SU425404A3 - COMPOSITION ON THE BASIS OF THE COPOLYMER OF UNSATURATED POLYESTER AND VINYL MONOMER - Google Patents

Description

one

The invention relates to the manufacture of polymeric compositions based on polyester resins.

Known composition based on a copolymer of unsaturated polyester and vinyl monomer, solid filler, plasticizer.

Fillers can be solid, fibrous and powdered mineral type, and plasticizers such as chloroparaffin, dioctyl phthalate, dibutyl phthalate. However, the known composition does not possess an insecticidal action.

It is proposed to introduce O, Odimethyl-0- (2,2-dichlorovinyl) -phosphoric acid ester (DDVP) in the weight ratio of the latter to the original unsaturated polyester resin from 1: 4 to 2: 1, preferably from 1: 3 to 1: one. The ester is introduced into the initial composition containing unsaturated polyester, vinyl monomer and auxiliary additives (plasticizer, initiator, filler).

By introducing ether, a compound with a long-lasting insecticidal action can be obtained.

It is proposed to use conventional mixtures of unsaturated polyethers and monomeric vinyl compounds attached to them in the polymerization process in a ratio from 20:80 to 90: 10 wt.%. The polyunsaturated polyethers are obtained via polycondensation of multi-, especially dihydric alcohols (for example, 1,2-propane, 1,3-butane- or 2,2-dimethyl-1, 3-: propandiol), then di-or triethylene glycol with a, p-unsaturated dicarboxylic acids or their anhydrides, such as fumaric acid or maleic anhydride, in this case with the addition of saturated dicarboxylic acids, as

phthalic acid or its anhydride, isophthalic, succinic, adipic or sebacic acid. As copolymerizable monomers, for example, styrene, MONO-, and dichloro-styrene, divinylbenzene, can be used,

vinyl toluene, vinyl esters (vinyl acetate and vinyl benzoate), acrylic acid esters and acrylonitrile, methacrylic acid esters, allyl esters (allyl acrylate), phthalic acid diallyl ester and triallyl phosphate. Among the inhibitors that are needed in this case, for example, quinone, hydroquinone, toluene hydroquinone, 2,5-di-t / 9et-butylquinop or 2,6-di-g;) et-butyln-cresol should be mentioned.

The following solid-state fillers are used, such as fibers from glass, sizava, hemp, muslin, coconut, flax and other natural products, or synthetic fibers or fillers having mineral

nature, such as titanium dioxide, oxide

iron, kaolin, quartz and other inert materials.

Of the plasticizers, dopoyl phthalate, chlornaraffines or alkylsulfonic aryl ethers are used.

Especially beneficial combined use of solid fillers and liquid plasticizers. The amount of filler and plasticizer in the composition is taken such that the weight ratios of the phosphorus-containing active (DDVP) to the polyester component of the copolymer is from 1: 4 to 2: 1, preferably from 1: 3 to 1: 1.

The compositions of the original composition are made by known methods, in which the curing of polyesters to copolymers takes place.

Curing is carried out by the radical polymerization mechanism at low temperatures (at high temperatures there is a loss of easily volatile biologically active substance), preferably already at room temperature. In addition, the formation (curing) can be carried out by means of a photolymerization mechanism by the action of electron radiation to activate the polymerization-causing radicals. In the case of radical curing at room temperature, conventional initiating systems consisting of diacetyl peroxide, such as benzoyl peroxide, and dialkylamine, such as dimethylaniline, or ketone peroxide, such as methyl ethyl ketone or peroxide of cyclohexanone and cobalt, such as methyl ethyl ketone or cyclohexanone and cobalt, are used to apply the initiating system. , octoate or acetylacetonate K0 | BALT), however, in the presence of active phosphoric ether, a reduced curing rate is necessary. The initiator-accelerator system from a soluble vanadium compound, for example, vanadium salts of a phosphoric acid partial ester or vanadium-α-toluenesulfonate, with a corresponding peroxide, such as peresters, perketals or alkyl hydroperoxides, is preferred by cumene peroxide, in the presence of an active phosphoric ester, in practice. varies and therefore preferred.

