RU2251550C1 - Method for production of phosphorous and chlorine containing methacrylates - Google Patents

Abstract

FIELD: organic chemistry, in particular improved method for production of phosphorinated and chlorinated methacrylates.

SUBSTANCE: invention relates to method for production of compounds having general formula

, wherein R is lower alkyl and R₁ is lower alkoxyl, phenoxyl, or group of formula

. Claimed method includes reaction of pentavalent phosphorous acid chloroanhydride with glycydil methacrylate at 20-50°C in presence of titanium tetrachloride as catalyst in amount of 0.02-0.05 % calculated as reagent mass.

EFFECT: one-step method for production of phosphorous and chlorine containing methacrylates with improved water resistance.

2 tbl, 7 ex

Description

The invention relates to the chemistry of organophosphorus compounds, and in particular to a new method for producing phosphorus chlorine-containing methacrylates (FMAK) of the General formula

where R = lower alkyl, chloralkyl;

R ₁ = lower alkoxyl, phenoxyl or group

which can be used to obtain polymeric, including composite materials with reduced flammability.

A known method of producing (olefinically unsaturated acyloxy) haloalkoxy phosphorus compounds, which include (meth) acrylic derivatives of a number of phosphorus acids. These products are obtained by the interaction of acid chlorides of the corresponding phosphorus acids with unsaturated epoxycarboxylic esters, in particular with methacrylic acid glycidyl ether (GMAK) at a temperature of 25-125 ° C (preferably 50-70 ° C) in the presence of a number of metal halides, in particular tetrachloride, as catalysts titanium. The catalyst is taken in an amount of 0.15-3.00% by weight of the acid chloride of the corresponding phosphorus acid (i.e., ~ 0.06-1.00% of the total weight of the starting reagents in the case of using GMAK as the starting epoxy compound). To prevent premature radical polymerization, inhibitors of this process are added to the unsaturated epoxy compound. After the completion of the synthesis, a water washing of the obtained product from the catalyst is carried out, and then residual water is removed by vacuum distillation. [Pat. UK No. 769027, class C 07 f 9, publ. 1957; Pat. Germany 1050760, class 12o, publ. 1959].

In these patents there is no indication of the possibility of obtaining in this method phosphorus chlorine-containing methacrylates based on GMAA and acid chlorides of alkyl (chloroalkyl) phosphonic acids. Probably, due to the high reactivity of the latter, their interaction with GMAA under the above conditions is complicated by the formation of a significant amount of side (polymer) products. The disadvantages of the discussed method is the use of a relatively large amount of synthesis catalyst and the need for its water washing, which not only complicates the process, but should also lead to the loss of part of the target product.

A known method of producing FMAK by the interaction of acid chlorides of pentavalent phosphorus with GMAA when heated from room temperature to 50-60 ° C in the presence of dimethylformamide or hexamethylphosphoric triamide synthesis catalyst in an amount of 1-2% of the reaction mass [A.S. USSR No. 1205530, class C 07 f 9/40, publ. B.I. No. 18, 2000].

The disadvantages of this method is the use of a large number of synthesis catalysts, the relatively low water resistance of the products of curing (polymerization) of the obtained PMACs and the long-term retention of surface stickiness in the manufacture of fiberglass based on them. All this suggests the necessity of the stage of removal of synthesis catalysts from target products, which will complicate this process.

There is a method of producing phosphorus chlorine-containing methacrylates by the interaction of acid chlorides of pentavalent phosphorus with HMAA at a temperature of 30-50 ° C in the presence of β-methacryloyl-α-chloromethylethoxymethylamidomethylphosphonate synthesis catalyst in an amount of 2-5% by weight of the starting reagents [A.S. USSR No. 1254701, class C 07 f 9/09; 9/40, publ. B.I. No. 18, 2000]. This method of obtaining FMAK, as well as the previous one, requires the use of a sufficiently large amount of synthesis catalyst. The products of (co) polymerization of FMAK obtained by this method have not sufficiently high hardness and heat resistance, and the presence of a phosphamide catalyst structure in them can contribute to the formation of toxic cyanide compounds during heating and combustion.

