DE2105188C3 - Thermosetting compositions and their use for producing fire-retardant coatings, molded parts, laminates and composites - Google Patents

Description

(a) 5 to 70 parts by weight of a polyunsaturated monomer with C-C multiple bonds,

(b) 110 to 20 parts by weight (bl) of a polyunsaturated Polymers with C-C multiple bonds or (bll) a polyphenylene ether or a mixture of (bl) and (bll),

(c) 5 to 50 parts by weight per 100 parts of (a) + (b) of a polychlorinated aromatic hydrocarbon having a molecular weight in excess of 200 which is at least 50 percent by weight bound Contains chlorine and

(d) where appropriate, customary amounts of curing catalysts used in thermosetting compositions, Pigments, solvents, fillers, reinforcing fibers, inhibitors, mold release agents, Adhesion promoters and other aids,

which are characterized in that they are at least

3. Compounds according to claim 1, characterized in 1 mole of the monomer (a) to 3 moles of the multiple draws that as a peroxide catalyst dicumyl per- 65 chlorinated aromatic hydrocarbon (c) and oxide, tert-butyl perbenzoate, 2,5-dimethyl-2,5-di- contain a peroxide catalyst that is present in benzene

(tert -. butylperoxy) - hexyne-3 or 2,5 - dimethyl-2,5-di- (tert-butylperoxy) hexane or a mixture temperatures above 100 ⁰ C has a half-life of at least 10 hours, and that she against-

if necessary, the polychlorinated aromatic 2.5 to 30 parts by weight of the brominated aromatic hydrocarbon (c) in the form of a reaction pro- see hydrocarbon (c), product which consists of 3 to 2 mol of the hydrocarbon (c) with 2 to 3 mol of the monomer (a) 3. 20 to 60 parts by weight of the polyphenylene ether p. at Temperataren of at least 130 ⁰ C in 5 counter (bll), waiting of the peroxide catalyst has been prepared

Surprisingly, it succeeds in curing 4.0 to 30 parts by weight of the multiple un-

these masses, known as "inert", halogenated saturated polymers (bl) and aromatic hydrocarbons in thermosets

to be built in. In this way, the flame retardant can 5. 2 to 10 parts by weight, based on 100 mixtures Additives no softening effect weight parts of components 1) to 4), the perfolding, and the cured masses have a non-oxide catalyst. changes good physical and electrical properties. In some cases the mechanical specific examples of suitable multiple brominated Properties compared to moldings made from additional aromatic hydrocarbons (c) are brominated free masses even improved. Diphenyl, brominated terphenyl, tribromobenzene, bro-

It has been found that when brominated naphthalene and brominated terphenylphosphate are used

mated aromatic hydrocarbons instead of the phat.

chlorinated aromatic hydrocarbon (el just- Suitable examples of monomers (a) are diallyl

if thermosetting materials with excellent intrinsic *> phthalate, diallyl phthalate, diallyl chlorendate, di-

properties are preserved. allyl maleate, triallyl cyanurate, glycol dimethacrylate and

Thus the invention relates to new thermosetting divinylbenzene. Masses consisting of Specific examples of suitable peroxide catalysts

gates are dicumyl peroxide, tert-butyl benzoate,

»5 2.5 - Dime & yi - 2.5 - di - (tert - butylperoxy) - hexyne - 3

, .- .., _ ". ... ... ,. . and 2,5-dimethyl-2,5-di- (tert-butylperoxy) -hexane so-

(a) 5 to 70 weightsteden of a multiply unsuitable _{as mixtures of these} catalysts with benzoylpersatögten monomers with CC- _{Mehrfachbmdunoxjd}

8 ^en 'As a polyunsaturated polymer (bl) is pre-

... _1in .. ^ _n /i^.· lm -i /. η ..τ u ³⁰ preferably a prepolymer of diallyl orthophthalate,

