FR2579212A1 - POLYMERS AND COPOLYMERS OF METHYL METHACRYLATE CONTAINING PHOSPHORUS DERIVATIVES AS FLAME RETARDANT AGENTS - Google Patents

Abstract

THE INVENTION CONCERNS POLYMERS AND COPOLYMERS OF METHYL METHACRYLATE CONTAINING, AS A FLAME RETARDANT AGENT, A COMPOUND OF FORMULA I (CF DRAWING IN BOPI) IN WHICH THE R SYMBOLS, INDEPENDENT OF ONE OF THE OTHER, REPRESENT HYDROGEN AN ALKYL GROUP IN CC, PHENYL, -CO-O-ALKYL IN CC OR -CH-O-ALKYL IN CC, THE R SYMBOLS, INDEPENDENT OF ONE OF THE OTHER, REPRESENT HYDROGEN OR AN ALKYL GROUP IN CC OR -CO-O-ALKYL IN CC, THE R SYMBOLS, INDEPENDENTLY OF ONE OF THE OTHER, REPRESENT HYDROGEN OR AN ALKYL GROUP IN CC, THE R SYMBOLS, INDEPENDENT OF ONE OF THE OTHER, REPRESENT HYDROGEN OR A GROUP METHYL, AND X REPRESENTS OXYGEN OR SULFUR.

Description

The present invention relates to polymers and copolymers

  methyl methacrylate containing derivatives of

  phosphorus as flame retardants.

  In particular, the invention relates to polymers and copolymers of methyl methacrylate containing, as an igniting agent, a compound of formula I

R5 R4 R R4

R C0 C -O O / (I)

1 N ', x / ...... C C c R

R2 / "\ CH - 0 2

  in which the symbols Rj, independently of each other, represent hydrogen or a C1-C4 alkyl, phenyl, -CO-0C1-C6alkyl or -CH2-O-C1-C2alkyl, the symbols R2, independently of each other, represent hydrogen, a C1-C4 alkyl group or -CO-O-C1-C6 alkyl, the symbols R4 independently of one another represent hydrogen or a C1-C4 alkyl group, the symbols R5, independently of one another, represent hydrogen or a methyl group, and

  X represents oxygen or sulfur.

  Unless otherwise indicated, C1-C6 alkyl groups

  preferably represent a C1-C4 alkyl group, more particularly

  first a methyl or ethyl group.

  R1 preferably means R1 ', ie hydrogen, C1-C4alkyl, -CH2-O-C1-C2alkyl or -CO-O-C1-C2alkyl; . R.sub.1 is more particularly R.sub.1, that is C.sub.1 -C.sub.3 alkyl, especially C.sub.1 -C.sub.22 alkyl, more preferably methyl, R.sub.2 is preferably R.sub.2 ', i.e. hydrogen or C1-C4alkyl or -CO-O-C1-C2alkyl, R2 is more particularly R2 ", ie C1-C4alkyl, especially C1alkyl; -C2, especially a group

ethyl.

  R4 preferably means R4 ', i.e. hydrogen or

  a C1-C3 alkyl group, more particularly hydrogen.

  R5 is preferably hydrogen.

  X is preferably oxygen.

  The preferred compounds of the formula I are the compounds corresponding to the formula ## STR1 ## wherein: ## STR2 ##

/ \ / \\

2 CH- 0 0 CH R '

ó R4i R

  in which the symbols have the meanings given above.

  ously. The compounds of formula I which are more particularly preferred are those corresponding to the formula Ib CH 3 - / CH 2 OO CH 2 / CH 3 C PP-O-p Cb / C, o / POPC (Ib)

2 CH2 0 --- CH2 R2

2 2

7 9 2 12

- 3-

  in which R2 "has the meaning given above.

  The compounds of formula I can be prepared according to known methods from suitable reagents, for example by reacting 1 mole of a compound of formula II

R4 / R5

R1.c-O0

\ C p R7 (II)

R CH-

CH-Q R4

  wherein R1, R2, R4 and R5 have the given meanings given in

  and R7 represents chlorine or bromine, with 1 mole of a compound of formula III

R

NZ / R

/ X

C P-R7

R2 CH-0 O

R4

  in which X, R 1, R 2, R 4, R 5 and R 7 have the meanings given above,

  and 1 mole of water in the presence of a halogenated acid acceptor

water such as pyridine.