Closest to the proposed invention is a method for producing phosphorus chlorine-containing methacrylates by the interaction of acid chlorides of pentavalent phosphorus with GMAA at 20-50 ° C in the presence of 0.3-1.5% by weight of reagents as a catalyst for the synthesis of methacrylate of chromium oxychloride [A.S. USSR No. 1389237, cl. C 07 f 9/113; 9/32; 9/40, publ. B.I. No. 18, 2000].

The disadvantages of this method are the use of a relatively large amount of synthesis catalyst, the complexity of the dosage of this initially solid substance, spreading out in air due to its high hygroscopicity, the long duration of the process of dissolution of chromium methacrylate in the starting acid chlorides. The products of (co) polymerization of FMAK obtained in the presence of this catalyst have insufficiently low water absorption. The ability of chromium oxychloride methacrylate to activate radical polymerization processes necessitates constant adjustment of the composition of standard redox initiating systems traditionally used for curing oligoester acrylates, unsaturated polyester resins and other industrial monomers and their compositions.

The objective of the invention is to develop a technologically advanced one-step method for the synthesis of phosphorus chlorine-containing methacrylates (FMAK) - derivatives of alkyl (chloralkyl) phosphonic acids, the products of (co) polymerization of which, obtained in the presence of traditionally used initiating systems, have reduced water absorption (i.e., increased water resistance).

The technical result is to simplify the method of obtaining these PMAC, reduce water absorption of their products (co) polymerization while maintaining the level of other characteristics.

This technical result is achieved in a new method for producing phosphorus-chlorinated methacrylates of the General formula

where R = lower alkyl, chloralkyl;

R ₁ = lower alkoxyl, phenoxyl or group

consisting in the interaction of the corresponding acid chlorides of pentavalent phosphorus with glycidyl ether of methacrylic acid at 20-50 ° C in the presence of a catalyst, moreover, titanium tetrachloride taken in an amount of 0.02-0.05% by weight of the reactants is used as a catalyst.

The essence of the method is the reaction of addition of the acid chloride of the corresponding alkyl (chloroalkyl) phosphonic acid to the epoxy group of methacrylic acid glycidyl ether in the presence of titanium tetrachloride as a catalyst.

The high reactivity of the alkyl (chloroalkyl) phosphonic acid chlorides makes it possible to easily obtain the target products - the corresponding phosphorus chlorine-containing methacrylates with a quantitative yield even at a titanium tetrachloride content of 0.02-0.05% by weight of the starting reagents and a temperature of 20-50 ° C. The use of amounts of catalyst below 0.02% of the mass. leads to a noticeable decrease in the speed of the process. The increase in catalyst content in excess of 0.05% of the mass. it is not advisable, since this leads to overheating of the reaction mass due to the high speed of the exothermic synthesis reaction and the appearance of polymerization products in it both in vinyl and in epoxy groups.

Titanium tetrachloride is a mobile, easily dosed liquid, highly soluble in the starting acid chlorides. The use of these very small amounts of catalyst allows to obtain the target products, on the one hand, with almost 100% yield, on the other hand, with a stable high polymerization ability, which makes it possible to use traditional redox initiating systems without additional adjustment of their standard formulations. Moreover, the target product is stable during storage for a long time (several years). (Co) polymerization of the obtained FMAK leads to the formation of polymer products with reduced water absorption and a sufficiently high level of other characteristics. The reduced water absorption of these (co) polymers is probably due to the absence of noticeable amounts of hydrophilic impurities (derivatives of chromium, titanium, dimethylformamide, etc.) in their composition.

The method is as follows.

