Note: Descriptions are shown in the official language in which they were submitted.
13399~
Antistatic and electrically conducting composition
This application is a first divisional application of
application 612,781 filed on September 25th, 1989.
The invention of the parent application relates to a
composition of a) a thermoplastic polymer containing active Cl, Br
and/or I atoms, and b) a substituted or unsubstituted tetrathio-,
tetraseleno- or tetratelluro-naphthalene or -tetracene or mixtures
thereof, to a composition containing said polymer and a charge
transfer complex (CT complex) of these naphthalenes and tetracenes
and Cl, Br and/or I, to a process for the preparation of this
composition and to the use thereof for the production of
antistatic or electrically conducting mouldings, filaments,
fibres, sheets, coatings and composites.
German patent application A-3005849 discloses
electrically conducting moulding compounds consisting of a
thermoplastic and a CT complex, these CT complexes being in the
form of fibres or needles. Compounds containing N, 0 and/or S are
used as electron donors and polycyano compounds are used as
electron acceptors. The moulding compounds can be prepared by
adding the acceptor to a polymer solution in which the donor is
dissolved, and then evaporating off the solvent. In Pure and
Applied Chemistry, vol. 56, no~ 3, pages 355-368 (1984), M.
Kryszewski et al. describe electrically conducting polymer
compositions containing, as CT complexes, those consisting of
tetrathiotetracene as electron donor and tetracyanoquinodimethane,
tetracyanoethylene or chloranil as electron acceptor. The
electrical conductivity of these systems is low on account of the
relatively low conductivity of the pure CT complexes.
la
The stability of the CT complexes with
tetracyanoquinodimethane is low. It is known that these CT
complexes have t,o be stabilized against HCN elimination, q.v.
German patent application A-3335513.
1~3994~
In Organometallics, 3, p. 732-735 (1984), J.C. Stark et al. describe
peridichalcogenated polyacenes, certain salts of which possess a high
electrical conductivity. Such halides are described in US patents
4 384 025 and 4 522 754, German Offenlegungsschriften 3 510 072 and
3 635 124 and European patent application A-O 153 905. These halides
generally melt above 300~C. They are also practically insoluble in
organic solvents. Because of these properties, the halides can only be
incorporated in the form of powders into polymers. Such polymer composi-
tions have a very low electrical conductivity since the conducting
particles are isolated in the polymer matrix.
m e invention of the parent a~plication relates to a composition comprisinq
a) a thermoplastic polymer soluble in an inert organic solvent, which
contains aliphatic or cycloaliphatic side groups bonded to a polymer
backbone via a group -O-, -O-CO-, -CO-OR2 2 -OCO- or -CO-O-, said side
groups containing at least one Cl, Br or I atom in the a-, B-, r- or
~-position, R22 being C2-C12alkylene, C4-C12cycloalkylene, C4-C1zcyclo-
alkylene-CH2-, C4-C1zcycloalkylene-(CH2)z-, benzylene or xylylene which
is unsubstituted or substituted by OH, Cl, Br or phenyl, and
b) a charge transfer complex (CT complex) formed of chlorine, bromine or
iotine and a compound of formula I or Ia
R ~
~z ~ 2- (I), 16 1l . 1 31 (Ia),
R2/ ~ \R4 R6/ ~ \4.~ ~R8
or mixtures thereof, wherein X is S, Se or Te, Rl, R2, R3 and R4 are
independently of the others a hydrogen atom or Cl, or R1 and R2, and R3
and R4, together are each
~-\ /S\ ~N\ /S\
I 1l or I il or
~-/ \S/ ~N/ \S/
13 3994a
Rl, R2, R3 and R4 are each phenylthio, 4-methylphenylthio, 4-methoxy-
phenylthio or pyrid-4-ylthio, and Rs, R6, R7 and R8 are independently of
the others H or F, or R5 is CH3 and R6, R7 and R8 are H, or Rs, R6, R7
and R8 are CH3, or Rs and R6 are CH3 or Cl and R7 and R8 are H, or Rs and
R6 are H , R7 is -COR9 and R8 is H or -COR9, or Rs and Rs are H and R7 and
R8 together are -CO-O-CO- or -CO-NRl~-CO-, wherein R9 is halogen, -OH,
-NH2, the radical of an alcohol or of a primary or secondary amine, or
-OM, M being a cation, and Rl~ is H or the radical of a primary amine
from which the NHz group has been removed.
Component b) is preferably present in an amount of 0.01 to 20 % by
weight, more preferably 0.05 to 10 % by weight and most preferably 0.1 to
5 % by weight, based on polymer a).
Some of the compounds of component b) and their preparation are described
in the afore-mentioned publications. Preferred CT complexes of component
b) are those formed of compounds of formula Ia and especially of tetra-
thiotetracene, tetraselenotetracene or 2-fluoro- or 2,3-difluoro-tetra-
selenotetracene.
The CT complex formed of Cl and a compound of formula Ia is especially
preferred. The CT complex of component b) is (tetraselenotetracene)2Cl in
particular.
In a preferred embodiment, the CT complex of component b) is in the form
of a needle network of crystal needles.
The novel compounds of formula II or IIa
Rl 5 ~ Rl s Rl l ~ . Rl 3
i1 1 ( II), i1 i i i i ( IIa),
Rl 6 / ~ \Rl 6 Rl 2 / \ ~ ~ \Rl 4
wherein Rls and Rl 6 are each phenylthio, 4-methylphenylthio, 4-methoxy-
phenylthio or pyrid-4-ylthio, or wherein Rls and Rl6 together are
133934a
-- 4 --
~-\ /S\ ~N\ /S\
i! or ! i!
~- S ~N S/
R11 is -CH3 and R12, R13 and R14 are H, or R11 and R12 are Cl or CH3 and
R13 and R14 are H, or R11, R12, R13 and R14 are -CH3 or F, and X is S, Se
or Te can be prepared e.g. as described below:
a) Tetramethyltetracenes
The known starting compounds 4,5-dimethylphthalic anhydride and
2,3-dimethyl-6,7-dihydroxynaphthalene are reacted in the presence of B2O3
to give 2,3,8,9-tetramethyl-5,12-dihydroxy-6,12-dioxotetracene (A). This
reaction and the subsequent chlorination and reduction to give the pro-
duct tetrachlorinated in the 5-, 6-, 11- and 12-positions are described
in German Offenlegungsschrift 3635124. Reaction with NazX2 yields the
corresponding tetrachalcogenated tetracene. In a variant, 2,3,8,9-tetra-
methyl-5,5,6,11,12,12-hexachlorodihydrotetracene (obtained on chlorina-
tion with PCls/POCl3) can be reacted with 1 equivalent of Na2Se2 and 2
equivalents of Na2Se to give the corresponding tetraselenotetracene
direct. Compound A can also be alkylated with dimethyl sulfate to give
the 5,12-dimethoxy derivative [q.v. Chem. Pharm. Bull. 20(4), 827
(1972)]. Reaction of this derivative with P4S1o in tetrahydrofuran,
followed by oxidation with Br2 and then reduction with TiCl3, yields
2,3,8,9-tetramethyl-5,6,11,12-tetrathiotetracene.
b) 2-Methyltetracenes
2-Methyl-5,12-dioxodihydrotetracene is obtained according to the instruc-
tions in Chem. Ber. 64, 1713 (1931). Reduction with Zn in alkaline solu-
tion yields 2-methyl-5,12-tetrahydrotetracene, which can be dehydro-
genated with chloranil to give 2-methyltetracene. Reaction with S (see US
patent 3 723 417) gives 2-methyl-5,6,11,12-tetrathiotetracene. Another
possibility is to prepare 2-methyl-5,6,11,12-tetrachlorotetracene as
described in a) and react it with NazX2.
- 5 - 1 3399~ ~
c) Tetrafluorotetracenes
According to the instructions in Chem. Ber. 31, 1159 and 1272 (1898),
2,3,8,9-tetrafluoro-5,12-dihydroxy-6,12-dioxotetracene (B) is obtained by
condensing 2,3-difluorophthalic anhydride with succinic acid and then
treating the condensation product with sodium ethylate in ethanol.
