CS227494B1 - Polymeric material with ester and acetal groups and and method of preparing same - Google Patents

Description

The present invention relates to polymeric materials having ester and acetal groups, copolymers thereof and processes for their preparation.

These polymeric materials have not yet been known. Similar polymers of compounds with amide and etetal groups, N- (2,2-dimethoxyethyl) acrylamide, are known which, however, are highly hydrophilic materials, which is undesirable for many applications.

The present invention relates to polymeric materials having ester and acetal groups of mol. masses of 1x10 ⁶ to 2x10 ⁶ , which contain repeating units of omega, omega-dialkoxyelkyl methacrylate of the formula I ch ₃ in the polymer chain

-CH-C-OR. ( ¹ ), ¹ /

COO-R-CH 2 wherein H is -CH 8 - or -CH 8 -CH 8 -, R 8 is methyl or ethyl, optionally in combination with repeating units derived from 2-hydroxyethyl methacrylate β / or ethylenedl methacrylate.

They are produced by polymerizing an omega, omege-dialkoxyalkylmethacrylate of formula II

STEED,

CH ₂ = C-C00-R-CH 2 (Π),

OR, wherein R e R, are as defined above, under free-radical solution polymerization conditions, or the compound of formula II is copolymerized with 2-hydroxyethyloethacrylate and / or ethylenedimethacrylate under suspension free-radical polymerization conditions.

The solution radical polymerization is carried out at a temperature of preferably 40 to 90 ° C, depending on the radical initiator used. As the initiator, for example, azoisobutyronitrile or benzoyl peroxide may be used. The solvents used are preferably toluene or dioxane.

The polymeric materials of the present invention can also be prepared by copolymerizing compounds of formula II with at least one free-radically polymerizable monomer under suspension free-radical polymerization conditions.

The free-radically polymerizable comonomer may be, for example, alkylene di-acrylates, alkylene-dimethylacrylates, divinylbenzene, hydroxyalkyl acrylate Si methacrylates, vinyl acetate and the like.

The suspension radical polymerization is preferably carried out in a water, cyclohexanol, dodecanol system.

The polymeric materials of the invention have a well-defined structure formed by units for the polymerization of the monomers used. Homopolymers are polymeric materials of low hydrophilicity and the ecelectric groups have a suitable distance from the polymer chain for carrying out modification reactions based on acetal group reactions. Choice of comonomer can influence their properties.

Spherical macroporous polymeric materials suitable, for example, as carriers of biologically active substances can be prepared by suspension radical copolymerization.

In the following, the invention is illustrated in more detail by way of examples.

Example)

Poles (2,2-diethoxyethyl methacrylate) (poly / DEEMA /)

A solution of DEEMA (4.382 g, 4.50 mL, 21.7 mmol) with azoisobutyronitrile (22.2 mg, 0.135 mmol) in absolute toluene (9.0 mL) was bubbled with nitrogen for 20 minutes in a screw cap and whisper polymerization vial and it was polymerized at 60.0 ° C for 4 hours with magnetic stirring. The cooled polymer solution was added dropwise with stirring to absolute petroleum ether (dist. Range 34-60 ° C, 300 mL), the emulsion was stirred for 1 hour and left overnight. The solvent layer was decanted, the residual oil was allowed to dry to a semi-solid, which was dissolved in absolute dioxane (50 mL) and the solution was added dropwise to water (1000 mL), the packaged precipitated polymer was finely sheared and further stirred for 1 hour. Then, water (1000 mL) was changed, stirred for 1 hour and left overnight. The polymer was dried for several days from reduced printing (130 Fa) over solid potassium hydroxide.

Yield 2.290 g (52 ") of soft, slightly sticky poles (PLATE). IR spectrum (film. Substance, cm ^-1): 1723 (C »0, 1376 (-CH _3), 1170, 1132, 1076 (C-0 aeetel). 'Η-MIR spectra (deuteriochloroform 58 ° C, beta)! 4.68 (t, J = 4.5Hz, H, CH), 3.96 (d, 2H, _COO-CH2-CH), 3.65 (m, * = 56Hz, 4H, O-CH ₂ -C), 1.89 (br s, W _{/ 2} = 24Hz, 2H, _C-CH2 -C), 1.22 (t, J = 7Hz, 6H, CH ^ CJ) 1.155 0.95 (br, s, br, s, 1: 3, W1 _/ 2-15Hz, 3H, CH-1C).

