SU1567569A1 - 4,5-dibrom-3-chlorcyclohexan-1,2-dicarboxylic acid as additive to polyesters used for obtaining glass plastics with higher fire resistance - Google Patents

Abstract

The invention relates to acyclic compounds, in particular to 4,5-dibromo-3-chlorocyclohexane-1,2-dicarboxylic acid as an additive to polyesters, used to obtain glass fiber-reinforced plastics with a high flame retardancy. The purpose of the invention is the detection of compounds with useful properties. The preparation is carried out by condensation of 1-chloro-1,3-butadiene (percentage ratio of trans and cis isomers 67:33) with maleic anhydride followed by bromination of the resulting adduct in water in the same reactor, pre-distilled unreacted cis-α-chloroprene, or in inert solvents, with further distillation of the solvent and treatment with water, followed by separation of the target product. Yield 85.5%. T.pl. 208 - 209 ° С. Gross F la C ₈ H ₉ O ₄ BR ₂ CL. The use of a new compound provides for obtaining glass fiber plastics with higher indices. 2 tab.

Description

This invention relates to a new chemical alicyclic compound, 4,5-dibromo-3-chlorocyclohexane-1, 2-dicarboxylic acid of the formula

C1

BF-T-C0011 (1)

Br-l i-COOH

He also added a cement to the polyester to obtain polyesters used to make glass-reinforced plastics with high fire resistance.

The purpose of the invention is to improve the fire resistance of glass-reinforced plastics without deteriorating their physico-chemical characteristics.

The invention is illustrated by the following make-up artists.

Example 1. A mixture of 88.5 g (1 mol) of 1-chloro-1,3-butadiene (ratio of trans and cis-67gr 67:33), 53.9 g (0.55 mol) of malsin anhydride n 0.1 g hyfnon is heated for 4.5 hours at 55-60 ° C, 300 ml of water are added and the unreacted cis-1-chloro-1,3-butydiene is removed under reduced pressure (300 mmHg). To the remaining mixture with ppt-nsipnom overeating

C5 J

SP

se co

while stirring, 86, U t (0.54 mol) of bromine are added dropwise at such a rate that the temperature of the reaction mixture is maintained at 25-35 ° C (due to the thermal effect of the reaction). After the addition of bromine, stirring is continued for another 2 hours at room temperature, the precipitated precipitate is filtered off and dried, to obtain a white powder with mp. 208-209 ° C. The yield of 4,5-dibromo-3-chlorocyclohexane-1,2-dicarboxylic acid is 85.5% (167.8 g).

Found,%: C 26.33; H 2.44; C1 9.69; Br 43.80

C6Hq04Br2Cl

Calculated,%: C 26.35; H 2.47; C1 9.74; Br 43.86.

IR spectrum,), 1715 (COOH).

PMR spectrum, 8, ppm: 11.0 (2H, s, 2COOH); 5.2-4.1 (3N, m, 5.4-Br-CH,

2-CH); 3.401-CH).

3-C1-CH); 3.65 (1H, 2.40 (3N, m, 6-CHg,

PRI mme R 2. Similarly to the example

1, 3-chloro-L-cyclohexene-1,2-dicarboxylic acid anhydride is obtained. The precipitated adduct is filtered from unreacted Pus-1-chloro-1,3-butadiene. 100.5 g (98%) of anhydride of 3-chloro-L-cyclohexene-1,2-dncrboxylic acid (calculated on maleic anhydride) were isolated, m.p. 129-130 ° C. To 43.3 g (0.5 mol) of 3-chloro-D4-piclogeken-1,2-dicarboxylic anhydride in 750 ml of chloroform with vigorous stirring, 80 g (0.50 mol) of bromine in 150 ml are added dropwise. chloroform, maintaining the temperature of 25-35 ° C. After the addition of bromine, stirring is continued for another 2 hours at room temperature, the solvent is removed under reduced pressure, and the residue is boiled with 200 ml of water for 2 hours. After cooling, the precipitated precipitate is filtered and dried. The yield of 4,5-dibromo-3-chloro-cyclohexane-1,2-dicarboxylic acid is 92.7% (168.9 g).