  The polymers according to the invention can be prepared

  according to known methods from appropriate reagents, possibly

  with comonomers. For the copolymerization, the following unsaturated comonomers a and 8 can be used: a C 2 -C 8 alkyl methacrylate, a C 1 -C 8 alkyl acrylate, a C 1 -C 8 alkyl acylanoacrylate (as the ethyl ester,

  butyl or cyclohexyl), styrene, methylstyrene, acrylic acid,

  lonitrile, methacrylonitrile or α-chloroacrylonitrile.

  A preferred copolymer according to the invention is obtained by polymerization of methyl methacrylate in the presence of glycidyl acrylate and / or glycidyl methacrylate, preferably in the presence of glycidyl methacrylate. Such a copolymer preferably contains between 0.1 and 10%, more particularly between 0.5 and

  6% by weight of glycidyl compound relative to the weight of the metha

  crylate and other comonomers, if present.

  The incorporation of the compound of formula I into the polymer or copolymer of the invention may be carried out according to conventional methods. The compound of formula I may, for example, be added to the monomer or prepolymer at ambient temperature or at higher temperatures, since the compounds of formula I dissolve therein at temperatures between 20 and C. The polymers and the copolymers of the invention can be

  prepared according to known methods from suitable reagents

  preferably by polymerization in the presence of a polymerization catalyst, for example azobisisobutyronitrile,

  dibenzoyl peroxide, dilauryl peroxide or peroxy-

  O-tert pivalate. butyl. The compounds of formula I can also

  These can be incorporated by known methods into the molten polymer or copolymer, for example by extrusion, and the polymer can be formed into shaped articles. Preferably between 3 and 30%, more preferably between 8 and 25% by weight of the compound of formula I relative to the weight of the polymer or monomers is used.

2 5 7 9 2 1 2

-5-

  A preferred method of preparing copolymers of the invention

  The invention is copolymerization with glycidyl acrylate or glycidyl methacrylate. When glycidyl acrylate or glycidyl methacrylate is employed, a smaller amount of the compound of formula I may be used for flame retardancy.

  In this case, the preferred amount of compound of formula I is

  between 3 and 25%, more particularly between 8 and 15% by weight

  relative to the weight of the polymer or comonomers used.

  Other additives may be added to the polymer or copolymer

  of the invention such as polymerization regulators, softeners, stabilizers against U.V. rays,

antioxidants and pigments.

  The polymers and copolymers of the invention can be converted according to known methods into shaped articles.

  various such as plates, tubes or sheets.

  The term "compound of formula I" also includes mixtures of compounds of formula I or mixtures of one or more compounds of formula I with one or more other flame retardants. The following examples illustrate the present invention

  without in any way limiting its scope. In these examples, the

  percentages and percentages are by weight and the temperatures are

data in degrees Celsius.

Example 1

  In a vessel, 23.6 parts of 2-ethyl-2-methyl-1,3-propanediol are melted. 30.7 is added dropwise

  parts of phosphorus oxychloride and the reaction mixture is stirred

  at room temperature for 15 minutes. We heat up

  The mixture was then added under vacuum for 1 hour. We add to the

  crystalline mass thus obtained 21 parts of pyridine and 1.8 parts

  of water and the reaction mixture is stirred for 1 hour at room temperature and then for 4 hours at 40.degree. The mixture is then brought to ambient temperature and the precipitate is removed by filtration.

7 9212

  After concentration of the organic phase, the residue is taken up in toluene, the organic phase is washed with acid

  diluted hydrochloric acid, dried over sodium sulfate and evaporated.

  The compound of formula CH 3 CH 3 --O C P -O (la) is obtained

C2H5 CH - O

  having a melting point of 154-155.

Example 2

  By proceeding as described in Example 1, a mixture consisting of 10.4 parts of 2,2-dimethyl-1,3-propanediol and

  of 11.8 parts of 2-ethyl-2-methyl-1,3-propanediol with 30.7 parts of

phosphorus oxychloride.