Further reaction with PCl5 and then with SnCl2/CH3COOH to give 2,3,8,9-
tetrafluoro-5,6,11,12-tetrachlorotetracene is carried out analogously to
the instructions in Zhuv. Org. Kim. 15(2), 391 (1979). Reaction with
Na2X2 gives the corresponding 2,3,8,9-tetrafluorotetrachalcogenotetra-
cenes. Reduction of compound B with Al in cyclohexanol yields 2,3,8,9-
tetrafluorotetracene, which reacts with sulfur [see Bull. Soc. Chim. 15,
27 (1948)] to give 2,3,8,9-tetrafluoro-5,6,11,12-tetrathiotetracene.
d) Naphthalenes
Starting from known 2,3,6,7-tetrachlorotetrachalcogenonaphthalenes (see
US patent 3 769 276), it is possible to obtain the corresponding 2,3,6,7-
substituted tetrachalcogenonaphthalenes by reaction with the potassium
salts of thiophenol, 4-methylthiophenol, 4-methoxythiophenol, 4-mercapto-
pyridine, 1,2-benzodithiol or pyrazine-2,3-dithiol.
e) Dimethyl- and dichloro-tetracenes
The procedure is analogous to that described under a), except that
4,5-dimethyl- and 4,5-dichloro-phthalic anhydrides are reacted with
6,7-dihydroxynaphthalene as starting compounds and chlorination is
carried out with PCls/POCl3.
In formulae I, Ia, II and IIa, X is preferably S or Se. R9 as halogen is
especially chlorine.
In the radical -OM, M can be a metal or ammonium cation. Typical metal
cations are especially those of the alkali metals and alkaline earth
metals, e.g. Li , Na , K , Mg2 , Ca2 , Sr2 and Ba2 . Zn2 and Cd2 are
also suitable. Examples of typical ammonium cations are NH4 and primary,
secondary, tertiary or quaternary ammonium, which can preferably contain
133994~
-- 6 --
C1-C1zalkyl, cyclohexyl, cyclopentyl, phenyl or benzyl groups. The
ammonium cations can also be derived from 5- or 6-membered heterocyclic
amines, e.g. piperidine, pyrrole and morpholine.
R9 as the radical of an alcohol is preferably C1-C6alkoxy or Cz-C6-
hydroxyalkoxy, benzyloxy, phenoxy, cyclopentoxy or cyclohexyloxy.
R9 as the radical of a primary or secondary amine is preferably derivedfrom alkylamines containing one or two C1-C6alkyl groups.
R10 is preferably H, C1-C1galkyl, phenyl or benzyl.
R10 as alkyl preferably contains 1 to 12 and especially 1 to 6 C atoms.
Examples of alkyl, which can be linear or branched, are: methyl, ethyl,n- or i-propyl, n-, i- or t-butyl, pentyl, hexyl, 2-ethylhexyl, heptyl,
octyl, nonyl, decyl, undecyl and dodecyl.
Examples of alkoxy and hydroxyalkoxy are: methoxy, ethoxy, propoxy,
butoxy, pentoxy, hexyloxy, B-hydroxyethoxy, r-hydroxypropoxy, ~-hydroxy-
butoxy and ~-hydroxyhexyloxy.
In a preferred embodiment, the composition contains up to 95 % by weight,
based on polymer a), of at least one thermoplastic or elastomeric polymer
differing from component a). In particular, the composition contains up
to 80 % by weight of the additional polymer.
The additional polymers are advantageously inert towards the compounds of
component b). The polymers therefore preferably contain essentially no
strongly acidic groups, e.g. carboxyl groups, or strongly basic groups,
e.g. primary or secondary amine groups. The polymers can be e.g. thermo-
plastics or elastomers.
In a preferred embodiment, the thermoplastic polymers are polymers of
monoolefins and diolefins copolymers of monoolefins and/or diolefins
polystyrene, poly(p-methylstyrene) or poly(~-methylstyrene) copolymers
13393~
-- 7 --
of styrene or ~-methylstyrene; graft copolymers of styrene or ~-methyl-
styrene; halogen-containing polymers; polymers and copolymers of deriva-
tives of ~,B-unsaturated acids; polymers derived from acyl derivatives or
acetates of unsaturated alcohols; homopolymers and copolymers of cyclic
ethers; polyacetals; polyphenylene oxides and sulfides and mixtures
thereof with styrene polymers; polyurethanes; polyureas; polyimides;
polybenzimidazoles; polycarbonates; polyesters; polyester-carbonates;
polysulfones; polyether-sulfones; polyether-ketones; polyvinylcarbazole;
polyadducts of unsubstituted or hydroxyalkylated epoxy compounds contain-
ing an average of more than one epoxy group per molecule, and diols,
primary monoamines, disecondary diamines, disecondary linear or cyclic
dicarboxylic acid diamides or dicarboxylic acids; cellulose derivatives;
sulfur-crosslinked products derived from polymers containing double
bonds; and mixtures of the afore-mentioned polymers.
Examples of polymers are:
1. Polymers of monoolefins and diolefins, for example polypropylene,
polyisobutylene, polybut-l-ene, polymethylpent-1-ene, polyisoprene or
polybutadiene, and polymers of cycloolefins such as cyclopentene or
norbornene, and also polyethylene, e.g. high density polyethylene (HDPE),
low density polyethylene (LDPE) or linear low density polyethylene
(LLDPE).
2. Mixtures of the polymers mentioned under 1), e.g. mixtures of poly-
propylene with polyisobutylene and polypropylene with polyethylene (e.g.
PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (e.g.
LDPE/HDPE).
3. Copolymers of monoolefins and diolefins with one another or with other
vinyl monomers, e.g. ethylene/propylene copolymers, propylene/but-1-ene
copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene
copolymers, ethylene/hexene copolymers, ethylene/methylpentene
copolymers, ethylene/heptene copolymers, ethylene/octene copolymers,
propylene/butadiene copolymers, isobutylene/isoprene copolymers,
ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate
1~994a
-- 8 --
copolymers and ethylene/vinyl acetate copolymers, and terpolymers of
ethylene with propylene and a diene such as hexadiene, dicyclopentadiene
or ethylidenenorbornene, and also mixtures of such copolymers with one
another and with polymers mentioned under 1), e.g. polypropylene with
ethylene/propylene copolymers, LDPE with ethylene/vinyl acetate
copolymers, LDPE with ethylene/acrylic acid ester copolymers, LLDPE with
ethylene/vinyl acetate copolymers and LLDPE with ethylene/acrylic acid
ester copolymers.
4. Polystyrene, poly(p-methylstyrene) and poly(~-methylstyrene).
5. Copolymers of styrene or ~-methylstyrene with dienes or acrylic
derivatives, e.g. styrene/butadiene, styrene/acrylonitrile, styrene/alkyl
methacrylate, styrene/butadiene/alkyl acrylate, styrene/maleic anhydride
and styrene/acrylonitrile/methyl acrylate, high impact strength mixtures
of styrene copolymers and another polymer, e.g. a polyacrylate, a diene
polymer or an ethylene/propylene/diene terpolymer, and block copolymers
of s tyrene, e.g. styrene/butadienelstyrene, styrene/isoprene/styrene,
styrene/ethylene-butylene/styrene, styrene/ethylene-propylene/styrene or
styrene/4-vinylpyridine/styrene.
6. Graft copolymers of styrene or ~-methylstyrene, e.g. styrene on poly-
butadiene, styrene on polybutadiene/styrene or polybutadiene/acrylo-
nitrile copolymers, styrene and acrylonitrile (or methacrylonitrile) on
polybutadiene, styrene, acrylonitrile and methyl methacrylate on poly-
butadiene, styrene and maleic anhydride on polybutadiene, styrene,
acrylonitrile and maleic anhydride or maleimide on polybutadiene, styrene
and maleimide on polybutadiene, styrene and alkyl acrylates or alkyl
methacrylates on polybutadiene, styrene and acrylonitrile on
ethylenelpropylene/diene terpolymers, styrene and acrylonitrile on poly-
alkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on
acrylate/butadiene copolymers, and mixtures thereof with the copolymers
mentioned under 5), e.g. those known as ABS, MBS, ASA or AES polymers.
_ 9 _ 1 3 39 9 ~ ~
7. Halogen-containing polymers, e.g. polychloroprene, chlorinated rubber,
chlorinated or chlorosulfonated polyethylene, epichlorohydrin homopoly-
mers and copolymers, especially polymers of halogen-containing vinyl
compounds, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl
fluoride or polyvinylidene fluoride, and copolymers thereof such as vinyl
chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene
chloride/vinyl acetate.
8. Polymers derived from derivatives of ~,B-unsaturated acids, such as
polyacrylates, polymethacrylates and polyacrylonitriles.
9. Copolymers of the monomers mentioned under 8) with one another or with
other unsaturated monomers, e.g. acrylonitrile/butadiene copolymers,
acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl
acrylate copolymers, acrylonitrile/vinyl halide copolymers,
acrylonitrile/alkyl methacrylate/butadiene terpolymers or alkyl
methacrylate/4-vinylpyridine copolymers.
10. Polymers derived from acyl derivatives or acetals of unsaturated
alcohols, such as polyvinyl acetate, stearate, benzoate or maleate,
polyvinylbutyral or polyallyl phthalate, and copolymers thereof with
olefins mentioned in section 1.