(b) UOb ^^ wic ^ flenibOeines ^ hrfachun- _Di ti, _y ii _SO p _ht halar or diallyl terephthalate or a saturated polymer with CC multiple bonds ^ J _{polyester resin} used in the at least gene or (bü) of a polyphenylene ether or _{50O / der in the} ^ _olyestcr contained dicarboxylic acid one of a mixture of (bl) and (bll), unsaturated dicarboxylic acid and in which the

,. , .. __. ...., _1ΛΛ ~., / * ... 35 alcohol component a cyclic or acyclic

(C) 5 to 50 parts by weight per 100 parts of (a) + (b) _di ^ _{col having} ^H _{2 to g} carbon atoms.

of a "» Μ ** halogenated aromatic carbon j & thermosetting compositions of the invention

lenwasserstoffsnyt a molecular weight over _{z ß We to 2} 00 parts by weight of an inert mineral

200, of at least 50 percent by weight of bonded _{material> an} inert fiber filler, one

contains denes halogen and _{+ o fiber} mat or a fiber fleece or up to 400 Ge

... ... _.,. . .. ...,. contain important parts of glass fibers.

(d) Any customary amounts of heat-hardened _A , _{s usual additional can be used in the compositions of the invention} .

hardening catalysts used in _{addition to} hardening catalysts, pigments, solvents

gates pigments, solvents fillers, _sun | _agents> fillers, reinforcing fibers, ingredients

reinforcing fibers inhibitors, mold release agents and demolding _w * adhesion promoters also

mitteta, Haf ^ ermittlern and other HiJs _dispersants . As solvents are

means, said mass at least 1 mol of ^H _{chlo ated} hydrocarbons and aromatic carbonic

Monomers (a) to 3 mol of the polyhalogen _{hydrogen are} preferred.

The aromatic hydrocarbon (c) and the compositions of _{the invention are} particularly suitable

contain a peroxide catalyst which is contained in benzene _ZUf Manufacture of fire-retardant coatings, molding

at temperatures of over 100 _{° C, a half-teU of laminates and} composites, e.g. B. copper

has a value of at least 10 hours of _clad composites,

and the masses of the optionally multiply ^F _{The ßeis ω "l§iUteTt the} invention, halogenated aromatic hydrocarbon (c)
contained in the form of a reaction product that

of 3 to 2 moles of the hydrocarbon (c) with Examples 2 to 3 moles of the monomers (a), at temperatures of at least 13O ⁰ C in the presence _There laminates _are prepared using the _1S prepared in the peroxide catalyst t, _{the TabeUe Matching Caps} ngcstellten formulations hergegemaB Patent ZU 32 3.38, _{6o ste} " _{t Here,} glass fiber fabric (type 181) with the

Impregnated mass and ^{dried at 25 0} C for 48 hours. The impregnated fiberglass fabrics are in

which are characterized by the fact that the composite squares with an edge length of 30.5 cm

nente (c) a multi-brominated aromatic cut and 18 layers deep with a parallel arrangement

65 of the warp threads are superimposed on hydrogen. The hardening

Preferred compositions of the invention consist of follows the rubber bag process. After 15 min

at 150 ^° C., complete curing is achieved. the

1 10 to 50 parts by weight of the monomer (a), results are shown in the table.

Recipe

Diallyl isophthalate monomer

Diallyl isophthalate prepolymer

Hexabromobiphenyl

Dicumyl peroxide

γ-methacryloxypropyltrimethylsilane

Hydroquinone

Alumina trihydrate, methyl ethyl ketone

Polyphenylene ether mixture «»

Physical Properties

Resin content, weight percent

Rockwell hardness, M.

Compressive strength (kg / cm *)

Table <«' Gevichtstefle

250

650

200

30th

0.3 70 400

29.8 120 1860

350

310

150

30th

0.3 40 400

285

35.1 122 3130

(a) The properties of the diallyl isophthalate prepolymer, of the polyphenylene ether and the implementation of the physical test are in patent application P 20 32 338.0 described.

