IE903693A1

IE903693A1 - Polymers having pendant thiuram disulphide functions, their¹preparation and their application to the preparation of¹graft copolymers

Info

Publication number: IE903693A1
Application number: IE369390A
Authority: IE
Original assignee: Atochem
Priority date: 1989-10-19
Filing date: 1990-10-15
Publication date: 1991-04-24
Also published as: JPH03170508A; JPH0717701B2; CA2042015A1; CA2027612A1; FR2653434A1; KR910008026A

Abstract

These polymers consist of a chain sequence of units: <IMAGE> it being possible for this chain sequence to comprise, randomly distributed, other units originating from at least one vinyl monomer, R1 = H; allyl, cycloalkyl or aryl optionally substituted by at least one halogen; <IMAGE> alkyl, cycloalkyl or aryl); A = single bond; alkylene, cycloalkylene or arylene; or <IMAGE> (B = alkylene, cycloalkylene or arylene); R2, R3 and R4 = alkyl, cycloalkyl or aryl; it being possible for at least one of R3 and R4 to denote a polyoxyethylene or polyester block. These polymers are used as a base for the preparation of graft copolymers containing units of formula: <IMAGE> where Po = vinyl or dienic polymer block, and other vinyl units. These graft copolymers are useful especially as compatibilising agents. [FR2653434A1]

Description

it being possible far this chain linkage ta comprise a tandem distribution of ether units derived from at iaast one vinyl monomer, R, is H; alkyl, cycle alkyl or aryl each of which is unsub stituted tr substituted by at Least one halogen; -C-O-RT (R7 is E, alkyl, II a cyciaaikyi or aryL); A is a single bend; alkylene, cycioaikylena ar arylene; or -C-O-a- (3 is alkyLene, II o cycioaikylena or arylene); R», R, and -ζ are alkyl, cyciaaikyi or aryl; it being passible for at least one of R, and. R* ta represent a polyoxyethylene or polyester segnence. i These polymers ses7& as bases for tha preparation of graft copolymers gsm-.v·”'·^ che units of the formula: «ί Oifig Na bPaitinni IE 9 3 ό 3 The Patents Office R, Γ -C-ch2-c-«- (VT) A-NR,-C-5-?o-5~:-N-R. ’ il 111 S 3 R3 where ?o is a vinyl ar diene polymer sequence, and other vinyl units. These graft ccpclyrers are useful especially as compatibility agents. 4r··. rt t PATENTS ACT, 19 COMPLETE SPECIFICATTom ........... ON W L 11 3ΊΑ8 GNV 60 N0IJL03S H3QNA NOLLO3d8Ni OHSAd GJ_ N3dO arrcL-cog F_ nu POLYMERS HAVING PENDANT THIURAM DISULPHIDE FUNCTIONS, THEIR PREPARATION AND THEIR APPLICATION TO THE PREPARATION OF GRAFT COPOLYMERS ...vXH i V £ U bu’> O >bi MJ I ΐCr'· j UNDER SECTION 09 AND RULE 117 Jnl. NO. OF D&t A.. . .

:- ATOCHEM, a French company, 92800 Puteaux, France of La Defense 10, & 8 Cours Michelet, -1IE 903693 S FUNCTIONS AND ft THEIR PREPARATION The present invention relates to hcmcpolyners and copolymers having pendant thiuran disulphide functions, the abbreviation iniferters”) in free-radical polymerization of vinyl and diene monomers leading to graft. copolymers.

The present invention first provides polymers consisting of a chain linkage of units: P.

A-NR, -C-S-S-C-X-R, II II I it being possible for this chain linkage to comprise in 15 random distribution other units derived from at least one vinylic monomer, where: Rz represents a hydrogen atom or a monovalent organic radical selected from: an alkyl, cycloalkyl or aryl radical or a combination of at least two of these radicals; a -C-O-R7 radical, II where R7 represents hydrogen, an alkyl, cycloalkyl or aryl radical or a combination of at least two of these radicals, or an alkyl, cycloalkyl or aryl radical or a combination of at least two of them (in different units) substituted by at least one halogen atom, for example a 3,3,3-trifluoropropyl radical; A represents a single bond; an alkylene, cycloalkvlene or arylene radical or a combination of at least two of these radicals; or a -C—0-30 radical, where B represents an alkylene, cycloalkylene or arylene radical or a combination of at least two of these radicals; R2, R3 and R4 each represent independently an alkyl, cycloalkyl or aryl radical or a combination of at least two of these radicals; it being also possible for at least one of R3 and R4 to contain at least one hydroxyl or carboxylic acid group or represent a polyoxyethylene or polyester sequence derived from a polyoxyethylene or a polyester terminated by a hydroxyl function, respectively; it being possible for the alkyl, cycloalkyl, aryl radicals or their combinations, the alkylene, cycloalkylene, arylene radicals or their combinations which are covered by the definitions given above to contain at least one heteroatom, such as O or S, and/or at least one -N- radical, where R 1 R represents alkyl, cycloalkyl or aryl or a combination of at least two of these radicals.