11. Homopolymers and copolymers of cyclic ethers, such as polyalkylene
glycols, polyethylene oxide, polypropylene oxide or polybutylene glycol.
12. Polyacetals such as polyoxymethylene and polyoxymethylenes which
contain comonomers such as ethylene oxide, and polyacetals modified with
thermoplastic polyurethanes, acrylates or MBS.
13. Polyphenylene oxides and sulfides and mixtures thereof with styrene
polymers.
14. Polyurethanes derived on the one hand from polyethers, polyesters and
polybutadienes containing terminal hydroxyl groups and on the other hand
from aliphatic or aromatic polyisocyanates, and precursors thereof.
1~9~4~
-- ~o --
15. Polyureas, polyimides and polybenzimidazoles. Among the polyimides,
soluble polyimides are especially preferred, such as those disclosed e.g.
in German Auslegeschrift 1962588 and European patent applications
A-132221, A-134752, A-162017, A-181837 and A-182745.
16. Polycarbonates, polyesters, e.g. polyalkylene terephthalates, and
polyester-carbonates.
17. Polysulfones, polyether-sulfones and polyether-ketones.
18. Polyvinylcarbazole.
19. Polyadducts of unsubstituted or hydroxyalkylated epoxy compounds
containing an average of more than one epoxy group per molecule, and
diols, primary monoamines, disecondary diamines, disecondary linear or
cyclic dicarboxylic acid diamides or dicarboxylic acids.
20. Cellulose derivatives chemically modified in a polymer-homologous
manner, such as cellulose acetates, propionates and butyrates, or
cellulose ethers such as methyl cellulose.
21. Sulfur-crosslinked (vulcanized) products derived from polymers
containing double bonds, e.g. natural rubber, synthetic rubber and
butadiene or isoprene polymers or copolymers.
22. Mixtures (polyblends) of the afore-mentioned polymers, e.g. PP/EPDM,
PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PC/ASA, PC/PBT, PVC/CPE,
PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate,
POM/MBS and PPO/HIPS.
A preferred group of thermoplastic polymers comprises polyolefins, poly-
styrene, polyvinyl chloride, polyvinylidene chloride, polyvinylidene
fluoride, polyacrylates, polymethacrylates, polycarbonates, aromatic
polysulfones, aromatic polyethers, aromatic polyether-sulfones and poly-
imides, as well as polyvinylcarbazole.
133994a
- 11
The thermoplastic polymers of component a) can have a degree of poly-
merization of 5 to 10,000, preferably 10 to 5000 and in particular 10 to
1 000 .
The composition of the invention can also contain thermosetting polymers,
e.g. up to 95 ~/O by weight and especially up to 80 % by weight.
Examples are:
1. Crosslinked unsaturated polyesters of e.g. maleic acid and diols and,
if desired, comonomers such as styrene.
2. Crosslinked epoxy resins derived from polyepoxides, e.g. from bis-
glycidyl ethers or cycloaliphatic diepoxides. They can be thermally
crosslinked e.g. with anhydrides or using curing catalysts.
The aliphatic and cycloaliphatic side groups of component a) are sub-
stituted by Cl, Br or I, especially in the ~-, B- or ~-position and more
especially in the ~- and/or B-position. The aliphatic group preferably
contains 1 to 4 C atoms which are partially or totally substituted by Cl,
Br or I. Substitution by Cl is especially preferred.
The aliphatic side group can be e.g. linear or branched C1-C1-2,
especially C1-C6 and more especially C1-C~alkyl. Examples are methyl,
ethyl and the isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl,
nonyl, decyl, undecyl and dodecyl. Examples of cycloaliphatic groups are,
in particular, cyclopentyl and cyclohexyl. Methyl or ethyl monosubsti-
tuted or polysubstituted by Cl, Br or I, in particular Cl, are especially
preferred, e.g. -CH2Cl, -CHClz, -CCl3, -CHClCH3, -CClzCH3, -CHCl-CHzCl,
-CCl2-CH2Cl, -CHCl-CHCl2, -CClz-CHCl2~ -CCl2-CCl3, -CHz~CH2Cl~ -CH2-CHCl2
or -CHz-CCl3.
The groups -O-, -O-C0-, -CO-OR22-O-CO- or -CO-O- preferably have groups~f the formula -C H X2 bonded to them, wherein m is a number from 1 to
m n o
12, n is 0 or a number from 1 to 24, o is a number from 1 to 25 and
13~994~
- 12 -
n + o = 2m + 1, x2 is Cl, Br or I and R22 is C2-C12alkylene, C4-C12cyclo-
alkylene, C4-C1zcycloalkylene-CH2-, Cz-Cl2cycloalkylene-~CH2~,
benzylene or xylylene which is unsubstituted or substituted by OH, Cl, Br
or phenyl. x2 is preferably Cl, m is preferably 1 to 6, especially 1 to
4, n is preferably 0 or 1 to 12, especially 1 to 8, o is preferably 1 to
13, especially 1 to 9, and n + o = 2m + 1.
The thermoplastic polymers can be based on different polymers containing
hydroxyl groups or carboxyl groups, or mixtures of said polymers, e.g.
polyesters, polyester-amides, polyurethanes, polyamides, polycarbonates
and polyimides derived from monomers containing hydroxyl groups,
saponified and unsubstituted or hydroxyalkylated polymers of vinyl esters
or ethers, hydroxylated polydiolefins such as polybutadiene or polyiso-
prene, polyacrylates or polymethacrylates containing hydroxyalkyl
radicals in the ester group, polyacrylic or polymethacrylic acids, or
reduced polyketones or copolymers thereof, as well as copolymers of
unsubstituted or hydroxyalkylated vinyl alcohol, acrylates or
methacrylates, acrylic acids or methacrylic acids or diolefins with
comonomers such as acrylonitrile, olefins, diolefins, vinyl chloride,
vinylidene chloride, vinyl fluoride, vinylidene fluoride, styrene,
~-methylstyrene, maleic anhydride, maleimide, vinyl ethers and vinyl
esters, and polyadducts of unsubstituted or hydroxyalkylated epoxy com-
pounds containing an average of more than one epoxy group per molecule,
and diols, primary monoamines, disecondary diamines, disecondary linear
or cyclic dicarboxylic acid diamides or dicarboxylic acids.
In a preferred embodiment, the thermoplastic polymer of component a) is a
linear polyadduct of a glycidyl compound containing an average of more
than one epoxy group, and a diol, a primary monoamine, a disecondary
diamine, a disecondary linear or cyclic dicarboxylic acid diamide or a
dicarboxylic acid, in which polyadduct the H atom of the secondary OH
groups is at least partially substituted by a group -CO-C H X2, wherein
m is a number from 1 to 12, n is O or a number from 1 to 24, o is a
number from 1 to 25 and n + o = 2m + 1, and x2 is Cl, Br or I.
- 13 - 13 ~ ~ ~ 4 ~
The polyadducts are preferably based on glycidyl compounds containing an
average of two epoxy groups per molecule.
Especially suitable glycidyl compounds are those containing two glycidyl
groups, B-methylglycidyl groups or 2,3-epoxycyclopentyl groups bonded to
a heteroatom (e.g. sulfur or, preferably, oxygen or nitrogen), especially
bis(2,3-epoxycyclopentyl) ether; diglycidyl ethers of polyhydric
aliphatic alcohols such as butane-1,4-diol, or of polyalkylene glycols
such as polypropylene glycol; diglycidyl ethers of cycloaliphatic polyols
such as 2,2-bis(4-hydroxycyclohexyl)propane; diglycidyl ethers of poly-
hydric phenols such as resorcinol, bis(p-hydroxyphenyl)methane, 2,2-bis-
(p-hydroxyphenyl)propane (= diomethane), 2,2-bis(4'-hydroxy-3',5'-di-
bromophenyl)propane and 1,3-di(p-hydroxyphenyl)ethane: di(B-methyl-
glycidyl) ethers of the dihydric alcohols or dihydric phenols listed
above; diglycidyl esters of dicarboxylic acids such as phthalic acid,
terephthalic acid, ~4-tetrahydrophthalic acid and hexahydrophthalic acid;
N,N-diglycidyl derivatives of primary amines and amides and heterocyclic
nitrogen bases containing two N atoms, and N,N'-diglycidyl derivatives of
disecondary diamides and diamines, such as N,N-diglycidylaniline, N,N-di-
glycidyltoluidine, N,N-diglycidyl-p-aminophenyl methyl ether and N,N'-di-
methyl-N,N'-diglycidyl-bis(p-aminophenyl)methane; N',N"-diglycidyl-N-
phenyl isocyanurate; N,N'-diglycidylethyleneurea; N,N'-diglycidyl-5,5-
dimethylhydantoin, N,N'-diglycidyl-5-isopropylhydantoin, N,N-methylene-
bis(N',N'-diglycidyl-5,5-dimethylhydantoin) and 1,3-bis(N-glycidyl-5,5-
dimethylhydantoin)-2-hydroxypropane; and N,N'-diglycidyl-5,5-dimethyl-6-
isopropyl-5,6-dihydrouracil.