In a three-necked reactor with a stirrer, a thermometer and a dropping funnel, the specified amounts of the acid chloride of the corresponding pentavalent phosphorus acid and synthesis catalyst, titanium tetrachloride, are placed. Then, the specified amount of methacrylic acid glycidyl ester is added from the dropping funnel to the resulting solution with stirring and the required starting temperature. The flow of GMAK in this case is regulated so that the temperature of the reaction mass is maintained at a given level. Upon completion of the addition of GMAA, the reaction mass is stirred for a certain time at the required temperature. The obtained target product (FMAK) is analyzed for the content of residual GMAA by gas-liquid chromatography, its density and refractive index are also determined.

The invention is illustrated by the following examples.

Example 1. Synthesis of di (1-methacryloxy-3-chloropropoxy-2-) methylphosphonate

.

.

=1,2615 г/см³ и

=1,4812, что соответствует литературным данным.To a solution of 0.021 g (0.02% by weight of the sum of the starting reagents) of titanium tetrachloride in 33.25 g (0.25 mol) of methylphosphonic acid dichloride with stirring at a temperature of + 35 ° С 71 g (0.5 mol) begin to be added. glycidyl ether of methacrylic acid so that the temperature of the reaction mass does not exceed + 50 ° C. After that, the mixture is stirred at this temperature for another 2 hours until the residual GMAA content is 0.23% of the mass. As a result, a target product having practically quantitative yield is obtained having

= 1.2615 g / cm ³ and

= 1.4812, which corresponds to literature data.

Example 2. Synthesis of di (1-methacryloxy-3-chloropropoxy-2-) methylphosphonate

=1,2612 г/см³ и

=1,4810.The process is carried out analogously to example 1, using 33.25 g (0.25 mol) of methylphosphonic dichloride and 71 g (0.5 mol) of glycidyl ester of methacrylic acid in the presence of 0.052 g (0.05% by weight of the total reagents) titanium tetrachloride at a temperature of 20-45 ° C. After adding the entire amount of GMAA, the reaction mixture is stirred for 1 hour at a temperature of + 45 ° C until the residual GMAA content is 0.15% of the mass. Get monomer with characteristics -

= 1.2612 g / cm ³ and

= 1.4810.

Example 3. Synthesis of di (1-methacryloxy-3-chloropropoxy-2-) methylphosphonate

=1,2614 г/см³ и

=1,4815.The process is carried out analogously to example 1, using 33.25 g (0.25 mol) of methylphosphonic acid dichloride and 71 g (0.5 mol) of glycidyl ester of methacrylic acid in the presence of 0.0365 g (0.035% by weight of the total reagents) titanium tetrachloride at a temperature of 20-45 ° C. After that, the reaction mass is stirred for another 1.5 hours at + 50 ° C until the content of unreacted GMAK is 0.18% of the mass. Get monomer with characteristics -

= 1.2614 g / cm ³ and

= 1.4815.

Example 4. Synthesis of di (1-methacryloxy-3-chloropropoxy-2-) chloromethylphosphonate

=1,3155 г/см³ и

=1,4908, что соответствует литературным данным.The process is carried out analogously to example 1, using 41.87 g (0.25 mol) of dichloride of chloromethylphosphonic acid and 71 g (0.5 mol) of glycidyl ester of methacrylic acid in the presence of 0.04 g (0.035% by weight of the total reagents) titanium tetrachloride at a temperature of 20-50 ° C. Upon completion of the addition of GMAA, the mass is stirred for another 1.75 hours at + 50 ° C until the content of residual GMAA is 0.20% of the mass. Receive in quantitative yield a product having the characteristics -

= 1.3155 g / cm ³ and

= 1.4908, which corresponds to literature data.

