DE1595381C3 - - Google Patents

Description

T>

R ₅

in which R ₁ to R _{5 represent} hydrogen atoms, aliphatic or cycloaliphatic, aromatic or heterocyclic radicals, but at least two radicals hydrogen atoms, polymerized in the presence of cationic catalysts at temperatures between 120 and 200 ⁰ C, according to Patent 1206 585, characterized in that mixtures polymerized various Δ ² -oxazolines of the above general formula, one of which contains as radical R ₁ an alkyl radical with 1 to 17 carbon atoms which carries one or more chlorine or bromine atoms in the α-position, and where the molar ratio of the halogen-free Δ ² - Oxazoline to the halogen-containing / J ² -oxazoline is between 99.9: 1 and 80:20.

The subject of patent 1 206 585 is a process for the polymerization of Δ ² -oxazolines to give high molecular weight, nitrogen-containing, linear polymers, one being uniform A ² -oxazolines of the general formula

-N

R ₄

R ₅

CR ₁

in which R ₁ to R _{5 are} hydrogen atoms, aliphatic or cycloaliphatic, aromatic or heterocyclic radicals, but at least two radicals are hydrogen atoms represent, cation-active in the presence of catalysts at temperatures between 120 and 200 ⁰ C polymerized.

From Acta Chim. Hung., Tomus 19, pp. 1 ff. (1959), in connection with J. Gen. Chem. USSR, 31, 3382 ff. (1961), it is known that Δ ² -oxazolines can be polymerized at low temperatures . However, it can be seen from the publications that only low molecular weight products (K value = 20) can be obtained. A copolymerization of different zl ² -oxazolines is not described.

It has now been found that this process can be further developed by polymerizing mixtures of different /! ^ Oxazolines of the above general formula, one of which contains an alkyl radical with 1 to 17 carbon atoms _{as the radical R 1, one or more in the α-position} Bears chlorine or bromine atoms, and the molar ratio of the halogen-free Zl ² -oxazolines to the halogen-containing zd ² -oxazoline is between 99.9: 1 and 80:20.
Oxazolines suitable for copolymerization are, for. B.

2-chloro-methyl-zl ² -oxazoline,

2-trichloromethyl-2l ² -oxazoline,

2- (a-chloroethyl) -Zl ² -oxazoline,

2- (a, a-dichloroethyl) - / l ² -oxazoline,

2- (a-chloro-n-propyl) -zl ² -oxazoline,

2- (a-dichloro-n-propyl) -zl ² -oxazoline,

2- (a-chloro-iso-propyl) -zl ² -oxazoline,

2 - («- chlorine-n-pentyl) -zl ² -oxazoline,

2- (a, a-dichloro-n-pentyl) -, d ² -oxazoline,

2- (a-chloro-n-undecyl) -zl ² -oxazoline,

2- (a, a-dichloro-n-undecyl) -Zl ² -oxazoline,

2 - («- chlorine-n-pentadecyl) -zJ ² -oxazoline,
_ao 2- (a, a-dichloro-n-pentadecyl) -Zl ² -oxazoline,

2- (a-chloro-n-heptadecyl) -zl ² -oxazoline,

2 - («, a-dichloro-n-heptadecyl) - <d ² -oxazoline,

2-tribromomethyl-Zl ² -oxazoline,

2 - («,« - dibromoethyl) -zl ² -oxazoline,
_a 2- (a, a-dibromo-n-propyl) -zl ² -oxazoline,

2- (a, a-dibromo-n-undecyl) -zl ² -oxazoline and

2- (a, «- dibromo-n-heptadecyl) -zl ² -oxazoline.

The mixtures used for the polymerization can consist of two or more Δ ² -oxazolines, but two Δ ² -oxazolines are preferably used. The molar ratio of the halogen-free Δ ² -oxazolines to the halogen-containing Δ ² -oxazoline is between 99.9: 0.1 and 80:20.

To carry out the polymerization, the monomers are polymerized Δ ² -oxazolines at temperatures between 0 and 12O ⁰ C, preferably at room temperature, mixed together and the mixture as described in the main Patent manner in the presence of cation-active catalysts. Catalysts such as those described in the additional application P 12 15 930.7-44 can also be used.

