DE1099742B - Process for the production of polymers - Google Patents

Description

It has been found that 5,6-bis-methylene-l, 2,3,4, 7,7-hexachlorobicyclo- [2,2,1] -hepten- (2)

Cl

Method of manufacture
of polymers

(hereinafter referred to as BHH for short) alone or omit other monomeric polymerizable compounds Can polymerize homopolymers or copolymers with valuable properties.

The BHH can by reacting 1, ^ dichlorobutenes with hexachlorocyclopentadiene in the manner of a Diels-Alder reaction to give 5,6-bischlarm.ethyl-1,2,3,4,7,74iexacMorbicyclo- [2,2,1} -hepten - (2) and subsequent elimination of hydrogen chloride with the help of sodium methylate.

If, in addition to the BHH, compounds are used in the production of copolymers which contain two or more polymerizable double bonds which are not in a conjugated position to one another, crosslinked, insoluble and no longer thermoplastic polymers are formed. The homopolymers of BHH also seem to be crosslinked, because they are also insoluble in the usual solvents. Surprisingly, the copolymers with monofunctional polymerizable. Compounds however soluble ^: and thermoplastic.

Polymerizable compounds with which BHH can be copolymerized are, for example Vinyl compounds such as styrene, alkylstyrenes, halostyrenes, divinylbenzenes or vinylnaphthalene, furthermore Vinyl pyridine, N-vinyl carbazole, α, / 3-unsaturated vinyl ketones, like vinyl methyl ketone, a, /? - unsaturated vinyl sulfones, z. B. methyl vinyl sulfone or divinyl sulfone, vinyl ester of saturated and .unsaturated mono- and Polycarboxylic acids, ζ. Β. Vinyl acetate, vinyl propionate or divinyl succinate, N-vinyl lactams, such as N-vinylpyrrolidone or N-vinylcaprolactam, vinyl chloride, Vinylidene chloride, vinylidenecyanide, and vinyl ethers of mono- and polyoxy compounds, e.g. B. isobutyl vinyl ether or butanediol-1,4-divinyl ether. Also α, ^ - unsaturated mono- and dicarboxylic acids and their Derivatives such as esters, amides, nitriles are often suitable, e.g. B. acrylic acid, methyl acrylate, ethyl acrylate, Acrylic acid butyl ester, acrylic acid amide, N-substituted acrylic acid amide, acrylonitrile, methacrylic acid, Methacrylic acid methyl ester, methacrylic acid amide, N-substituted methacrylic acid amide, methacrylic acid nitrile, Glycol dimethacrylate, a-chloroacrylic acid methyl ester, maleic acid, maleic anhydride, maleic acid diethyl ester. Allyl compounds, e.g. B. allyl esters Applicant;

Aniline & Soda Factory in Baden

Corporation,

Ludwigshafen / Rhem

Dr. Herbert Willersinn, I> r. Gerhard Dietrich,
Dr. Klaus Jürgen F.ust, Ludwigshafen / Rhine,

Dr. Herbert Friederich., Worms,

and Dr. Hans Peter Siebel, Ludwigshäfen / Rhein-Oppau, have been named as inventors

of saturated or unsaturated mono- or polycarboxylic acids or inorganic acids, such as allyl acetate, Allyl acrylate, diallyl phthalate, diallyl maleate, triallyl cyanurate or triallyl phosphate, and allyl ethers from Mono- or polyoxy compounds, allyl butyl ether, diallyl ether, glycol dialryl ether, pentaerythritol tetraallyl ether, Tetraallyl ether of tetramethylolacetylenediurea and its still soluble condensation products. Butadiene and its derivatives are also used,

z. B. chloroprene, i-dimethylbutadiene, in question.

Particularly valuable products are obtained if, in addition to iBJäH, the mixed polymer component used is unsaturated polyesters, preferably in a mixture with other polymerizable compounds, such as styrene. The unsaturated polyesters are known in a known manner, for. B. by polycondensation of a, ß-un saturated dicarboxylic acids with preferably dihydric saturated alcohols. Some of the, - unsaturated dicarboxylic acids can be replaced by saturated polycarboxylic acids. Suitable α, / 5-unsaturated dicarboxylic acids come, for. B. in question: maleic acid, fumaric acid, itaconic acid, citraconic acid, aconitic acid or their substitution products, e.g. B. chloromaleic acid or anhydrides of these acids. The saturated polycarboxylic acids optionally used can be aliphatic, cycloaliphatic or mixed aliphatic-aromatic, optionally substituted dibasic or polybasic carboxylic acids, for example succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, suberic acid, ct-methylglutaric acid, ct-methylglutaric acid, endomethyl-phthalic acid, endomethyl-sulfondibutyric acid, oxadibutyric acid, -endomethylene tetrahydrophthalic acid, tetrachlorophthalic acid, tetrabromophthalic acid, phenylenedibutyric acid or anhydrides