Other suitable vinylic units include units of the formula: R5 where R5 and Rg represent hydrogen, an alkyl, cycloalkyl or aryl radical or a combination of at least two of these radicals; an alkyl, cycloalkyl or aryl radical or a combination of at least two of these radicals substituted by at least one halogen atom; a radical -C=N; -C-O-D-CN, where H 0 D is alkylene, cycloalkylene, arylene or a combination of at least two of these radicals; 10 — C—NH2 ; — C-NHR^g or —C—NR^yR^g, where R^g, Rj_y and O O O R]_8 represent an alkyl, cycloalkyl or aryl radical or a combination of at least two of these radicals; or a pyridine radical; with the proviso that R5 and Rg never represent hydrogen simultaneously.

Units derived from maleic anhydride and maleimides substituted on the nitrogen by an alkyl, cycloalkyl or aryl radical are also suitable.

The molecular weights of these random 20 copolymers and homopolymers are in particular between 500 and 2,000,000. The proportion of unit (I) can vary within wide limits, since at least one unit (I) can be present per copolymer chain.

The alkyl groups covered by the above 25 definitions are especially C]_-C12-, in particular C1-C6-alkyl groups; the cycloalkyl groups are especially C3-C]_2-, in particular C1-C7-cycloalkyl groups; and the aryl groups are, for example, phenyl or naphthyl groups. Furthermore, the definition of a group as an alkyl, cycloalkyl or aryl radical or an alkylene, cycloalkylene or arylene radical likewise includes the combination of at least two of these radicals, for example, an aralkyl, alkaryl radical etc.

The polyalkylene sequence covered by the definition of R3 or R4 can be derived from the following polyoxyalkylenes without the terminal CH function: Rg -3- ( -CH2-CX2 -0-) a~CH2 ----2 OH Rq-O-(-CH2-CH-O-) -CH2-CH-3H 3 I I ch3 cx 2 Rq-0-(-CX-CX7-0-) -CH-CH2-0K 3 I I cx3 ch3 where; Rg-O-(-(CH2)4-0-)a-(CH2)4-OK Rg represents an alkyl, cycloalkyl or aryl radical or a combination of at least two of these radicals and - a denotes 1 to 1,000, preferably 1 to 200.

The polyester sequence covered by the definition of R5 can be derived from the following polyesters without the terminal OH function: Ο Ο Ο ϋ II ίΙ R9-C-O-R10-r-O-C-RL1-C-O-RI0-]b-OH Ο ο H Η Rg-r-c-Rj., -C-O-R-. g-]b-OH ; at Ο Ο II .1 Rg- c -O-C-R^-C-R^- ] b-CH where: Rg is as defined above for Rg ; R]_o and R22 each independently represent an alkylene, cycloalkylene, arylene, alkenylene, arylene radical substituted by alkenyl, it being possible for these radicals to contain at least one heteroatom and/or at least one -N- radical, I R12 where R12 is chosen from alkyl, cycloalkyl and aryl groups and can contain substituents; and b denotes 1 to 300, preferably 1 co 50.

Examples of suitable radicals Rlo and R21 containing at least one unsaturation are the radicals: -ch=ch-ch2- ΐ14 Rl Λ 1 *14 '^15“ -a, ,-c-r, X J 1 -1-2 (ch2)c 1 0 | (CH,) 1 “ 1 CH (CH2)c 1 0 If 1 1 ch2 CH C=Q ll 1 ch2 CH II ch2 where c denotes 1 to 12; R13 and Rj_5 each independently represent a single bond, an alkylene, cycloalkylene or arylene radical or a combination of at least two of these radicals; R14 represents hydrogen, alkyl, cycloalkyl or aryl or a combination of at least two of these radicals; ζ3®® / ~ \ The present invention also relates to a process for the preparation of these polymers, which is characterized in that: in a first step, the polymerization of at least one monomer of the formula: 3X1 / Ri CH,=C / \ ch2=c (III) or a-nh2-r2 (III') \ φ a-nh-r2 c, x“ in which X represents a counterion, such as a halide or an acid radical, such as HSO3, and, if desired, of at least one vinylic comonomer is carried out; in a second step, the polymer obtained and 903693 comprising one units: (~Ί or P-i r I A-NH-R-C-c-::-c-3ί λ-ΜΗ,-?., IV' and, where appropriate, units tetived from the comonomer (s), is reacted in the presence of at Least one oxidizing agent with carbon, disulphide and a compound of the formula: ?·3“Τγ*2'54 R-J-NK-R, (V) or ' c?. (v') X Suitable monomers of the formula (III) are, inter alia, N-t-butylaminoethyl methacrylate, N-lbutylaminoethyl methacrylate, N-ethylaminoethyl methacrylate, N-methylaminoethyl methacrylate and the corresponding acrylates.

