DE1595381A1 - Process for the polymerization of mixtures of different delta? -Oxazolines - Google Patents

Description

CHEMICAL WORKS HOIS AO
- Patent Department -

1) 70 Mari, September 16, 1969, 2070 / Mö

Unaer sign: O.Z. 2048

Process for the polymerization of mixtures

Various / S -oxazoline additions to patent application P 12 06 585.9-44

The subject of patent application P 12 06 585.9-44 is a ".

drive for the polymerization of ZX -oxazolines to high molecular weight, nitrogen-containing, linear polymers, where one uniform / A » -oxazolines of the general formula

in which R ₁ to R ₁ - hydrogen atoms, aliphatic or cycloaliphatic, aromatic or heterocyclic radicals, but at least 2 radicals represent hydrogen atoms, polymerized in the presence of cationic catalysts

It has now been found * that this method is further developed

2 can by polymerizing mixtures of different Δ-oxazolines of the above general formula, one of which _{contains an alkyl radical with 1 to 17 carbon atoms as the radical R 1} , which carries one or more chlorine or bromine atoms in delivery.

Oxazolines suitable for copolymerization are, for example, 2-chloroethyl-Δ ² -oxazoline, 2-triohlomethyl-A -oxazoline, 2- (oc-chloroethyl) -

A ² -oxazoline, 2- (oC, oC-Dichlorätnyl) -A ² -oxazoline, 2 - (* - chlorine-

2 2

n-propyl) - Δ »oxazoline, 2 - (<* - dichloro-n-propyl) -Δ -oxazoline,

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2- (rv-chloro-iso-propyl) - Λ -oxazoline, 2 - (* c-chloro-n-penkyl) -

2 2

Λ -oxazoline, 2- (oC, o (-Dichlor-n-pentyl) - A -oxazoline, 2- (rt-chloro-n-undecyl) -A -oxazoline, 2 - (*, ^ - dichloro- »~ wB £ lg! cy.l) -Δ -

oxazoline, 2- (oC-chloro-n-pentadecyl) - Λ -oxazoline, 2 - ^ / X-dichloro-n-pentad0cyl) -z \ -oxazoline, 2 - (<* - chloro-n-heptadecyl) - Δ oxazoline, 2- (oc, c <-Dichlor.-n-heptadecyl) - A -oxazoline, 2-tribromomethyl- Λ -oxazoline, 2- (f </ <- dibromoethyl) - Δ -oxazoline,

, p

2- (ci / X-dibromo-n-propyl) - «_ \ -oxazoline, 2- (cv, oC-dibromo-n-undecyl) -

P ρ

A -oxazoline, 2- (r /, oC-dibromo-n-heptadecyl) - «A -oxazoline etc ·

The mixtures used for the polymerization may consist of two or more / \ -oxazolines exist vorzucsweise be JE

but two Z ^ -oxazolines used. The molar ratio of the ha-

ρ ρ

Log-free <l \ -oxazoline to halo-containing ζΛ -oxazoline can vary between 99.9: 0.1 and 80:20.

To carry out the polymerization the monomeric oxazolines at temperatures between 0 and 120 ⁰ C, vorzugsv / else at room temperature, mixed together and the mixture is polymerized by the method described in the main Patent manner in the presence of cation-active catalysts. Catalysts such as those described in additional application P 12 13 930.7-44 can also be used.

According to a special embodiment, you can first prepolymerize a ^ - \ -oxazoline, mix the prepolymer with one or more other Z ^ -oxazolines and then complete the polymerization. If the prepolymer is solid, it is dissolved in the monomeric copolymerization components before the copolymerization.

The polymerization is generally carried out in the absence of solvents carried out. You can do the polymerization though

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also perform as solution polymerization, using inert solvents with boiling points at or above the desired polymerization temperature, such as toluene or xylene, be used.

The copolymers prepared according to the invention are suitable sur Production of films, foils and coatings; because of their thermoplastic character, they can be used as casting resins or for Find production of injection molded articles use. The copolymers prepared according to the invention are notable here compared to the halogen-free polyoxazolines in that they contain easily substitutable halogen radicals; because of this you can they in the course of their processing by post-curing with suitable compounds be remunerated. Furthermore, the inventively produced

compared halogen-containing copolymers to halogen-free poly-

2
Δ-oxazolines due to their increased adhesive strength on metals, e.g. B. iron, zinc and aluminum. In addition, the halogen-containing copoly-

2 merisate less inflammable than the halogen-free poly-Δ, -oxazolines.

