DE1806623A1 - Process for the production of molded parts and coatings from polyadducts by reacting glycidyl ethers of derivatives of endomethylene cyclohexene with customary polyadduct formers - Google Patents

Description

Corporation Frankfurt am Main

Pat-590-R

Patent application:

Process for the production of forint parts and coatings from polyadducts by reacting glycidyl ethers from Derivatives of endomethylenecyclohexene with customary polyadduct formers. ...

The invention relates to a method for producing Molded parts or coatings made from polyadducts using glycidyl ethers of derivatives of endomethylene cyclohexene.

To produce the glycidyl ethers, according to the invention, 3,6-endomethylene-1,2,3 »6-tetrahydrophthalyl alcohol are added the formula

its substitution products or the oxalkylation pro duktc of these compounds are used. Substitution products in the context of the invention are alkyl and / or Halogen derivatives 'to' understand. The ones from these glycidyl ethers by reacting with the usual polyadduct formers. for. Molded parts and coatings made from epoxy compounds show both good mechanical and good electrical properties. Their "flexibility, especially in the case of moldings made from glycidyl ethers of the oxalkylated" th endomethylenetetrahydrophthalyl alcohol or its Substitution products. In addition, they “I have very little water absorption”.

The «endomethylenetetrahydro-

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Phthalyl alcohol or its substitution products are easily accessible by diene synthesis from butene- (2) -diol- (1 .k) and cyclopentadiene or its corresponding substitution products.

Ethylene oxide, propylene oxide, butylene oxide, etc., and mixtures of these alkylene oxides can be used for the preparation of the oxyalkylation products. The elasticity of the molded parts and coatings can be varied within wide limits by the type and amount of alkylene oxides. As a rule, however, not more than k moles of alkylene oxide are incorporated per mole of endomethylenetetrahydrophthalyl alcohol. The oxyalkylation can be carried out according to the customary processes, for example by addition in the presence of Friedel-Crafts catalysts or basic catalysts such as NaOH or Na alcoholate *.

The GIy- ■ used for the method according to the invention Cidyl ethers can be produced in a manner known per se by reacting endomethylenetetrahydrophthalyl alcohol or its Substitution products with epihalohydrins ^, in one One-step or, preferably, a two-step process getting produced. The latter takes place in the first Stage the conversion of the hydroxyl groups with the halohydrin in the presence of suitable catalysts, such as BF. , to the corresponding halohydrin ethers, which are then converted into the glycidylfc by alkali in the second reaction stage ether be transferred. '

The glycidyl ethers produced in this way have more than one epoxide group in the molecule and are liquids with low viscosity at room temperature, which is advantageous for processing allowed. You can use the acidic, basic or phenolic polyadduct formers customary for epoxy compounds, possibly with the addition of known, accelerating compounds, through polyadduct formation be networked in the cold or in the heat.

Acid polyadduct formers are mainly used for this organic dicarboxylic acids such as as.B. Phthalic acid, maleic acid, Tetrahydr © phthalic acid, endoraethyl ate tetrahydrophthalic acid, Methylendomethylenetetrahydrophthalic acid, HexftchlorendorEjethvlentetrahydrophthalic acid, or their

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BATHROOM ORIGINAL " ³ "

^ :. .:; "".;j> ff} | ·, "' i > ί JiC

Anhydrides and others are in question.

For the formation of polyadducts with basic compounds Amines such as primary aliphatic, cycloaliphatic or aromatic, secondary and tertiary Amines, such as Mono-, di- and tributylamine, ρ-phenylenediamine, 4,4'-diaminodiphenylmethane, diethylenetriamine, Guanidine and acidic derivatives, or polyamides like them e.g. from aliphatic polyamines with dimerized or trimerized unsaturated fatty acids can, and polyvalent as phenolic adduct formers Phenols such as bisphenol A and others more can be used.

The glycidyl ethers according to the invention of Endoraethylenetrahydrophthalylalkoholsbzw. its substitution products can also be mixed with other polyepoxide compounds can be used, whereby e.g. a flexibilization of the molded parts or coatings made of polyadducts that are too brittle leading epoxy compounds can be brought about. You can use the usual processing techniques with or without fillers, optionally also with reactive diluents containing epoxy groups.

The polyepoxide compounds used according to the invention, which are derived from endomethylenetetrahydrophthalyl alcohol, its substitution products or the oxyalkylation products of these compounds, are prepared in the general procedure described below:. Fan lets, for example, 1 mole of endomethylenetetrahydrophthalyl alcohol react slowly with 2.2 moles of epichlorohydrin at 90 ° C. after adding 3-1 ml of boron trifluoride dietherate. After the epichlorohydrin has been added, the reaction is allowed to continue for a further hour. With the aid of the appropriate amount of 50 Jig sodium hydroxide solution, the glycidyl ethers are formed from the chlorohydrin ethers formed at 40 ° C. After the usual work-up, glycidyl ether of endomethylenetetrahydrophthalyl alcohol with more than one epoxide group in the molecule is obtained as a thin, yellow-colored product

When using oxyalkylation products of endomothylenetetrohydrophthalyl alcohol or their substitution products for the preparation of the polyepoxide compounds, are the oxyalkylation products by the addition of

009821/1800 _eAD0RialNAU . _% ..

