SU611911A1 - Poly(ester-alkyleneoxide)block copolymers as antistatic materials and additives and method of obtaining same - Google Patents

Description

the temporary introduction of phenol into a mixture of phenol and a polysplate, which leads to a v. This is an example of statistical bpo copolymers with relatively low molecular weights. This method of synthesis does not allow rbgly-alternating block copolymers. Hadrophilic polymers (urethanalkylene oxide) and poly (ethylene terephthalate and enoxide) block copolymers are also known. exhibiting antistatic properties 2, 3. However, due to the incompatibility of these copolymers with many polymeric laterals that are commercially available today, their use as heat-resistant antistatic coatings and additives is very limited. The best results are achieved when the hard block of the copolymer (polyurethane, polyethylene terephthalate) is compatible with the homopolymer undergoing ash processing. In particular, poly (ztileshvreftalat-etsh1enoksidnye) block copolymers find wide primenesh for antistatic poliechileigereftalatno Lavsan of fiber 14. In the last decade, extensive use in the electronics, instrument-making and elektrotehnicheosoy promshsheshyusti acquired new structural materials: solid, stable termoi himikasi poliarilensulfonoksida (polysulfones ) and polyarylates having excellent electrical insulating properties. However, due to the high dielectric properties of polysulfones and polyarylates, electric charges are accumulated on their surfaces due to friction or the breaking of contact between the polymer and conductors or dielectrics, which is often a very undesirable phenomenon. In this regard, there is the problem of high-quality antistatic processing of these materials. The aim of the invention is the synthesis of poly (alkylene oxide ether) block copolymers which can be used as antistatic materials and additives for polysulfones and polyarylates. In accordance with the invention, a method for producing poly (ether-alkylene oxide) block copolymers consists in that oligo-alkylene oxides, containing terminal hydroxyl groups, are reacted with dacarboxylic dichloride hydride with a subsequent polycondensation of leacrodlorohydride, d-chloroacid hydride, with the addition of docarboxylic acid by digesting with lyricrodlorohydride, dycarboxylic acid by dichloroacid, with the addition of docarboxylic acid; , СН, Г1 Кр-С- | -с-, СН, in 1-20 in the presence of trmethylamigy at 15-20 ° С. The block copoly of the esters occurs in the medium of 1,2-dichloroethane at 15-20 ° С in acceptor conditions shticheskoy condensation. In the role of an acceptor catalyst, tertiary amines, in particular, triztilakos, can be used. The presence of a significant area aliphatic and aromatic esters have led to the following two-step scheme for the preparation of poly dnyh) block copolymers: a) gradually introducing oligozlkilenoksida solution and an equimolar amount of a solution trietilaMfflia odnomol molar excess dichloro) diosarbonovoy acid anhydride to give rise to the formation makrodihlorangadrida b) introducing aromatic dazirovannoe solution; and oligoether and an equimolar amount of triethylamine in the solution of the obtained macrodichloride. The properties of poly (ester-alkylene oxide) block copolymers can be purposefully varied over a wide range by changing the molecular weight, on the one hand, of polyethylene oxide and, on the other hand, polysulfone or polyarylate blocks. The structure of the synthesized block-cellulimers was confirmed by high yields close to the theoretical, as well as by various analytical methods: IR and NMR ectroscopy, elemental analysis. Try on Synthesis of SEO-2 To a 250-ml three-necked flask equipped with a mechanical millicle and tubes for inlet and outlet of dry argon, 1,854 g (0.00912 mol) of terephthalic acid dichloride and 10 ml of 1,2-dichloroethane are charged. To the resulting solution from a dropping funnel, a solution of 13.696 g (0.00457 mol) of oligo-ethyleneoxide from mole is noshepically added dropwise. 3000 (x 68) and 1.72 ml (0.00912 M) of T1-ethylamine in 40 ml of 1,2-dichloroethane. Then, a solution of 21.0 g (0.00456 mol) of oligosulfone is squeezed from the other dropping funnel to the resulting solution of macrodisysoperations. based on 4,4dkoksidnofensh | -2,2-propane and 4,4-dichlorodiphenylsulfone with a molecular weight of 4600 () and 1.72 ml (0.00912 M) of triethylamine in 60 ml of 1,2-dichloroethane. The reaction is continued for 2 hours, then the reaction mass is diluted with chloroform to 600 ml and the polymer is precipitated in sulfuric ether. (Here and in the following examples, petroleum ether and other aliphatic and cycloaliphatic hydrocarbons can also be used as a precipitant). The precipitated precipitate is filtered off, and the precipitates are dried and removed with water from hydrochloric triethyl amine. The output of the block copolymer of 34.8 g or 9% of theoretical. The reduced viscosity of its EO, 5% solution in tetrachloroethane at 25 ° С is 0.86 dp / g. . 