DE1520780C3 - Process for the production of flame-retardant epoxy polyadducts - Google Patents

Description

(HO ■■

k .- .., Nz (OH) ₂ , ■ · ■ I! i

N V V —c - c + Ho— + —c — c - ο

χ · ι ■■ \ 1 '\ /' 1 '

■ V Ί °. ·.

Cl «ei,« .55 -

The amount of material used to make the polyadducts

is used, in which the sum of λ: + y has the values 2 ,. Chlorinated polyphenols used depends on the

3 or 4 and the sum of η + m the values 6, 7 type of epoxy compound and the desired

or 8, where the sum of λ- + y + η + m properties of the end product depend on. In general

equals 10. This amount is between 0.8 and 1.2, preferably

According to the invention, 1 hydroxyl equivalent per epoxy equivalent can be used as epoxy compounds. Under

in particular the following compounds are used »equivalent« is the amount of substance in grams

are: stand that contain a hydroxyl group or an epoxy

group contains.

a) of a 65 containing several hydroxyl groups. An advantage of the invention is the ease with which

organic compound derived glycidyl poly- mixtures of chlorinated polyphenol with the

ethers that can produce more than two epoxy groups in the mole epoxy compound. It

contain kül; is sufficient to use the polyphenol in small amounts to ep-

To give oxide compound, which is brought to a temperature between 40 and 120 ⁰ C, preferably between 60 and 80 ⁰ C, if this is liquid and slightly above its softening point, if it is solid. It is also possible to incorporate the polyphenol as a solution in a solvent. The non-toxic mixtures have sufficient use or Pot life that is comparable to that of classic acid anhydride and epoxy resin systems. It is also possible to manufacture products with a longer shelf life by cold mixing the chlorinated polyphenol and the epoxy compound in powder form.

In a manner known per se, different amounts of one or more other known hardeners of an acidic or basic nature can be added to the chlorinated polyphenol without impairing the flame resistance of the polyadducts. Organic polycarboxylic acids or their anhydrides, such as maleic anhydride, phthalic anhydride, succinic anhydride, dodecylsuccinic anhydride, or primary, secondary and / or tertiary amines, such as diethylenetriamine, triethylenetetramine, diethylenetetramine, diethylaminopropylamine, dimethylaniline, or amine-complexesulfide-polyaniline, or amine-complexesulfide, are suitable as additional hardeners. The amounts of the hardener mixtures, with the exception of those containing tertiary amines or complexes of BF ₃ and tertiary amines, are chosen so that the thermosetting compositions contain 0.8 to 1.2, preferably one effective group of the hardener mixture per epoxy group. 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 chlorinated polyphenol to an oxygen atom, in the case of primary and / or secondary amines and in the case of polyamides to a nitrogen atom and in the case of polysulfides, is bonded to a sulfur atom. In contrast, the tertiary amines and the complexes of BF ₃ and tertiary amines are used only in very small amounts due to their catalytic and / or accelerating properties.

It is always possible to add inert fillers, pigments, plasticizers, reactive and non-reactive diluents or mixtures of these different Substances to use.

The optionally modified thermosetting starting mixtures for the process according to the invention can be used for the production of casting compounds, laminates, paints, during manufacture of electrotechnical and / or electronic parts and for encasing electrical and / or electronic parts.

The hardening conditions in the process according to the invention essentially depend on the type of epoxy compound and on the other hardeners which may be used in connection with the chlorinated polyphenol. Optimum conditions can be seen in general, cure times of 24 to 48 hours and temperatures between 20 and 200 ⁰ C, preferably 20-140 ⁰ C. The polyadducts obtained under these conditions have excellent flame resistance and interesting mechanical and thermal properties, as shown in the following examples is. In these examples, parts are parts by weight.

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

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

Impact strength according to the

Izod method (with notched

Test stick) ASTM D 256-56

Rockwell hardness ASTM D 785-51

Dimensional stability in the

Heat below 18.56 kg / cm ² ... ASTM D 648-56

1/10 Vicat point (temperature,

with a 1 mm needle ⁸

Cross section under one

Load of 1 kg 0.1 mm deep

penetrates) ASTM D 1525-58T

Flame retardancy ASTM D 757-49

and ASTM D 635-56T

Example 1 "- ■""'

100 parts Octochlordihydroxydiphenyl, 100 parts of epoxidised polybutadiene, 20 parts of maleic anhydride and 50 parts of chlorinated paraffin containing 55% of chlorine were blended at 8O ⁰ C under reduced pressure. The mixture was ^{cured at 120 °} C. for 24 hours. The fully cured product was transparent, dark yellow, hard and flame retardant according to ASTM D 635-56T.

