DE1520780A1 - Process for the production of flame retardant epoxy-based resins - Google Patents

Description

SociSte d'Electro-Chimie, d'Electro-Metallurgie et des Aeieries Electriques d'Ugine, 10, Rue du G & ieral Foy, Paris (France.)

Process for the production of flameproof resins

Epoxy base

The invention relates to a method for producing

~ lambproof_ ^ ■■. , . _,. . . . arzen from mixtures of at least one epoxy resin with one

used as hardener for the resin, derived from diphenyl halogenated polyphenol.

All compounds can be used for the process according to the invention used the epoxy groups of the formula

! I.

.0

contain. However, preference is given to epoxy resins which contain more than two epoxy groups in the molecule, in particular:

A. From an organic containing multiple hydroxyl groups Compound derived glycid, T '?, Po? -Yät? IGr, the more contain as two epoxy groups in the molecule;

B. compounds containing more than two epoxy groups per mole, which are not glycidyl compounds;

G »Mixtures of compounds A and B in various proportions optionally with further compounds which contain two or fewer epoxy groups per mole, provided that the mixture obtained has a valence greater than two.

, 0 09836/2117 BAD ORidlNAL ^r

As Group A epoxy resins, all reaction products are between A-alcohol and phenolic compounds with more than two hydroxyl

suitable

groups per mol, such as glycerine, trimethylolpropane, pentaerythritol, Phloroglucinol, hydroxyhydroquinone, catechol, novolak, and an epihalohydrin such as epichlorohydrin, The pure diglycidyl derivatives, e.g. the diglycidyl ethers of phenols with several hydroxyl groups, are not suitable for the purposes of the invention as they do not result in thermosetting resins with good mechanical properties. Against it these diglycidylderiva-fce can be mixed with others Derivatives are used which, like the compounds under A), contain more than two epoxy groups per mole.

The Group B epoxy resins include aliphatic acyclic ones Products, e.g. epoxidized polyolefins. Best known of these are the "OXIRON" resins (trademarks of Food Machinery & Chemical Corporation for epoxidized polybutadienes) , epoxidized derivatives of unsaturated fatty acid glycerides and cyclic aliphatic products such as limonene dioxide, Vinyl cyclohexene dioxide and dicyelopentadiene dioxide.

A perchlorinated polyphenol is suitable as the halogenated polyphenol ■ ^ olyphenol produced by phenolisation of decachlorodiphenyl is obtained with an alkali compound. The invention is applicable to polyfunctional compounds of the general formula

Shark

in which the sum of χ + y values from 2 to 4 and the sum of η + m can have values from 8 to 6. The sum of χ + y + η + m is always equal to 10.

Particularly suitable for. The method of the invention are the different isomers of Octochlorodihydroxy'diphenyls alone or in a mixture with each other. These are white, solid ones

009836/2111

Products that are soluble in most common solvents and decompose alkali carbonate solutions.

The tetonte acidity of the hydroxyl groups of these perchlorinated polyphenols enables the opening of the epoxy groups of basic character and the formation of an ether. This can be represented by the following reaction equation I-I

The proportions of perchlorinated polyphenol in the thermosetting products depend on the type of epoxy resin and the desired properties of the final cured product. In general, the amount used is between 0.8 and 1.2, preferably 1 hydroxyl equivalent per epoxy equivalent. "Equivalent ^Ir is to be understood as the amount of substance in grams that contains a hydroxyl group or an epoxy group.

An advantage of the invention is the ease with which Semicons of the perhalogenated lolyphenol with the epoxy resin can be produced. It is enough to add the former in small quantities to the resin brought to a temperature which is between 40 and 120 °, preferably between 60 and 80 when the resin is liquid, and slightly above its softening point is when it is solid. It is also possible to incorporate the polyphenol as a solution in a solvent * The non-toxic mixtures have sufficient Utility or pot tents that match those of the classic Systems made from acid anhydride and epoxy resin are comparable. It is also possible to sell products with a longer usage time, by cold mixing the halogenated polyphenol and the solid resin in powder form.

According to another embodiment of the invention, different amounts of one or more hardeners of acidic or basic nature can be added to the perhalogenated polyphenol without the flame resistance of the resin compositions being impaired. As an additional hardening i ttel are organic polycarboxylic acids or their anhydrides, such as maleic anhydride, phthalic anhydride are suitable,

. 009836/2117 BAD OFUGINAU

Succinic anhydride, dodeey succinic anhydride, or primary, secondary and / or tertiary amines, such as diethylenetriamine,! priethylenetetramine, diethylaminopropylamine, dimethyl aniline, or polyamides / polysulfides, BF-j-amine complexes. The characteristics of the hardener mixtures with the exception of those containing tertiary amines or complexes of BF ^ and tertiary amines contain, are chosen so that the thermosetting compositions according to the invention 0.8 to 1.2, preferably 1 effective Group of hard mineral before s included per epoxy group. Of the The term "effective group" means a carboxyl group in the case of an acid anhydride and / or an organic acid or a hydrogen atom, which in the case of a perchlorinated polyphenyl to an oxygen atom, in the case of primary and / or secondary amines and in the case of polyamides on a nitrogen atom and in the case of polysulfides on a sulfur atom is bound. In contrast, the tertiary amines and the complexes of BPt and tertiary amines due to their catalytic and / or accelerating properties only used in very small amounts.