  A mixture of 5.2 parts of the compound of

mule 2a

CH3 CH - OOCH2 CH3

x C P-O C (2a)

CH3 CH2 - 0 - CH2 CH3

  6.2 parts of the compound of formula 2b C 2 H 5 CH 3 O-CH 2 CH 3 30 / C 2 OP-O / C (2b) KB 0

C3 2 O-CH2 C2H5

  And 12.0 parts of the compound of formula 2c CH3 / 0.2 oh0 0 -CH2 yCH3 \ C / \ P-OO-P / C (2c)

CH3 CH-O O-CH2 C2H5

(determined by HPLC).

Example 3

  By proceeding as described in Example 1, 13.2 parts of 2-methyl-2-n-propyl-1,3-propanediol and 10.4 parts are reacted.

2,2-dimethyl-1,3-propanediol.

  A mixture consisting of 3.9 parts of the compound of formula 2a defined in example 2, 5.9 parts of compound of formula 3a is obtained.

CH3, CH - O O - CH2 CH3

c. / co 22 0 c3

\ C / \ P -O - P / \ C /

  n 3 CH 7 CH 3 O-CH 2 n 3 CH 7 (3a) and 11.4 parts of the compound of formula 3b

CH CH- 0 O ---- CH2 CH3

c P-OO / C CH-CH2 nC3H7

CH23 C7-

(3b) - 8 -

Example 4

  By using appropriate starting materials, a mixture consisting of 46.4% of the compound of formula 4a can be prepared by the method described in Example 1.

\ C / \ P O \ C

CH3 CH-o CH2 CH3

CH3 CH-O 0 Z CH3

  ng3H7 {4a) of 36.3% of the compound of formula 4b

CH R CH2 00-4 - O / O CH2 CH

3ccF- 2/0 2 3

/ C P- 0 P C

CH3 CH OON 0 - CHX CH3

i I nC3H7 nC3H7 (4b)

  and 17.3% of the compound of formula 2a (defined in Example 2).

Examples 5 to 15

  From the appropriate starting materials, it is possible to prepare

  the compounds indicated in the following table by proceeding from

  analogous to that described in Example 1.

2 5 7 9212

- 9-

BOARD

  Ex. ## EQU1 ## Melting Point CH 2 CH 3 CH 2 Cl 2 CH 3 aC 2%. z4- 26 [To

N) C3HECH3.0.

  6C 3m 7 CH 0 m 62-65 / 0. CR.:,.,./ecE 20 7 EiC4 - jj. we - 78-80 8 lCH 115-116 CH3

9 C P OHP0 111-114

H O0 CH3

7 9212

- 10 -

  TABLE (Continued from the previous page) Ex. No S tructure Melting Point A (CI,) o <L 1o j; HO zC2 103-104 I, a% - C2 0 1 [_ HsOj o 11i [c1N And KE20N o3 194 -196

CI 0 C CH '2 0 2

  12 L0CH: 3 0CH202.7 iquid 123H -L '"25 / CKzO! 194-196 2 O 14 [to C l 2> 115-122

44C \ P - O-- \ C <155

CH3 CH20 CH2 3

CH3 0CH2O "'NCH2" O 15509

_________j_____________CH3_

- 11 -

  Application Example A 100 parts of freshly distilled methyl methacrylate are thoroughly mixed with 0.08 parts of dilauryl peroxide, 0.06 parts of the azoisobutanoic acid dinitrile and 20 parts of the compound of formula Ia of Example 1. The mixture is heated to boiling and poured between

  glass plates which are sealed with rubber patches

  rubber and tape. The glass plates are immersed for 16 hours in a water bath at 50, and then heated at 100 in an oven for 3 hours. When removing the glass plates,

  polymethacrylate plates 3 mm thick are obtained.

  These plates are self-extinguishing according to the standard

ASTM D 635.

  Application Example B 100 parts of freshly distilled methyl methacrylate are intimately admixed with 2.2 parts of glycidyl methacrylate, 0.1 part of dilauryl peroxide, 0.08 parts of azoisobutanoic acid dinitrile and 8.3 parts of parts of the compound of formula Ia of Example 1. The mixture is then treated in a manner analogous to that described in Application Example A. The products

  obtained are self-extinguishing according to ASTM D 635.

