JPS603102B2 - Stabilized brominated polyester - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the production of transparent, light-resistant brominated polyester resins, more specifically stabilized against coloration caused by ultraviolet light exposure and clouding due to aging by the inclusion of dimethyl methylphosphonate. The present invention relates to a polyester composition comprising dibromoneobentyl glycol.

The polyesters useful in this invention are unsaturated polyesters that contain sufficient olefinic unsaturation to be thermosetting and contain significant amounts of bromine to make them flame resistant; Preferably, it is provided in the polyester in the form of an olefinically unsaturated dibasic acid group. The other portions of the preferred polyester molecule should consist of saturated dibasic acids, aliphatic polyhydric alcohols and aromatic polyhydric alcohol residues, and also contain some dibromoneobentyl glycol. Examples of olefinic unsaturated dibasic acids and their anhydrides, saturated dibasic acids and their anhydrides, aliphatic polyhydric alcohols, and aromatic polyhydric alcohols useful in producing the polyesters of the present invention include the following. Unsaturated dibasic acids and their anhydrides: maleic acid, chloromaleic acid, ethylmaleic acid, maleic anhydride, citraconic anhydride, muconic acid, fumaric acid, aconitic acid, mesaconic acid, itaconic acid, tetrahydrophthalic acid.

Saturated dibasic acids and their anhydrides: Adipic acid, Azelaic acid, sebacic acid, dodecylsuccinic acid, succinic acid, tetrachlorophthalic anhydride, phthalic anhydride, phthalic acid, isophthalic acid, hexahydrophthalic anhydride, malonic acid, citric acid.

Aliphatic polyhydric alcohols: ethylene glycol, propylene glycol, trimethylene glycol, triethylene glycol, pentaethylene glycol, polyethylene glycol, 1,4-butanediol, diethylene glycol, dipropylene glycol, 2,2-dimethyl-1,3-pro/ hexamethylene glycol, 1,4-cyclohexanedimethanol and the required dibromoneobentyl glycol.

Aromatic polyhydric alcohol (having a structural formula): xylene alcohols, ethylresorcinol, propylresorcinol, 2,4-dimethylresorcinol, 3,6-dimethyl-1,2,4-benzenetriol,
Ethylpyrogallol, 2-methyl-1,4-dihydroxynaphthalene, 3-methyl-1,4,5-naphthalenetriol, dimethyloltoluene, dimethylolxylene, resorcil, dichloromethane, or bishydroxyethyl or pishydroxy of hydroquinone Propyl ether, 1,5-dihydroxynaphthalene, 4,4-isopropylidene-bisphenol.

Preferably, the polyester of the invention is mixed with polymerizable monomers into a liquid curable mixture. The copolymerizable monomer used in combination with the unsaturated polyester in the present invention is preferably a liquid vinyl monomer that acts as a solvent for the polyester and provides a fluid solution when mixed with the polyester. Useful copolymerizable monomers include styrene, substituted styrenes such as Q-methylstyrene, pinyltoluene, vinylxylene: nuclear halogenated styrenes such as o-chlorostyrene, p-chlorostyrene, m-chlorostyrene and mixtures thereof, and the corresponding promolystyrenes. Contains styrene, liquid acrylate, methacrylate, etc. Most preferred is styrene. The weight ratio of unsaturated polyester to polymerizable monomer is preferably about 5:50 to 75:25.
Useful catalysts include quaternary ammonium salts alone or in combination with cobalt organic salts, quinone, hydroquinone, calcium, magnesium, vanadium, copper salts; Contains hydrogen oxide, cumene hydroperoxide, alkyl peroxy carbonate, or methyl ethyl ketone peroxide. It is preferred that from 0 to about 3 parts by weight cocatalyst be present for every 10 parts by weight of the unsaturated polyester-comonomer polymer. It is preferred to include UV stabilizers such as penzophenones, benzotriazoles, salicylic acid, and the like. The dimethyl methylphosphonate useful in the present invention has a structural formula, and is useful in amounts of 1 to 1q parts by weight per 100 parts by weight of the unsaturated polyester-polymerizable monomer mixture.

Dimethyl methylphosphonate provides excellent resistance to yellowing under ultraviolet light exposure in hard squid fin fat compositions.
The dipromoneobentyl glycol-based polyesters embodied herein can be mixed with other polyesters and still be within the scope of the invention as long as the amount of bromine in the product is within the range of 4 to 4% by weight. It is in.

Mixtures of unsaturated polyesters containing dibromoneobentyl glycol with other types of unsaturated polyesters are intended to be within the scope of this invention.

Example 1A A flame-resistant styrene-containing dibromoneobentyl glycol unsaturated polyester was produced as follows.