71,000 (). EXAMPLE 2. Synthesis of SEO-3 A 75 ml three-necked flask was charged with 0.265 g (0.0013 mol) of terephthalic acid dichlorohydride and 3 ml of 1,2-dichloroethane. To the solution obtained, a solution of 0.652 g (0.000625 mol) of oligoE1ilen (W (I1da with mol. In. 1000 () and 0.18 ml (0.0013 mol) of triethylamine in 4 ml of 1,2-dichloroethane. Then, a solution of 3.0 g (0.000625 mol) of oligosulfone with a molar concentration of 4600 () and 0.18 ml (0.0013 mol) of triethylamine in 12 ml of 1,2- is added to the resulting solution of macrodichloroanhydrin from another drip {funnel). dichloroethane. 1 share is continued for 2 hours, then the reaction mass is diluted with chloroform to 100 ml and precipitated with polymer in sulfuric ether. The precipitated precipitate is filtered, dried 1 (and vodish from triethylamine hydrochloride; block copolymer yield 3.5 g or 96% of the theoretical one. The reduced viscosity of its 0.59 & solution in tetrachloroethane at 25 ° C is 0.5 dl / g. Mol.v. ) Oppes SEO-5 A 75 ml three-neck bottle of 75 ml is loaded with 0.135 g (0.00066 mol) of terephthalic acid dichlorogens and 3 ml of 1,2-dnloro-etag. To a solution obtained from dropping Voroshsi papyvak solution of 0.994 g (0, 00033 mol) oligoethylene oxide smol.V. 3000 () IO, 10mp (0.00066 mol) t of ethylamine in 4 mp of 1,2-dichloroethane. Then, a solution of 3.0 g (0.00033 mol) of oligosulfone and mol. at. 9050 () and 0.10 ml (0.00066 mol of methylamine in 11 MP of 1,2-dichloroethane. The reaction is continued for 2 hours, then the reaction mass is diluted with chloroform to 150 ml and the polymer is precipitated in sulfuric ether. The precipitate is filtered off , dried and washed with triethylamine hydrochloride with water.The yield of the block copolymer is 4.6 g or 96% of the theoretical.The reduced viscosity of its 0.5% solution in tetrachloroethane at 0.50 ° C is 0.60 dp / g Mol. V. 58000 (). PRI me R 4. Ontez SEO-6 In a three-neck flask per 75 ml load 0.338 g (0.001666 mol) of terephthalic acid dichlorohydride and 4 ml of 1,2-dichloro ana. To the resulting solution, a solution of 2.5 g (0.000833 mol) of oligoethylene oxide, mol 3000 () and 23 ml (0.001666 mol) of triethylamine in 1 ml of 1,2-dichloroethane, is added dropwise from a dropping funnel. A solution of 2 g (0.000833 mol) of oligosulfone with a molecular weight of 2400 () and 0.23 mp (0.001666 mol) of triethylamine in 8 ml of 1,2-dichloroethane is added to the resulting solution of macrodichlorohydride from another dropping funnel. The reaction is continued for 2 hours, then the reaction mass is diluted with chloroform to 200 ml and the polymer is precipitated in sulfuric ether. The precipitated precipitate is filtered off, dried and washed with water from triethylamine hydrochloride. The output of the block copolymer of 4.4 g or 94% of theoretical. The reduced viscosity of its 0.5% solution in tetrachloroethane at 25 ° С is 0.84 dl / g. Mol at. 68000 (). EXAMPLE 5. OSTEZ-7. A 75 ml three-neck flask is charged with 0.406 g (0.002 mol) of terephthalic acid dichloride and 4 ml of 1,2-dichloroethane. To the solution obtained from a dropping funnel, a solution of 3.0 g (0.001 mol) of oligoethylenssss and mol. at. 3000 () and 0.20 mp (0.002 mol) of trtetilamine. Then, to the solution of the formed macrodichlorakgid {I1da from rruss. dropping funnel protolay solution of 1.5 g (0.001 mol) of oligosulfone mol. at. 1500 () and 0.20 ml (0.002 mol) of triethylamine in 6 ml of 1,2-dachloroethane. The reaction is continued for 2 hours, then the suspended mass is diluted with chloroform to 100 ml and the polymer is precipitated in sulfuric ether. The precipitate formed is filtered off, dried and taken up with water and triethylamine hydrochloride. The output of the block copolymer is 4.5 g or 95% of theoretical. The reduced viscosity of its 0.59 & h solution in carbon tetrachloride at 25 ° C is 0.50 dl / g. Mol at. 24,000 (). Example 6: Synthesis of SEO-9 A 100 ml three-neck flask was added 0.6 24 g (0.00308 mol) of terephthalic acid dichloride and 5 ml of 1,2-dichloroethane. A solution of 1.54 g (0.00154 mol) of molar oligoethyleoxide is added to the solution obtained from the dropping funnel. 