  Application Example C 300 parts of commercial polymethyl methacrylate granules having an average molecular weight of 120,000 are dried for 4 hours at 80 ° under a vacuum of 20 mm Hg and then dry blended in a shaker with 53 parts of the compound of

  Example 11. The mixture is extruded into a wire at 230, then

  formed into granules. These granules are dried for 6 hours at 80 at 20 mm Hg and then pressed to form plates 3 mm thick. These plates give good results when they

  are subjected to the oxygen index test (ASTM D 2863-77).

  They are self-extinguishing according to ASTM D 635.

- 12 -

  Application example D In application example A, the compound of formula Ia is replaced by 25 parts of the mixture of example 2. The product

  obtained is self-extinguishing (ASTM D 635).

  In Application Examples A to C, an appropriate amount of any of the

  Examples 2 to 15, instead of the compounds of formula Ia.

2 5 7 9 2 1 2

- 13-

Claims (11)

  1. Polymers and copolymers of methyl methacrylate containing, as flame retardant, a compound of formula I R5 R4 R R4 R. C - O 0 X / O C Y Y R1 R i 'O CH / \ R3 i0CJ 2 13i I R4 R4   wherein the symbols R1, independently of each other, represent hydrogen, C1-C4alkyl, phenyl, -CO-C1-C6alkyl or -CH2-O-C1-C2alkyl, the symbols R2, independently of each other, represent hydrogen, a C1-C4 alkyl group or -CO-O-C1-C6 alkyl, the symbols R4, independently of one another, represent the hydrogen or a C1-C4 alkyl group, the symbols R5, independently of one another, represent hydrogen or a methyl group, and   X represents oxygen or sulfur.   2. Polymers or copolymers according to the claim   1, characterized in that R 1 in the compound of formula I represents hydrogen, C 1 -C 4 alkyl, -CH 2 -O-alkyl, C1-C2 or -CO-O-C1-C2alkyl.   3. Polymers or copolymers according to the claim   1 or 2, characterized in that R2 in the compound of formula I represents hydrogen or a C1-C4 alkyl group or -CO-O-C1-C2alkyl. 7 9212 - 14 -   4. Polymers or copolymers according to any one   Claims 1 to 3, characterized in that R4 in the   compound of formula I, represents hydrogen or a C1-C3 alkyl group. 5. Polymers or copolymers according to any one   Claims 1 to 4, characterized in that X, in the   compound of formula I represents oxygen.   6. Polywères or copolymers according to the claim   1, characterized in that the compound of formula I corresponds to the formula Ia / c Ri CH 2 0 0 CH 2 Ri C \ / P-0O P C \ (& R2 CH 0 0- CH R I I R4 R '   R 4 in which the symbols R 1 ', independently of one another, represent hydrogen or a C 1 -C 4 alkyl, -CH 2 -O-C 1 -C 2 alkyl or -CO-O-C 1 -C 4 alkyl group; C2, the symbols R2 ', independently of each other, represent hydrogen or a C1-C4 alkyl group or -CO-0 C1-C2alkyl, and the symbols R4t, independently of one of the other, represent   hydrogen or a C1-C3 alkyl group.   7. Polymers or copolymers according to the claim   1, characterized in that the compound of formula I corresponds to formula Ib CH 0 O.-CHS "CH3 3 3 O-H C / P -O0-P C (Ib) CH ans - - n no-CH2 R-   in which 2 "represents a gro2   Wherein R2 "represents a C1-C4 alkyl group. - 15 -   8. Polymers or copolymers according to any one   that claims 1 to 7, characterized in that they contain   from 3 to 30% by weight of a compound of formula I defined in claim cation 1.   9. A copolymer according to any one of claims 1 to 8, characterized in that the polymer has been copolymerized with one or more comonomers selected from methacrylates   C2-C8 alkyl, C1-C8 alkyl acrylates, α-cyano-   C1-C8 alkyl acrylates, styrene, methylstyrene, acrylic acid,   lonitrile, methacrylonitrile or α-chloroacrylonitrile.   10. A copolymer according to any one of the claims   1 to 9, characterized in that the polymer has been copolymerized   with glycidyl acrylate or glycidyl methacrylate.   11. Polymers or copolymers according to any one   claims 1 to 10, characterized in that they contain   one or more additives chosen from polymerization regulators, softeners, stabilizers against   U.V. rays, antioxidants and pigments.