Suitable comonomers are, inter alia, alkyl 15 methacrylates and acrylates, in which the alkyl group contains, for example, 1 to 8 carbon atoms, vinyl aromatic hydrocarbons, unsaturated nitriles, cyanoethyl acrylates, acrylamide, lower hydroxyalkyl acrylates and methacrylates, acrylic acid and methacrylic acid, maleic anhydride and maieimides substituted by alkyl or aryl groups. Particularly suitable comonomers are methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, 2ethylhexyl methacrylate, isobutyl methacrylate and tertbutyl methacrylate, styrene, alpha-methylstyrene, monochlorostyrene, tert-butylstyrene, vinyltoluene, 25 vinylpyridine and 4-vinylpyridine.

Preferred embodiments of the two steps of this process will now be described.

First step The polymerization is carried out either as 10 bulk, suspension, emulsion or solution polymerization at a temperature from, for example, 30 to ISO’C. The solvent is one capable of solubilizing the polymer chain, for example tetrahydrofuran, toluene, ethanol or mixtures thereof.

The initiator is a compound generating free 15 radicals, such as peroxides, azo compounds, peracids and redox systems. The polymerization can be effected by photochemistry or radiochemistry.

Second step In accordance with the preferred embodiments, 20 an approximately equimolar amount of CS2 with respect to the overall number of secondary amine groups is used: those carried by units (IV) and (IV) of the polymer of the last step, plus those carried by the compound of the formula (V) or (V), the latter being used in a large molar excess with respect to (IV) or (IV), it being possible for the reaction to be carried out in the presence of a tertiary amine (for example triethylamine or pyridine), typically in an amount of about 1 mol per mole of compound (III) or in an amount of about 2 mol per mol cf compound (III1)· An oxidizing agent is added, for example, in an amount of about 1 mole per mole of CS2. It is typically, inter alia, iodine, hydrogen peroxide, a hypocniorite of an alkali metal or alkyl or aryl hydroperoxides, or potassium hexacyanoferrate.

The reaction can be carried out in a solvent, 10 for example in water, alcohol or a water/alcohol mixture, it also being possible for CS2 or the tertiary amine to function as the solvent. The reaction is in general carried out at a temperature from -20’C and ambient temperature.

The present invention also provides graft 15 copolymers whose grafts contain vinyl or diene sequences, these copolymers consisting of a chain linkage of units: Ri -- r i (VI) I A-NR2-C-S-?o-5-C-M-R. il il i SR, where Po represents a vinyl or a diene polymer sequence, it being possible for this chain linkage to contain a random distribution of units derived from at least one other vinyl monomer.

The molecular weights of the Po sequence are in general from 100 to 1,000,000 and preferably about 1,000 to 100,000.

The invention also provides a process for the preparation of these graft copolymers, whicii rs characterized in that the polymerization of a vinyl or diene monomer is carried out at a temperature of about 50 to 160 °C in the presence of an iniferter polymer, such as defined above, the latter being preferably introduced at the beginning of the polymerization together with the monomers.

The amount of iniferter polymer introduced is in general from 10”5 to 0.5 mole/1, relative to the vinyl or diene monomers.

Suitable vinyl monomers are those mentioned above.

Suitable diene monomers are, inter alia, butadiene, isoprene, 1,3-pentadiene, 1,4-pentadiene, 1,4hexadiene, 1,5-hexadiene, 1,9-decadiene, 5-methylene-2norbornene, 5-vinyl-2-norbornene, the 2-alkyl-2,5norbornadienes, 5-ethylidene-2-norbornene, 5-(2-propenyl)-220 norbornene, 5-(5-hexenyl)-2-norbornene, 1,5-cyclooctadiene, bicyclo[2.2.2]octa-2,5-diene, cyclopentadiene, 4,7,8,9tetrahydroindene and isopropylidenyltetrahydroindene.

These graft copolymers can serve to render a mixture of homopolymers PA and PB compatible with one another, in which case the chemical nature of the Po sequence is the same as that of, for example, PA, while the nature of the monomer B is the same as that of the comonomer which was used to synthesize the polymer of the invention.