Therefore, they can optionally be mixed with others known per se flame-retardant substances, such as B. chlorinated paraffins or antimony trioxide can be added to other polymers to increase the flame resistance. Those copolymers have proven to be special for many purposes

_{2 suitable, in which the radicals R 0} to R_ are hydrogen atoms in the halogen-containing and halogen-free A -oxazoline.

example 1

76.50 parts by weight of 2-methyl- / ^ ² -oxazoline, 11.96 parts by weight of 2-chloromethyl-A ² -oxazoline (molar ratio 90:10) and 0.417 parts by weight of 1,4-phenylene bis (2-oxazolinium) diperchlorate are mixed at room temperature and ^{heated with stirring initially to 120 °} C., then slowly increasing to 140 ^° C. over the course of one hour. Then, without stirring a further 4 hours in length (at 140 ⁰ C and 20 hours to I50 C ⁰ Ölbadtempera-

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doors) heated. The work-up of the resulting polymer product takes place by dissolving in chloroform, precipitation by dropwise addition of the solution with stirring in pentane and then Drying in a high vacuum.

The reduced specific viscosity of the reprecipitated product is 0.1, measured in 0.5 #iger chloroform solution at 25 ⁰ C. The chlorine content is 4.54% *

Example 2

80, 77 parts by weight of 2-methyl -, ^ - oxazoline, 5, 97 parts by weight of 2-chlorine

2
methyl-Δ-oxazoline (molar ratio 95: 5) and 0.417 parts by weight of 1,4-phenylene-bis- (2-oxazolinium) -diperchlorate are mixed at room temperature and initially to 120 ° C., then within 3/4 with initial stirring Hourly slowly increasing to 130 * C (oil bath temperatures) heated. This temperature was maintained for 3 1/2 hours and the reaction mixture was then heated to 150 ° C. for 20 hours. The polymer product is worked up as described in Example 1. The reduced specific viscosity of the reprecipitated product is O ₄ 1, measured in 0.5% chloroform solution at 25 ° C. The chlorine content is 3.01%.

Example 3

107.4 parts by weight of 2-iso-propyl-A -oxazoline, 5.87 parts by weight 2-

2
Chloromethyl-Δ-oxazoline (molar ratio 95: 5) and 0.417 parts by weight of 1,4-phenylene-bis (2-oxazolinium) -diperchlorate are mixed at room temperature and heated to 120 ° C. for one hour with stirring. The batch is then kept at 120 ° C. for 4 hours and at 150 ° C. (oil bath temperatures) for 20 hours without stirring . The polymer «

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product is as described in Example 1, worked up. The reduced specific viscosity of the reprecipitated product is 0.56, measured in 0.5% chloroform solution at 25 ° C. The chlorine content is 2.53%.

Example 4

ο
80.76 parts by weight of 2-methyl-Δ. -oxazoline, 6, 67 parts by weight 2- (a-

2
ChloräthyD-Δ oxazoline (molar ratio 95: 5) and 0.417 parts by weight of 1,4-phenylenebis (2-oxazolinium) diperchlorate are mixed at room temperature and with initial stirring for 3 hours to 125 bis

lj50 ⁰ C heated. Subsequently, 3 hours, heated at 170 ⁰ C (oil bath temperatures) to 150 ⁰ C and 15 hours. The polymer product is worked up as described in Example 1. The reduced specific viscosity of the reprecipitated product is 0.16, measured in 0.5 Seiger chloroform solution at 25 ⁰ C. The chlorine content is 1.89% ·

Example 5

94.12 parts by weight of 2 ₇ ethyl-Δ? -Oxazoline, 6, 68 parts by weight of 2- (a-chloroethyl) - £? -Oxazoline (molar ratio 95; S) and 0.209 parts by weight of 1,4-phenylene -bis- (2- osaaolinium be) diperchlorate mixed at room temperature and with stirring by means .a long Hela and cooling bath hour (at 135 * C Innenterr.peratur) held "mixture is then heated for a further 20 hours at 150 ⁴ C (oil bath temperature), Dae polymer product, as described in Example 1, worked out. The reduced specific viscosity of the reprecipitated product is 0.89, measured in 0.8 ftger Chloreformlösung at 25 ^e C, The Chlorgehsl * is 1.40%. ':