The glycidyl compounds can be reacted with aliphatic, cycloaliphatic oraromatic diols to give the preferred polyadducts, a secondary alcohol
group, which can be esterified with carboxylic acids containing Cl, Br
and/or I, being formed by addition on to the glycidyl group.
However, the glycidyl compounds can also be reacted with the following
compounds to give linear polyadducts by polyaddition: primary aliphatic,
cycloaliphatic or aromatic monoamines (e.g. aniline, toluidine, Cl-C12-
alkylamines, C2-C12hydroxyalkylamines), aliphatic, cycloaliphatic or
13~9~
- 14 - 21489-7823D
aromatic dicarboxylic acids (e.g. maleic acid, adipic acid, trimethyl-
adipic acid, sebacic acid, azelaic acid, succinic acid, dodecylsuccinic
acid, phthalic acid, terephthalic acid, ~4-tetrahydrophthalic acid, hexa-
hydrophthalic acid, ~4-methylhexahydrophthalic acid, 3,6-endomethylene-
~4-tetrahydrophthalic acid, 4-methyl-3,6-endomethylene-~4-tetrahydro-
phthalic acid) or aliphatic, cycloaliphatic, heterocyclic or aromatic
bis-secondary amines or bis-secondary carboxamides (e.g. N,N'-dimethyl-
ethylenediamine, N,N'-dimethylpropylene-1,3-diamine, N,N'-dimethylhexa-
methylenediamine, N,N'-dicyclohexylhexamethylenediamine, N,N',N"-tri-
methyldiethylenetriamine, N,N'-diethylpropylene-1,3-diamine, N-methyl-
3,5,5-trimethyl-3-(methylaminomethyl)cyclohexylamine, N,N'-dimethylated
or N,N'-diethylated aromatic diamines, e.g. m- or p-phenylenediamine,
bis(4-aminophenyl)methane or bis(4-aminophenyl) sulfone, 2,2-bis(4-amino-
phenyl)propane, N,N-dimethyl-m-xylylenediamine, as well as ethyleneurea,
5,5-dimethylhydantoin, 5-isopropylhydantoin, N,N-methylene-bis-5,5-
dimethylhydantoin, 1,3-bis(5,5-dimethylhydantoin)-2-hydroxypropane,
5,5-dimethyl-6-isopropyl-5,6-dihydrouracil).
It is preferred to use a compound in which the polyadduct
contains
a) 100 to 0.1 mol% of identical or different structural units of
formula V
_o-R2 4 -O-CHz-lCH-CH2-OR2s~ (V)
OR260COC H x2
m n o
and
b) 99.9 to O mol% of identical or different structural units of
formula VI
_o-R2 4 -O-CHz-lCH-CH2-OR2s- (VI)
R'
based on the polyadduct, wherein R24 and R2s are independently of the
other the radical of a diol containing aliphatic or aromatic diol groups,
from which two hydroxyl groups have been removed, R' is H, unsubstituted
- 15 - ~ ~ 39 9 4 ~
or OH-substituted Cl-Czoalkyl~ C1-Czoacyl or aminocarbonyl N-substituted
by a C1-C2ohydrocarbon radical, -oR2 6 - iS a direct bond or R2 6 iS
ethylene which is unsubstituted or substituted by C1-C16alkyl.
The composition preferably contains 100 to 20 and especially 30 to
100 mol% of structural units of formula V and 80 to 0 and especially 70
to 0 mol% of structural units of formula VI.
In a preferred embodiment, R24 and R2s are identical radicals. R24 and
R2s as radicals having aliphatic diol groups preferably contain 2 to 12
and especially 2 to 8 C atoms. The hydroxyl groups can be bonded to open-
chain or cyclic aliphatic radicals. Examples of typical aliphatic
radicals are linear or branched Cz-Cl2alkylene, C3-Cscycloalkylene,
C1-C4alkyl-Cs-C8cycloalkyl, cyclohexylmethylene or cyclohexyldimethylene.
Examples are ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3- or 1,4-butylene,
1,2-, 1,3-, 1,4- or 1,5-pentylene, 1,2-, 1,3-, 1,4-, 1,5- or
1,6-hexylene, heptylene, octylene, nonylene, decylene, undecylene,
dodecylene, 1,3-cyclopentylene, 1,3- or 1,4-cyclohexylene, 2-methyl-1,4-
cyclohexylene and cyclohexyl-1,4-dimethylene.
The aromatic diol groups of the diols used for the polyadducts are
especially phenolic groups. The diol radicals having phenolic groups
preferably contain 6-30 and especially 6-20 C atoms. A preferred
embodiment consists of compositions in which R24 and R2s are
independently of the other a radical of the formula
wherein X1 is a direct bond, C1-C4alkylene, C2-C12alkylidene, Cs-C8cyclo-
alkylidene, -O-, -S-, -SO-, -SOz-, -CO-, -CO2-, -N(C1-C4alkyl)- or
-Si(CH3)2-, R27 and R23 are independently of the other H, halogen, Cl-C4-
alkyl or C1-C4alkoxy, x is 0, 1 or 2 and y is 0 or 1.
16 1 3 3 9 3 4 A~
Xl is preferably a direct bond, methylene, ethylene, C2-C6alkylidene,
cyclohexylidene, cyclopentylidene, -O- or -S-. R27 and R23 are preferably
H or methyl and y is preferably 1.
R2 4 and R25 are especially the radical
~=- H3 ~=-
R26 as alkyl-substituted ethylene preferably contains C1-C4alkyl and
especially Cl or C2alkyl. Ethylene, 1,2-propylene and 1,2- or
2,3-butylene are especially preferred.
R' as Cl-Czoalkyl can be linear or branched. R' as acyl can be e.g.
Cl-C2oalkyl-CO-, Cs-Cgcycloalkyl-CO-, Cl-Clsalkyl-Cs-Cgcycloalkyl-CO-,
Cs-Cgcycloalkyl-CH2-CO-, C1-Cl4alkyl-C5-Cgcycloalkyl-CH2-CO-, phenyl-CO-,
benzyl-CO-, Cl-Cl4alkyl-phenyl-CO- or Cl-Cl4alkyl-benzyl-CO-. The hydro-
carbon radical in the aminocarbonyl can be e.g. Cl-Czoalkyl-~ Cs-Cgcyclo-
alkyl-, Cl-Clsalkyl-Cs-c8cycloalkyl-~ Cs-Cgcycloalkyl-CH2-, Cl-Cl4alkyl-
Cs-Cgcycloalkyl-CH2-, phenyl-, benzyl-, Cl-Cl4alkyl-phenyl- or Cl-Cl4-
alkyl-benzyl-. R' is preferably H.
In another preferred embodiment, the thermoplastic polymer of componenta) is a homopolymer or copolymer of an acrylic acid or methacrylic acid
ester containing chlorinated, brominated and/or iodinated aliphatic or
cycloaliphatic groups in the ester group.
In an especially preferred embodiment, the polymer contains
a) 0.1 to 100 mol% of at least one structural unit of formula III
Rl7
-CHz-~-o (III),
Rls
~339~34~
and
b) O to 99.9 mol% of at least one structural unit of formula IV
~ ~20
- ¢ ¢ - (IV)
Rl 9 R2 1
based on the polymer, wherein Rl7 is H or methyl; Rl8 is a radical
~~R22-O-CO~--C H X2, wherein z is O or 1, m is a number from 1 to
z m n o
12, n is O or a number from 1 to 24, o is a number from 1 to 25 and
n + o = 2m + 1, x2 is Cl, Br or I and R22 is Cz-Cl2alkylene, C4-C1zcyclo-
alkylene, C4-Cl 2Cycloalkylene-cH2-~ Cz-cl 2Cycloalkylene~cH2~
benzylene or xylylene which is unsubstituted or substituted by OH, Cl, Br
or phenyl; R19 is H, C1-C6alkyl or -COOR2 3; R20 is H, F, Cl, CN or C1-C6-
alkyl; and R21 is H, F, Cl, CN, R23-o-, C1-C12alkyl, -CooR23, -o-Co-R23,
-COOR22-OH, -COOCH2C~-~H2 or phenyl, wherein R2 2 is as defined above and
R23 is C1-C18alkyl, Cs-C7cycloalkyl, (C1-C1zalkyl)-Cs-C7cycloalkyl,
phenyl, (C1-C12alkyl)phenyl, benzyl or (Cl-Clzalkyl)benzyl.