1000 () and 0.43 ml (0.00308 mol) of triztilamine in 6 ml of 1,2-dichloroethane. Then, a solution of 0.92 g (0.00154 mol) of oligosulfine based on 4.4 diox difesxoxda and 4.4 dkhlorodiphenylsulfone with MOL.V is added dropwise to a yoluchenous solution of macrodichlorohydrin from each other dropping funnel. 598 () and 0.43 ml of triethylamine in 3 ml of 1,2-dichloroethane. The reaction is continued for another 2 hours, then the reaction mixture is diluted with chloroform to 80 ml and the polymer precipitated with sulfuric ether. The precipitated precipitate is filtered off, suspended and removed from the hydrochloric acid triethylamine with water. The output of block copolymers 2.76 g or 96.5% of the theoretical. The reduced viscosity of its 0.5% pacTBoja in tetrachloroethane at 25 ° С is 0.86 dl / g. Mol at. 6SOOO (). Example. Oitez LEO-1 In a three-neck flask of 100 ml load 0.0677 g (0.00033 mol) of terephthalic acid dichloroiadride and 1 ml of 1,2-dichloroethane. A solution of 2.5 g (0.000167 mol) of oligoethylene oxide and mol% is dropped to a solution from a dropping funnel. at. 15000 () and 0.047 ml (0, SOUZZ mol) of triethyl aldane in 8 ml of 1,2-dichloroethane. Then, a solution of 1.6 g (0.000167 mole) of oligoarylate and mole was added dropwise to a solution of the resulting macrodaccharide from the other dropping funnel. at. 9600 () based on phenolphthalein and terephthalic acid dichloride and 0.047 ml (0.00033 mol) of triethylamine B 10 ml of 1,2-dichloroethane. The casting is continued for 2 hours. The reaction mixture is diluted with chloroform to 90 ml and the polymer is precipitated in sulfuric ether. The precipitated precipitated filter is drained, podsushivayut and washed with water from hydrochloric triztilamine. The output of the block-copolymer 3.3 g or 80% of theoretical. The reduced viscosity of its 0.5% solution in techlochloroethane at 25 ° С is 1.26 da / g. Mol at. 148,000 (). Example 8. Synthesis of AZO-4 A 150 ml three-neck flask is charged with 0.203 g (0.001 mol) of terephthalic acid dichloride and 1 ml of 1,2-dichloroethane. To the solution obtained from a dropping funnel, a solution of 3.0 g (0.0005 mol) of oligosthylene oxide with mol. at. 6000 () and 0.14 ml (0.001 mol) of triethylamine in 8 ml of 1,2-dichloroethane. Then, a solution of 2.4 g of 0.0005 mol of a-polyoarylate mol and mol of droplets was added dropwise to a solution of the formed macrodichlorohydrin from another dropping funnel. at. 4800 () oligoarilata based on phenolphthalene and dichlorohydrin terephthalic acid and 0.14 MP (0.001 mol) of triethylamine in 15 ml of 1,2-dichloroethane. The reaction is continued for 2 hours, then the reaction mixture is diluted with chloroform to 120 mt and the polymer is precipitated in sulfuric ether. The deposited precipitate is filtered, dried and washed off with water from hydrochloric triethylamine. The output of the block copolymer of 5.5 g or 97.7% of theoretical. The reduced viscosity of its 0.5% solution in tetrachloroethane at 25 ° С is equal to 1.92 dl / g. Mol at. FTAA (). PRI me R 9. Using AEO-6 In a three-neck flask per 100 ml, 0.406 g (0.002 mol) of terephthalic acid dichloride are loaded into 2 ml of 1,2-dichloroethane. A solution of 1.0 g (0.001 mol) of oligo-ethylene oxide with mol. at. 1000 () And 0.28 ml (0.002 mol) of triethylamine in 2 ml of 1,2-dichloroethane. Then, a solution of 2.4 g (0.001 mol) of oligoa {phenolphthalein-based dichloride and hydrochloride acid of molar acid is added to a solution of the formed macrodichlorohydrin from another dropping funnel. at. 2400 (5) and 0.28 ml (0.002 mol) of triethylamine in 15 ml of 1,2-dichloroethane. The reaction is continued for 2 hours, then the reaction mixture is diluted with chloroform to 100 ml and the polymer is precipitated in sulfuric ether. The precipitated precipitate is filtered off, dried and richer from triacium hydrochloride; imine. The output of the block copolymer of 3.7 g or 98.8% of theoretical. The reduced viscosity of its 0.5% solution in tetrachloroethane at 25 ° С is 1.14 dl / g. Mol at. 143,000 (). Example 10. Synthesis of AEO-B In a three-neck flask per 100 ml, 0.558 g (0.002 mol), diphenyl dicarboxylic acid dichloride and 2 ml of 1,2-dichloroethane are introduced. A solution of 2.0 g (0.001 mol) of oligo-ethylene oxide with mol. at. 2000 () and 0.28 ml (0.002 mol) of triethylamine in 4 ml of 