DE1070373B - - Google Patents

Description

GERMAN

INTERNAT KL

PATENT OFFICE

C 08g

REGISTRATION DAY

NOTICE THE REGISTRATION AND ISSUE OF THE DECISION

S 53098 IVb / 39b

April 11, 1957
3 DECEMBER 1959

The invention relates to the use of certain Antimony alcoholates for the production of self-extinguishing polymers, in particular chlorine-containing polyester resin polymers By the expression "self-extinguishing" it should be printed out that the polymers lit up can be extinguished if the fire source is removed (see e.g. ASTM D 635-44)

Further definitions are defined below. The expression "polyester resin" is a condensation product of a glycol or a mixture of glycols with an unsaturated dibasic acid (or usually a mixture of unsaturated and saturated dibasic acids) or the anhydrides of such acids. Such polyester resins are per se known The expression " polyester resin solution" means a solution of such polyester resin in a solvent that consists of an unsaturated monomer or a mixture of such monomers Unsaturated, monomeric solvent present in the polyester resin solution is formed under the influence of suitable catalysts. This process is also known. Polymerization of the polyester resin with the unsaturated monomers Ren can take place without the presence of a filler and thus a clear casting can be obtained, or a filler, such as a glass fiber mat or glass fiber fabric, can be introduced into the polyester resin solution immediately before curing, which creates a polyester polymer-glass fiber laminate.This process is also Known The expression "polyester resin polymer saturated" used in the following means clear castings or polyester polymer-glass fiber laminates of this type

It is known that the introduction of chlorine into polyester resins ζ B by replacing some or all of the saturated dibasic acids commonly used with either tetrachlorophthalic acid (or its anhydride) or hexachlorendomethylenetetrahydrophthalic acid (or its anhydride) gives the polyester resin polymers a certain flame resistance insufficient. It is known that this can be caused by the incorporation of small amounts, e.g. B 5% antimony oxide, Sb ₂ O ₃ , can be improved into the polyester resin solution. This gives a self-extinguishing polyester resin polymer which, however, is opaque

The present invention now relates to the use new flame retardants that reduce light transmission in polyester resin polymers do not significantly affect, in the form of soluble, counter-use of soluble compounds of antimony as a flame retardant

in curable, halogen-containing

Polyester masses

Applicant:

Peter Spence & Sons Limited,
Widnes, Lancashire (UK)

Representative Dr W. Schalk, Dipl -Ing P Wirth,

Dipl -Ing. G. E M Dannenberg

and Dr V Schmied-Kowarzik, patent attorneys,

Frankfurt / M, Große Eschenheimer Str 39

Claimed priority
Great Britain from April 12 and September 4, 1956

Leslie Williams and Richard Sidlow,

Liverpool, Lancashire (UK),

have been named as inventors

if necessary partially acyherten alcoholates of antimony m curable halogen-containing polyester compositions, consisting made of unsaturated polyesters, which can be polymerized onto them monomeric unsaturated compounds and optionally highly chlorinated inert compounds

A preferred embodiment consists of the use unsaturated organic, optionally partially acyherted antimony alcoholates

In this way, in conjunction with the antimony unsaturated residues introduced into the resin during The hardening of the polyester resin solution occurs when polymerisation is complete, as a result of which the flame retardants are introduced an integral part of the polyester resin polymer which is then free of volatile or extractable substances

Suitable soluble, unsaturated antimony compounds smd ζ Β those of the following types

1 Unsaturated antimony alcoholates, ζ B antimony allylate, -tnmethallylate or -tncrotylate, and

2 partially acylated unsaturated antimony alcoholates, ζ B antimony monoallylate dimethacrylate

The antimony can also be used in the polyester resin polymers be incorporated by adding the antimony derivatives to the Polyester resin must be "boiled down" before thinning takes place with the corresponding monomers

909 «87/431

3 4

The antimony ammonia preferred for such a process is introduced until an excess is present

The derivatives are saturated, possibly partially with the temperature kept below 25 ° C throughout

Acid units Antimony alcoholates The precipitated ammonium chloride is filtered off as alcoholates

Veribmdungen are also used, which differ from and the solvent as well as the small excess of the

Glycols derive 5 alcohol evaporated under reduced pressure

These derivatives, ζ B antimony isopropylate and anti-alcoholate, can be distilled under reduced pressure

ethylene glycolate, will preferably become a * ~

Zeitptinkt incorporated, where the esterification reaction between the various partially acyherten alcoholates can

see the dibasic acids and the glycols practically by reacting the corresponding acid with the

table is ended, and a temperature that is preferably obtained io speaking antimony alcoholate, ζ Β