It is always possible in the various ways described above Masses of inert fillers, pigments, leveling agents, reactive and non-reactive diluents or mixtures of these different substances.

The optionally modified thermosetting resin compositions According to the invention can be used for the production of casting compounds, laminates, paints, in the production of electrical and / or electronic parts, for encasing electrical and / or electronic parts, To be sent. «-

The hardening conditions of the resin solutions depend essentially on the type of resin and on those optionally used in connection with the perhalogenated polyphenol other hardeners. Optimal conditions are generally curing times of 24 to 48 hours and temperatures between 20 and 200 °, preferably between 20 and 10 °. Bie Resins cured under these conditions are excellent Flaramen resistance and interesting mechanical and

009836/2117 BATH

.thermal properties, as in the following examples can be seen. In these examples the parts are Parts by weight.

The octochlorodihydroxydiphenyl contained in the thermosetting compositions described below is a mixture of isomers with a melting point around 240 °.

The results given in the examples were obtained by the following methods:

Impact strength according to the Izod method

(with notched test bar) ASTM D 256-56

Rockwell hardness ASTM D 785-51

Dimensional stability under heat

18.56 kg / cm ² - ASTM D 648-56

1/10 yieat point (temperature at which one

! Censure of 1 mm ² cross-section under one

Load of 1 kg penetrates 0.1 mm deep) ASTM D 1525-58T

Flame retardancy ASTM D 757-49

and ASTM D 635-56T.

example 1

100 parts of octochlorodihydroxydiphenyl, 100 parts of OXIROH (epoxidized polybutadiene), 20 parts of maleic anhydride and 50 parts of chlorinated paraffin with 55% chlorine mixed at 80 under reduced pressure. The mixture was cured at 120 ° for 24 hours. The hardened product was transparent, dark yellow, hard and flame retardant according to ASTM D 635-56T.

Example 2

100 parts octochlorodihydroxydiphenyl, 100 parts epoxidized Soybean oil with 6.5 $ epoxy oxygen was used at 60 - 80 ° mixed. The mixture was cured at 140 ° for 24 hours. The product obtained was transparent, dark yellow and had the following properties;

Density, g / cm ³ 1.325

Notched impact strength, mkg / 25 mm notch 0.069 Rockwell hardness M 60.6

009836/2117
BATH ORIGINAL

Dimensional stability under heat

18.56 kg / cm ² 49.0 ⁰ C

1 / 10th Vicat point 51.5 ⁰ C

Flame retardancy, mm / min. 7.5 in 1, 2.

Minutes then went out by itself.

Example 3

At 80 °, 100 "parts of epoxidized soybean oil were with 6.5 $ epoxy oxygen and 100 parts octochlorodihydroxydiphenyl mixed. After the mixture had become homogeneous, it was cooled to 30 ° and 1 part of dimethyl aniline was added. The mass obtained was cured at 100 ° for 24 hours and formed a transparent, light yellow product with the following properties!

Density, g / cnr * 1.31

Notched impact strength j mkg / 25 mm notch 0.032

Rockwell hardness M 56.8

Dimensional stability in the Y / ärme _s C 48

1/10 Vicat point, ⁰ C 53

Flame retardancy, mm / min. 7.5 in 1 min.

and 20 seconds; then went out by itself.

Example 4

At 80 ° 100 parts of epoxidized soybean oil with 6.5 $ epoxy oxygen, 85 parts of octochlorodihydroxydiphenyl and 6 parts maleic anhydride mixed. The mixture was cured at 120 ° for hours. The product obtained was transparent and dark yellow and had the following properties:

Density, g / cm 1.35

Notched impact strength, mkg / 25 mm notch 0.078 _f

Sockwell hardness M 56

Dimensional stability in heat, ⁰ C 58.5

1/10 Vicat point, ⁰ C 50.5

Flame retardancy, inm / tan., 13.0 in 2 min .;

then went out by itself

For comparison, an identical mixture was prepared in which

009838/2117

BADORlGfNAL

but the OctoehlOrdihydröxyäiphenyl by a chemical equivalent amount of maleic anhydride was replaced. This mixture "consisted of 100 parts, epoxidized soybean oil and 4-0 parts of maleic anhydride. It was 48 hours at Hardened at 120 °. The product obtained was transparent, dark yellow, not very hard and very brittle. It wasn't flame retardant j its combustion rate was 21.8 mm / Min. According to ASTM D 757-49 and 15.2 mm / min, according to ASTM D 635-56T.

