U.S. patent application number 12/435463 was filed with the patent office on 2009-11-12 for polytriazinyl compounds as flame retardants and light stabilizers.
This patent application is currently assigned to MCA Technologies GmbH. Invention is credited to Bansi Lal Kaul.
Application Number | 20090281215 12/435463 |
Document ID | / |
Family ID | 41010055 |
Filed Date | 2009-11-12 |
United States Patent
Application |
20090281215 |
Kind Code |
A1 |
Kaul; Bansi Lal |
November 12, 2009 |
Polytriazinyl Compounds as Flame Retardants and Light
Stabilizers
Abstract
Compounds consisting of an oligomer or a polymer of a
1,3,5-triazine derivative, having the general formula I:
##STR00001## wherein: X is selected from: ##STR00002## or X is a
heterocyclic radical containing in the ring at least one nitrogen
atom which radical is linked to the triazine ring through one of
such nitrogen atoms, R.sub.2 is alkyl or cycloalkyl, R.sub.1 is a
divalent radical of piperazine of the formula ##STR00003## or
R.sub.2 is a divalent radical according to the formula ##STR00004##
or R.sub.2 is a radical according to the formula Y ##STR00005## n
is an integer from 2 to 30, inclusive, m is an integer from 2 to 6,
inclusive, p is an integer from 2 to 12, inclusive, and
X.sub.1.dbd.OH,NH.sub.2 or X whereby X and X.sub.1 may be the same
or different, and, X.sub.2.dbd.H or is a C.sub.1-C.sub.4 alkyl
group, and a solvent-free process for the production of the
compounds of Formula I as well as the use of the self-extinguishing
oligomeric or polymeric compounds as flame retardants and light
stabilizers in thermoplastic polymers such as polypropylene or
regenerated cellulose or polyester.
Inventors: |
Kaul; Bansi Lal;
(Biel-Benken, CH) |
Correspondence
Address: |
NORRIS, MCLAUGHLIN & MARCUS
875 THIRD AVE, 18TH FLOOR
NEW YORK
NY
10022
US
|
Assignee: |
MCA Technologies GmbH
Biel-Benken
CH
|
Family ID: |
41010055 |
Appl. No.: |
12/435463 |
Filed: |
May 5, 2009 |
Current U.S.
Class: |
524/97 ;
544/113 |
Current CPC
Class: |
C08G 73/0644 20130101;
C08L 2201/08 20130101; C08K 5/357 20130101; C08L 79/04 20130101;
C08L 2201/02 20130101; C09D 7/48 20180101; C07D 251/50 20130101;
C08G 73/0655 20130101; C08K 5/3492 20130101; C08L 23/12 20130101;
C07D 251/64 20130101; C09D 5/185 20130101; C08L 79/00 20130101;
C08K 5/34926 20130101; C07D 471/12 20130101; C08L 23/12 20130101;
C08L 2666/20 20130101 |
Class at
Publication: |
524/97 ;
544/113 |
International
Class: |
C08K 5/357 20060101
C08K005/357; C07D 413/14 20060101 C07D413/14 |
Foreign Application Data
Date |
Code |
Application Number |
May 9, 2008 |
EP |
08008717.4 |
Sep 1, 2008 |
EP |
08015381.0 |
Claims
1. A compound consisting of an oligomer or a polymer of a
1,3,5-triazine derivative, having the general formula I:
##STR00044## wherein: X is selected from: ##STR00045## or X is a
heterocyclic radical containing in the ring at least one nitrogen
atom which radical is linked to the triazine ring through one of
such nitrogen atoms, R.sub.2 is alkyl or cycloalkyl, R.sub.1 is a
divalent radical of piperazine of the formula ##STR00046## or
R.sub.2 is a divalent radical according to the formula ##STR00047##
or R.sub.2 is a radical according to the formula Y ##STR00048## n
is an integer from 2 to 30, inclusive, m is an integer from 2 to 6,
inclusive, p is an integer from 2 to 12, inclusive, and
X.sub.1.dbd.OH,NH.sub.2 or X whereby X and XI may be the same or
different, and, X.sub.2.dbd.H or is a C.sub.1-C.sub.4 alkyl
group.
2. A compound of formula I according to claim 1 wherein R.sub.1 is
a divalent radical of piperazine or a divalent radical of a diamine
wherein m is an integer from 2 to 6.
3. A compound of formula I according to claim 1 wherein R.sub.2 is
an alkyl radical containing from 1 to 20 carbon atoms or is a
cycloalkyl radical containing from 6 to 20 carbon atoms.
4. A compound of formula I according to claim 1 wherein
R.sub.1=hexamethylenediamine, piperazine or an alkyl-substituted
piperazine.