175 ° C, if used alcoholates 2MoI methacrylic acid and 1 mol Antimomopropylat

or partially acylated alcoholates are used, the mixture is then placed on a water bath at a

The alcohols and acids are released and evaporated, temperature not exceeding 35 ° C below a possible temperature

while the antimony evaporates a complex with the polyester low pressure

Resin forms When antimony glycol derivatives are used

are used, the antimony forms a complex with glycols, which have a boiling point above isopropanol

the polyester resin, and the glycol residues are attached to the, it is often advisable to use the appropriate

Acid residues that remain in the polyester resin, bound the amount of alcohol or glycol required for antimony

Add the pre-propylate in the finished polyester resin polymer and the isopropanol released

Existing combined chlorine can be removed in various ways by distillation under reduced pressure.

As already stated, the Pole can be guided

Ester resin made from tetrachlorophthalic acid or hexachlorendo- It is known to use phenylstibm as a flame retardant

methylentetrahydrophthalic acid must be made to use this, however, has a strong plasticizing effect

On the other hand, a polyester resin that is different from one and is therefore unsuitable for many areas of application

chlorine-free acid, ζ phthalic acid or adipic acid, 25 In addition, the phenylstibm is relatively heavy

inferred, can be made self-extinguishing by making the accessible

Chlorine as a highly chlorinated high-molecular compound. The invention is illustrated by the following examples

together with the soluble antimony compound, in which the use of soluble organ-

A suitable chlorinated mixture of antimony compounds for the production of self-assembly is added.

bmdung is a highly chlorinated paraffin wax with about 30 extinguishing polymers of chlorinated and non-chlorinated

70 ° / _{0 combined} chlorine (e.g. the polyester resins described by ICI Ltd are examples 1 and 2

under the name »Cereclor 70« in the trade describes the use of commercially available poly-

brought product) ester resin solutions

The unsaturated, in connection with the antimony

compound and the chlorine-containing resin used 35 Example 1
Monomers are those commonly used monomers, ζ B, vinyltoluene, Divmylbenzol and the preparation of a m of the heat curable, selbstver-allyl esters of phthalic acid, maleic acid and diglycolic losch forming polymer from a chlorine-containing polyacid ¹ esterharzlosung, the 25 to 30 ° / _0-bound Chlorine

A third method for introducing chlorine is 40 halts.

m the use of chlorinated monomers, ζ B Chloi- polyester resin solution in styrene. 95.2 parts

styrene and diallyl tetrachlorophthalate antimony allylate 4.8 ,,

Polyester resin solutions containing soluble antimony compounds (equivalent to

contain fertilizers, can m usually by warmth 2 ° / ₀ antimony)

are hardened, ζ B by hardening with about 45 7öÖ ~ 5

1 ° / o benzoyl peroxide at 95 to 110 ° C In some cases'

must, due to the hardening of the treated resin solution due to the antimony compound

delayed the normal curing time, 1 part benzoyl peroxide, preferably as a paste, in 100 parts

For a long time, polyester resin solutions are dispersed, the antimony as th resin solution, which then in a mold

Unsaturated alcoholate, ζ B as allylate, contained, 5c poured or with ζ B a glass mat in the usual way

are uncoated due to the low activity of this and then for 45 to 60 minutes at 12O ⁰ C äus-

saturated alcohol is preferably hardened at 120 ° C

For cold curing of antimony-containing polyester resin - Example 2
solutions are preferably used where

the antimony is either incorporated into the polyester resin 55 producing a thermosetting self-extinguishing one

or as an unsaturated, partially acylated alcoholate of the polymer made from a polyester which does not contain chlorine

Polyester resin solution was added when the over- hold

borrowed, accelerated by cobalt hydroperoxide polyester resin solution in styrene 76.1 parts

Catalyst systems are used, certain chlorinated paraffin wax are 70 ° / ₀

Modifications to the commonly used catalyst 60 Cl content 14.3

sysiems necessary, as curing is inhibited (equivalent to

Good results are achieved if ζ B em benzoyl- 10 ° / ₀ chlorine)

peroxide dimethylanuine catalyst system applied antimony allylate 9.6 parts

becomes (equivalent to

The saturated or unsaturated antimony alcoholates 65 4Oy ₀ antimony)

can be made by adding antimony trichloride in one innn

5% excess over the corresponding saturated lUU.U

or unsaturated alcohol together with an inert The components were in the above order

