FR2623515A1 - POLYMERIC COMPOSITION BASED ON METHYL METHACRYLATE - Google Patents

Abstract

The present invention relates to a polymer or a copolymer of methyl methacrylate containing: a) a stabilizer against the effects of light derived from an oxanilide or a 2, 2, 6, 6-tetramethylpiperidine, and b) a flame retardant containing phosphorus.

Description

The subject of the present invention is a polymer composition containing a

oxanilide and an agent

flame retardant containing phosphorus.

  The invention particularly relates to a polymer or copolymer of methyl methacrylate containing a) a stabilizer against the effects of light

  derived from an oxanilide or 2,2,6,6-tetramethyl-

  piperidine (hereinafter referred to as component a), and

  (b) a flame retardant agent containing phosphorus (

hereinafter component b).

  When component a) is a stabilizer against the effects of light derived from an oxanilide, it is preferably a compound of formula I

(R2) 2 R2) 2

(- -co-co --.- L?

RJ R R I

1 1

  wherein each R 1 is, independently, hydrogen, halogen, C 1 -C 1 4 alkyl, C 1 -C 18 alkoxy, hydroxy, phenyl or phenoxy, each R 2 is, independently, hydrogen, halogen or hydroxy, C1-C4alkyl or C1-C6alkoxy, and each R is, independently, hydrogen or

methyl group.

  R1 preferably means R1 ', R1' means

  hydrogen, hydroxy, C1-C4 alkyl or C1-C4 alkoxy; R1 more preferably means hydrogen.

  R2 preferably R2 ', R2' means

  hydrogen, hydroxy, C1-C4 alkyl or C1-C4 alkoxy; R2 is more preferably R2 ", R2" is C1-C4 alkyl or alkoxy

in C1-C4.

  R preferably means hydrogen.

  R2 is preferably located in the ortho position. When component a) means 2,2,6,6-tetramethylpiperidine, it is a compound of formula II

H3 CH3

12 (II)

R-N

CH3 CH3

  wherein Rlo is hydrogen, oxygen or a C1-C8 alkyl group or -COR15 where R15 is C (R) = CH2, C1-C6 alkyl, phenyl, -NR17 R1, -CO-C6 H5, -CH2C6H5, -COO-C1-C12alkyl or -COOH; R17 is hydrogen, C1-C12alkyl, C5C6cycloalkyl (preferably cyclohexyl), phenyl, (C1-C4alkyl) -alkyl or (C1-C12alkyl) phenyl, and R18 is hydrogen or an alkyl group

C1 -CI 2,

  R1, is hydrogen, C1-C22alkyl, C1-C22alkoxy, -N (R) -CO-CO-R20 or

-NH-C (R) -N-R2 1,

  R20 means with the group -CO- an amide group and R21 signifies a C1-C18 alkyl group,

  phenyl optionally substituted from 1 to 3

  selected from halogens and C1-C8alkyl and C1-C4alkoxy; or R2 means a group of formula

R12 CI3 CH3

-O-CO (CH2) 6 -CO-R, o

CH3CH3

  and R12 is hydrogen or (C1-C6) alkyl, or R1 and R12 together with the carbon atom to which they are attached form a group of formula a)

(CH2) '

  O-C / C 1 / C-N. (C 2 -C 4) alkylene-COO (C 1 -C 22) alkyl (a)

  The 2,2,6,6-tetramethylpiperidines

  particularly preferred formula IIa or IIb

R12 R12 3

R Rglo (la) Rso W C- (CH2) - Ia

CH 3 O H3 CH

  (IIb) / C - N-CH2CH2-COO (C8-C18 alkyl)

CH3 CH3

  in which R10 'is hydrogen or (C1-C4) alkyl or -CO-R5', where R5 'is (C1-C4) alkyl or -CO-O (C1-C4) alkyl, and R12' means hydrogen or a methyl group,

preferably hydrogen.

  Component b) preferably means a compound of formula III or IV R3O-P-CHO-P CHO-P-OR3 (III)

R30 R30 R3

n R I

R7 CH -O \ X

| o / I-O-R C- (CH 2 R 5) 2

R7 CH

R 2

  wherein each R 3 is, independently, a C 1 -C 6 alkyl group optionally substituted with 1 or 2 halogen atoms, or a C 2 -C 6 alkenyl group optionally substituted with a halogen atom and / or an alkoxy group with C1-C4 or R3 is phenyl, n is an integer of 1 to 10, R4 is C1-C17 alkyl, R is hydrogen or methyl, each R5 is independently a halogen, each R6 means, independently, a C1-C4 alkylene group, X means O or S and R7 has the meaning of R3 independently of R3. Preferably, R20 has the preferred meanings of R4 of British Patent Application No. 2180537, the contents of which are incorporated herein.

request for reference.

  Any C1-C18 alkyl group preferably means a C1-C8 alkyl group; any C1-C4 alkyl group preferably means a C1-C4 alkyl group and any C1-C4 alkyl group means

  preferably a methyl or ethyl group.

  By halogen, is meant in this application fluorine, chlorine, bromine or iodine,

preferably chlorine or bromine.

