DE2003579B2 - - Google Patents

Description

The amount of the phenolic agent added according to the invention and the water are mutually exclusive in the water thiazine can be 1000 ppm, based on the amount of separator separated. The separated azeotropic de-acrylic acid, or less, the polymerization watering agent is returned to the reaction vessel To prevent acrylic acid. It can usually be passed in, and the separated water is taken from the Amounts from about 100 to 500 ppm are present. Is the 5 system removed. When the amount of water exceeds the calc-amount too small, the polymerization will only have reached a lower value, the reaction has ended, sufficiently inhibited; if the amount is greater than about After cooling, the reaction mixture will with 1000 ppm, the purity of the obtained aqueous alkali solution and with an aqueous one is reduced ten polymers, and the polymerization properties solution of a salt washed. After washing deteriorate? themselves; Furthermore, a cleaning of the io becomes the azeotropic dehydrating agent from the gePolymer required in a further stage. washing reaction mixture under reduced

According to the invention, the dicarboxylic acids are recovered under pressure, a polyester diacrylate

for example aliphatic dicarboxylic acids such as amber is obtained. The polyester diacrylate thus obtained

steinsäurc, adipic acid, 1,12-Dodecanuicarböiisäure, optionally with active clay, activated carbon

aromatic dicarboxylic acids, such as phthalic anhydride 15 or the like. Purified. Even if part of the azeotropic

drid, isophthalic acid, terephthalic acid or maleic dehydrating agent remains in the product

acid anhydride is used. These dicarboxylic acids cannot prevent the polymerization of the oligo-

can be used alone or as a mixture. As meren, if this is further processed.
Diule are for example ethylene glycol, propylene The two-stage process can be such as

glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 20 can be carried out as follows:

Diethylene glycol, triethylene glycol, tetraethylene glycol, at least one dicarboxylic acid, at least one

Dipropylene glycol, neopentyl glycol, xyiideneglycol diol, an esterification catalyst and an azeotropic one

or 1,4-cyclohexanedimethanol is used. These dehydrating agents are used in certain proportions

Diols can be used alone or in a mixture in a mixer, dropping funnel, water separator

will. 25 and condenser equipped reaction vessel filled. the

As esterification catalysts according to the invention are implemented in the same way as with the Sulfuric acid, p-toluenesulfonic acid, benzenesulfonic acid carried out one-step process. When the water or Naphthalenesulfonic acid suitable. If the amount of the amount reaches the calculated value, a catalyst will be for example sulfuric acid, a certain amount of acrylic acid and phenothiazine expediently carries 0.3 to 1.0 percent by weight, based on the dropping funnel added, and the reaction is carried out on the concentration of the solution. continued until a certain amount of water

The azeotropic used according to the invention has been distilled off. Then the reaction mixture is in

An example of a watering agent is cyclohexane, in the same manner as in the one-step process

η-hexane, benzene, toluene, xylene, isopropyl ether, treated to obtain the product.
Trichlorethylene or perchlorethylene. The crowd 35 The conditions and working methods involved in the

of the dehydrating agent is preferably used in this way. Implementation of the present process

selects that the concentration of polyester diacrylate are known per se; but it can also

after implementation about 20 to 50 percent by weight other, different conditions and work

amount Is the amount of azeotropic wise used to be applied.

Too little drainage agent, the insulation is 40. The invention is based on the following

of the desired product explained in more detail on the following examples.
Inadequate wash-out stage and there is B is ρ ie 1 1

Risk of polymerization of the monomer

takes place during the condensation reaction. Is a mixture of 600 g benzene, 4 cm 98 / £ ige

on the other hand the amount of azeotropic ent- 4.5 H ₂ SO .. 59 g (0.5 mol) succinic acid, 150 g (1 mol)

The watering agent is too large, the reaction is triethylene glycol, 90.5 g (1.05 mol) of Metnacryisaurc

speed low, and the recovery of the and 0.06 g phenothiazine is carried out in a with agitator,

desired product becomes uneconomical. 1-1-glass water separator and cooler

The reaction temperature depends on the type and flask is filled and heated. The steam from the

the amount of azeotropic dehydrating agent, 50 azeotropic mixture of benzene and water

is, however, usually ^{cooled at about 70 to 120 0} C., and the liquid is in the separator m

The reaction time depends on the type and the benzene and water separated. The formed water

Amount of catalyst and reaction is removed from the system, and the benzene layer

speed, but is preferably 10 hours, it is fed back into the reaction vessel
that or less. 55 At a reaction temperature of 77 to 81 C.