Example 2

100 parts of octochlorodihydroxydiphenyl, 100 parts of epoxidized soybean oil with 6.5% epoxy oxygen were mixed at 60 to 80 ° C. The mixture was ^{cured at 140 °} C. 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

Dimensional stability when heated below 18.56 kg / cm ² 49.0 ° C

1 / 10th Vicat point 51.5 ⁰ C

Flame retardancy, mm / min 7.5

in 1.2 minutes; then went out by itself.

Example3

At 8O ⁰ C, 100 parts of epoxidized soybean oil were mixed with 6.5% and 100 parts Epoxydsauerstoff Octochlordihydroxydiphenyl. After the mixture had become homogeneous, it was ^{cooled to 30 °} C. and 1 part of dimethylaniline was added. The mass obtained was ^{cured for 24 hours at 100 °} C. and formed a transparent, light yellow product with the following properties:

Density, g / cm ³ 1.31

Notched impact strength,
mkg / 25 mm notch ..... 0.032

Rockwell hardness M 56.8

Dimensional stability in the
Heat, 48 ° C

1/10 Vicat point, 53 ° C

Flame retardancy, mm / min. ... 7.5

in 1 minute
and 20 seconds; then went out by itself.

Example 4

At 80 ° C., 100 parts of epoxidized soybean oil were mixed with 6.5 % of epoxy oxygen, 85 parts of octochlorodihydroxydiphenyl and 6 parts of maleic anhydride. The mixture was cured at 120 ° C for 24 hours. The product obtained was transparent and dark yellow and had the following properties:

Density, g / cm ³ , 1.35

Notched impact strength, mkg / 25 mm

■ Notch, 0.078

Rockwell hardness M ^ 56

. Dimensional stability in heat,

⁶ C 58.5

1/10 Vicat point, 50.5 ° C

Flame resistance, mm / min. 13.0

in 2 minutes; then went out by itself.

For comparison, an identical mixture was prepared, but in which the octochlorodihydroxydiphenyl by a chemically equivalent amount of maleic anhydride was replaced. This mixture consisted of 100 parts of epoxidized soybean oil and 40 parts Maleic anhydride. It would be cured at 120 ° C for 48 hours. The product obtained was transparent, dark yellow, not very hard and very brittle. It wasn't flame retardant; its rate of burn 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 a condensation product of glycerol and epichlorohydrin were mixed at 60 to 100 ° C under vacuum. The mixture was left at 120 ° C for 24 hours hardened. The product obtained was transparent and light yellow. It had the following properties:

Density, g / cm ³ 1.56

Notched impact strength,

mkg / 25 mm notch 0.073

Rockwell hardness M 80.6

Dimensional stability in the

Heat, 49 ° C

1/10 Vicat point, ⁰ C 67

Flame retardancy, mm / min. ... 7.7

in 1 minute

and 12 seconds;

then went out of

self.

Example 6

150 parts Octochlordihydroxydiphenyl, 100 parts of said condensation product in Example 5 and 10 parts of chlorinated paraffin with 55 ° / ₀ were mixed chlorine between 60 and 80 ° C under vacuum. The mixture was cured at 120 ° C for 24 hours. The cured product had the same shape as the product according to Example 5 and the following ίο properties:

. Density, g / cm ³ 1.55

Notched impact strength, mkg / 25 mm

Notch 0.069

Rockwell hardness M 84

Dimensional stability in heat,

OQ 55

1/10 Vicat point, 55.5 ° C

Flame retardancy, mm / min. ...... 6.15.

in 2 minutes; then went out

by itself. For example, 7

100 parts of octochlorodihydroxydiphenyl, 20 parts of maleic anhydride and 100 parts of the condensation product of glycerine and epichlorohydrin were mixed between 10 and 80 ° C in a vacuum.

The mixture was cured at 120 ° C for 24 hours.