Alkylene oxide obtained from the Endomethylente.trahydrophthalylalkohol or its substitution products. For this one can, for example, 1 Mol.Endomethylentetrahydrophthalylalkohol in the presence of catalytic amounts BF_ diet herat (ca, 1%) at about 70 ⁰ C and 1-4 moles of alkylene oxide react with the speed, as the latter is consumed. After the main reaction is allowed 1 hr. To react at 90 ⁰ C. The resulting oxyalkylation products are liquid products. To form the polyepoxide compounds according to the invention, they are reacted with halohydrin in the manner described above.

The products obtained are hereinafter referred to as "glycidyl ethers" for short. * The following examples fc are some preferred embodiments of the invention explain: .

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BAD ORlGiNAL

example 1

From 1 mole of 3 »6-endomethylene-1,2,3,6-tetrahydrophthalyl alcohol and 2.2 moles of epichlorohydrin becomes the corresponding diglycidyl ether according to the above procedure produced (glycidyl ether A).

Epoxy equivalent: 178 Viscosity at 25 ° C: approx. 500 cP

100 g of glycidyl ether A "and 80 g of hexahydr © phthalic anhydride are mixed together. The mixture is poured into standard rod molds and then at 1 ^ 0 C for 17 hours held. The physical properties of the thus obtained Table I contains standard bars.

Example 2

From 1 mole of 4-methyl-3,6-endomethylene-l, 2,3,6-tetrahydrophthalyl alcohol and 2.2 moles of epichlorohydrin, as in Example 1 the corresponding diglycidyl ether prepared (glycidyl ether B). .

Epoxy equivalent: I85 Viscosity at 25 ° C: 620 cP

100 g of "glycidyl ether B" and 80 g of methylendomethylene tetrahydrophthalic anhydride are mixed. The mixture is poured into standard rod molds and then at 10 ° C held for 17 hours. The physical properties the standard bars thus obtained are shown in Table I.

■ ν "-

contain"

Example 3

1 mole of 3,6-endoniethylene-1,2,3,6-tetrahydrophthalyl alcohol becomes the corresponding oxyalkylation product with 2 moles of butylene oxide implemented and therefrom by reaction with 2.2 moles of epichlorohydrin as in Example 1 of the corresponding Diglycidyl ether produced (glycidyl ether C).

Epoxy equivalent ι 25k viscosity at 25 ° C % 8 $ 0 cP

100 g of "glycidyl ether C" and 55 _{g of} hexahydrophthalic acid

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BATH

anhydride are mixed together. The mix will cast in standard rod forms and the formation of polyadducts carried out at 1ΛΟ ° Ο for 17 hours. The physical Properties of the standard bars thus obtained are given in Table I.

example k

100 g of the "glycidyl ether A" obtained according to Example 1 are mixed with 12 parts of diethylenetriamine and cast in standard rod molds. The polyadduct formation is allowed to proceed for 2k hours at room temperature. This is followed by tempering at 80 ° C. for a further 2 hours. The standard bars have the physical properties listed in Table II.

Example 5

75 g of the "glycidyl ether A" obtained in Example 1 and 25 g of the "glycidyl ether C" obtained in Example 3 are mixed (referred to as "glycidyl ether D"), mixed with 15 g of triethylenetetramine and cast in standard rod forms. The polyadduct is allowed during 2k hours at RäumtBtnperatür proceed * Then another 2 hours at 8O ⁰ C is tempered. The standard rods possess the mechanical properties listed in ψ Table II.

00982 1/180 0

BATH ORIGINAL. Glycidyl ether

A DC

Impact strength kpcm / cm 22 l8 - ♦

Notched impact strength kpcm / cm 2.8 2.7 - * '

Flexural strength kp / cm 1250. 1290 -

Tensile strength kp / cm ² 707 695 II8

Elongation % - - 8l.

Dimensional stability in the

Martens C 67 heat

Tracking resistance level KA 3c

Arc resistance L 4

Water absorption max.% 0.25 Shore hardness

too elastic

71 - * KA 3c KA 3c L 4 L 4 0.2 1.35 D 56

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Table II

Glycidyl ether

A D

Impact strength kpcm / cm 66.5 ■ - *

Notched impact strength kpcm / cm ² 2.5 - *

Flexural strength kp / cm ² 986 - *

Tensile strength kp / cm ² 450

"Elongation % - 27

Dimensional stability in the WSrne n. Martens ⁰ C 55 '- *

* Creep chromium grease level KA 3c KA 3c

Arc resistance L k Lk

Shore hardness - D

* too elastic

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Claims (2)

Claims; ■ si- ■ ■■ ■■■ g 1806G23 l) Process for the production of molded parts and coatings from polyadducts by reacting glycidyl ethers of Derivatives of endomethylenecyclohexene with common polyadduct formers for epoxy compounds, characterized, that the glycidyl ethers used are those which of 3,6-endomethylene-1,2,3,6-tetrahydrophthalyl alcohol the formula of its substitution products and of oxyalkylation products derive these compounds and which contain more than one epoxy group in the molecule. 2) Method according to claim 1, characterized in that that as polyadduct formers for epoxy compounds, organic dicarboxylic acids or their anhydrides or aliphatic, cycloaliphatic or aromatic polyamines or polyamides or polyhydric phenols, optionally with the addition of a known accelerator, are used. Dbg.-Meiderich, October 29, 1968
Patent department Dr.Ko / Dr.Rae / schü 009 8 21'18OO