Method for production of complex curing accelerator for unsaturated compounds

FIELD: organic chemistry, in particular curing accelerators for unsaturated polyester resins and acrylate oligomers.

SUBSTANCE: claimed method includes reaction of vanadium pentaoxide, or ammonium metavanadate, or metavanadic acid with phosphoric acid aqueous solution and optionally with butylic alcohol or 2-ethyl hexanol, at 110-125°C for 0.5-2.5 h (from heating start to cooling).

EFFECT: economy method for production of complex curing accelerator from inexpensive raw material by simplified technology.

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The invention relates to polymer chemistry, in particular to methods for producing a catalyst for the curing of unsaturated polyesters, acrylic monomers and oligomers, and can be used in paint and the medical industry as an accelerator for the curing of varnishes, paints, plastics, in the manufacture of abrasive tools, etc.

For curing a significant part of unsaturated compounds using different initiating system consisting of initiators and accelerators.

The choice of initiator and accelerator, as well as their dosage depend on the composition of the unsaturated polymer, oligomer and monomer, the balance.

Known technical solutions in the initiator system which is used as accelerator - NK (cobalt naphthenate), linoleic cobalt and the initiator is a peroxide methyl ethyl ketone, Gidropress cumene (see SU # 827509, EN 2049752).

Accelerators for the curing of unsaturated polyester resins and oligopyrroles obtained by dissolving cobalt naphthenate in styrene or toluene ineffective because for curing takes 3-8% of the accelerator by weight curable oligomer or polyester and 3-6% of a polymerization initiator (gidroperekisi of cumene - gitaris). The curing time is 10-30 minutes

The combination of hyperize with a powerful accelerator-based vanadium pentoxide (V 2O5allows dozens of times to reduce the consumption of initiator additives and provides a maximum speed of gelation (see Handbook of plastic masses. Ed. Vmichael and others-M.: Chemistry, 1975, Vol. 2. -S).

In practice, the derivatives of vanadium have been used not only for curing strazdeliai resins, such as MO-1, but for polyesters - malaikat-acrylate binder MO-62, phosphorous self-extinguishing resins, solutions of maleates oxopropylidene of novalucol in the air TGM-3, etc. in the Presence of the initiating system of the accelerator (0,25%solution of V2About5in acidic phosphate) can dramatically increase the speed of gelation compared with 8%solution in styrene (see Sedov L., Mikhailov ZINAIDA Unsaturated polyesters. -M.: Chemistry, 1977. -S.89).

Also known is a method of obtaining a molded plastic products RU # 2005739, in which the accelerator used toluene solution of cobalt naphthenate or a solution of vanadium pentoxide in monobutyltin acid as a solution of unsaturated polyester in mixing the monomer - semi-lacquer-based preferment grades PE-232, PE-246 and PE-265.

The closest analogue to the claimed invention is a method for accelerator by reacting vanadium pentoxide with monobutyltin acid with education is the use of complex accelerator No. 31, part varnish PE-265. This accelerator is highly effective. For example, polyester resin grade MO -1 0.1% mass complex compounds vanadium pentoxide with monobutyltin acid and 0.07% mass hyperize cures for 10-30 min at room temperature. However monobutyltin acid costly and not produced by the domestic industry.

The objective of the invention is to simplify the technology for accelerator complex, the expansion of the scope and reducing the cost of its production.

The technical result is achieved in that a method of obtaining an integrated accelerator for the curing of unsaturated polyester resins and acrylic oligomers, carry out the interaction of vanadium pentoxide or metavanadate ammonium or metavanadate acid with an aqueous solution of orthophosphoric acid and, if necessary, with butyl alcohol or 2-ethylhexanol, 110-125°and synthesis time from start of heating to cooling of 0.5-2.5 hours, at the following mass ratio of ingredients, parts by weight:

vanadium pentoxide or metavanadate

ammonium or metavanadate acid - 0,015-0,026

phosphoric acid - 1,0

water - 0,19-0,37

butyl alcohol or 2-ethylhexanol - 0-0,02

Technology of preparation and application of the curing accelerator on this from the retenu illustrated in 7 examples.

To obtain a curing accelerator were used:

accelerator, representing a complex chemical compound of vanadium pentoxide V2About5and derivatives of phosphoric acid, with the following characteristics: density -1,49-1,53 g/cm3the content of metal (vanadium) - 0,5±0,9%; homogeneous liquid from Golobokova to green; transparent liquid without mechanical impurities.

- pentoxide (TU 6-09-4093-88);

- orthophosphoric acid, H3RHO4colorless non-flammable liquid; soluble in water;

- butyl alcohol (GOST 5208 -76);

the ammonium Vanadate MN4VO3(GOST 9336 -75);

- monobutyltin acid flash - 63°C;

- metavanadate acid (TU 6-09-02-128-75);

- 2-ethylhexyloxy alcohol CH3(CH2)3CH(C2H3)CH2HE, flammable liquid solubility in water of 0.1%.