The polymerization is generally in the absence carried out by solvents. However, the polymerization can also be carried out as a solution polymerization perform, using inert solvents with boiling points at or above the desired Polymerization temperature, such as. B. toluene or xylene can be used.

The copolymers produced according to the invention are suitable for producing films, foils and coatings; Because of their thermoplastic character, they can be used as casting resins or for the production of injection molded articles. The copolymers prepared according to the invention are distinguished from the halogen-free polyoxazolines in that they contain easily substitutable halogen radicals; Due to this, they can be remunerated in the course of their processing by post-curing with suitable compounds. Furthermore, the drawing produced according to the invention, halogen-containing copolymers with respect to the halogen-free PoIyzl ² oxazolines by their increased adhesive strength to metals, z. B. iron, zinc and aluminum. In addition, the halogen-containing copolymers are more difficult to ignite than the halogen-free poly- Δ ² -oxazolines. Therefore, they can optionally be mixed with other known flame-retardant substances, such as. B. Chlorinated paraffins

3 4

or antimony trioxide to increase the flame retardancy - Example 4

ability to be added to other polymers. For many

Purposes, those copolymers proved to be 80.76 parts by weight of 2-methyl-zJ ² -oxazoline, 6.67 parts

particularly suitable for those in the halogen-containing and parts by weight 2 - («- chloroethyl) -Zl ² -oxazoline (molar ratio-

in the halogen-free Zl ² -oxazoline the radicals R ₂ to R ₅ 5 to 95: 5) and 0.417 parts by weight of 1,4-phenylene-bis-

Are hydrogen atoms. (2-oxazolinium) diperchlorate are produced at room temperature

Compared to the known measures of the prior art mixed temperature and with initial stirring of the technology, it is surprising that heated to 125 to 130 ° C for 3 hours. Subsequent processes according to the invention thermoplastic masses are obtained for 3 hours at 150 ° C. and a high K value, which can be processed according to known processes for 15 hours at 170 ° C. (oil bath temperatures). Still heated. The polymer product is, as in Example 1, unexpectedly, the possibility is described at high temperatures, worked up. The reduced specific doors to be able to work without the liquid, low viscosity of the reprecipitated product being 0.16, molecular products being obtained. At the same strength measure chloroform solution in 0.5% at 25 ⁰ C. The method of the invention offers the possibility 15 The chlorine content is 1.89%.
ability, products with different molecular weights. .
To manufacture weights. Example 5

. . 94.12 parts by weight of 2-ethyl-zl ² -oxazoline, 6.68 Ge

^ßeis P ^{ie11 parts by} weight 2 - (<x-chloroethyl) -Zl ² -oxazoline, (molar

76.50 parts by weight of 2-methyl-zl ² -oxazoline, 11.96 parts by weight of 95: 5) and 0.209 parts by weight of 1,4-phenylene 2-chloromethyl-zl ² -oxazoline (molar ratio of bis (2-oxazolinium) diperchlorate are mixed at room-90: 10) and 0.417 parts by weight of 1,4-phenylene-bis-temperature and with stirring by means of heating (2-oxazolinium) -diperchlorate are mixed at room temperature and cooling bath for 1 hour at 135 ° C (internal temperature and initially kept at 120 ° C., temperature) with stirring. The mixture is then heated slowly increasing to 35 ° C. (oil bath temperature) for a further 20 hours over the course of one hour. The poly-140 ° C is heated. Subsequently merprodukt is without agitation, as described in Example 1, placed for 4 hours long operates to 14O ⁰ C and 20 hours. The reduced specific viscosity of the heated to 150 ° C (oil bath temperatures). The up precipitated product is 0.39, measured in 0.5% strength by processing the resulting polymer product takes place chloroform solution at 25 ⁰ C. The chlorine content is prepared by dissolving in chloroform, precipitating it by input 30 1.49%.

drop the solution with stirring in pentane and an- B ice η ie 1 6
final drying in a high vacuum.