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Example 6

2
ή3, 72 parts by weight of 2-n-propyl - ^ - oxazoline, 3.28 parts by weight of 2- (a-

2
Chlorine; ithyl) -A -oxazoline (molar ratio 95.1: 4, 9) and 0.417 parts by weight 1,4-phenylene-bis- (2-oxazolinium) -diperchlorate are mixed at room temperature and with initial stirring for three hours by means of Heating and cooling bath kept at 135 * C (internal temperature). Then another 21 hours is heated to 150 ^e C (oil bath temperature) long. The polymer product is worked up as described in Example 1. The reduced specific viscosity of the reprecipitated product is 0.24, measured in 0.5% chloroform solution at 25 ° C. The chlorine content is 1.07%.

Example 7

69.87 parts by weight of 2-phenyl-, A ² -oxazoline, 3 * 28 parts by weight of 2- (oC-chloroethyl) - ^ \ ² -oxazoline (molar ratio 95.1: 4.9) and 0.417 parts by weight of l ^ -phenylene-bis - ^ - oxazoliniunO diperchlorate are mixed at room temperature and heated with stirring for an hour at 120 ⁰ C. Subsequently, half an hour is heated at 130 ⁰ C and 2JJ hours at 150 ⁰ C (oil bath temperatures). The polymer product is as in example. 1 described, worked up. The reduced specific viscosity of the reprecipitated product is 0.23, measured in 0.5 #iger chloroform solution at 25 ⁰ C. The chlorine content is 4.02 Ji.

Example 8

94.08 parts by weight of 2-ethyl- ^ ² -oxazoline, 16.08 parts by weight of 2-tribromomethyl-zl ² -oxazoline (molar ratio 95: 5) and 0.417 parts by weight of 1,4-phenylene bis (2-oxazoliniura) diperchlorate mixed at room temperature and heated with stirring, whereby the Innentetnperatur means of heating and cooling bath is held for 3.5 hours at l40 to 145 ⁰ C. Then will

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£ Ό hours heated at 150 ⁰ C (oil bath temperature). Since "polymer product is as described in Example 1, worked up, The reduced specific viscosity of the product is umcefällten 0.09, measured in 0.5 #iger Chloroformlönung at 25 ⁰ C. The bromine content is 9 * 89%.

Example 9

4.2.4 parts by weight of 2-iso-propyl - ^ _ \ -oxazoline, 6.5 parts by weight of 2-Tr i bromine thy 1- Δ -oxazoline (molar ratio 95: 5) and 0.169 parts by weight of 1,4-phenylene-bis- (2-oxazolinium) -diporchlorat, are mixed at room temperature and heated under initial stirring for 4 hours at 120 ⁰ C. Then, 20 hours, heated to 150 ⁰ C (oil bath temperatures) long. The polymer product is worked up as described in Example 1. The reduced specific viscosity of the reprecipitated product is 0.10, measured in 0.5 pointer chloroform solution at 25 ⁰ C. The bromine content is 8.11% "

Example 10

66.65 parts by weight of 2-phenyl- / ^/ \ -oxazoline, 7.67 parts by weight of 2-tribromomethyl-Z. ^/ \ ² -oxazoline (molar ratio 95: 5) and 0.199 parts by weight of l, 4-phenylene-bis- (2-oxazoliniura) diperchlorate are mixed at room temperature and heated under initial stirring for 4 hours at 120 ⁰ C. Then, 20 hours, reheated to 150 ⁰ C (ölbadtemperatur.en) long. The polymer product is worked up as described in Example 1. The reduced specific viscosity of the reprecipitated product is 0.24, measured in 0.5 pointer chloroform solution at 25 ⁰ C. The bromine content is 6.38%.