5. A compound of formula I according to claim 1 wherein X.sub.1 and
X are identical and are selected from morpholino, piperidino or
piperazino moieties.
6. A process for the production of compounds of formula I according
to claim 1, said process comprising the steps of: condensing a
cyanuric halogenide with one or more amines and/or one or more
heterocyclic compounds in two or three steps.
7. A process for the preparation of a self-extinguishing polymeric
composition based on synthetic polymers which process comprises the
step of: incorporating a compound of formula I according to claim 1
into a synthetic polymer containing composition.
8. A self-extinguishing synthetic polymeric composition comprising
a thermoplastic polymer and a compound of formula I according to
claim 1.
9. A composition according to claim 8 in which the thermoplastic
polymer is an olefinic polymer or copolymer.
10. A composition according to claim 8 in which the thermoplastic
polymer is a polyester material.
Description
[0001] The present application claims priority from EP 08008717.4
filed on May 9, 2008 and EP 08015381.0 filed on Sep. 1, 2008.
[0002] The present invention relates to chemical compounds useful
as flame retardardants which are adapted to be incorporated into
further materials, or used with further materials, e.g. synthetic
polymers.
[0003] The present invention relates to chemical compounds useful
as light stabilizers which are adapted to be incorporated into
further materials, or used with further materials, e.g. synthetic
polymers.
[0004] Water-insoluble nitrogen containing compounds, consisting of
an oligomer or a polymer of a 1,3,5-triazine derivative, and having
the general formula A
##STR00006##
wherein X is selected from:
##STR00007##
a heterocyclic radical containing in the ring at least one nitrogen
atom which radical is linked to the triazine ring through one of
such nitrogen atoms, R.sub.1 is a divalent piperazine radical of
the formula
##STR00008##
a divalent radical of the type
##STR00009##
R.sub.2 is alkyl or cycloalkyl, n is an integer from 10 to 30,
extremes included, and m is an integer from 2 to 6, [0005]
X.sub.1=halogen, [0006] are known to the art and have been
disclosed in the U.S. Pat. No. 4,504,610.
[0007] Compounds of formula A are known to impart satisfactory
flame retardant properties to the thermoplastic polymers by
addition of particular phosphonitrogenous additives which do not
comprise aminoplastic resins and offer the advantage of, in case of
fire, to prevent proliferation of fires, particularly where the
plastics and coatings are involved as materials.
[0008] According to the prior art, the compounds of formula A are
prepared by first reacting cyanuric acid chloride at temperatures
ranging from -10.degree. C. to +10.degree. C., at a pH from 5 to 7,
in water and in the presence of a polar solvent, such as acetone,
etc. with an amine of the formula R.sub.2--NH.sub.2 or with a
heterocyclic compound containing in the ring a nitrogen atom, in a
molar ratio of 1:1, where R.sub.2 has the value indicated
hereinabove, whereupon the 4-amino derivative of
2,6-dichloro-1,3,5-triazine is obtained.
[0009] Such derivative, after separation, is then reacted at
elevated temperatures, in an apolar solvent, with an amine of
formula H.sub.2N--(CH.sub.2).sub.m--NH.sub.2 or with piperazine or
an alkyl-substituted derivative thereof, or with a mixture of such
compounds, employing a molar ratio between triazine derivative and
amine and/or piperazine equal to 1:1.
[0010] Compounds of Formula A in wherein R.sub.1 is Y which is
represented in the following
##STR00010##
are also known to the art and are disclosed in the U.S. Pat. No.
4,086,204. Such compounds of Formula A are known to be valuable
light stabilizers for synthetic polymers. The preparation of such
compounds is described for example in U.S. Pat. No. 4,086,204, U.S.
Pat. No. 4,331,586, U.S. Pat. No. 4,335,242, U.S. Pat. No.
4,492,791, U.S. Pat. No. 5,919,929, as well as in EP-A-357 223 and
EP-A-377 324. Processes for the preparation of a product
corresponding to the formula A wherein R.sub.1.dbd.Y is may be
carried out in an inert organic solvent such as acetone, dioxane,
toluene, xylene, in a temperature range from -10.degree. C. and the
solvent boiling temperature; or may be carried out in a closed
system under nitrogen, such as disclosed in (U.S. Pat. No.
5919929). The organic solvent used is preferably one or more of
toluene, xylene, trimethylbenzene, isopropylbenzene,
diisopropylbenzene or t-butylbenzene, especially toluene, xylene or
trimethylbenzene. Xylene is especially preferred. The reaction is
carried out in the presence of organic or inorganic bases for
fixing hydrogen halide. Preferred examples of bases useful for said
purpose are triethylamine or tributylamine, sodium hydroxide,
carbonate or bicarbonate, potassium hydroxide or carbonate, sodium
alcoholates
[0011] The use of solvents in the synthesis of the compounds of
formula A makes these processes potentially hazardous,
environmentally unfriendly and expensive. Moreover, the use of
solvents requires expensive equipment for their regeneration after
their use.