The reduced specific viscosity of the equivalent 53.72 parts by weight of 2-n-propyl-z! ^2- oxazoline, 3.28

precipitated product is 0.1, measured in 0.5% parts by weight of 2- (a-chloroethyl) -ü ² -oxazoline (molar

Chloroform solution at 25 ⁰ C. The chlorine content is 35 ratio 95.1: 4.9) and 0.417 parts by weight of 1,4-Phe-

4.54%. Nylene bis (2-oxazolinium) diperchlorate are used in

In the case of the 1 2 room temperature mixed and under initial

Stir for 3 hours using a heating and cooling bath

80.77 parts by weight of 2-methyl-zl ² -oxazoline, 5.97 Ge kept at 135 ° C (internal temperature). Then parts by weight of 2-chloromethyl-zl ² -oxazoline (molar ratio 40 is heated for a further 21 hours at 150 ° C. (oil bath temperature 95: 5) and 0.417 parts by weight of 1,4-phenylene bis-door). The polymer product is worked up as described in Example 1 (2-oxazolinium) diperchlorate, the room temperatures are described. Mixing the reduced specific temperature and supply under stirring initial viscosity of the reprecipitated product is 0.24, next to 12O ⁰ C, then within _^3/4 time slowly measured in a 0.5% chloroform solution at 25 ° C. increasing to 13O ⁰ C (oil bath temperatures) heated. 45 The chlorine content is 1.07%.
This temperature was held at and for ^{3 x} / _{2 hours.} .
The reaction mixture was then heated to Example 7 for 20 hours
heated at 15O ⁰ C. 3.28 GeBeispiel 1 is The polymer product as oxazoline in 69.87 parts by weight of ^2-phenyl-2 zl described, worked up. The reduced parts by weight of 2- (α-chloroethyl) -zl ² -oxazoline (molar ratio-specific viscosity of the reprecipitated product from 50 to 95.1: 4.9) and 0.417 parts by weight of 1,4-phenylene is 0.1, measured in 0.5 % strength chloroform solution at bis- (2-oxazolinium) diperchlorate at room-25 ⁰ C. The chlorine content is 3.01%. temperature mixed and stirring 1 hour

heated ^{to 120 °} C. for a long time. Then a half

Example at 130 ° C for 3 hours and at 150 ° C for 23 hours

55 (oil bath temperatures) heated. The polymer product

107.4 parts by weight of 2-iso-propyl-zl ² -oxazoline, 5.87 is, as described in Example 1, worked up. The parts by weight of 2-chloromethyl-zl ² -oxazoline (molar ratio - reduced specific viscosity of the reprecipitated Pronis 95: 5) and 0.417 parts by weight of 1,4-phenylene bis-duct is 0.23, measured in 0.5% chloroform ( 2-oxazolinium) -disperchlorat be solution at room at 25 ⁰ C. The chlorine content is 4.02%.
The temperature is mixed and heated to 60 for 1 hour with stirring.
120 ° C heated. The batch is then used without Example 8
Stir for a further 4 hours at 120 ° C and for 20 hours 94.08 parts by weight of 2-ethyl-zl ² -oxazoline, 16.08 Geden heated to 150 ° C (oil bath temperatures). The parts by weight of 2-tribromomethyl-zl ² -oxazoline (Molver polymer product is worked up as described in Example 1, ratio 95: 5) and 0.417 parts by weight of 1,4-phenylene. The reduced specific viscosity of the 65 bis (2-oxazolinium) diperchlorate is 0.56 in the case of room-reprecipitated product, measured in temperature, mixed and heated with stirring, with 0.5% chloroform solution at 25 ^° C. The chlorine is the internal temperature by means of heating and cooling bath content is 2.53%. Is held at 140 to 145 ° C for 3.5 hours.

6 5

This is followed by 20 hours at 150 ° C (oil bath chloroform solution at 25 ° C. The bromine content is

temperature) heated. The polymer product becomes as in 8.92%.