1,2-dichloroethane. Then, a solution of 5.9 g (0.001 mol) of oligoarylate based on 9.9-bis (4-oxhphenyl) -fluorerene and di-chloro-di-di-dicarboxylic acid dichloroacid is added to the obtained solution of macrodichlorohydride from another dropping funnel. at. 5900 () and 0.28 ml (0.002 mol) of triethylamine in 25 ml of 1,2 dichloroethane. The reaction is continued for another 2 hours, then the reaction mixture is diluted with chloroform to 100 ml and the polymer is precipitated in sulfuric ether. The deposited precipitate is filtered, dried and washed off with water from hydrochloride triethylamine. The output of the block copolymer of 8.1 g or 97.5% of theoretical. The reduced viscosity of its 0.5% solution in tetrachloroethane at 25 ° С is 1.12 dl / g. Mol at. 92000 (). P p and h. e 11. Synthesis of AEO-9 To a three-neck flask per 100 ml, 0.406 g (0.002 mol) of isophthalic acid dichloride and 2 ml of 1,2-dichloroethane are introduced. A solution of 6.0 g (0.001 mol) of ethylene ethylene chloride with mol. at. 6000 (x 136) and 0.28 ml (0.002 mol) of triethylamine in 12 ml of 1,2-dichloroethane. Then, a solution of 3.8 g (0.001 mol) of oligoarylate based on 4 Lioxidiphene 1-2, 2-propane dichlorohydride of isophthalic acid with mol.% Is added to the obtained solution of macrodichloroanhydride from another dropping funnel. at. 3800 () and 0.28 ml (0.002 mol) of triethylamine in 20 ml of 1,2-dichloroethane. Rhakia was continued for another 2 hours, then the reaction mixture was diluted with chloroform to 90 ml and the polymer precipitated in sulfuric ether. The precipitate formed is filtered off, dried and washed with water from triethylamine hydrochloride. The output of the block copolymer of 9.5 g or 94% of theoretical. The reduced viscosity of its 0.5% solution in tetrachloroethane at 25 ° С is 0.93 dl / g. Mol at. 60,000 (). Example 12 Synthesis of AEO-10 A 75 ml three-neck flask was added 0.46 g (0.002 mol) of terephthalic acid dichloride and 2 ml of 1,2-ichloroethane. A solution of 0.9 g (0.001 mol) of butylene glycol and mol. at. 90 (); and 0.28 ml (0.002 mol) of triztilamine in 2 ml of 1,2-dichloroethane. Then, a solution of 2.6 g (0.001 moles) of methyl phenyl-4,4-dioxydiphenylmethane oligoarylate oligoarylate and acylchloride {I1da terephthalic acid, mol.%) Is added to the resulting solution of macrodichloroanhydride from another dropping funnel. at. 2600 () and 0.28 ml (0.002 mol) of triethylamine in 8 ml of 1,2-dichloro-ethylate. The reaction is continued for another 2 hours, then the reactive CNffiCb is diluted with chloroform to 60 ml and the polymer is precipitated in sulfuric acid. The precipitates that are deposited are filtered, dried, and washed away from tristilamine hydrochloride. The output of the block copolymer of 2.8 g or 93i5% of theoretical. The givedened viscosity of its 0.5% solution in tetrachloroethane at 25 0.87 dl / g. Mol at. 61,000 (). Example 13: Synthesis of AEO-11 Into a three-neck flask per 100 ml, 0.46 g (0.002 mol) of terephthalic acid dichloride and 2 MP of 1,2-dichloroethane are introduced. To the resulting solution from a droplet of the funnel, add a jiacTHop 2.0 g (0.001 mop) about the ioprogipoensa 1 mol. 2000 () and 0.28 ml (0.002 mol) of T1zhetilsmin in 4 ml of 1,2-dichloroethane. Then, a solution of 2.4 g (0.001 mol of phenolphthalein-based oligoarylate and terephthalic acid dichlorohydride (mol) in 2400 () and 0.28 ml (0.002 mol) of triethylamine in 15 ml 1 is added dropwise to the educational solution of lacrodichloroanhydride from another droplet Voropole and 1, 2-dichloroethane. 1 action is continued for another 2 hours, the reaction mixture is then diluted with chloroform to 80 ml and the polymer is precipitated in sulfuric sulfur. The precipitate is filtered off, dried and washed off with water from hydrochloric triethylamine. The yield of 4.4 g is 4.4 g. or 95% of theoretical. Given in The viscosity of its 0.5% solution in tetrachloroethane at 25 ° С is 0.94 dl / g, mol 72.6000 (). The synthesized block copolymers have high strength properties, which is very important for high molecular weight antistatic agents with film forming properties. Such block copolymer antistatic agents are compatible with polysulfones and polyarylates, which will ensure high reliability of coatings in mechanical wear. In addition, the compatibility of antistatic agents with polymers will leave the color and optical appearance of the latter unchanged. In tab. 1 shows the physico-mechanical properties of the synthesized poly (ether-alkypenoxidic) bls with copoly.