For C ₁₀ H ₁₆ O ₄ (202.27):

calculated: 59.38% C, 8.98% H;

Found: C, 59.44; H, 9.05.

(toluene) 197.10, (2-butanol) 370.10 ³ . Equilibrium swelling in water: 6.1% by weight gain. Solubilities (10 mg of polymer per 0.2 ml of absolute solvent): petroleum ether (43-60 ° C) - swellable (boiling), toluene - sol, chloroform - sol, ethanol - sol, dloxane - rozp. (viscous), acetone - sol, ethyl acetate - sol, pyridine sol. (yellowish solution), dimethylsulphoxide - swellable (at 100 ° C sol., exits by cooling), dimethylformamide - solubilized, water - insoluble (even at boiling), hexanethylphosphoric triamide - solubilized (slowly, viscous solution).

Example 2

Spherical copolymers of 2,2-diethoxyethyl methacrylate (DEEMA), 2-hydroxyethyl methacrylate (HEMA) and ethylenedimethacrylate (EBiA) (general regulation)

In a cylindrical reactor (47 mm ID) with a spherical bottom, the polymerization batch was bubbled with nitrogen for 20 minutes and agitated by an anchor-shaped agitator (agitator speed 580 rpm) polymerized at 60 ° C for 15 hours. The polymer slurry was decanted with ethanol 99% (2 x 100 mL), distilled water (5 x 100 mL), ethanol 99% (4 x 100 mL), the polymer was dried under successive depressurization and dried for several days under reduced pressure (13 Pa / min). 0.1 torr) at 35 ° C.

Example 3

DEEMA-HEMA-EDMA (3,0: 58,0: 39,0)

For the polymerization according to Example 2, the following batches were used: water (100 ml), polyvinylpyrrolidone wt. 360.10 ³ (1.00 g), DEEMA (0.41 g, 2.07 mmol), HEMA (7.90 g, 60.5 mmol), EDMA (5.31 g)

26.8 mmol), cyclohexanol (16.40 g); dodecanol (1.63 g) and azoisobutyronitrile (0.136 g,

0.828 mmol). Yield 10.20 g (75%) of DEEMA-HEMA-EDMA spherical terpolymer (3:58:39).

IR spectrum (potassium bromide, cm ^-1 ): 3520 (OH), 1728 (C = O), 1162, 1080, 1030 (CO). For 3.0% C ₁₀ H ₈ O ₄ (202.27); 58.0% CGH, ₀ O ₃ (130.15), and 39.0% Ο, θΗ, ^ (198.23):

calculated: 57.53% C, 7.54% H;

Found:% C, 57.72;% H, 7.77.

Specific surface area 38 m @ 2 / g. Ball size 71 to 193 µm.

Example 4

DEEMA-HEMA-EDMA torpolymer (12,2: 48,8: 39,0)

The polymerization of Example 2 was carried out using the following: water (100 ml), polyvinylpyrrolidone wt. 360.10 ³ (1.00 g), DEEMA (1.66 g, 8.20 mmol), HEMA (6.65 g, 51.1 mmol), EDMA (5.31 g)

26.8 mmol), cyclohexanol (16.4 g), dodecanol (1.63 g) and isoisobutyronitrile (0.136 g,

0.828 mmol). Yield 9.83 g (72%) of spherical brittle DEEMA-HEMA-EDMA polymer (12.2: 48.8: 39.0). IR spectrum (potassium bromide, cm ^-1 ): 3522 (OH), 1728 (C = O), 1160,

078, 1030 (C-0).

For 12.2% _of C ₁₀ H ₁₈ O ₄ (202.27) 48.8% _{CGH) 0} O ₃ (130.15) and 39.0% (198.23) Calculated: C 57.90%, H, 7.66;

Found: C, 57.65; H, 7.84.

Specific surface 5.1 m ² / g. Bead sizes 45 to 109 fxn.

Example 5

DEEMA-HEMA EDMA terpolymer (30.5: 30.5: 39.0)

The polymerization according to Example 2 was carried out using the batches: water (100 ml), polyvinylpyrrolidone m. 360, 0 ³ (1.00 g) deem (4.15 g, 20.5 mmol), HEMA (4.15 g, 31 9 mmol), EDMA (5.31 g,

26.8 mmol), cyclohexanol (14.4 g), dodecanol (3.6 g) and azoisobutyronitrile (0.136 g,

0.829 mmol). Yield 10.38 g (76%) of spherical brittle DEEMA-HEMA-EDMA polymer (30.5: 30.5: 39.0). IR spectrum (potassium bromide, cm ^-1 : 3,528 (OH), 1,726 (C = O), 1,160, 1,068, 1,030 (C-0), 1,132 (C-0 acetal)).