The Examples which follow further illustrate the present invention.

Examples 1 to 6 Free-radical copolymerization of methyl methacrylate (MMA) with N-t-butylamincethyl methacrylate (3aeM) (Ex. 1 to 3) and n-butyl methacrylate (MM3) with 3aeM (Ex. 4 to 6) .

General procedure The copolymerizations were carried out as bulk or solution polymerization in benzene, tetrahydrofuran (THF) or dimethylformamide (DMF) at a concentration of the order of 2 mol/1 of monomer and an initiator concentration (azo or peroxide compound) of the order of 2 10-3 mol/1. The copolymerizations are carried out, protected against light, in flasks equipped with a stirrer and sealed under vacuum or maintained under an inert gas (N2, argon) after introduction of the reactants. The polymerization is carried out by immersing the flask into an oil bath with temperature control at the required temperature and over the period desired. After the copolymerization, the flask is removed and cooled in an isopropanol/dry ice mixture. The polymer is diluted in toluene, THF or any other solvent, and is then precipitated by dropwise addition to heptane or methanol. The precipitate or resinous product obtained is collected in a sintered glass crucible, washed with heptane or methanol, dried at 45’2 under a vacuum to constant weight (for 12 to 24 hours;. ?o ’erlcatlon reactions carried cut J.t 50 a2 t ~2 at on times cetwegn 4 5 en ;o.utuon 2x. .Monomers Molar fraction of M2 in the reaction mixture Mn x 10'· 1 Ϊ 1 1 Molar fraction of M2 in the copolymer Ml M2 1_ MMA BaeM 0.1 9.6 k.36 0.101 2 MMA rt O.d 10.9 ; 2 33 O.dl 3 II '* 0.7 11.5 <.53 i 1 0.595 d MMB BaeM 0.1 t» »1 0.25 0.55 .3 2.35 3.20 0.23 0.50 0.33 •Ε 903693 Examples 7a and 7b Synthesis of polviniferters having pendant thiuram groups Example 7a) g (1.56 x 10-^ mole) of the copolymer of Example 1 (containing 1.56 x 10”5 mole of secondary amine) are dissolved in 150 ml of toluene to which 1 ml (1.56 χ 102 mole) of CS2, and then 1.56 g (1.56 x 10“2 mole) of triethylamine are added. 2 g (1.56 χ 10-2 mole) of iodine dissolved in 50 ml of toluene are then added to the reaction mixture which is maintained at 20’C with stirring.

The mixture is stirred until the iodine has completely disappeared. It is then poured into a methanol/water mixture. The precipitate is redissolved in toluene, dried and recovered by evaporation of the solvent under partial vacuum.

Example 7b) 4.34 g (6.78 x 10-5 mole) of the copolymer of Example 6 containing (1.56 x 10“5 mole) of secondary amine 32ccr.da.ry amine ire treated in. one sire manner is in Example 7a.

Examples '3 co Ιό VTtTl 1“.SS Ϊ.S ?f 7CCC ΙνΤΓ.Θ Γζ Erse-radical polymerization. oi a vinyl monomer: styrene (Ex. 3 oo 11) ar.d .oydrcxyethyi methacrylate (XEMA) (Ex. 12 to Ιό) from one graft polyiniferters of Examples 7a and o.

General procedure The polymerizations are carried out in flasks (or tubes) equipped with a stirrer and, after introduction of the reactants, sealed under a vacuum or maintained under an inert gas (N2, argon) . (The graft polyiniferters obtained in Examples 7a and 7b are dissolved in toluene). The polymerizations are carried out by immersing the flasks in an oil bath with temperature control at the required temperature over the desired period. At the end of the polymerization, the flask is removed from the oil bath, cooled in an isopropanol/dry ice mixture, and the graft copolymer is poured dropwise in heptane or methanol, depending on the graft copolymer. The soluble fraction is redissolved in toluene (or methanol in the case of HE24A. as graft comonomer) and reprecipitatad in adequate nonsolvents.

The graft copolymer is then dried at 45 C to constant weight (24 to 48 hours).

Various polymerizations of styrene (Examples -3 11) and ΗΞΜΑ (Examples 12 to 15) were carried out ζ·? varying the concentration of the 'graft coiyinifarter in gram per litre of mcncmer, the temperature and the duration of polymerization with the compounds obtained by Examples 7a and 7b.