Example 5

150 parts of octochlorodihydroxydiphenyl and 100 parts of one The condensation product of glycerine and epichlorohydrin ("Epikote 812" from Shell-Berre) were measured at 60-100 ° mixed under vacuum. The mixture was cured at 120 ° for 24 hours. The product obtained was transparent and light yellow * It had the following properties;

Density, g / cm 1.56

Notched impact strength, mkg / 25 sm notch 0.073

Rockwell hardness M 80.6

Dimensional stability in the noise, ⁰ C 49

1/10-Vicat-Puttkt » ⁰ C 67

Flame retardancy, nm / Uin. 7.7 in 1 min. And

12 sec, then j went out by itself.

Example 6

ISO parts Octochlor'lihydroxydiphenyl, 100 parts of the in Beiapiel 5 mentioned condensation product ("Epikote 812") and to feile chlorinated paraffin sit 55 $ chlorine were between 60 and 80 ° adjusted under vacuum. The mixture was 24 hours hardened at 120 °. The cured product had the same shape as the product according to Example 5 and following Features i

Density g / cm ³ 1.55

Notched impact strength, mkg / 25 mm notch 0.069

Rockwell hardness M 84

Dimensional stability in the Warne, ⁰ C 55

i / 10 Vicat point ⁰ C 55.5

009836/2117

Flame retardancy, mm / min. 6.15 in. 2 minutes; went out

then by itself.

Example 7

Parts of octochlorodihydroxydiphenyl, 20 parts of maleic anhydride and 100 parts of the condensation product of Glycerin and epichlorohydrin ("Epikote 812") were between and mixed at 80 ° in a vacuum. The mixture was cured at 120 ° for 24 hours. The cured product was the same Appearance like the products obtained according to Examples 5 and 6 and the following properties: '

Density, g / cm ³ 1.50

Notched impact strength, mkg / 25 mm notch 0.16

Rockwell hardness M 81.6

Dimensional stability when heated, ⁰ G 60

1/10 Vicat point ⁰ C '64

Flame retardancy, mm / min. 6.3 in 1 min. And

35 sec .; then went out by itself,

For comparison, an identical mixture was prepared in which However, the octochlorodihydroxydiphenyl by a chemical equivalent amount of maleic anhydride was replaced. This mixture had the following composition;

100 pieces "Epikote 812"
65 "maleic anhydride.

It was cured at 120 ° for 24 hours. The product obtained was transparent, light yellow and had the following properties:

Density »g / cm ³ 1.37

Impact strength » mkg / 25 mm notch 0.15

Rockwell hardness M- 84

Dimensional stability in heat, ⁰ G 48

1/10 Vicat point, ⁰ C 50

Flame retardancy: Does not go out of

self.

üSTM D 635-56T mm / min. 30.0

ASTM D 757-49 »30.0

009836/2117

Claims (1)

: Claims 1 ») Process for the production of flameproof resins based on epics, characterized * that at least one epoxy resin with one serving as a hardener for the resin, of Mixes diphenyl derived halogenated polyphenol and cures at elevated oil temperature. 2,) Method according to claim 1, characterized in that epoxy resins with more than two epoxy groups in the molecule are used, 3,) Method according to claim 1 and 2, characterized in that that one uses G-lyoidylpolyäther, which from one several Hydroxyl group-containing organic compound are derived. 4 ·) · Method according to claim 1 "to 3, characterized in that» that reaction products from alcohols or phenols with more than two hydroxyl groups and epihalohydrins are used 5.) Method according to claim 1 and 2, characterized in that that epoxidized aliphatic and acyclic compounds are used, in particular epoxidized polyolefins or epoxidized derivatives of unsaturated fatty acid glycerides or cyclic aliphatic compounds. 6,) Method according to claim 1, characterized in that halogenated polyphenols are those of the general formula (HO) _x ' . _v , _. (0H) HaI _n Hal _m used, in which the sum of x + y values from 2 to 4 and'the sum of η + m can have values from 8 to 6 and the sum of χ + y + η -t- m is always equal to 10. 0 098 36/21 7.) Method according to claim 1 and 6, characterized in that that as halogenated polyphenols isomers of the oeto-. chlorodihydroxydiphenyl used. 8.) Process according to claim 1 to 7, characterized in that the halogenated polyphenol is one or more Adding hardeners of acidic or basic nature, in particular organic polycarboxylic acids or their anhydrides, organic Amines, polyamides, polysulfides or amine complexes des Boron trifluoride. 9 ·) Process according to claim 1 to 8, characterized in that the mixtures at temperatures between 20 and 200 G, preferably cures between 20 and 140 ° C. 009836/2117