The polymer preferably contains 100 to 20 and especially 100 to 30 mol~/O
of structural units of formula III and 80 to O and especially 70 to
O mol% of structural units of formula IV.
Rl7 is preferably methyl. X2, m, n and o have the preferred meanings
given above and z is preferably 1.
R2 2 is preferably unsubstituted or substituted by OH or Cl. R2 2 as
alkylene preferably contains 2 to 6 C atoms. The alkylene can be linear
or branched. Examples are ethylene and the isomers of propylene,
butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene,
undecylene and dodecylene. R22 as cycloalkylene is especially cyclo-
hexylene and, in the radicals containing cycloalkylene, is preferably
cyclohexylene.
~3.~994.~-
-- 18 --
R2 3 can be linear or branched C1-C1 8, preferably C1-C1 2 and especially
Cl-C6alkyl- R2 3 as cycloalkyl is especially cyclopentyl or cyclohexyl.
When R23 is (C1-C12alkyl)cycloalkyl, the cycloalkyl is especially cyclo-
pentyl or cyclohexyl and the alkyl group can be linear or branched and
preferably contains 1 to 6 and especially l to 4 C atoms. When R2 3 iS
alkylphenyl or alkylbenzyl, the alkyl group can be linear or branched and
preferably contains 1 to 6 and especially 1 to 4 C atoms.
Rl9 is preferably H. R19 as alkyl is preferably methyl or ethyl. When Rl9
is -CooR23, R23 is preferably C1-Cl2 and especially Cl-C6alkyl.
R20 as alkyl is preferably Cl-C4alkyl, e.g. methyl, ethyl, n-propyl or
n-butyl. R20 is preferably H, Cl or Cl-C4alkyl.
When R2l is the group R2 3 -O-, R2 3 iS preferably Cl-Cl 2 and especially
Cl-C6alkyl. R21 as alkyl preferably contains 1 to 6 and especially 1 to
4 C atoms. When R21 is the group -COOR2 3, R2 3 iS preferably Cl-Cl 2 and
especially Cl-C6alkyl, cyclopentyl or cyclohexyl. When R21 is the group
-oCo-R23, R23 is preferably Cl-Cl2 and especially Cl-C6alkyl, phenyl or
benzyl.
When R21 is the group -COOR220H, R22 has the preferred meanings given
above.
In a preferred embodiment, Rl9 is H, R20 is H, F, Cl, methyl or ethyl and
R21 is F, Cl, CN, Cl-C4alkyl, Cl-C6alkoxy, -COO-Cl-C6alkyl, -COO-R22-OH,
-OOC-C1-C6alkyl or phenyl.
In a preferred composition, Rl7 is methyl; Rl3 is a radical
~R22-O-CO-C H X2, wherein m is a number from 1 to 6, n is O or a number
m n o
from 1 to 12, o is a number from 1 to 13 and n + o = 2m + 1, x2 is Cl and
R22 is C2-C6alkylene, cyclopentylene, cyclohexylene, cyclopentylene-CHz-,
cyclohexylene-CH2- or cyclohexylene-~CH2~7 which is unsubstituted
or substituted by OH or Cl; Rl9 is H; R20 is H, F, Cl or C~-C4alkyl; and
R21 is H, F, Cl, CN, R23-o-, C1-C6alkyl, -CooR23, -o-Co-R23, -COOR22-OH,
1~39~4 :~
- 19 -
-COOCHzC~-~Hz or phenyl, R22 being as defined above and R23 being
o
C1-C6alkyl, Cs or C6cycloalkyl, phenyl or benzyl.
In another preferred composition, R17 is methyl; R13 is a radical
~R22-O-CO-C H X2, wherein m is a number from 1 to 4, n is O or a number
m n o
from 1 to 8, o is a number from 1 to 13 and n + o = 2m + 1, x2 is Cl and
R22 is linear Cz-C6alkylene or -CH2CHOHCHz-; R19 and R20 are H; and R
is -COOR22OH or -COOR2 3, wherein R22 is as defined above and R23 is
C 1 -C 6 alkyl.
Especially preferred compositions are those in which, in formula III, R17
is H or CH3 and R2 2 is linear or branched Cz-C6alkylene, cyclopentylene
or cyclohexylene, and in formula IV, R19 is H, R20 is H or methyl and R
is -CooR23 or -COOR220H, R22 and R23 being as defined above, intluding
the preferred meanings.
In another preferred embodiment, the thermoplastic polymer of componenta) is a homopolymer or copolymer of vinyl alcohol in which the H atom of
the secondary OH group is at least partially substituted by a group
-Y-C H X2, wherein Ylis a direct bond, -CO- or -R26-O-CO-, x2 is Cl, Br
m n o
or I, m is a number from 1 to 12, n is O or a number from 1 to 24, o is a
number from 1 to 25 and n + o = 2m + 1, R26 being ethylene which is
unsubstituted or substituted by C1-C16alkyl.
The compositions preferably contain copolymers.
Preferred compositions are those in which the copolymer contains
a) 90 to 0.1 mol% of structural units of formula VII
-IC - ~- (VII),
OYC H x2
m n o
133!~4~
- 20 -
and
b) 99.9 to 10 mol% of identical or different structural units of
formula VIII
~ ~20
¢ 1- (VIII),
R19 29
wherein Y is a direct bond, -CO- or -R26-O-CO-, R26 being ethylene which
is unsubstituted or substituted by C1-C16alkyl; x2 is Cl, Br or I; m is a
number from 1 to 12, n is O or a number from 1 to 24, o is a number from
1 to 25 and n + o = 2m + 1; R19 is H, C1-C6alkyl or -CooR23; R20 is H, F,
Cl, CN or C1-C6alkyl; and R29 is H, F, Cl, CN, OH, R230-, C1-C12alkyl,
-CooR23, -o-Co-R23, -OR220H or phenyl, R23 being C1-C1galkyl, Cs-C7cyclo-
alkyl, (C1-C12alkyl)-Cs-C 7cyc loalkyl, phenyl, (C1-C12alkyl)phenyl, benzyl
or (C1-Cl2alkyl)benzyl and R22 being ethylene which is unsubstituted or
substituted by C1-C16alkyl.
The compositions preferably contain 70 to 10 and especially 60 to 20 mol%
of structural units of formula VII and 30 to 90 and especially 40 to
80 mol% of structural units of formula VIII.
R19 and R20 in formula VIII have the preferred meanings given above. R22
and R2 3 also have the preferred meanings given above.
R29is preferably H, F, Cl, CN, OH, R23-o-, C1-C4alkyl, -CooR23,
-o-Co-R23, phenyl, -OCHzCH20H or -OCH2CH(CH3)0H, R23 being C1-C6alkyl.
Especially preferred compositions are those in which R19 and R20 are H
and R29 is -oCoR23, wherein R23 is C1-C1galkyl, Cs-C~cycloalkyl, (C1-C12-
alkyl)-Cs-C7cycloalkyl, phenyl, benzyl, (C1-C12alkyl)phenyl or (C1-C12-
alkyl)benzyl.
In a preferred embodiment, Ylis a direct bond, -CO-, -CH2CHzO-CO- or
-CH2CH(CH3)0-CO-; x2 is Cl; m is a number from 1 to 6, n is O or a number
from 1 to 12, o is a number from 1 to 13 and n + o = 2m + 1; R19 and R20
13~994~
- 21 -
are H; and R29 is H, F, Cl, CN, OH, R230-, cl-c4alkyl~ -CooR23,
-O-CO-R2 3, phenyl, -OCH 2 CH2OH o r - OCH2CH(CH 3 ) OH, R2 3 being C1-C 6 alkyl, Cs
or C6cycloalkyl, phenyl or benzyl.