The process according to the invention comprises a distilling 97% of the theoretical amount of water in a one-stage process and a two-stage process. half of 5.5 hours. The reaction mixture was For example, the one-step process will be like homogeneous, and there were no polymeric substances carried out as follows: formed.

In a 60 with stirrer, water separator and condenser. The reaction mixture obtained in this way is heated to 3C

equipped reaction vessel are cooled at least one and then with a diluted one

Dicarboxylic acid, at least one diol, acrylic acid, an aqueous ammonia solution, the ammonium result

Esterification catalyst, containing phenothiazine and an azeo-, and then with an aqueous ammonium

tropic dehydrating agent washed in certain proportions of sulfate solution. Then the benzene is poured out. While stirring and heating, the overall ₅ is 6 to the washed reaction mixture is removed by

get mixed when simmering. The vapors of the azeo- the mixture at a pressure of about 100 to

Tropical dehydrator and water become 10 mm Hg at a temperature of 40 to M ^

cooled in the condenser, and the azeotropic dehydration is heated for 3 hours, with 224 g of a gemen

Product are obtained which contains bis (triethylene glycol) succinate dimethacrylate as the main component. The viscosity of this product is 7OcP (20 ° C). The yield is 86.5%.

Example 2

A mixture of 300 g of benzene, 2 cm ^{3 of} 98% H ₂ SO ₄ , 36.5 g (0.25 mol) of adipic acid, 56.5 g (0.375 mol) of triethylene glycol, 21.5 g (0.25 mol) Methacrylic acid and 0.01 g of phenothiazine were poured into one with a stirrer. Filled in a ^{500 cm 3} flask equipped with a water separator and cooler and heated. The vapor of the azeotropic mixture of benzene and water was cooled and the condensate was separated into benzene and water in the separator. The water formed was removed from the system and the benzene layer was returned to the reaction vessel, ao

At a reaction temperature of about 81 to 83 ⁰ C, 96% of the theoretical amount of water distills off in 8 hours. The reaction mixture was homogeneous and no polymeric substances were found.

The reaction mixture was washed with an alkaline aqueous solution and then with an aqueous solution of the salt in the same manner as in Example 1. The benzene was removed from the washed reaction mixture by heating it at a temperature of about 40 to 50 ° C under a pressure of about 100 to 10 mm Hg for 3 hours. 90.0 g of a yellow product were obtained, the main component of which was poly (triethylene glycol adipate) dimethacrylate (degree of condensation η = 2). The viscosity of this product was 20OcP (20 ° C). The yield was 89.1%.

Example 3

A mixture of 300 g benzene, 6 g p-toluenesulfonic acid, 37 g (0.25 mol) phthalic anhydride, 45 g (0.5 mol) 1,4-butanediol, 43 g (0.5 mol) methacrylic acid, 3.6 g (0.05 mol) of acrylic acid and 0.02 g of phenothiazine were ^{poured into a 500 cm 3} flask equipped with a stirrer, water separator and condenser and then heated. The benzene layer was returned to the reaction vessel and the water was removed from the system.

At a reaction temperature of 83 to 85 ° C, 92 ⁿ _{u of} the theoretical amount of water distilled off in 6 hours. The reaction mixture was homogeneous and no polymeric substances could be found.

The main product was a mixture of bis- (1,4-butanediol) phthalate dimethacrylate and bis (1,4-butanediol) phthalate methacrylate acrylate and bis (1,4-butanediol) phthalate diacrylate.

Example 4

60

A mixture of 222.1 g (1.5 mol) of phthalic anhydride, 318.3 g (3.0 mol) of diethylene glycol, 238.0 g (3.3 mol) of acrylic acid, 2000 g of toluene, 10 cm ^{3 of} 98% H ₂ SO ₁ and 0.17 g of phenothiazine were poured into a 3-1 glass flask equipped with a stirrer, water separator and condenser and then heated, the mixture was cooled by steam from an azeotropic mixture of toluene and water, and the condensate was dissolved in toluene in a water separator and water separately. The toluene layer was returned to the reaction system while the water layer was removed from the system.