The graft copolymer is characterized by its weucht average molecular weight (Mw; and its percentage by weight of graft comonomer. Ξκ., G?I Duration of polym. •c Duration of ooivm. = (>.)' Percentage by weight of graft monomer Type Cone, in g/1 3 7a 400 70 35 73 9 7a 200 80 24 36 LO 7b 300 70 35 50 -- 7b 100 80 24 30 «te 7a 100 85 17 40 13 7a 100 85 26 61 14 7b 100 85 20 67 15 7b 100 85 33 80 1 G?T: graft polyiniferter of Example 7a or 7b ie 90S693 1.

Claims

CLAIMS A polymer comprising chain unit: Η, Γ — 1 —τ — «- —*2. - I A—MR-, -C-S-5—C-N-3 “ Η (Π 3 5 R, and, optionally, in random distribution other units derived from at least one vinylic monomer, where: Rj. represents a hydrogen atom or an alkyl, cycloalkyl or aryl radical; a -C-0-R7 radical, II where R 7 represents hydrogen, an alkyl, cycloalkyl or aryl radical optionally substituted by at least one halogen atom; - A represents a single bond; an alkylene, cycloalkylene or arylene radical or a -C-O-BII 0 radical, where B represents an alkylene, cycloalkylene or arylene radical; R 2 , R3 and R 4 each represent independently an alkyl, cycloalkyl or aryl radical; it also being possible for at least one of R 3 and R 4 to contain at least one hydroxyl or carboxylic acid group or represent a polyoxyethylene or polyester sequence derived by the removal of a hydroxyl function from a polyoxyethylene or a polyester terminated by a hydroxyl function, respectively; it being possible for the alkyl, cycloaikyl, aryl, alkylene, cycloalkylene and arylene radicals to contain at least one heteroatom, and/or at least one -N- radical, where R R represents an alkyl, cycloalkyl or aryl radical, and for different units of formula I, to contain different R 2 , R 7 , A, B, R 2 , R3 and/or R 4 radicals.
2. A polymer according to Claim 1, which has a molecular weight from 500 to 2,000,000.
3. A polymer according to claim 1 substantially as hereinbefore described.
4. Process for the preparation of a polymer as defined in Claim 1 or 2, which comprises: - in a first step, polymerizing at least one monomer of the formula: R, / ' \ A-NE-H(ΞΣΙ) or ch 2 =c ,-3, i. z. in which X represents a cation, and, X if desired, of at least one vinylic comonomer; in a second step, reacting the resulting polymer comprising the units: IE 9036 Ri (ZV) or a-nh-r 2 I -C-ch 2 -C-J- m I Α-ΗΗ,-R, Θ Θ X and, where appropriate, units derived from the comonomer(s), in the presence of at least one oxidizing agent with carbon disulphide and a compound of the formula: R 3 -nh-R 4 (V) or (V') X.
5. Process according to Claim 4, in which the monomer of formula (III) is N-t-butylaminoethyl methacrylate, N-l-butylaminoethyl methacrylate, N-ethylaminoethyl methacrylate, N-methylaminoethyl methacrylate or a corresponding acrylate.
6. Process according to Claim 4 or 5 in which in the second step at least 1 mole of CS 2 is used per secondary amine group carried by the units (IV) or (IV) of the polymer obtained in the first step, and the compound of the formula (V) or (V) is
7. . in which tertiary compound compound used in a molar excess. Process according to any one of Claims 4 to 6, the second step is carried out in the presence of a amine in an amount: of about 1 mole per mole of (III) or in an amount of about 2 moles per mole of (HI') · 3. Process according to claim 4 substantially as described in any one of Examples 1 to 7.
8. 9. A polymer as defined in claim 1 whenever prepared by a process as claimed in any one of claims 4 to 8.
9. 10. A graft copolymer whose grafts contain vinyl or diene sequences, these copolymers comprising chain units: Γ (Vi) - I II I S s R 1 where Po represents a vinyl or diene polymer sequence, it being possible for this chain linkage to contain a random distribution of units derived from at least one vinylic monomer.
10. 11. A polymer according to Claim 10 in which the molecular weight of the Po sequence is from 100 to 1,000,000.
11. 12. A polymer according to claim 10 substantially as hereinbefore described.
12. 13. Process for the preparation of a graft copolymer as defined in Claim 10 or 11, which comprises polymerizing a vinyl or diene monomer in the presence of an polymer as claimed in any one of claims 1 to 3 at a temperature of 50 to 16O°C.
13. 14. Process according to claim 13 substantially as described in any one of Examples 3 to 15.
14.
15. A graft copolymer as defined in claim 10 whenever prepared by a process as claimed in claim 13 or 14. Dated this the 15th day of October, 1990 F. R. KELLY & CO.