For 30.5% ₁₀ ^Η θ 'ΐ8 ° 4 ^{(202> 2} 7). 30.5% CgH, ^ (130.15) and 39.0% Ο, θΗ, ^ (198.23):

calculated: 58.63% C, 7.88% H;

Found: C, 57.95; H, 7.78.

Specific surface area, 0 m ² / g. Ball size 59 to 201

Example 6

DEEMA-EDMA copolymer (61,0: 39,0)

For the polymerization according to Example 2, the following batches were used: water (100 ml), polyvinylpyrrolidone wt. 360.10 ³ (1.00 g), DEEMA (8.30 g, 41.0 mmol), EDMA (5.31 g, 26.8 mmol), cyclohexanol (12.60 g), dodecanol (5.40 g) and azoisobutyronitrile (0.136 g, 0.828 mmol). Yield 9.78 g (72%) of spherical brittle DEEMA-EDMA polymer (61:39). IR spectrum (potassium bromide, cm ^-1 ): 1730 (C = O), 1162, 1068 (C-O), 1132 (C-O acetal).

For 61.0% C, _o H ₁₈ O ₄ (202.27), and 39.0 C _Q H ₄ O ₄ (198.23):

C, 59.86; H, 8.25.

Found:% C, 59.89;% H, 8.29.

Specific surface area 34 m ² / g. Bead size, 19 to 2.3 µm.

Example 7

Poly (3,3-diethoxypropyl methacrylate) (poly (DEPMA);)

A solution of 3,3-diethoxypropyl methyl acrylate (DEPMA) (1.500 g, 1.50 mL, 6.93 mmol) and aziosobutyronitrile (7.4 mg, 0.045 mmol) in absolute toluene (3.00 mL) was in a polymer ampoule with was purged with nitrogen through the screw cap and the whisper for 20 minutes and polymerized at 60 ° C for 8 hours from magnetic stirring.

The cooled solution was added dropwise with stirring to absolute petroleum ether (dist. Range 43-60 ° C, 200 ml), the emulsion was stirred for 1 hour and allowed to settle overnight. The solvent was decanted and absolute petroleum ether (200 ml) was added, stirred for 1 hour, allowed to settle, the solvent decanted and the residual oil dried under reduced pressure in a water pump. The residue was dissolved in absolute dioxane (13 ml), the solution was added dropwise to water (250 ml) with stirring, the precipitated and packed polymer was finely sheared and further stirred for 1 hour, the water was changed (250 ml) and stirred for 4 hours.

The polymer was dried from reduced printing (130 Pa over solid potassium hydroxide. Yield 0.680 g (45 soft, slightly tacky poly (DEPMA)). IR spectrum (film substance, em ^- ^):

729 (C = O), 1376 (CH3), 1175, 1112, 1062 (C-O acetal). @ 1 H NMR (CDCl3, 22 DEG C., .delta.): 4.63 (t, J = 5 Hz, 1H, CH), 4.05 (br s, W1 _{/ 2} = 23 Hz, 2H, COO-CS2 ₎ -CH),

3.61 (m, 1H-57Hz, 4H, O-CH3-CH2), 1.99; 1.95 (hr s-1 * _{) / 2} = 6Hz, W1 _{/ 2} = 10Hz, 2 + 2H, CHg _{CH-CH₂-C-CH2} -C), 1.22 (t, J = 5, 4 Hz, 6H, CHyCHg), 1.08; 0.92 (s; s, 1: 3, W _{) / 2} = 11 Hz, 3H, CH 3 C).

For C 11 H ₂₀ O ₄ (216.30):

calculated:

nelezeno:

61.09% C, 61.08% C,

9.33% H; 9.24% H.

(Toluene) 280 10 ³ Bw dimethylformamide) 286.10. Equilibrium swelling in water: 5.6% weight gain. Solubilities (10 mg of polymer per 0.2 ml of absolute solvent): petroleum ether (dist. Range 43-60 ° C) - swollen (also at 40 ° C), toluene - sol, chloroform - sol, ethanol - sol, dioxane - sol., acetone - sol., ethyl acetate - sol., pyridine - sol., dimethylsulfoxide - insoluble at 100 ° C sol., cooling off), dimethylformamide sol., water - sol. (boiling), hexymethylphosphoric triamide - diss.