PRI me R 3. Similar to the example

2 Bromination is carried out in benzene. 162.9 g (89.4%) of 4,5-dibromo-3-chlorocyclo-hexane-1,2-dicarboxylic acid are obtained.

The resulting 4,5-dibromo-3-chlorocyclohexane-1,2-dicarboxylic acid I is used in the preparation of unsaturated polyesters. Polyesters are obtained on the basis of maleic epichlorohydrin and ft of left anhydrides and of compound (I) in

Q

five

0

five

0

five

40

45

50

55

the presence of ZnCL4 or KI as a catalyst. The resulting bromine-containing polyesters are used to prepare polyester resins — styrene (resin 1) and styrene-free (resin 2), as well as glass-based plastics,

In tab. I shows the properties of glass-reinforced plastics based on resins containing compound (I) in comparison with the properties of glass-reinforced plastics based on resins PNEHG-1 (styrene) and PNEHG-2 (styrene-free) of a similar composition, but not containing bromine.

From tab. I, it can be seen that the use of compound (I) for the synthesis of unsaturated polyesters provides fiberglass with high fire resistance.

To prove the advantages of the proposed additive, the following bromine-containing flame retardants — tetrabromophthalic anhydride (II) and hexabromobenzene (III) — were also synthesized and tested.

In tab. 2 shows the properties of glass plastics based on resins containing compound (I) 4,5-dibromo-3-chlorocyclohexane-1,2-dicarboxylic acid (resin I), compound (II) (resin 3) and compound (III) (resin 4 ).

From tab. 2, it can be seen that the use of compound (I) for the synthesis of unsaturated polyesters provides glass fiber plastics with higher indicators than when using bromine-containing compounds (II) and (III).

The proposed additive contains two carboxyl groups, which allows it to be incorporated into the chain of polyester.

The presence of links of the specified additive in the polyester chain is preferable, since it cannot migrate or wash out during operation of the product, unlike the additive (flame retardant), which is simply introduced into the composition, and thus ensures the stability of properties over time and lower toxicity of the product.

Claims (1)

The proposed additive also solves the problem of disposal of large-scale waste from the production of chloroprene-I-chloroprene (1-chloro-1, 3-butadiene). Invention Formula 4,5-Dibromo-3-chlorocyclohexane-1,2-dicarboxylic acid of formula Cl Br br : 6 COOH soon 15675696 as an additive to polyesters used to obtain glass-reinforced plastics with expanded fire resistance. Indicators Resin-based fiberglass Stirolna I Content in resin,% Chlorine 12.5 ± 0, l 13, OfO, l I 0.5 ± 0, l 10, OfO, l Brom 5,010,1-3,, 1 Oxygen index,% 40.0-40.5 36.4-37.1 38.0-38.4 36.0-36.6 Flammability index for CT 0.9-0.95 1.2-1.31 , 2-1,31,4-1,6 Class of fuel - Difficult - Combustible Difficult to flame, flexural strength, MPa 250-260 250-270 190-210 200-250 Table 2 Indicators of glass resin based : I :: T: I ::: XI; :: Z Content in resin, .7. Chlorine 12.5 ± 0.1 9.8 ± 0.1 9.6 U, 1 Bromine 5.0 ± 0.1 3.510.1 3.6 ± 0.1 Oxygen index,% 40.0-40.5 35 , 6-36.5 35.5-36.0 Flammability index for KT 0.9-0.95 1.2-1.5 1.2-1.5 Fuel class - Slightly combustible - Slightly flammable Flexural strength, MPa 250-260 190-250 190-230 Compiled by E. Utkin Editor M. Nedoluzhenko Tehred L. Oliynyk Proofreader M. Kucher va Order 1299 Circulation 341 Subscription VNIIPI State Committee for Inventions and Discoveries at the State Committee for Science and Technology SSGR 113035, Moscow, Zh-35, Raushsk nab. 4/5 Production and publishing plant Patent, Uzhgorod, st. Gagarin, 101 --L Table I i: Bezstyrolna I PNEHG-1 I PNEHG-2