The cured product had the same appearance as the products obtained in Examples 5 and 6 and the following properties:

Density, g / cm ³ 1.50

Notched impact strength,
mkg / 25mm notch 0.16

Rockwell hardness M: 81.6

Dimensional stability in the
Heat, 60 ° C

1/10 Vicat point, ⁰ C 64

Flame retardancy, mm / min. ... 6.3

in 1 minute and 35 seconds; then went out by itself.

35 For comparison, a similar blend was prepared, but the Octochlordihydroxydiphenyl was replaced by a chemically equivalent amount of maleic anhydride in the. This mixture had the following composition:

100 parts of a condensation product

Glycerine from epichlorohydrin 65 parts maleic anhydride.

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

Density, g / cm ^3. ' 1.37

Notched impact strength, mkg / 25 mm

Notch 0.15

Rockwell hardness M 84

Dimensional stability in heat,

⁰ C 48

1/10 Vicat point, ⁰ C 50

Flame resistance: Does not go out

by itself.

ASTM D 635-56 T, mm / min. ... 30.0

ASTM D 757-49, mm / min 30.0

Claims (2)

"I. 1 -. ■ 2 b) more than two epoxy groups in the molecule. 1. Process for the preparation of flame-retardant c) mixtures of compounds a and b in ver-epoxy polyadducts with shaping by 5 different proportions, if necessary conversion of epoxy compounds, the min- with other compounds, the two or less have at least two epoxy groups in the molecule, contain epoxy groups in the molecule, beforehand chlorine-containing compounds, characterized in that the mixture obtained has a value that one has a chlorine content of more than 2. Compounds of chlorinated polyphenols in general my formula. ■ .. _Λ -. As epoxy compounds of group a are all - _Hn . .; '. ".. Reaction products between alcohols and phenols ' Α \\ "' / ' X ^{with menr a} ' ^{s two} 'hydroxyl groups per mole, like - ■ -. '■ , _j_ ''"~ ^ J y glycerine, trimethylolpropane, pentaerythritol, phloro- f ~ 'ι'. 15 glucine, hydroxyhydroquinone, catechol, novolak, Q ·· ■■ · '· ■ ^ j and an epihalohydrin, such as epichlorohydrin, ^m suitable. The pure diglycidyl derivatives, for example • used, in which the sum of χ + y represents the diglycidyl ethers of phenols with several hy- Values 2, 3 or 4 and the sum of n + m hydroxyl groups are not suitable for the purposes of the the values 6, 7. or 8 have * with the sum 20 invention, since they do not result in thermosetting polyadducts of χ + y + η + m is 10. with good mechanical properties. There- 2. The method according to claim 1, characterized against kann'diese diglycidyl derivatives in a mixture that one uses as chlorinated polyphenols with other derivatives which, like isomers of octochlorodihydroxydiphenyl, use more than two epoxy compounds. Contains 25 groups in the molecule. "" ■ "' . The epoxy compounds of group b include aliphatic acyclic products, for example epoxy Dated polyolefins. The best known are in this - - connection epoxidized polybutadienes, epoxy- 30 dated derivatives of unsaturated fatty acid glycerides and cyclic aliphatic products such as limonene • Dioxide, vinylcyclohexenedioxide and dicyclopentadiene There are already processes for the production of flame dioxide. solid epoxy polyadducts known in which z. B. The chlorine-containing compounds are suitable a mixture of chlorinated and unchlorinated 35 chlorinated polyphenols of the formula given above, Epoxy compounds containing aromatic nuclei by phenolizing decachlorodiphenyl with hold without or with hardener additives an alkali compound is obtained, (See French patent specification 1,216,284). The well-known is particularly suitable for the method according to th methods and products have disadvantages, the invention is the different isomers of octo- especially with regard to processability and toxi- 40 chlorodihydroxydiphenyls alone or as a mixture ity on. together. These are white, solid products that are in The invention relates to a process for which most common solvents are soluble Decomposition of flame-retardant epoxy polyadducts and alkali carbonate solutions, under shaping by converting epoxy * The pronounced acidity of the hydroxyl groups compounds that allow at least two epoxy groups 45 of these perchlorinated polyphenols have in the molecule, with chlorine-containing compounds unopening the epoxy groups of basic character gene, which is characterized in that as and the formation of an ether. This can be done through the chlorinated compounds chlorinated polyphenols the following reaction equation is shown:
the general formula ^: '50, ■