The invention further relates to a composition comprising
a) a thermoplastic polymer which contains aliphatic or cycloaliphatic
side groups bonded to a polymer backbone via a group -O-, -O-CO-,
-CO-OR22-OCO- or -CO-O-, said side groups containing at least one Cl, Br
or I atom in the ~-, B-, r- or ~-position, R22 being C2-C12alkylene,
C4-Cl2cycloalkylene, C4-Cl2cycloalkylene-CH2-, C4-cl2cyclo-
alkylene-~CH2~, benzylene or xylylene which is unsubstituted or
substituted by OH, Cl, Br or phenyl, and
b) a compound of formula I and/or formula Ia
Rl ~ , R3 \ . ~3\ . / ~ . / ~ . /; ~ . /
!6 '! 3 ! (I), !6 1! ! ! 3 ! (Ia),
~--X R6 ~ R8
wherein X is S, Se or Te, R1, R2, R3 and R4 are independently of the
others a hydrogen atom or Cl, or R1 and R2, and R3 and R4, together are
each
~-\ /S\ ~N\ /S
! i! or ! i! or
~-/ \S/ ~N S
Rl, R2, R3 and R4 are each phenylthio, 4-methylphenylthio, 4-methoxy-
phenylthio or pyrid-4-ylthio, and Rs, R6, R7 and R3 are independently of
the others H or F, or Rs is CH3 and R6, R7 and R3 are H, or Rs, R6, R7
and R3 are CH3, or Rs and R6 are CH3 or Cl and R7 and R3 are H, or Rs and
R6 are H, R7 is -COR9 and R3 is H or -COR9, or Rs and R6 are H and R7 and
R3 together are -CO-O-CO- or -CO-NR1~-CO-, wherein R9 is halogen, -OH,
-NHz, the radical of an alcohol or of a primary or secondary amine, or
-OM, M being a cation, and R10 is H or the radical of a primary amine
from which the NH2 group has been removed, and
- 22 - 13~g~
c) if desired, an inert organic solvent.
The composition of the invention can additionally contain a solvent for a
soluble polymer and component b). Examples of suitable solvents are polar
aprotic solvents, which can be used by themselves or in mixtures of at
least two solvents. Examples are: ethers such as dibutyl ether, tetra-
hydrofuran and dioxane, methylene glycol, dimethylethylene glycol,
dimethyldiethylene glycol, diethyldiethylene glycol and dimethyltri-
ethylene glycol, halogenated hydrocarbons such as methylene chloride,
chloroform, l,2-dichloroethane, l,l,l-trichloroethane and 1,1,2,2-tetra-
chloroethane, carboxylic acid esters and lactones such as ethyl acetate,
methyl propionate, ethyl benzoate, 2-methoxyethyl acetate, r-butYro-
lactone, ~-valerolactone and pivalolactone, carboxamides and lactams such
as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide,
N,N-dimethylacetamide, N,N-diethylacetamide, r-butyrolactam, E-capro-
lactam, N-methylpyrrolidone, N-acetylpyrrolidone, N-methylcaprolactam,
tetramethylurea and hexamethylphosphoric acid triamide, sulfoxides such
as dimethyl sulfoxide, sulfones such as dimethyl sulfone, diethyl
sulfone, trimethylene sulfone and tetramethylene sulfone, N-methyl-
pyrrolidine, N-methylpiperidine, N-methylmorpholine, and substituted
benzenes such as benzonitrile, chlorobenzene, o-dichlorobenzene, 1,2,4-
trichlorobenzene, nitrobenzene, toluene and xylene.
The composition of the invention can additionally contain auxiliaries
required for processing and use, e.g. plasticizers, flow control agents,
mould release agents, fillers, flameproofing agents, antioxidants and
light stabilizers, other stabilizers, dyes and pigments.
Most preferably, the composition of the invention additionally contains a
thermoplastic polymer differing from component a). Examples of additional
polymers have been described previously. The addition of these polymers
makes it possible to avoid too high a proportion of the halogenated poly-
mer of component a). The proportion of the thermoplastic polymer can be
e.g. up to 95 % by weight and preferably up to 80 % by weight, based on
the halogenated polymer of component a).
1 ~ 3 ~
- 23 - 2l489-7823D
The halogenated polymer of component a) is conveniently present at least
in a sufficient amount to form CT complexes of the compounds of com-
ponent b). The amount to be used depends essentially on the degree of
halogenation of the side groups of polymer a) and on the proportion of
such side groups in polymer a). The amount can be chosen so that 0.5 to 2
and especially 1 to 2 mol of halogen (Cl, Br, I) are present in the side
groups of the polymer of component a), per mol of compound of formula I
or Ia. It is advantageous to use an excess of polymer a).
Component b) is preferably present in an amount of 0.01 to 20 % by
weight, especially 0.05 to 10 % by weight and more especially 0.1 to 5 %
by weight, based on the polymer of component a).
In other respects, the preferences indicated above apply to this compound.
This compound of the invention is prepared simply by mixing the com-
ponents, a solvent being used as well if desired. The mixing process can
also be combined with a shaping process using known methods, e.g.
casting, injection moulding, calendering or extrusion.
The invention of the parent application further relates to a
process for the Preparation of the compositions containin~ CT
complexes, which comprises allowing
a) a thermoplastic polymer which contains aliphatic or cycloaliphatic
side groups bonded to a polymer backbone via a group -0-, -0-C0-,
-CO-ORZ2-OCO- or -CO-O-, said side groups containing at least one Cl, Br
or I atom in the ~-, B-, ~- or ~-position, to act on
b) a compound of formula I and/or formula Ia
i7 i1 2l (I), ~7 ~ . ~ 2- (Ia),
R2/ ~ \R4 R6/ ~ \4 ~ ~
- 24 - 1 ~ 3 g ~3 ~ ~
wherein X is S, Se or Te, Rl, R2, R3 and R4 are independently of the
others a hydrogen atom or Cl, or Rl and R2, and R3 and R4, together are
each
~-\ /S\ ~N\ /S\
I 11 or i i1 or
~- S/ ~N S
Rl, R2, R3 and R4 are each phenylthio, 4-methylphenylthio, 4-methoxy-
phenylthio or pyrid-4-ylthio, and Rs, R6, R7 and R8 are independently of
the others H or F, or Rs is CH3 and R6, R7 and R8 are H, or Rs, R6, R7
and R8 are CH3, or Rs and Rs are CH3 or Cl and R7 and R8 are H, or Rs and
Rs are H, R7 is -COR9 and R8 is H or -COR9, or Rs and Rs are H and R7 and
R8 together are -CO-O-CO- or -CO-NRl~-CO-, wherein R9 is halogen, -OH,
-NHz, the radical of an alcohol or of a primary or secondary amine, or
-OM, M being a cation, and Rl~ is H or the radical of a primary amine
from which the NHz group has been removed.
The process is advantageously carried out with an input of energy. The
energy can be e.g. thermal energy or radiation energy. In the case of
radiation energy, irradiation can be carried out e.g. imagewise through a
mask or by means of imagewise control of a light beam, or over the whole
surface. Thermal energy means, for example, an elevated temperature such
as a temperature of 25 to 350~C, especially 50 to 200~C. Simultaneous
thermal curing is possible when thermoset-forming constituents are also
used.
In one preferred embodiment, the process is carried out in the presenceof an inert organic solvent which evaporates at elevated temperature.
In another preferred embodiment, component a) is used in a greater amount
than is necessary to form the CT complex.
The halogen-containing polymer a) can be mixed e.g. with a compound of
formula I and/or Ia and, if desired, with solvents and additional poly-
mers. The mixing process can be combined with a simultaneous shaping
1339 1~:~
21489-7823D
process, e.g. casting, injection moulding, extrusion or
calendering. The temperature required to form CT complexes can be
reached e.g. during the shaping process. However, heat can also
be applied after the shaping process. When solvents are also
used, they are advantageously removed by heating.
The invention of the parent application further relates
to electrically conclucting or antistatic compositions obtainable
by the process of the invention.
The compositions of the invention of the parent
application containing a CT complex produce valuable semifinished
products or shaped articles, or mouldings, e.g. sheets, films,
filaments, fibres, composites or coatings, which are antistatic or
electrically conducting.
The invention of the parent application further relates
to the use of the composition of the invention, containing a
compound of formula I or Ia, for the production of a) antistatic
and~or b) electrically conducting mouldings, sheets, filaments,
fibres, coatings or composites.
The invention of the parent application further relates
to shaped articles, films, coatings and composites produced from a
composition of the invention containing a CT complex.
A preferred field of application is the production of
coatings or sheets e.g. by extrusion or by casting or coating.
They can be used for the electrostatic shielding of components.
The sheets are flexible electrical conductors from which
electrodes can be produced, e.g. for display elements.
Transparent embodiments are also possible, depending on the
polymer or polymer mixture used.
133994'j
25a 21489-7823D
The compositions of the invention of the parent
application containing a CT complex are distinguished by a high
chemical stability and heat stability and a low migration of the
CT complexes. Furthermore, surprisingly high conductivities are
achieved, which can be as much as 25% of the conductivity of the
1339'34~
pure CT complexes. The CT complexes form a network of
electrlcally conducting crystal needles ln the polymer matrlx.
The high stabillty is such that there ls llttle or no loss of
electrlcal conductivlty in use.