Solvent, ζ B carbon tetrachloride or toluene, mixed and then as in Example 1 by means of the catalyst

It is then cured anhydrous, gaseous 70 sator

In the above examples, normal, commercially available Polyester resin solutions used However, slightly better results are achieved if a polyester resin solution is used in which the styrene content is reduced so that it is stochiometnsch the Amount of the added unsaturated antimondevate corresponds This has a twofold advantage, because on the one hand the amount of the highly flammable formed during the thermal decomposition of the polymer Styrene is reduced and, on the other hand, the relative chlorine content of the polymer is increased

In the following examples the preparation is described of antimony and chlorine-containing polyester resin solutions The m Examples 3, 5 and 7 chlonerte polyester resin used contains 39 till 40 ° / ₀ chlorine and is usually dissolved in styrene so that a 75 ° / _o strength resin solution arises whose chlorine content is about 30 ° / ₀ amounts to chlorine-free, resin used in examples 4 and 6 is normally dissolved in styrene so that a 65% strength resin solution is formed.

Example 3

Preparation containing a warmehartbaren, selbstverloschenden Polymensates from a chlorine-containing polyester resin containing 39 till 40 ° / ₀ bound chlorine

Polyester resin 75.2 parts

Styrene 20.0 "

Antimony oxide. 4.8 ,,

(equivalent to
2% antimony)

100.0

The polyester resin and the styrene were at as possible mixed at low temperatures until homogeneous (preferably with the addition of 0.1% p-tert -butylpyrocatechm or other stabilizers) and the antimony allylate added The treated solution was how described in Example 1, hardened

Example 4

Production of a self-extinguishing polyester polymer from a chlorine-free polyester resin

Polyester resin
Styrene

Chlorinated paraffin wax with
70 ° / ₀ Cl content

Antunontnallylat

56.1 parts
20.0 "

14.3 "
(equivalent to
10 parts chlorine)
9.6 parts
(equivalent to
4 parts antimony)

100.0

After boiling, the resin was cooled to 110 ° C. and the antunon triisopropoxide was slowly added with stirring. After completion of the addition and after the foam had largely subsided, the resin was heated to 160 to 170 ° C for 15 to 30 minutes. The treated resin was then slightly cooled - ζ to 100 ° C - and after stabilization with 0.1 part p -tert -Butylbrenzcatechin with styrene diluted, the polyester resin solution thus obtained can be cured hot, adding 1 part of benzoyl peroxide dispersed in 100 parts of solution, and then 30 minutes, heated to 100 to 120 ⁰ C Em cold Hard can be obtained, adding from 0.05 to 0, 15 parts of dimethylanulin or dimethyl-p-toluldin are added to 100 parts of the resin solution to which 1 part of benzoyl peroxide has been thoroughly mixed in beforehand. The curing takes 15 to 30 minutes

Example 6

Production of a self-extinguishing polyester polymer made of a chlorine-free polyester resin

After boiling the resin of this ° to about 100 C was cooled and 0.1 ° / ₀ hydroquinone or other stabilizer added were then admixed with the styrene and the chlorinated paraffin, and finally the Antimontnallylat inflicted The resin solution obtained was as outgoing degenerates in Example 1

Example 5

Producing a selbstverloschenden Polyesterpolymensates from a chlorine-containing polyester resin at 39 to 40 ° / ₀ bound chlorine

Polyester resin 73.5 parts

Antunon triisopropoxide. 4.9 "

(equivalent to
2% antimony)
Styrene 24.5 parts

Polyester resin
Antimony sec -butylate

53.1 parts

11.2 "
(equivalent to

4 parts antimony)
Chlorinated paraffin wax with
70% Cl content 14.3 parts

(equivalent to

10 parts chlorine)

Styrene. . . 28.6 parts

After the resin was boiled, it was heated to about 110 ° C cooled and the antimony sec-butylate was slowly added with stirring. After the addition was complete the pressure is reduced and the resin slowly to 150 to Heated to 160 ° C and this temperature 15 to 30 minutes maintained to the released secondary butyl alcohol deduct