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Example 11

80.76 parts by weight 2-methyl- ^ - oxazoline, 12.84 parts by weight 2- (a, a-

2 DibromäthyD-Δ-oxazoline (molar ratio 95: 5) and 0.417 parts by weight 1,4-Phenylenebis (2-oxazolinium) diperchlorate are mixed at room temperature and heated to 125 ° C. for 2 hours with initial stirring. This is followed by heating to 150 ° C. for 3 hours and to 170 ° C. (oil bath temperatures) for 15 hours. The polymer product is worked up as described in Example 1. The reduced specific viscosity of the reprecipitated product is 0.18, measured in 0.18. of 6% chloroform solution at 25 ⁰ C. The bromine content is 8.92%. "'

Example 12

2
Θ4.08 parts by weight 2-ethyl-A -oxazoline, 12.84 parts by weight 2- (α, α-

2 DibromäthyD-Δ. -oxazoline (molar ratio 95: 5) and 0.417 parts by weight 1,4-Phenylene-bi8- (2-oxazolinium) diperchlorate are mixed at room temperature and heated to 125 ° C. for 1.5 hours with stirring. The mixture is then heated to 150 ° C. for 3 hours and half an hour to 200 ° C. (oil bath temperatures) without stirring. The polymer product is worked up as described in Example 1. The reduced specific viscosity of the reprecipitated product is measured to be 0.12 in 0.5% chloroform solution at 25 ° C. The Brdm content is 6.42 %

Example 13

107.3Θ parts by weight of 2-n-propyl-Δ ² -oxazoline, 12.84 parts by weight 2- (α, a-dibromethyl) -A ² -oxazoline (molar ratio 95: 5) and 0.417 parts by weight of 1,4-phenylene- bii- (2-oxasolinium) -diperchlorate are milked at room temperature and under initial 'ltttkr ·· I fturten'

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Maintained at 135 ° C (internal temperature) for a long time by means of a heating and cooling bath. The mixture is then heated to 150 ° C. for 3 hours and to 170 ° C. (oil bath temperatures) for 15 hours. The polymer product is as described in Example 1, worked up. The reduced specific viscosity of the reprecipitated product is 0.11, measured in 0.5% chloroform solution at 25 ° C. The bromine content is 5.86 %.

Example 14

2
110.0 parts by weight of 2-phenyl -Δ -oxazoline, 10.11 parts by weight of 2- (α, α-

2
Dibromoethyl) & oxazoline (molar ratio 95: 5) and 0.329 parts by weight of 1,4-phenylene bis (2-oxazolinium) diperchlorate are mixed at room temperature and heated to 125 ° C. for 2 hours with stirring. The mixture is then heated to 135 ° C. for 11/2 hours, to 150 ° C. for 1 hour and to 200 ° C. for half an hour (oil bath temperatures). The polymer product is worked up as described in Example 1. The reduced specific viscosity of the reprecipitated product is 0.42, measured in 0.5% chloroform solution at 25 ° C. The bromine content is 9, 36%.

BATH ORIGINAL

Claims (1)

- 10 - OZ 2048 I6.9.I969 Claims 1. Further development of the process for the polymerization of / \ -Oxazolinen to high molecular weight, nitrogen-containing, linear 'polymers according to patent application P 12 06 505 · 9-Μ * where one uniform Z- oxazolines of the general formula C N in which R 1 to R 1 represent hydrogen atoms, aliphatic or cycloaliphatic, aromatic or heterocyclic radicals, but at least 2 radicals hydrogen atoms, polymerized in the presence of cationic catalysts, characterized in that mixtures of different IS -oxazolines of the above general formula are polymerized, of which one as radical R, contains an alkyl radical with 1 to 17 carbon atoms which has one or more chlorine or bromine atoms in the <* position 2. The method according to claim 1, through this . characterized in that in the-oxazolines used for the copolymerization, the radicals R ₂ to B ~ represent hydrogen atoms ·· V > · Method according to claim X ₉ * characterized by the fact that the molar ratio of the halogen-free A ^ oxazolines to halogen-containing ^ ² -oxazoline is between 99.9 % 1 and 4 QO Ϊ 20 . QQ98timt $ - 11 - OZ 2048 16.9.1969 4. The method according to claim 1, characterized in that a mixture of an at least partially polymerized and a monomeric S. \ -oxazoline is polymerized. BATH 001111 / UtI