The thermoplastic polymers of component a) can be
prepared ln a manner known per se by esterlfylng a polymer
containing carboxyl groups, or its ester-formlng derlvatlves
(e.g. polymethacryllc acld or esters thereof), wlth a Cl-,
Bri- and/or I-substituted alcohol, or etherifying a polymer
containing hydroxyl groups (e.g. polyadducts of compounds
containing 2 epoxy groups or hydroxyalkylated derlvatives
thereof, polyhydroxyalkyl methacrylates, polyvinyl alcohols
or hydroxyalkylated derivatives thereof) with a Cl-, Br- or
I-substltuted alcohol, or esterifying it with a Cl-l Br- or
I-substituted carboxylic acid or its ester-forming
derivatives, e.g. esters or acid halides. The reaction is
conveniently carried out in a solvent and in the temperature
range from -20~C to 100~C. The desired polymer can be
isolated e.g. by evaporating off the volatile constituents, if
necessary under vacuum, or precipitatlng the polymer from the
reaction solution with water and drylng it. In this case,
however halogenated carboxylic acid radicals can be partially
cleaved by hydrolysis.
The invention of this application relates to a
homopolymer or copolymer of acrylic acid or methacrylic acid
esters which contains aliphatic or cycloallphatic groups in
the ester group, sald aliphatic or cycloaliphatic groups being
-~ 21489-7823D
133934S
- 26a -
chlorinated, bromlnated or lodinated in the a-, ~ - or
~-positlon, ln which the ester group contains groups
-tR22-0-COt~-CmHnXo bonded to the O atom of the carboxyl
group, wherein z is 1, m is a number from 1 to 12, n is 0 or
a number from 1 to 24, o is a number from 1 to 25 and n + o =
2m + 1, x2 ls Cl, Br or I and R22 ls C2-C12alkylene,
C4-C12cycloalklene, C4-C12cycloalkylene-CH2-, C2-C12_
cycloalkylene tCH2~, benzylene or xylylene whlch is
unsubstituted or substltuted by OH, Cl, Br or phenyl.
2]489-7823D
- 27 - 1 ~ 3 9 ~3 4 5
In a preferred embodiment, the homopolymer or copolymer contains
a) 0.1 to 100 mol% of at least one structural unit of formula III
~17
-CH2-¢- (III),
¢=o
ORl 8
and
b) 0 to 99.9 mol% of at least one structural unit of formula IV
~ ~20
_ ¢ I _ (IV)
R19 21
based on the polymer, wherein R17 is H or methyl; R13 is a radical
~(R22-O-CO~--C H X2, uherein z is O or 1, m is a number from 1 to
z m n o
12, n is 0 or a number from 1 to 24, o is a number from 1 to 25 and
n + o = 2m + 1, x2 is Cl, Br or I and R22 is C2-C1zalkylene, C4-C1zcyclo-
alkylene, C4-C1zcycloalkylene-CH2-~ C2-Cl2cycloalkylene-~CH2~7,
benzylene or xylylene which is unsubstituted or substituted by OH, Cl, Br
or phenyl; R19 is H, C1-C6alkyl or -COOR2 3; R20 is H, F, Cl, CN or C1-C6-
alkyl; and R21 is H, F, Cl, CN, RZ3-o-, C1-C12alkyl, -CooR23, -o-Co-R23,
-COOR22-OH, -COOCH2C~-~H2 or phenyl, R22 being as defined above and R23
being C1-C1galkyl, Cs-C7cycloalkyl, (C1-C12alkyl)-Cs-C7cycloalkyl,
phenyl, (C1-C12alkyl)phenyl, benzyl or (C1-C1 2 alkyl)benzyl.
In an especially preferred embodiment, R17 is methyl; R18 is a radical
~R22-O-CO-C H X2, wherein m is a number from 1 to 6, n is 0 or a number
m n o
from 1 to 12, o is a number from 1 to 13 and n + o = 2m + 1, x2 is Cl and
R22 is Cz-C6alkylene, cyclopentylene, cyclohexylene, cyclopentylene-CHz
cyclohexylene-CHz- or cyclohexylene-~CHz~ which is unsubstituted
or substituted by OH or Cl; R19 is H; R20 is H, F, Cl or C1-C4alkyl; and
R21 is H, F, Cl, CN, R23-o-, C1-C6alkyl, -CooR23, -o-Co-R23, -COOR22-OH,
-COOCHzC~-~H2 or phenyl, R22 being as defined above and R23 being
C1-C6alkyl, Cs or C6cycloalkyl, phenyl or benzyl.
1~399~
- 28 -
Rl8 is in particular a radical -R22-O-CO-C H X2, wherein R22 is linear
m n o
or branched C2-C6alkylene, x2 is Cl, m is a number from 1 to 4, n is O
or a number from 1 to 8, o is a number from 1 to 9 and n ~ o = 2m + 1.
The group -C H x2 is in particular -CH2Cl, -CHCl2, -CCl3, -CHClCH3,
-CClzCH3~ -CHCl-CH2Cl, -CC12-CH2Cl, -CHCl-CHC12, -CCl2-CHCl2, -CCl2-CCl3,
-CHz-CH2Cl, -CH2-CHC12 or -CH 2 -CCl3.
The invention of a second divisional application relates to a
homopolymer or copolymer which is a linear polyadduct of a
glycidyl compound containing an average of more than one e~oxy
group, and a diol, a primary monoamine, a disecondary diamine, a
disecondary linear or cyclic dicarboxylic acid diamide or a
dicarboxylic acid, in which polyadduct the H atom of the secondary
OH groups is at least partially substituted by a group -CO-CmHnXo,
wherein m is a number from 1 to 12, n is 0 or a number from
1 to 24, o is a number from 1 to 25 and n + o = 2m+1, and X is
Cl, Br or I.
In a preferred embodiment, the polyadduct contains
a) 100 to 0.1 mol% of identical or different structural units of
formula V
_o-R2 4 -O-CH 2 - ICH-CH 2 - oR2 5 - ( V )
OR2~0COC H x2
m n o
and
b) 99.9 to O mol% of identical or different structural units of
formula VI
-O-R2~-O-CHz~C~H~CH2~0R2s- (VI)
R'
based on the polyadduct, wherein R2 4 and R2s are independently of the
other the radical of a diol containing aliphatic or aromatic diol groups,
from which two hydroxyl groups have been removed, R' is H, unsubstituted
or OH-substituted C1-C2oalkyl, Cl-C2~acyl or aminocarbonyl N-substituted
133994 ~i
- 29 -
by a C1-C20hydrocarbon radlcal, -oR25- is a direct bond or R26 is
ethylene which is unsubstituted or substituted by Cl-C16alkyl, and X2, m,
n and o are as defined above.
In particular, R2 4 and R2s are independently of the other a radical ofthe formula
fx~
\.=./ y
wherein X1 is a direct bond, C1-C4alkylene, C2-C12alkylidene, Cs-Cgcyclo-
alkylidene, -O-, -S-, -SO-, -SO2-, -CO-, -CO2-, -N(C1-C4alkyl)- or
-Si(CH3)2-, R27 and R23 are independently of the other H, halogen, C1-C4-
alkyl or C1-C4alkoxy, x is 0, 1 or 2 and y is O or 1.
R24 and R2s are most especially the radical
\-=-/ CH3\-=-/
In a preferred embodiment, -oR2 6 - is a direct bond, x2 is Cl, m is a
number from 1 to 4, n is O or a number from 1 to 8, o is a number from 1
to 9 and n + o = 2m + 1.
In an especially preferred embodiment, the group -CmHnXo is -CHzCl,
-CHClz, -CCl3, -CHClCH3, -CClzCH3, -CHCl-CHzCl, -CCl2-CHzCl, -CHCl-CHClz,
-CCl2-CHCl2, -CCl2-CCl3, -CH2-CH2Cl, -CH2-CHCl2 or -CH2-CCl3.
The invention further relates to a homopolymer or copolymer which is a
homopolymer or copolymer of vinyl alcohol in which the H atom of the
secondary OH group is at least partially substituted by a group
-Y1-C H Xl, wherein y1 is -CO- or -R26-O-CO-, X1 is Cl, Br or I, m is a
m n o
number from 1 to 12, n is O or a number from 1 to 24, o is a number from
1 to 25 and n + o = 2m + 1, R26 being ethylene which is unsubstituted or
substituted by C1-C16alkyl.