1D9 510/475

3 4

of these acids. Instead of the free acids can also! .Liegt at 94 ⁰ C. It is in the common solvents

their esters with low molecular weight alcohols at the insoluble and infusible.

Production of the unsaturated polyester used is processed using the one described above with catalysts. Polymerizable co-acids added to the mixture by using monovalent carbonizers and activators or alcohols in the polycondensation can be mixed in the usual way with glass fiber Degree of condensation of the unsaturated polyester and weave, then you get a self-extinguishing layerwith it the viscosity of their solutions in the monomeric substance, which is made up of compounds due to its very good flame retardancy can be set. draws. Replaced in the polymerizable mixture

The ratio of the BHH to the other BHH components by styrene, then you get laminates that

in the polymerizable mixtures can be largely not self-extinguishing.

Areas can be changed and z. B. 1: 100. .

up to 100: 1. -,. Example 2

The polymerization of BHH and its copolymers - A solution of 20 parts of BHH in 80 parts of styrene

sation with other polymerizable compounds is mixed with 0.1% benzoyl peroxide and 15 hours

can by known polymerization processes, such as 15 at 80 ° C, then 8 hours at 100 ⁰ C and finally

Block polymerization, solution polymerization, emulsion borrowed. Polymerized for 15 hours at 120 ^° C.,

Polymerization, suspension polymerization, precipitation A hard, tough polymer is obtained, the one

polymerization. has slight opalescent haze, with a

The polymerization or copolymerization can have a K value according to Fikentscher of 76. It is soluble in

in some cases solely through thermal activation from benzene, toluene and chloroform. The softening point

be solved. However, it is advantageous to accelerate 'is at 104 ° C.

the reaction by exposure to radiation, e.g. B. Example 3
Light, especially UV light, or by adding

Polymerization catalysts capable of dissolving in a solution of 50 parts of BHH in 50 parts of styrene

polymerisation-initiating radicals to disintegrate. 25 is, as described in Example 1, polymerized. Man

Suitable polymerization catalysts of this type give a product with similar properties. Of the

z. B. Benzoyl peroxide, lauroyl peroxide, perlauric acid, K value according to Fikentscher is 64, the softening

Cumene hydroperoxide, tert-butyl hydroperoxide, ditert-point at 143 ° C.

Butyl peroxide, methyl ethyl ketone peroxide, cyclohexanone - example 4
peroxide, further labile azo compounds, e.g. B. Azodi- 30

isobutyric acid dinitrile. A solution of 50 parts of BHH in 100 parts of benzene

In the case of polymerization in emulsion, 0.25 part of benzoyl peroxide is added and

advantageously water-soluble per compounds, e.g. B. polymerized for 16 hours at 8O ⁰ C under nitrogen. To

Hydrogen peroxide or potassium persulfate. -8 hours a further 0.25 parts of benzoyl peroxide are added

The polymerization can be given in the customary manner by means of an. After cooling down, you get a gelatinous

application of redox systems and metal redox systems-like, cloudy paste. After removing the benzene in the

"Accelerated by applying the above vacuum one obtains a fine, white powder that is in the

Per compounds in combination with reducing agents, common solvents is insoluble.

-such as benzoin, sodium formaldehyde sulfoxylate, sugar. .

and / or, if appropriate, of metal compounds

turns. A polymerizable mixture that is resistant to a

The polymers and copolymers of BHH early polymerization by adding 0.01% p-tert-have valuable properties. Depending on whether butyl catechol is stabilized, consisting of 40 partial degrees of polymerisation and structure, you can find use of 45 phthalic acid and 1,2-propylene glycol with the acid, both on the synthetic of an unsaturated polyester from maleic acid, tetra-substance area and as lacquer raw materials. Polymerizable mixtures which contain 50 unsaturated numbers (in a molar ratio of 1: 1: 2.2), 30 parts of BHH and polyester with α, / 3-unsaturated dicarboxylic acid esters, contain 30 parts of styrene with a viscosity of 19.3 Din-sec as casting resins for the production of form (Din cup No. 4;. 20 ⁰ C) a cyclo bodies, glass fiber-reinforced laminates, corrugated glasses is hexanonperoxydpaste (40 _^0/0 iginDibutylphthalat) andwith ■ or components used at 2%. Due to the high chlorine content of 50 0.4% of a cobalt naphthenate solution (10% in styrene), the polymers and copolymers are difficult to remove and poured into molds.