At a distillation temperature of 102 to 112.4 ° C, the calculated amount of water distilled in 2.5 hours.

After cooling, the reaction mixture was washed with an alkaline aqueous solution and then with an aqueous solution of a salt in the same manner as in Example 1. After washing, the toluene was removed from the washed reaction product by heating it at a pressure of 100 to 5 mm Hg at a temperature of 25 to 50 ° C. in the presence of methoxyhydroquinone for 3.5 hours. This gave 494 g of a yellow product, the main component of which was bis (diethylene glycol) phthalate diacrylate. The viscosity of this product was 109 cP (25 ^° C.) and the yield was 95.1%.

Example 5

A mixture of 59 g (0.5 mol) of succinic acid, 106 g (1.0 mol) of diethylene glycol, 600 g of benzene and 4 cm ^{3 of} 98% H ₂ SO ₄ was poured into a 1- 1 glass flask filled and then heated. The vaporous mixture of benzene and water was cooled in the cooler and separated into benzene and water in a water separator. The separated benzene was returned to the reaction system while the water was removed from the system.

At a distillation temperature of 77 to 81 ° C, the calculated amount of water distilled in 2 hours away. A mixture of 90.5 g (1.05 mol) of methacrylic acid and 0.04 g of phenothiazine was then passed through the Dropping funnel added. The deposited benzene was put into the reaction system in the same manner as above returned while the water was removed from the system.

At a distillation temperature of 81 to 84 ° C, the calculated amount of water distilled in 5 hours away.

The reaction mixture treated in this way, after cooling to 30 ^° C., was washed with an alkaline aqueous solution and then with an aqueous solution of a salt in the same way as in Example 1. After washing, the benzene was removed from the reaction mixture by heating it to 40 to 55 ° C under a pressure of 100 to 10 mm Hg for 3 hours. 186.6 g of a yellow product were obtained, the main component of which was bis-i-diethylenglycoO-succinate dimethacrylate. The viscosity of this product was 36 cP (20 ° C.) and the yield was 86.8%.

Comparison example

The procedure of Example 1 was repeated with the difference that instead of the phenothiazine the polymerization inhibitors indicated in the table were used and that instead of sulfuric acid the esterification catalysts given in the table were used. The results obtained are shown in the table.

Tabel

Polymerization inhibitor lot
(G) Esterification
catalyst Result Hydroquinone 0.06 H ₂ SO ₄ Divorced 2 hours after the start of the reaction gradually a large amount of one insoluble polymer Hydroquinone monomethyl 0.06 H ₂ SO ₄ Divorced 2 hours after the start of the reaction ether gradually a large amount of unresolvable Lich polymer from N-phenyl-ß-naphthylamine 0.06 H ₂ SO ₁ Started 2 hours after the start of the reaction to form a polymer Hydroquinone 1.0 H ^ SO ₄ Started 3 hours after the start of the reaction a large amount of polymer form Hydroquinone 2.0 H ₂ SO ₄ Started 3.5 hours after the start of the reaction to form a polymer Hydroquinone 1.0 p-toluene 2.5 hours after the start of the reaction was sulfonic acid a relatively large amount of an un soluble polymer deposited

The results show that the phenothiazine is an excellent polymerization inhibitor in the production of polyester diacrylates of ₄ at least one dicarboxylic acid, at least one diol and acrylic acid.

Claims (1)