Example 1 described, worked up. The reduced ice cream 1 12
specific viscosity of the reprecipitated product

carries 0.09, measured in 0.5% chloroform solution 5 94.08 parts by weight of 2-ethyl- ^2- oxazoline, 12.84 parts

at 25 ° C. The bromine content is 9.89%. parts by weight 2- (a, «- dibromoethyl) - / l ² -oxazoline (MoI-

. -in a ratio of 95: 5) and 0.417 parts by weight 1,4-phenylene-

B e ι s ρ ι e 1 9 bis (2-oxazolinium) diperchlorate are used in space

43.4 parts by weight of 2-iso-propyl-zl ² -oxazoline, 6.5Ge temperature, mixed and with stirring for 1.5 hours by weight of 2-tribromomethyl-zl ² -oxazoline (molar ratio) heated to 125 ° C without nis 95: 5) and 0.169 parts by weight 1,4-phenylene-bis- stirring for 3 hours at 150 ° C and half a (2-oxazolinium) -diperchlorate are heated at room temperature for an hour at 200 ° C (oil bath temperatures), temperature and mixed, is under initial stirring 4 STUN The polymer product heated as in example 1 beschrieden heated at 12O ⁰ C. Then it is worked up. The reduced specific viscosity of the reprecipitated product at 150 ° C. (oil bath temperatures) for 20 hours is 0.12, measured in heated. The polymer product is, as in Example 1, 0.5% chloroform solution at 25 ° C. The bromine described, worked up. The reduced specific content is 6.42%.
Viscosity of the reprecipitated product is 0.10. .
measured in 0.5% chloroform solution at 25 ^° C. Example 13
The bromine content is 8.11%. 20 107.39 parts by weight of 2-n-propyI- / ^{I 2} -oxazoline, 12.84. . Parts by weight of 2 - («, a-dibromoethyl) - ^ ² -oxazoline (MoI example IU ratio 95: 5) and 0.417 parts by weight of 1,4-phenylene

66.65 parts by weight of 2-phenyl-Zl ² -oxazoline, 7.67 bis- (2-oxazolinium) -diperchlorate are mixed with parts by weight of 2-tribromomethyl-z] ² -oxazoline (molar temperature and with initial stirring ratio 95 : 5) and 0.199 parts by weight of 1,4-phenylene bis (2-oxazolinium) diperchlorate are kept at room (internal temperature) for 3 hours using a heating and cooling bath at 135 ° C. Then, 3 Stuntemperatur is mixed and heated with stirring initially at 150 ° C and for 15 hours at 170 ° C for 4 hours to 120 ⁰ C. It is then heated (oil bath temperatures). The polymer product is demand at 150 ⁰ C (oil bath temperatures) for 20 hours, worked up as described in Example. 1 The heats. The polymer product is worked up as described in Example 1, reduced specific viscosity of the reprecipitated sample. The reduced specific domestic product is 0.11, measured in 0.5% strength Chloro-viscosity of the product reprecipitated 0.24, form solution at 25 ⁰ C. The bromine content is 5.86%. measured in 0.5% chloroform solution at 25 ° C. .
The bromine content is 6.38%. B e 1 s ρ 1 e 1 14

. ■ 35 110.0 parts by weight of 2-phenyl-J ² -oxazoline, 10.11 parts

For example 11 parts by weight 2 - («,« - Dibromoethyl) -zl ² -oxazoline (MoI-

80.76 parts by weight of 2-methyl- ^{I 2} -oxazoline, 12.84 ratio 95: 5) and 0.329 parts by weight of 1,4-phenylene parts by weight of 2 - («, a-dibromoethyl) -Zl ² -oxazoline (mol- bis- (2-oxazolinium) diperchlorate are mixed at a space ratio of 95: 5) and 0.417 parts by weight of 1,4-phenylene temperature and bis- (2-oxazolinium) diperchlorate are heated to 125 ° C. at room temperature for 2 hours . Then I ¹ J ₂ stunt temperature is mixed and heated to 135 ° C for 1 hour, 150 ° C for 1 hour and 125 ° C for 2 hours with initial stirring. Subsequently, half an hour at 200 ° C (oil bath temperatures) is heated for 3 hours at 15O ⁰ C and 15 hours. The polymer product is heated as in Example 1 at 170 ⁰ C (oil bath temperatures). The polymer described, worked up. The reduced specific product is worked up as described in Example 1, the viscosity of the reprecipitated product is 0.42. The reduced specific viscosity of the environmentally measured in a 0.5% chloroform solution at 25 ⁰ C. the precipitated product is 0.18, measured in 0.5% The bromine content is 9.36%.

Claims (1)

Claim: Further development of the process for the polymerization of Δ ² -oxazolines to give high molecular weight, nitrogen-containing, linear polymers, using uniform Δ ² -oxazolines of the general formula R ₃ -C ■ N