Unsaturated polyester resins used as starting materials and substances are prepared as follows.

For the manufacture of resin A, polyester obtained from 7253 parts of maleic acid, 43883 parts of phthalic anhydride, 29267 parts of 1,2Npropane and 4.2 parts of hydroquinone, with an acid number of 44, are dissolved in 28000 parts of styrene. Resins B and C are prepared from maleic and phthalic anhydrides, 1,2-: propanediol and, respectively, with the addition of dipropylene glycol in one case and glycol and diglycol in the other.

Example 1. In a mixture of 1935 parts of polyester resin A and 774 parts of DDVP, 90 parts of a 40% aqueous solution of methyl ethyl ketone peroxide in dimethyl phthalate are successively introduced, and 30 parts of a solution of cobalt octoate in dioctyl phthalate, which contains 1 wt. % cobalt. From this initial mixture (composition) with the use of a glass fiber mat weighing 450 g / m in a closed form, a 5 mm thickness cast plate is prepared with a 30 wt.% Glass content. The plate is removed from the mold after 2 hours and finally cut into

molded products measuring 12X12 cm. The test product has a dry and non-adhesive surface.

Example 2. 1533 parts of unsaturated polyester resin In well mixed with 851 hours

DDVP, 596 parts of dioctyl phthalate, 90 parts of a 40% solution of methyl ethyl ketone peroxide in dimethyl phthalate and 30 parts of a solution of cobalt octoate in dioctyl phthalate, which contains 1% of cobalt. When using fiberglass

plates with a surface weight of 450 g / cm are prepared from this mixture in a closed thickness of | thickness | thickness of a glass plate with a closed thickness of | 5 | Plate with non-adhesive and dry surface through

24 hours removed from the mold and cut into molded products of size 12X12 cm

Example 3. Plate {comparative

experience), obtained according to examples 1 and 2,

suspended separately in the middle of the premises, equal in size, of 50 m and release 2,000 house flies into each. Watching all the flies nogibuyut in flow 24 hours. The experiments were repeated for several weeks, the review of the circumstances

100% mortality of flies was observed within 24 hours. The duration of the plate, which is manifested in this case, is as follows.

Duration of action, weeks 9-10 13-14

Example 4. To a mixture of 225 parts of polyester resin A and 75 parts of DDVP, 9 parts of a 40% aqueous solution of methyl ethyl ketone peroxide in dimethyl phthalate and 3 parts of a solution of cobalt octoate in dioctyl phthalate, which contains 1% cobalt, are sequentially added. From this composition, when using a glass fiber mat weighing 450 g / m in a closed form, a 5- mm thick plate is prepared.

about 30% by weight of glass. A plate with a non-adhesive surface is removed from the mold after 2 hours, then kept for 4 hours in a sealed package at 40 ° and cut into molded products

size 12X12 cm

Example 5. 66.5 parts of polyester resin B and 3.5 parts of DDVP are mixed with 1.75 parts of a 40% aqueous solution of methyl ethyl ketone peroxide in dimethyl phthalate and 0.7 parts of a solution of cobalt octoate in dioctyl phthalate, which contains

1 wt.% Cobalt. From the resulting mixture, using a glass fiber mat weighing 450 g / m, a 1-mm thick cast plate with about 30% by weight of glass is prepared. Thereafter, the cast plate is reinforced on both sides with 1 mm thickness plate, which contains about 30% by weight of glass mat and 10% by weight of DDVP. After applying these layers, the next 1-mm layer containing 50 wt.% DDVP and 30 wt.% Glass fiber is applied to the outer and inner surfaces and the molded products are packed in cellophane film (foil). After curing and removal

Foil surface molded products are glued and dry.

Example 6. Various molded products prepared according to examples 4 and

5, but they are suspended separately in the middle of rooms of the same size with a volume of 50 cm3, and 1000 house flies are placed in them (Musca domestica). Then, it is observed how long 50% of the flies will die (LTso). During the defined time intervals indicated in the table, new flies are added to the test space and the samples are summed up. Between separate experiences space is well ventilated.