- 30 - I~3994.~
It is preferred to use a homopolymer or copolymer in which the copolymer
contains
a) 90 to O.1 mol~O of structural units of formula VII
_¢ _ ~_ (VII),
OYC H x2
m n o
and
b) 99.9 to 10 mol% of identical or different structural units of
formula VIII
~ ~20
_¢ ¢_ (VIII),
Rl9 R29
wherein yl is -CO- or -R2 6 -O-cO-, R2 6 being ethylene which is unsubsti-
tuted or substituted by C1-C16alkyl; XZ is Cl, Br or I; m is a number
from 1 to 12, n is O or a number from 1 to 24, o is a number from 1 to 25
and n + o = 2m + 1; R19 is H, C1-C6alkyl or -CooR23; R20 is H, F, Cl, CN
or C1-C6alkyl; and R29 is H, F, Cl, CN, OH, R23O-, C1-C12alkyl, -CooR23,
-o-Co-R23, -OR22OH or phenyl, R23 being C1-C1galkyl, Cs-C7cycloalkyl,
(C1-C12alkyl)-Cs-C7cycloalkyl, phenyl, (Cl-Clzalkyl)phenyl, benzyl or
(C1-C12alkyl~benzyl and R22 being ethylene which is unsubstituted or
substituted by C1-C1 6 alkyl.
In a preferred embodiment, y1 is -CO-, -CH2CHzO-CO- or -CH2CH(CH2)O-CO-;
x2 is Cl; m is a number from 1 to 6, n is 0 or a number from 1 to 12, o
is a number from 1 to 13 and n + o = 2m + 1; R19 and R20 are H; and R29
is H, F, Cl, CN, OH, R23O-, C~-C4alkyl, -CooR23, -o-Co-R23, phenyl,
-OCH2CH2OH or -OCH2CH(CH3)OH, R23 being C1-C6alkyl, Cs or C6cycloalkyl,
phenyl or benzyl.
Preferably, x2 is Cl, m is a number from 1 to 4, n is O or a number from
1 to 8, o is a number from 1 to 9 and n + o = 2m + 1.
13~9~
- 31 -
The group -C H X2 is especially -CH2Cl, -CHCl2, -CC13, -CHClCH3,
-CCl2CH3, -CHCl-CH2Cl, -CCl2-CH2Cl, -CHCl-CHCl2, -ccl2-cHcl2~ -CClz-CCl3,
-CH2-CH2Cl, -CHz-CHCl2 o r -CH2-CCl3.
In other respects, the preferences indicated above for the
compositions apply to the polymers. It has been
found that, in addition to their property of forming CT complexes with
the compounts of formulae I and Ia, the polymers can substantially
improve the adhesiveness of thermoplastics and thermosets on substrates
such as metals, wood, glass and plastics, it being possible to incorpo-
rate only small amounts, e.g. up to 5 % by weight, of the polymers of the
invention into the thermoplastics or thermosets.
The following Examples illustrate the inventions of the parent
and divisional applications in greater detail.
A) Preparatory Examples
Examples 1-7- Preparation of
ÇH3
~ - O - CH2 - ÇH - CH2 - O----
H3 H a
_ ÇH3
~----O----CH2--fH--CH2--~--
H3
~=0
-b
28.4 g of a polyaddition polymer of bisphenol A and bisphenol A
diglycidyl ether (Mw - 20,000) are dissolved in 200 ml of dimethyl-
formamide and 60 ml of pyridine. 12.1 g of chloroacetyl chloride are
added dropwise at 0~C, with stirring and with the exclusion of moisture.
Stirring is continued for 8 h at room temperature and the product is
1 3 3 9 9 ~ ~
- 32 -
precipitated in water. The isolated polymer of Example 3 is dried at 80~C
under high vacuum. The content of incorporated chloroacetic acid ester
radicals is determined from the elemental analysis.
The polymers in Table 1 are prepared in analogous manner.
Table 1:
Example R n (calculated) n (found)Tg M
no. b b (~C) w
(n = ) (n =
a+b a+b
1 -CH2Cl 0,1 0,05 44100
2 -CHzCl 0,5 0,25 104 26500
3 -CH2Cl 1,0 0,75 83 26600
4 -CCl3 0,1 0,05 79000
-CCl3 1,0 1,0 66 94000
6 -CHCl-CH2Cl 0,1 0,03 102 65000
7 -CHCl-CHzCl 0,5 0,25 18000
1) Determined by gel permeation chromatography
Example 8: 27.8 g (0.19 mol) of glycidyl methacrylate and 122.92 g
(1.08 mol) of ethyl methacrylate are heated to 70~C in 600 ml of dioxane,
under nitrogen and with stirring, and 750 mg of AiBN are added. After
16 h, the polymer formed is isolated by precipitation in ice water.
Yield: 130.57 g (87 %), epoxy content: 1.27 meq/g (theoretical:
1.267 meq/g), M = 86,000.
7.87 g of polymer (10 mmol of epoxy groups) are dissolved in 80 ml of
dioxane, and 0.8 ml (0.01 mol) of chloroacetyl chloride and 2.4 ml of
pyridine are added dropwise at room temperature. When the addition is
complete, the mixture is heated for 1 h at 50~C and then left to cool and
the polymer is isolated by precipitation in diethyl ether.
- 33 - 1 ~ 3 9 ~ 4 ~
M = 32,700, T : 78~C, chlorine content: 6.54 % (calculated: 7.86 %).
Example 9: The procedure is as in Example 8, except that 0.005 mol of
benzoyl chloride is used instead of chloroacetyl chloride.
M = 17,300, Tg: 92~C, chlorine content: 1.2 % (calculated: 2.1 %).
Reaction with carboxylic acids
Example 10: 7.ô7 g (0.01 mol of epoxy groups) of poly(ethyl
methacrylate/glycidyl methacrylate - 85/15), prepared by the process
according to Example 8, are dissolved in 100 ml of dioxane, and 1.71 g
(0.01 mol) of 2,3-dichloropropionic acid and 96 mg of benzyltrimethyl-
ammonium chloride are added. After 10 h of reflux, the mixture is left to
cool and the converted polymer is isolated by precipitation in ice water.
Yield: 87.6 %, T : 93~C, chlorine content: 4.33 % (calculated: 7.74 %).
Example 11: The procedure is as in Example 10, except that 0.01 mol of
chloroacetic acid is used instead of 2,3-dichloropropionic acid.
M = 127,000, T : 88~C, chlorine content: 1.6 % (calculated: 4.02 %).
B) Application Examples:
Examples 12-23: 1.6 mg of tetraselenotetracene (TSeT) are dissolved in
9 ml of dimethylformamide (DMF) at 120~C and added to a solution of
100 mg of the polymer according to Example 1 in 1 ml of DMF. The solution
is then poured on to a preheated glass plate. A transparent film with a
needle network of crystal needles of electrically conducting (TSeT)2Cl in
a polymer matrix remains after evaporation of the solvent in the tempera-
ture range from 90 to 130~C. The films according to Examples 13 to 23 in
Tables 2 and 3 are produced in the same way, an additional polymer (poly-
mer 2) also being used in Examples 16 to 23. The conductivity of the
films is between 0.1 and 1 S/cm.
~ 34 ~ 133~ '3 4~
Table 2:
Example Polymer TSeT (mg) Morphology of the 1)
no. according ~ 100 needle network
to Exammple no. Polymer (mg)
12 7 1,6 +
13 1 1,6 ++
14 2 1,6 +
6 1,6 ++
) + extensively homogeneous needle networks (electrically conducting)
++ irregular needle networks (electrically conducting)
Table 3:
Example Polymer (1) Polymer (2) Polymer(1)in g TSeT Morphology of no. according to (mg) the needle
Example no. Polymer(2)in g network
16 5 Polyimide 1) 0,43 1,6 + 4)
17 7 Polyimide 1) 1 1,6 + 4 )
18 5 Polyimide 1) 0,1 1,5 ++
19 7 Polyimide 1) 0,05 1,6 _ 3
7 Polyimide 1) 0,1 1,6 ++
21 1 Phenoxy- 1,0 1,6 +
polymer 2 )
22 1 Phenoxy- 9 1,6 ++
polymer 2 )
23 1 Phenoxy- 0,1 1,5 (-)
polymer 2 )
) polyimide derived from benzophenonetetracarboxylic dianhydride,
diaminodurol and 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenyl-
methane (M = 40,000).
2 ) polyadduct of bisphenol A and bisphenol A diglycidyl ether
(M = 20,000)
3) short needles, not conducting over their whole surface
4 ) opaque sheets (demixing of the polymers)
35 - 1 3 3 9l3 4 ~
Examples 24-27: 100 mg of polymer are dissolved in 2 ml of DMF at 120~C.
This solution is added, with vigorous stirring, to a hot solution, at
120~C, of 1.6 mg of 2-fluorotetraselenotetracene in DMF and the resulting
solution is poured into hot Petri dishes at 100-140~C. Electrically con-
ducting polymer films remain after evaporation of the solvent. The
electrical conductivity is determined by the 4-point method (see
Table 4).
Table 4:
ExamplePolymer according Conductivity
to Example ( -1 -1
24 8 0,21
9 0,08
26 10 0,01
27 11 0,12