Example 5. Synthesis of (1-methacryloxy-3-chloropropoxy-2-) phenoxymethylphosphonate

=1,2432 г/см³ и

=1,508.To a solution of 0.067 g (0.04% by weight of the sum of the starting reagents) of titanium tetrachloride in 95.25 g (0.5 mol) of phenoxymethylphosphonic acid chlorohydride, with stirring at a temperature of + 25 ° C, 71 g (0.5 mol) begin to be added. glycidyl ether of methacrylic acid so that the temperature of the reaction mass does not exceed + 50 ° C. Then it is stirred for another 2 hours at a temperature of + 50 ° C. Get the monomer with a residual content of GMAK - 0.22% of the mass .;

= 1.2432 g / cm ³ and

= 1,508.

Example 6. Synthesis of (1-methacryloxy-3-chloropropoxy-2-) ethoxymethylphosphonate

=1,2096 г/см³ и

=1,4642, что соответствует литературным данным.The process is carried out analogously to example 5, using 71.25 g (0.5 mol) of ethoxymethylphosphonic acid chloride and 71 g (0.5 mol) of glycidyl ester of methacrylic acid in the presence of 0.043 g (0.03% by weight of the total reagents) titanium tetrachloride at a temperature of 20-50 ° C. After adding the entire amount of GMAA, the mass is stirred for 2 hours at a temperature of + 45-50 ° C until the residual GMAA content is 0.16% of the mass. Get the target product with the characteristics -

= 1.2096 g / cm ³ and

= 1.4642, which corresponds to literature data.

The characteristics of the proposed and known methods for producing phosphorus chlorine-containing methacrylates are presented in table 1 (paragraphs 1 and 2). This table also presents the data (p. 3) on the implementation of the proposed method for producing FMAK with the stage of water washing of the reaction mixture. These results indicate that there is no need for this stage of the process, since the yield of the obtained PMA is close to quantitative, and their characteristics and the properties of their polymerization products are practically unchanged.

Example 7. The results of radical copolymerization (curing) of phosphorus chlorine-containing methacrylates obtained in accordance with the description in Examples 1-6.

The synthesized FMAK copolymerized with industrial unsaturated polyester resin brand PN-609-21M in a mass ratio of 30:70, respectively. The process is carried out at a temperature of + 65 ° C for 3 hours in the presence of a redox system, mass. hours per 100 parts by weight the above composition FMAK - PN-609-21 M: cumene hydroperoxide (CCP) 4.0; cobalt naphthenate (NK) (16% solution in styrene) 5.0; organo manganese catalyst (IOC) -1.5. Get solid, glassy polymer products with water absorption values (+ 25 ° C) are given in table.2.

table 2
Water absorption of FMAK copolymers with unsaturated polyester resin PN-609-21M FMAK obtained in accordance with examples No. Water absorption of the cured compositions FMAK-PN-609-21M,% of the mass. for the specified number of days thirty 60 90 1 1.51 2.10 2,52 2 1.15 1.41 2.19 3 1.21 1,63 2.26 4 1.35 1.87 2.41 5 1.65 2,32 2.96 6 1.73 2.54 3.15

conclusions

1. The proposed method for the production of phosphorus-chlorinated methacrylates - derivatives of alkyl (chloralkyl) phosphonic acids - allows you to simplify the process while maintaining its one-stage and practically quantitative yield of the target products using much smaller amounts of catalyst.

2. The residual amount (0.02-0.05% by weight of reagents) used by the proposed method for the synthesis of PMAA titanium tetrachloride practically does not affect the polymerization activity of the final products and the main characteristics of their (co) polymers. Moreover, these copolymers have lower water absorption (see table. 2).

Claims (1)

The method of obtaining phosphorochlorine methacrylates of the General formula

where R is lower alkyl, chloralkyl; R ₁ is lower alkoxyl, phenoxyl or a group

consisting in the interaction of acid chlorides of pentavalent phosphorus with glycidyl ether of methacrylic acid at 20 ÷ 50 ° C in the presence of a catalyst, characterized in that titanium tetrachloride taken in an amount of 0.02 ÷ 0.05% by weight of the reactants is used as a catalyst.