Example 8

Spherical copolymers of 3,3-diethoxypropyl methacrylate (DEPMA), 2-hydroxyethyl methacrylate (HEMA) with ethylenedimethacrylate (EDMA) - general rule

The polymers were prepared analogously to Example 2. Stirrer speed 200 rpm.

Example 9

DEPMA-HEMA-EDMA terpolymer (12.2: 48.8: 39.0)

The polymerization of Example 8 was carried out using the following ingredients: water (100 ml), polyvinylpyrrolidone wt. 360.10 ³ (1.00 g). DEPMA (1.66 g, 7.7 mmol), HEMA (6.65 g, 51.1 mmol), EDMA (5.31 g,

26.8 mmol), cyclohexanol (14.40 g), dodecenol (3.60 g), azoisobutyronitrile (0.136 g,

0.828 mmol). Yield 10.056 g (74%) of DEPMA-HEMA-EDMA spherical terpolymer (12.2: 48.8: 39.0). IR spectrum (potassium bromide, cm ^-1 ): 3440 (OH), 1724 (C = O), 1163, 1081, 1030 (C-O).

For 12.2% C 11 H ₂₀ O ₄ (216.30), 48.8% C 8 H ₁₃ (130.15) and 39.0% Ο, θ, ₄ 0 ₄ (198.23) calculated: 58 H, 7.70; found: 58.13% C, 7.83% H.

Specific surface area 46 m ² / g. Bead size 29 to 90 µm.

Example 10

DEPMA-HEMA-EDMA terpolymer (30.5: 30.5: 39.0)

The polymerization of Example 8 was carried out using the following: water (100 mL), DEPMA (4.15 g, 19.2 mmol), HEMA (4.15 g, 31.9 mmol), EDMA (5.31 g, 26%), 8 mmol), cyclohexanol (12.60 g), dodecenol (5.40 g), azoisobutyronitrile (0.136 g, 0.828 mmol). Yield 7.553 g (55%) of DEPMA-HEMA-EDMA spherical terpolymer (30.5: 30.5: 39.0). IR spectrum (potassium bromide, cm ^-1 ): 3340 (OH), 1724 (C = O), 1153, 1058 (CO).

For 30.5% of ^_θ υ Η 20 O4 (216.30) 30.5% * CGH ^ O (130, 15), 39.0% β Ο, θΗ (198.23) calculated: 59.15% C, 7.99% Η;

Found: C, 58.57; H, 7.13.

Specific surface area 34 m ^ / g, Bead size 62,137 µm.

Example II

DEPMA-EDMA copolymer (61,0: 39,0)

The polymerization of Example 8 was carried out using water (100 mL), DEPMA (8.30 g, 38.4 mmol), EDMA (5.31 g, 26.8 mmol), cyclohexanol (9.00 g), dodecanol ( 9.00 g), azoisobutyronitrile (0.136 g, 0.828 mmol). Yield 10.186 g (75%) of the spherical DEPMA-EDMA copolymer (61:39).

IR spectrum (KBr, cm ^- '): 1724 (C = 0), 1162, 1059 (CO), 1128 (C-0 acetal).

For 61.0% C 11 H ₂₀ O ₄ (216.30j and 39.0% C ₁₃ H ₁₁ O 2 (198.23):

calculated: 60.89% C 8.47% H;

found: 61.03 «C, 8.75% H.

Specific surface area 11 m / g. Ball size 62-143 µm.

Claims (2)

SUBJECT OF THE INVENTION Polymeric materials having ester and acetal groups having a molecular weight of 1 x 10 @ -1: 2 * 10 @ 2 containing omega, omega-dialkoxyalkyl methacrylate repeating units of the formula I in the polymer chain CH ₂ -cOR, (I), COO-R-CH OR wherein R is -CH ₂ - or -CH ₂ -CH ₂ - and R 1 is methyl or ethyl, optionally in combination with repeating units derived from 2-hydroxyethyl methacrylate β / or ethylenedimethacrylate. 2. A process for the production of polymeric materials as claimed in claim 1, characterized in that an omega, omega-dalkalkoxyalkyl methacrylate of the formula II is polymerized. OR ch ₂ = c-coo-r-ch (II), CH ₃ OR, where R and R, are as defined above under free-radical solution polymerization conditions, or the compound of formula II is copolymerized with 2-hydroxyethyl methacrylate β / or ethylenedimethacrylate under suspension free-radical polymerization conditions.