flammable. By incorporating phosphorus-containing substances, the mixture begins to gel after about 3 hours

Substances or from z. B. Antimony trioxide can and hardens in an exothermic reaction. You get

Flame resistance can be increased even further. hard, firm, clear moldings that are self-extinguishing,

The parts mentioned in the examples are 55 d. H. which do not divide further after the pilot flame has been removed, burn. After a final temperature in Example 1 of 100 ° C. over a period of 12 hours, the polymers have a softening point of 114 ° C and a

56 parts of an unsaturated polyester made from Malein impact strength of 14.6 cm kg / cm ² ,

acid, tetrachlorophthalic acid and propylene glycol in the 60th

Molar ratio 1: 1: 2.2 (acid number 35), 24 parts styrene, example 6

20 parts BHH and 0.01 part hydroquinone (for stabilization) A polymerizable mixture that protects against

sierung) with 2 parts of cyclohexanone peroxide paste early polymerization by adding 0.01% hydro-

(40% in dibutyl phthalate) and 0.4 parts of a 10% quinone is stabilized, consisting of 40 parts of an un-

Solution of cobalt naphthenate in styrene added. The 65 saturated polyester made from maleic acid, hexachloro-endo-

The mixture is poured into molds and in the case of room methylene tetrahydrophthalic acid and 1,2-propylene glycol

temperature left to stand until the exothermic hardening in the molar ratio 2: 1: 3.3 with the acid number 51.7.30 parts

reaction has expired. Then it is tempered for 12 hours BBH and 30 parts of dichlorostyrene (mixture of isomers)

"at 100 ° C. A hard, firm and clear paste is obtained with 2% cyclohexanone peroxide paste (40% in

Moldings. The softening point of the polymer 70 dibutyl phthalate) and 0.4% of a cobalt naphthenate

solution (10 ° / ₀ ig in styrene) added and poured into molds.

The mixture begins to gel after about an hour and hardens in an exothermic reaction. The received hard and solid moldings with an extremely high halogen content are no longer flammable.

Example 7

A polymerizable mixture that prevents premature polymerization by adding 0.01% hydro- ίο quinone is stabilized, consisting of 50 parts of an unsaturated polyester of maleic acid, hexachloro-endomethylene-tetrahydrophthalic acid and 1,2-propylene glycol in a molar ratio of 2: 1: 3.3 with an acid number of 51.7.20 parts BHH and 30 parts of methyl styrene (vinyl toluene) are polymerized as in the examples. You get hard and solid Moldings that are self-extinguishing.

Example 8

A mixture of 120 parts of BHH, 40 parts of styrene and 600 parts is placed in a stirred vessel with a re-nut condenser Water, 0.75 part of azo-diisobutyric acid dinitrile and 0.75 part of gelatin heated to 85 ° C. for 10 hours.

The bead polymer obtained is washed out on a suction filter and then dried. A synthetic resin with a pale yellowish color and a Fikentscher K value of 44 and a softening point of 135 ^° C. is obtained.

Example 9

A mixture of 200 parts of water, 50 parts of BHH, parts of styrene, 2 parts of sodium alkylsulfonate C ₁₆ to C ₁₈ and 0.5 part of potassium persulfate is heated to 70 ° C. with stirring. Drying gives the dispersion a polymer with a K value of and a softening point of 106 ° C.

Claims (2)

Patent claims: 1. A process for the preparation of polymers or copolymers, characterized in that So-bis-methylene-l ^ A ^ J-hexachlorbicyclo- [2.2, l] -heptene- (2) Cl = CH ₂ polymerized alone or with other monomeric polymerizable compounds. 2. The method according to claim 1, characterized in that one is used as the copolymerization components unsaturated polyesters with α, / 3-unsaturated dicarboxylic acid esters - preferably in combination with other polymerizable compounds - used. © 109 510/475 2.61