  R3 preferably means R3 ', R3' means

  C1-C4 alkyl group monosubstituted with chlorine or bromine; R3 more preferably means

R3 ", R3" signifying -CH2CH2Cl.

  R4 preferably means R4 ', R4' means

  leaving a C1-C4 alkyl group; R4 is more preferably R4 ", R4" -CH3 or -C2H5, plus

preferably -CH3.

  n means on average preferably 2.

  R5 preferably means Rs ', R5' means

  Chlorine or bromine, more preferably chlorine.

  R6 preferably means R6 ', R6' means

  methylene or ethylene group, more preferably

a methylene group.

  Preferred compounds of formula III are those of formula III '

Q CH3 0 CH O

  192CH2H 2) 2- P --CH -0 - - -CH-OO-P-CH 2CH 2 R 1

  (R1 9CH2CH2O ± .--- p-O-P M OCH2CH2R19 (l ')

OCH2CH2R19

  where n 'means 2 and each R19 means

  a halogen, preferably chlorine.

  The preferred compounds of formula IV are those of formula IV ## STR2 ##

LR / 7 CH2,0 / ...

  wherein each R7 'independently means

  hydrogen or an ethyl or methyl group, preferably

  methyl, and x is O or S, preferably O. The compounds of formula I to III are known or may be prepared according to methods known in the art.

from known compounds.

  The polymers or copolymers of methyl methacrylate according to the invention can be prepared

  according to known methods from suitable reagents

  required, possibly with comonomers.

  For the copolymerization, the following unsaturated α, β-comonomers may be used: the C2-C8 alkyl esters of methacrylic acid, the C1-C8 alkyl esters of acrylic acid, the C1-C8 alkyl esters of c-cyanoacrylic acid (such as ethyl, butyl or cyclohexyl ester), styrene, methylstyrene, acrylonitrile,

  methacrylonitrile or α-chloroacrylonitrile.

  A preferred copolymer according to the invention is

  that formed by polymerization of the methacrylate of

  in the presence of glycidyl acrylate and / or glycidyl methacrylate, preferably presence of glycidyl methycrylate. Such a copolymer preferably contains from 0.1 to 10%, more preferably from 0.5 to 6% by weight of glycidyl compound relative to the weight of methacrylate and other comonomers.

possibly present.

  The incorporation of components a) and b) in the polymer or copolymer of methyl methacrylate can be carried out according to known methods. For example, components a) and b) can be added to the monomer or prepolymer at room temperature or

  at high temperatures. We can prepare the poly-

  and copolymers of the invention according to known methods from suitable reagents, preferably by sequential polymerization in the presence of

  a polymerization catalyst, for example azo

  bis-iso-butyronitrile, dibenzoyl peroxide or dilauryl peroxide. Components a) and b) can also be incorporated by known methods into a polymer or a melt copolymer, for example by extrusion, and the polymer can be further processed into shaped articles. Preferably from 3 to 30%, more preferably from 8 to 25% by weight of components a) and b) in the polymer, relative to

weight of the polymer or monomer.

  A preferred method of preparing a copolymer according to the invention is copolymerization with glycidyl acrylate or glycidyl methacrylate. By using glycidyl acrylate or

  glycidyl methacrylate, a quantity

  lower part of components a) and b) to obtain a flame retardant effect. In this case, a quantity of components a) and b) of between 3 and 25%, more preferably between 8 and 15% by weight with respect to

  weight of the polymer or comonomer.

  Other additives can be added to the poly-

  or copolymer according to the invention such as polymerization regulators, softeners,

  anti-UV stabilizers, antioxidants and pigments.

  Polymers and copolymers of the invention

  can be transformed according to known methods into various shaped articles such as

leaves, tubes or films.

  Component (a) or (b) also means mixtures of components a) or b) or a mixture of one or more components a) or b) with one or more

other flame retardants.

  Polymers and copolymers of metha-

  Methyl crylate according to the invention have good fastness to light and good flame retardant properties. The following examples illustrate the present invention without in any way limiting its scope. In these examples, the parts and percentages are by weight and the temperatures are indicated in degrees Celsius.

Example 1

  47.5 g of methyl methacrylate are mixed

  recently distilled with 0.04 g of diluent peroxide

  0.03 g of azoisobutyric acid dinitrile and 2.5 g of the compound of formula la are

CH3 CH 0 \ O 0

  ## STR2 ## and 0.1 g of the compound of formula Ib <NH-CO-CONH (1b)

C2H5 OC2H5

  The clear solution is maintained at 1150 for 7 minutes and poured between glass plates, separated by a 3 mm rubber washer.

  thick and sealed with transparent adhesive tape

  rent. The glass plates are held for 16 hours at 50 in a water bath and then for 4 hours.

115 hours in an oven.

  The transparent plates thus obtained have good fire-retardant properties and

good fastness to light.

Example 2

  In an Arbury extruder for injection, 200-220 parts of commercial methyl methacrylate are mixed with 0.2 part of the compound of formula Ib (of Example 1) and 10 parts of the compound of formula 2a.