The resin treated in this way was then cooled to about 100 ° C., the chlorinated paraffin wax was stirred in and after stabilization with 0.1 part hydroquinone, the styrene added The polyester resin solution obtained in this way can be heated according to the method described in Example 5 or be hardened cold

Example 7

Production of a self-extinguishing polyester polymer made of a chlorine-containing polyester resin with 39 to 40% combined chlorine

Polyester resin

Antimony ethylene glycolate

(made by heating
1 mole of antimony isopropylate and
3 moles of ethylene glycol)

Styrene

71.25 parts
5.0 "

(equivalent to
2% antimony)

23.75 parts
100.0

After boiling, the polyester resin was cooled to about 110 ° C. and the antimondvate was stirred in. The resin was then heated to a temperature not exceeding 175 ° C for about 30 minutes to complete the reaction After cooling to about 100 ° C and adding 0.1 part p-tert -Butylpyrocatechol or other stabilizers were added to styrene. This polyester resin solution can be cured warm or cold according to the method of Examples 1 and 2

In certain cases it may be useful to use the Decrease amount of glycol that is normally used to make the resin to an amount that corresponds to the added antimony derivative

In addition to good light transmission, the Polyester resin polymers prepared according to the invention contain a low amount of bound antimony than those made using antimony oxide, although the self-extinguishing ones Properties are retained In addition, the polymers obtained according to the invention can have a contain less amount of chlorine than the products that contain Contain anümonoxyd, which are also self-extinguishing Properties are retained The reduction in the chlorine content improves the light stability of the polymers

Example 8

Producing a selbstverloschenden Polyesterpolymerisates from a chlorine-containing polyester resin at 39 to 40 ° / ₀ bound chlorine

Polyester resin

Antimony hexylene glycolate
(produced by the transesterification of 2 moles of anhydrous isopropylate with 3 moles of 2-methyl-2,4-pentanediol)

Styrene

71.4 parts
4.8 "
(= 2 parts of antimony)

23.8 parts

100.0

Polyester resin.

Antimony -1,3-butylene glycolate
(produced by transesterification of 2 mol of antimony isopropylate and 3 mol
1,3-butylene glycol)

Styrene

71.9 parts
4.1 "
(= 2 parts of antimony)

24.0 parts

100.0

The resin was treated as in Example 8
Example 10

Production of a self-extinguishing polyester polymer made of a chlorine-free polyester

Polyester resin

Antimony 1,3-butylene glycolate

Styrene

Chlorinated paraffin wax with
70 ° / ₀ Cl content

51.7 parts
, ^ "

(= 4 parts of antimony)

25.8 parts

14.3 "

(= 10 parts chlorine)

100.0

Antimony hexylene glycolate can be used to make it easier to use can be used as a 50% solution in toluene

After boiling, the polyester resin was cooled to about 110 ° C and the Antimondvat or its solution stirred in toluene, when using a solution in Toluene then became the toluene under reduced pressure distilled off The resin was then heated to a temperature not above 170 ° C. for about 30 minutes and after cooling to about 100 ° C. and adding 0.1% of a stabilizer such as hydroquinone, the styrene is added

The resin solution was then cured for about 15 minutes at 100 to 120 ° C m the presence of about 1 ° / ₀ benzoyl peroxide

Example 9

Preparation containing a selbstverloschenden Polyesterpolymerisates from a chlorine-containing polyester resin containing 39 till 40 ° / ₀ bound chlorine

After normal boiling, the resin was brought to about 110 ° C cooled and the antimondevate or its solution in toluene added. The temperature slowly rose increased about 160 ° C, with when using a solution the toluene was distilled off under reduced pressure. After cooling to about 100 ° C., about 0.1% of one became Stabilizer and then the styrene and chlorinated paraffin wax are added

Claims (3)

Claims 1 Use of soluble, optionally partially acylated alcoholates of antimony as flame retardants in hardenable halogen-containing polyester compounds, consisting of unsaturated polyesters, monomeric unsaturated monomers which can be polymerized onto it Compounds and optionally highly chlorinated inert compounds 2 Use of a reactive carbon double bond containing, optionally partially acyhered antrmonal alcoholate according to claim 1 3 embodiment according to claim 1, characterized in that the unsaturated polyester and the Combustion of antimony before adding the unsaturated ones monomeric compound are reacted in the heat Documents considered
U.S. Patent No. 2,664,411,
Bntische patent specification no.650144,
Morgan "Glass Remforced Plastics", London, 1954, p 47 © 909 687/431 11