Continued table. I

a) SEA is a poly (sulfon-ethylene oxide) block copolymer; AEO is a poly (arylag-ethylene oxide) block copolymer;

b) X and Y - the number of elementary units (degree of polymerization) in the aliphatic and aromatic oligoester, respectively;

c) reduced viscosity with a 0.5% solution in tetrachloroethane at 25 C.

The introduction of high molecular antistatic agents as additives to polymers excludes their migration to the surface and thus makes the antischatical properties of plastics unchanged in time. An important factor is the high temperature resistance of poly (sulfonyl-alkylene carbon) and poly (arylate-alkylene oxide) block copolymers, 35

 4,4-dioxydiphenyl-2,2-propane and 4,4-dichloride) 1-phenylsulfone; n Phenolphthalein-based polyarylate and terephthalic acid dichlorohydrin. The electrical properties of the samples of poly (sulfone-ethylene oxide) and popy (arylate-ethylene oxide) block-cc olymers presented in Table 2,

as surfactants commonly used as antistatic agents reduce the thermal stability of polymers. These block copolymers will withstand the temperatures at which they process polysulfones and polyarylates (300-360 ° C). Vtabl; 2 shows the electrical properties of the webs made of poly (ether ethenylene oxide) block copolymers.

Table 2 shows that they can be considered as antistatic with good (/ O, 10th) efficiency (5.