A resin flask equipped with a heating mantle, a motor-driven stirrer, a total reflux condenser, and a nitrogen gas sparging tube was charged with 490 g of maleic anhydride, 740 g of chicken water phthalic acid, and 3140 g of dibromoneobentyl glycol.

The flask was then heated slowly under a nitrogen sparge to allow the contents to liquefy and begin stirring. Heating continued at a faster rate until a boiling temperature of 350T was reached.

The nitrogen flow rate through the spargeer is initially 0 per gallon of boiled material.
．． I set it to screaming cubic feet. At about 300 ml, the first esterified water occurred. At this point, the nitrogen flow through the sparger was increased to 0.1326 cubic feet per gallon of stew. The simmering was continued until the acid value reached a healthy level. The resulting polyester was diluted with 1690 g of styrene monomer containing 0.0662 g of hydroquinone. The mixture was rapidly cooled to obtain 50 styrene-containing dipromoneobentyl glycol polyester resin spheres. The product was a viscous, reddish colored liquid with a characteristic styrene odor. B A general-purpose polyester resin was manufactured as follows.

In a resin flask equipped with a heating mantle, a motor stirrer, a packed fractionator, a total reflux condenser, and a nitrogen gas sparging tube, add 1370 g of propylene glycol, 1 g of phthalic anhydride.
After 500 hours, 6 hours of maleic anhydride was charged. The flask was gradually aged under minimal nitrogen sparging to melt the contents into a slurry. The temperature was then gradually increased at a sparge rate of about 0.005 cubic feet of nitrogen per gallon of boil until a boil temperature of 400 T was reached. Is the initial reaction water 300-350? arose between. The rate of heat input to the stew was adjusted so as to maintain the temperature at 215 to 100 ml.
The mixture was simmered to an acid number of 20-30 and then cooled to 35°F. At this point, the styrene containing the above resin and 0.4 m of hydroquinone was cooled rapidly during well-stirred mixing.
414 days were mixed. C Resin A spots 50 days, Neighbor City*XI spots, and dimethyl methylphosphonate spots 7 days (6%)
A blend of the above resins was prepared by mixing the above resins.

The resulting mixture had a bromine content of approximately 19.5%. ○
A blend was made as in C above, except that 6% by weight of the blend was triethyl phosphate instead of dimethyl methylphosphonate.

Example 2 Blend samples of Examples IC and ID were treated with tinuvin (Ti
Each was stabilized with 0.7 phr (parts per 10 parts of resin) of nuvin) P (Geigy's penzotriazole ultraviolet absorber).

This resin contains 0.0% penzoyl peroxide. A mixture of sahr and 0.5 phr of cumene hydroperoxide was added as a catalyst. A hand laid laminate of this resin and glass fiber was made between two sheets of cellophane. This laminated product 2
It was placed between two flat metal sheets and cured in a 25F oven for 30 minutes. To test the sample in the Weather Ometer test, use a Model B Beckman spectrometer with a combined chamber to test the sample before exposure for 20 q hours on the Weather Ometer.
and yellowing of the sample after exposure was measured. The following observations were made: o* Yellowing Index (YI) measures the reflectance and is obtained from the following equation:

600 m - 420 m r It was also recognized that it can prevent

Example 3 In an experiment outside the scope of the present invention, Example IB also included Tinupin P, one containing no dimethyl methylphosphonate and the other containing % dimethyl methylphosphonate.
Samples were made according to Example 2 using the polyester monomer mixture described in .

Two samples were exposed to a fading tester for 100 minutes and the following results were obtained.

It can thus be seen that the inclusion of dimethyl methylphosphonate in a conventional type of polyester (non-brominated) does not essentially contribute anything to the UV stability of the cured product.

Example 4 In another experiment outside the scope of this invention, a polyester resin was made from tetrabromophthalic anhydride, propylene glycol, bran maleic acid by the procedure of Example IA and diluted with styrene.

This resin was mixed with the resin made in Example IB and had a bromine content of 22. A product having a mother weight % was obtained. This resin was compounded with Tinupin P and in some cases also 6% dimethyl methylphosphonate. Samples were prepared from each according to Example 3, and the following results were obtained in a fading tester. Therefore, bromine is dibromoneobentyl glyco
It is readily seen that the inclusion of dimethyl methylphosphonate in a non-containing bromine-containing polyester resin has no effect on the stability of the cured product against UV exposure.

Claims (1)

Claims: 1. Unsaturated polyester resin - about 4 bromines bound in the form of dibromoneopentyl glycol residues in the resin containing from 1 to 10 parts by weight of dimethyl methylphosphonate per 100 parts by weight of monomer. -40% by weight of an unsaturated polyester resin-monomer mixture. 2. The composition of claim 1, wherein the monomer is styrene. 3. The composition of claim 2, which contains a benzotriazole ultraviolet stabilizer in addition to dimethyl methylphosphonate.