CH3 OCH2CH2Cl, CH3 CH2CH2Cl

  (C CH 2 CH) 2 --- CH-O-P-. CHO-P (2a) ## STR2 ## wherein n is on average 2, and is extrude

  to form plates 3 mm thick.

  The plates thus obtained have good fastness to light and good flame retardant properties. Examples 3 and 4 The procedure is as described in Example 2, using instead of the compound of formula Ib an appropriate amount of the compound of formula 3a or 4a (CH 2) n -CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 COOC1 2H25 (n) (3a)

CH CH3 CH CH3

CH> @C (CH (4a)

CH3 0 - (H H3

H3 H3

Claims (8)

  1. A polymer or copolymer of methyl methacrylate, characterized. in that it contains a stabilizer against the effects of light   derived from an oxanilide or 2,2,6,6-tetramethyl- piperidine, and   b) a flame retardant agent containing phosphorus.   2. A polymer or copolymer according to claim 1, characterized in that component a) is a compound of formula I (R2) 2 R22 sS-CO-CO -t (IN R R R 1 R1   wherein each R 1 is, independently, hydrogen, halogen, C 1 -C 18 alkyl, C 1 -C 18 alkoxy, hydroxy, phenyl or phenoxy, each R 2 is, independently, hydrogen, halogen or a group hydroxy, C1-C4alkyl or C1-C8alkoxy, and each R is, independently, hydrogen or methyl group.   3. A polymer or copolymer according to claim 2, characterized in that in formula I, R1 is hydrogen, hydroxy, C1-C4 alkyl or C1-C4 alkoxy, R2 is hydrogen or hydroxy, C1-C4 alkyl or C1-C4 alkoxy and R is hydrogen.   4. A polymer or copolymer according to claim 1, characterized in that component a) is a compound of formula II H3 CH3 R-o N g (II) he CH3 CH3   wherein R10 is hydrogen, oxygen or C1-C8 alkyl or -COR15 where R15 is C (R) = CH2, C1-C6 alkyl, phenyl, -NR1 7R1 8, -Co- C6H5, -CH2C6H5, -COO-C1-C12alkyl or -COOH; R17 is hydrogen, C1-C12alkyl, C5C6cycloalkyl, phenyl, (phenyl) C1-C4alkyl or (C1-C12alkyl) phenyl and R18 is hydrogen or C1-6alkyl; -Cl2, R11 means hydrogen, C1-C22 alkyl, C1-C22 alkoxy, -N (R) -CO-COR20 or -NH-C (R) = N-R21,   R20 means with the group -CO- an amide group and R21 signifies a C1-C18 alkyl group,   phenyl optionally substituted from 1 to 3   selected from halogens and C1-C18alkyl and C1-C4alkoxy; or R21 means a group of formula N-Ro R HCH3 -o-CO (CH2) 6co12-- -Ro C H3 H3   and R12 is hydrogen or C1-C8alkyl, or R11 and R12 together with the carbon atom to which they are attached form a group of formula a) _ (CH2) 1 -   C 1 0 N 1 / C N (C 2 -C 4 alkylene) -COO (C 1 -C 22 alkyl) (a) O o 5. A polymer or copolymer according to claim 4, characterized in that component a) is a compound of formula IIa or IIb CH3 CH3 CH3 H 12 R12S 3 C - (CH3 - H2) 11-C-X_-   Rlo E | (IIb) / OC-N-CH2CH2-COO (C8-C18alkyl CH 3 c.32) 1 wherein R1t0 'is hydrogen or C1-C4alkyl or -COR5', where R5 'means a C 1 -C 4 alkyl group or -CO-O (C 1 -C 4 alkyl), and   R12 'means hydrogen or a methyl group.   6. A polymer or copolymer according to one   any of claims 1 to 5, characterized in that   that component b) is a compound of formula III or IV O R, 4 14 l R30-P - CHO-P-CHO-OR3 (III 3 R30 L R30 R3 n R R CH-O T / C 0 - R6 C- (CH2R5) 2 (IV) R7 CH-O   Wherein each R 3 is, independently, a C 1 -C 6 alkyl group optionally substituted with 1 or 2 halogen atoms, or a C 2 -C 6 alkenyl group optionally substituted by a halogen atom and / or by a group C 1 -C 4 alkoxy or R 3 is phenyl, n is an integer of 1 to 10, R 4 is C 1 -C 7 alkyl, R is hydrogen or methyl, each R 5 is, independently, halogen, each R6 is, independently, C1-C4alkylene, X is O or S and R7 is R3 independently of R3. 7. A polymer or copolymer according to claim 6, wherein the compound of formula III is a compound of formula III OCH2 CH2C2R119 where n 'is 2, and   each symbol R19 signifies a halogen.   8. A polymer or copolymer according to claim 6, characterized in that the compound of formula IV is a compound of formula IV ' R CH-0 7 2 cIgCi oP-O-CH 2 -C (CH 2 Cl) 2 (IV) R7 CHI 0 2   Wherein each R 7 'sign means, independently, hydrogen or an ethyl or methyl group, and X is O or S.