Example 1. In trekhgolovy reactor (volume 6 l), equipped with a reflux condenser, thermometer and mechanical stirrer, pour 5250 ml (8032,5 g) technical phosphoric acid, containing 27% of water (i.e. phosphoric acid to 1.0 parts by weight, the water - 0,37 parts by weight) and 105 ml (85,05 g) normal butyl alcohol (of 0.015 parts by weight). Then, 140 g of vanadium pentoxide (0,026 parts by weight) through the funnel download small portions when the agitator. At the end zagruzki the mixture is heated for t=1 h to a temperature of T=102° C. Later the contents of the reactor are heated to 118°t=30-45 min the mixture from the reactor is poured into the container.

The finished product can be used as an accelerator for the curing of varnishes, paints, glass-reinforced plastics in the manufacture of abrasive tools, etc.

Example 2. The preparation operation of the accelerator analogous to example 1; vanadium pentoxide is replaced by ammonium metavanadate - 109 g (0,019 by mass). The synthesis time increases by 10-30 minutes

The finished product is recommended for use as an accelerator for the curing caulking compounds, nalivochny floors, varnishes, paints, fiberglass, etc.

Example 3. In trekhgolovy reactor (volume 6 l)with obratnim fridge and a stirrer, a load of 5.39 kg (3.5 l) technical phosphoric acid (i.e. phosphoric acid to 1.0 parts by weight, the water - 0,37 parts by weight), 56 g (70 ml) butyl alcohol (0,014 by mass). Then load 70 g of vanadium pentoxide (parts by weight 0,018). The mixture is heated with stirring. For 1.5 h, the temperature is brought to 120°With, then mixing in t=2-3 minutes, cool. Obtained by this technology, the accelerator has a transparent blue color with no sediment and turbidity.

The resulting product can be used as an accelerator for the curing of polyester compositions.

Example 4. The operation is carried out analogously to example 1, the vanadium pentoxide replace metavanadate sour is Oh - 154 g (0,026 parts by weight). The total synthesis time before cooling the reaction mixture -110 minutes

Example 5. In the reactor (0.3 l) load 194 g of ice phosphoric acid (1 parts by weight), 37 g of distilled water (0,19 parts by weight), 2.4 g - butyl alcohol (0,012 parts by weight) and 3 g of vanadium pentoxide (0,016 parts by weight). For 30 minutes, the prepared mixture is heated up to T=120°and cool.

Example 6. Synthesis is carried out analogously to example 3 without adding butyl alcohol. For 2 hours the temperature is brought up to 118°C, then the mixture is stirred for 0.5 h and cooled.

Example 7. In example 3 carried out the synthesis, where instead of butyl alcohol use 85 ml (70,8 g), 2 - ethylhexanol alcohol (to 0.02 parts by weight). The density of the last 0,8328 g/cme.

The table shows the comparative characteristics of the proposed accelerator and prototype.

td align="center"> 12
Table 1
No. approx.Properties of accelerator
AppearanceDensity, g/cm3Activity (curing time), min
1Transparent liquid green-blue color1,49113
2Transparent liquid blue1,4914
3-“-1,498
4-“-1,5130
5-“-1,49212,5
6-“-1,520
7-“-1,5221
U-31Liquid brown1,24-1,2510-30

Obtained according to example 3, the product was used for curing polyester resins obtained by the interaction ftalievogo anhydride and diethylene glycol in equimolecular ratio and TGM-3 (tetrafunctional monomer - dimethacrylate triethylene glycol) in a mass ratio of 1: 1 (activity 30 min).

Obtained according to the examples of 1,2,4-7-product was used as an accelerator for curing the following polymer compositions (“g”):

Resin PN-1 - 38,0

Silicon dioxide - 60,0

Accelerator - 0,31

Gitaris - a 0.1

The analysis of the table shows that the proposed accelerator curing by their activity has equivalent performance with the prototype. However, obtaining claimed accelerator was run on cheap raw materials at a lower cost and simplified technology that is economically very advantageous.

The method of generating integrated accelerator for the curing of unsaturated polyester resins and Smoot the new oligomers, carried out by the interaction of vanadium pentoxide or metavanadate ammonium or metavanadate acid with an aqueous solution of orthophosphoric acid and, if necessary, with butyl alcohol or 2-ethylhexanol at 110-125°and synthesis time from start of heating to cooling of 0.5 - 2.5 hours, at the following mass ratio of ingredients, parts by weight:

vanadium pentoxide or metavanadate

ammonium or metavanadate acid 0,015 - 0,026

phosphoric acid 1,0

water for 0,19 0,37

butyl alcohol or 2-ethylhexanol 0 - 0,02



 

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FIELD: organic chemistry, in particular curing accelerators for unsaturated polyester resins and acrylate oligomers.

SUBSTANCE: claimed method includes reaction of vanadium pentaoxide, or ammonium metavanadate, or metavanadic acid with phosphoric acid aqueous solution and optionally with butylic alcohol or 2-ethyl hexanol, at 110-125°C for 0.5-2.5 h (from heating start to cooling).

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1 tbl, 7 ex

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