Since a polyester diacrylate is an easily polymerizable Claim: is a bares oligomer with polyfunctional groups, a polymerisation process is used in the condensation reaction to produce polyester dionion inhibitor. The type and amount of acrylates by reacting at least one polymerization inhibitor, which is the case with the condensation dicarboxylic acid, at least one diol and acrylic reaction is used, but have a strong influence acid and / or methacrylic acid in the presence of the yield and the purity of the desired oligoeines Esterification catalyst, one mixed with water. The one used in the condensation reaction an azeotropic mixture forming a polymerisation inhibitor which is different from the polymerisation agent and a polymerization inhibitor, ionization inhibitors for increasing the storage conditions, That the circumstance differs is therefore added to the polymerization of the polymerizable monomer in the presence of up to about 0.1 weight percent phenothiazine as a polymerization inhibitor, and oligomers under the conditions of the condensate on the amount of acrylic or methacrylic acid to inhibit the reaction, with the temperature is carried out. 15 high and the composition of the reaction system is complicated. In general, a higher one leads Amount of that added in the condensation reaction Polymerization inhibitor to increase the amount of impurities going into the product The invention relates to a method for producing 20 movements and for reducing the speed of polyester diacrylates, the easily polymerizable speed of the condensation reaction. Therefore should the Represent oligomers with polyfunctional groups, formation of polymers through a preferably of at least one dicarboxylic acid, at least a small amount of a polymerization inhibitor a diol and acrylic acid. The expression “to be acrylic-treated. acid "includes ordinary acrylic acid, methacrylic acid acid and mixtures of acrylic acid and methacrylic but hydroquinone as a polymerization inhibitor acid. The term polyester diacrylate includes applied, and in relatively large amounts, homely polyester diacrylate, polyester dimethacrylate compared to the amount of acrylic acid. That's why late and polyester-acrylate-methacrylate. the above procedure has the following From German patents 1,058,048 and 30 part that the amount of impurities in the product 1151 506 it is already known compounds which are high and the yield of product is low. Acetylene series or olefinically unsaturated monomers According to the invention, a process for the preparation is intended stabilize with phenothiazine. From J. Appl. Polymer of polyester diacrylates in high yield ScL, Vol. 9, 1965, pp. 2009 to 2018, however, has to be drafted. take that, for example, methyl methacrylate 35 According to the invention, a method for with phenothiazine worse than with hydroquinone Production of polyester diacrylates with high can stabilize. Purity are created, which as paints, For the production of polyester diacrylates from a crosslinking agent, molding compound, etc. excellent Dicarboxylic acid, a diol, and acrylic acid are some properties. Process known in which the said starting 4 ° Other objects and advantages of the invention result in compounds using an azeotropic result from the following description.
Enl: watering agent in the presence of an esterification This object is esterified according to the invention by means of a catalyst and a polymerization inhibitor process for the preparation of polyester diacrylates, whereupon before the end of the reaction. at least one Dicarbonestcrungsreaktion the azeotropic dehydrating agent 45 acid, at least one diol and acrylic acid and / or is removed. For example, in Doklady Akad. Methacrylic acid in the presence of an esterification Nauk., SSSR, 123, 282 to 284 (1958), or catalyst, a solvent which forms an azeotropic boiling Vyskomolekulyarnye Soedineniya 2, 441 to 446 mixture with water and a poly ( 1960), stated that the above-mentioned merization inhibitor dissolved, the marked polyester diacrylate or dimethacrylate is easily characterized by 50 that the reaction in the presence of condensation of a dibasic acid such as malonic at about 0.1 percent by weight phenothiazine as Polyacid, with acrylic acid or methacrylic acid and merization inhibitor, based on the acrylic or ethylene glycol can be obtained if toluene methacrylic acid is carried out,
or benzene as a solvent (azeotropic dehydration- With phenothiazine, the polyester diacrylate can be used), in the presence of 55 surprisingly obtained in high yield,
an esterification catalyst, such as sulfuric acid polyester diacrylate, which is worked from at least one di- or p-toluenesulfonic acid. In particular, carboxylic acid, at least one diol and acrylic acid are indicated there that dimethacrylate-bis-iäthylen- are produced, have the following structural glycol) phthalate by mixing 0.5 mol of formula: Phthalic anhydride, 1 mole of ethylene glycol, 1.05 mole of 60 M - G -C- A - G -V- M Methacrylic acid, 6 g sulfuric acid, 250 cm ³ toluene ^ " and 2 g of hydroquinone and reacting the thus obtained- wherein η is an integer not less than 1, A Tenen mixture at a temperature of 100 to a dicarboxylic acid residue, G a diol residue and M 12O ⁰ C can be obtained, where the so obtained means an acrylic acid or methacrylic acid residue. Dimethacrylate bis (ethylene glycol) phthalate is a special 65 The degree of polymerization of the polyester diacrylate can fish weight of 1.162, an acid number of 2.4, by changing the molar ratio between an esterification number of 552; and a viscosity of dibasic acid and monobasic acid of 77 cps. can be set.