Parts by weight 5900 Flexural strength (kg / cm ² ) 1550 at 25 ° C 4630 at 205 ^° C 2190 5410 after 2 hours in boiling water 3360 2.8 - 10 ^e Flexural modulus (kg / cm *) 1.8 · 10 ⁶ at 25 ° C 2.7 · 10 · at 205 ^° C 2.6 · 10 · 2.9 · 10 ⁶ after 2 hours in 3890 boiling water... 2.6 · 10 · Tensile strength (kg / cm ² ) 3700 380 Shear strength (kg / cm ² ) 103 at 25 ° C 211 at 205 ^° C 122 Water absorption (Weight percent), 0.08 48 hours in water 1.911 from 5C ⁰ C 0.44W density 1,974 4.30 Dielectric constant 4.33 at 10 ³ Hz, dry 4.53 not at 10 * Hz, dry 4.46 burning Flame test (ASTM D-635) not burning

(b) 200 parts of polyphenylene ether, 57 parts of diallyl isophthalate prepolymer and ground 28 parts of alumina trihydrate in a ball mill for 12 hours.

(c) Specimen contains some pores.

Claims (2)

Patent claims:
1. Thermosetting compositions, consisting of the aforementioned catalysts with benzoyl peroxide is included 4 Use of the masses according to claim 1 for Manufacture of fire retardant coatings, molded parts, laminates and composites. (a) 5 to 70 parts by weight of a polyunsaturated monomer with C-C multiple bonds, (b) 110 to 20 parts by weight (bl) of a polyunsaturated polymer with C-C multiple bonds or (bll) a polyphenylene ether or a mixture of (bl) and (bll), (c) 5 to 50 parts by weight per 100 parts of (a) + (b) a polyhalogenated aromatic Hydrocarbon with a molecular weight above 200, which is at least 50 percent by weight contains bound halogen and (d) optionally customary amounts of thermosetting Mass used curing catalysts, pigments, solvents, fillers, reinforcing fibers, inhibitors, mold release agents, adhesion promoters and others Tools, The masses contain at least 1 mol of the monomer (a) per 3 mol of the polyhalogenated aromatic hydrocarbon (c) and a peroxide catalyst which has a half-life of at least 10 hours in benzene at temperatures above 100 ° C, and the masses optionally the contain multiple halogenated »aromatic hydrocarbon (c) in the form of a reaction product which has been prepared from 3 to 2 mol of the hydrocarbon (c) with 2 to 3 mol of the monomer (a) at temperatures of at least 130 ^° C. in the presence of the peroxide catalyst, according to patent 2032338, characterized in that component (c) is a polybrominated aromatic hydrocarbon. 2. masses according to claim 1, characterized in that they (1) 10 to 50 parts by weight (a), (2) 5 to 30 parts by weight (c), (3) 20 to 60 parts by weight (bll), (4) 0 to 30 parts by weight (bl) and (5) 2 to 10 parts by weight, based on 100 parts by weight of the aforementioned components (1) to (4), of the peroxide catalyst. Aromatic halogen compounds are known as flammable firming additives for thermosets known due to their softening effect they lower however, the foaming temperature of the thermosetting plastics, like this that their further processing into molded bodies and laminates is impaired. These disadvantages can be avoided when using reactive flame retardants, which in contrast to the "inert" aromatic halogen compounds are built into the thermosets during hardening. The best-known example of such reactive flame »5 inhibiting agent is 1,4,5,6,7,7-hexachloro- (2 ^, 1) -5-hepten-2,3-dicarboxylic acid (HET acid). US Pat. No. 3,361,847 also discloses the use of complex halogen-containing hexahydrotriazine derivatives known as copolymerizable, fire retardant additives for polyester compositions. Each of these reactive flame retardant, however, has the disadvantage that it is expensive to manufacture and only on a relatively narrow field of application, primarily polyester compositions, is limited. The subject of patent 20 32 338 are thermosetting compositions