parts by weight (0.35 mol) parts by weight of 2-hydroxyethyl ethyl sulfide were stirred for 15 hours.

Hexahydrophthalic acid glycidate (color number 3, chlorides under nitrogen to 17O ⁰ C and then

value 0.96%, epoxy equivalent 160) with 42 weight 4 hours at 200 ⁰ C then heated

share (0.175 mol) 4,4-dihydroxydicyclohexyldunethyl- 15 hot resin poured onto a sheet and the following

methane and 0.02 parts by weight diepoxypropyl sulfide determined analysis data

heated to 150 ⁰ C. After 6 hours at 150 ⁰ C is Epoxidaquivalent 3080, color number 10, softening

cooled The addition product has the following point of 72 ⁰ C, chlorine content 0.11 ° / ₀
Analysis data

Epoxy equivalent 363, color number 3, chlorine content 0.67, 20 B e 1 s ρ 1 e 1 7

Viscosity ^ = 83 cP / 120 ° C. 296 parts by weight (1 mole) 3,6-endomethylene-tetra-

In this and the following examples, the hydrophthalic acid diglycidester (epoxy equivalent 198),

Color numbers according to the iodine scale DIN 6162, the viscosity 72 weight points (0.8 mol) butanediol-1,4 and 0.08 ge

un Haake rotary viscometer DIN 16945 and the weight parts of 2-hydroxyethyl-ethyl sulfide are 3 hours

Softening products according to the Kramer method, heated ^{to 150 ° C. under nitrogen.}

Sarnow, Nagel, DIN 53180, the analysis data are determined cold '

_. Epoxy equivalent 1240, chlorine content 0.93 ° / ₀ , viscous

^{a e] sp} * ^e ' ^l sitat 19 280 cP / 120 ° C, color number 15.

568 parts by weight (2 moles) of hexahydrophthalic acid

diglycidester (color number 0, epoxy equivalent 152) is 30 example
together with 240 parts by weight (1 mol) of 4,4'-di- 284 parts by weight (1 mol) of hexahydrophthalic acid dihydroxydicyclohexyldimethyl methane and 0.06 glycidate, 296 parts by weight (1 mol) of 3,6-endome weight parts of 2-hydroxyethylethylsulfide with stirring ethylene tetrahydrophthalate (Epoxidaqui-3 hours to 12O ⁰ C and then 2 hours to valent 198), 168 weight points (0.7 mol) 4,4'-Dihy-170 ⁰ C heated After cooling, you get em 35 droxydicyclohexyl-dunethylmethane, 83 2 parts by weight of colorless addition product with the following analysis - (0.8 mol) 2,2-dimethylpropanediol-1,3, 13.6 parts by weight (0.1 mol) of pentaerythritol and 0.15 point by weight

Epoxy equivalent 369, viscosity 9j _t = 83.5 cP / 120 ° C, 2-hydroxyethyl ethyl sulfide are on for 8 hours

Color number 1 to 2, chlorine content 0.11% 150 ⁰ C heated. It is then cooled and the

_, "40 analysis data determined

^{a e] s} P * ^{e l ό} epoxy equivalent 1274, chlorine content 0.67%, color

625 parts by weight (2.2 mol) of hexahydrophthalic acid number 20 to 25, softening product 76 ° C
diglycidester (epoxy equivalent 149), 480 weight

parts (2Mol) ^ '- Dihydroxydicyclohexyl-dimethylme- Example 9

than and 0.25 weight stede 2-hydroxyethyl-ethyl-45

sulfide are 6 hours at 170 ⁰ C under nitrogen 284 weight stede (1 mol) Hexahydrophthalsauredi-

Then the still hot product is heated glycidic ester, 81.2 parts by weight (0.7 mol) of cyclohexane

poured onto em sheet metal and the following analytical data diol-1,4 and 0.05 weight point 2-hydroxyethyl-ethyl-

determined sulfide are heated ^{to 150 0 C for 8 hours}

Color number 4, epoxy equivalent 1280, softening 50 cooling, the analysis data are determined

point 62 ° C, chlorine content 0.12% epoxy equivalent 490, chlorine value 0.24%, color

_n . ,. number 10, molecular weight 508.511, viscosity 1040 cP /

Example 4 120 ⁰ C ^e

568 parts by weight (2 moles) of hexahydrophthalic acid - Example 10
diglycidester (chlorine 0.96, color number 3, epoxidaqui- 55

valent 160), 120 parts by weight (0.5 mol) of 4,4'-dihy- 298 parts by weight (1 mol) of methylhexahydrophthaldroxydicyclohexyldimethylmethane and 0.14 parts by weight of acid diglycidate (epoxy equivalent 159), 86.4 parts of bis (2-hydroxyethyl) - Sulphide is heated for 13 hours to parts by weight (0.6 mol) of 2,2-4,4-tetramethylcyclobutane-150 ° C. After cooling, the analytical diol-1,3 and 0.03 parts by weight of 2-hydroxyethyl-ethyl data are determined 9 hours at 150 ⁰ C. The heated Pro color number 6, chlorine 0.78, Epoxidaquivalent 280 mol domestic product had the following characteristics
weight 441,442, viscosity ψ = 2500cP / 60 ° C. Epoxy equivalent 470, molecular weight 789.782, color _Ώ,. number 5 to 9, chlorine value 0.71%, viscosity ψ = 194 cP / example 5 120 ° C

284 parts by weight (1 mole) of hexahydrophthalic acid 65 _R , ^

glycidester (color number 0, epoxy equivalent 149), 59 Ge ^p

parts by weight (0.5 mol) of 1,6-hexanediol and 0.03 parts by weight of 284 parts by weight (1 mol) of hexahydrophthalic acid

teüe 2-hydroxyethyl ethyl sulfide are 4 hours on glycidester, 164 parts by weight (0.5 mol) of bis (2-hy-

hydroxyathoxycyclohexyl) - dimethylmethane (hydrogenated addition product of 2 moles of ethylene oxide to 1 mole 4,4'-dihydroxydiphenyl dimethyl methane and 0.03 part by weight 2-Hydroxyethyl-ethyl sulfide are 7 hours heated to 170 ° C and then cooled. The resin has the following characteristics

Epoxy equivalent 364, color number 30, chlorine value 0.71%, viscosity η ₍ = 194cP / 120 ° C

Claims (1)

Claim Process for the production of epoxy groups containing addition products with an epoxy equivalent greater than 1 due to the reaction of polyvalent organic hydroxyl compounds with epoxy compounds that have more than one epoxy group contained per molecule in the presence of one Catalyst at temperatures of 100 to 200 ⁰ C, optionally m a solvent, characterized in that polyvalent aliphatic and / or cycloaliphatic alcohols and di- and poly-2,3-epoxypropyl esters of polyvalent cycloaliphatic ^! Carboxylic acids, 1.1 to 4 epoxy equivalents of the carboxylic acid ester being used for a hydroxyl group of the polyhydric alcohols, in the presence of low molecular weight aliphatic thioethers of the general formula R ₁ -SR ₂ worm R ₁ and R _{2 can represent} a) C ₁ - to C ₁₂ -alkyls, b) co-hydroxyalkyls, c) epoxypropyl groups. 709 618/575 7 67 © ^s Bundesdruckerei Berlin