[0012] Also, the compounds of formula A made by these certain of
these prior art processes, particularly the processes described in
U.S. Pat. No. 4,504,610 and U.S. Pat. No. 4,086,204) usually
contain up to 2% organically bound halogen ("AOX") wherein group X
of the formula A is usually a halogen atom. Thus a popular and
presently commercially available flame retardant
poly-2,4-piperazinyl-6-morpholinyl-1,3,5-triazine; CAS Nr.:
93058-67-4, formerly offered by Degussa AG (Germany) as
"PPM-TRIAZINE" and now commercially available from AlzChem,
(Germany), contains up to 1.5% organic chlorine (AOX).
[0013] Similarly the commercially available light stabilizers
presently commercially available as "CHIMASORB 944", offered by
Ciba Specialty Chemicals, as well as "CYASORB UV-3346" and "CYASORB
UV-3529" offered by Cytec Industries Inc., (USA) can contain up to
2% organic chlorine, calculated on the basis of their average
molecular weights of 1600-3000
[0014] The presence of organically bound halogen (AOX) in flame
retardants and light stabilizers is desirably avoided for important
environmental reasons, for safety in case of fire, for safe
disposal of the waste containing such additives, and in many
countries the use of flame retardants and light stabilizers
comprising organically bound halogen (AOX) is presently, or may be
soon legally controlled or restricted for use.
[0015] The present invention addresses and overcomes many of the
shortcomings extant in the prior art.
[0016] In one aspect, the present invention relates to the
halogen-free compounds of Formula I,
##STR00011##
wherein X is selected from:
##STR00012##
or, X is a heterocyclic radical containing in the ring at least one
nitrogen atom which radical is linked to the triazine ring through
one of such nitrogen atoms, [0017] R.sub.2 is alkyl or cycloalkyl,
R.sub.1 is a divalent radical of piperazine of the formula
##STR00013##
[0017] or R.sub.1 is a divalent radical according to the
formula
##STR00014##
or R.sub.1 may be a radical according to the formula (Y)
illustrated as follows
##STR00015## [0018] n is an integer from 2 to 30, inclusive, [0019]
m is an integer from 2 to 6, inclusive, [0020] p is an integer from
2 to 12, inclusive, [0021] X.sub.2 is a hydrogen or an
C.sub.1-C.sub.4 alkyl group, and [0022] X.sub.1.dbd.OH, NH.sub.2 or
X, whereby X.sub.1 and X may be the same or different.
[0023] The present invention also relates to the process of making
the compounds of Formula A and of Formula I, which process proceeds
preferably without the use of any organic solvents, preferably in
the presence of a surface active agent.
[0024] The first step of the process according to the invention is
the reaction of cyanuric acid halogenide at temperatures ranging
from -10.degree. C. to +10.degree. C., at a pH from 5 to 7, in a
polar solvent, such as acetone, water, etc. but preferably without
the use of any organic solvent, with an amine of formula
R.sub.2--NH.sub.2 or with a heterocyclic compound containing in the
ring a nitrogen atom, in a molar ratio of about 1:1, preferably in
a molar ratio of 1:1, to produce the 4-amino derivative of
2,6-dichloro-1,3,5-triazine, in an intermediate suspension.
[0025] Without separation, the intermediate suspension is then
reacted at an elevated temperature, preferably in the range of
100.degree. C. -200.degree. C., within water or a polar solvent,
but preferably without any organic solvent with an amine of formula
H.sub.2N--(CH.sub.2).sub.m--NH.sub.2, or with piperazine or an
alkyl-substituted derivative thereof, or with
4-amino-2,2,6,6-tetramethylpiperidine or with
N,N'-bis-(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexandiamine, or
with a mixture of such compounds, employing a molar ratio between
triazine derivative and amine and/or piperazine of about 1:1,
preferably in a respective molar ratio of 1:1.
[0026] The compounds of Formula I are then obtained by reacting the
compounds of Formula A with a compound of the formula HX.sub.1 at
temperatures ranging from about 90.degree. C. to about 150.degree.
C., more preferably at a temperature of from 100.degree. C. to
130.degree. C. in the presence of a base such as an excess of
HX.sub.1 and/or a base such as one or more alkali metal
hydroxides.
[0027] A further aspect of the invention, is a process for the
production of a water-insoluble oligomer or polymer of a
1,3,5-triazine derivative having the general formula:
##STR00016##
wherein X is selected from:
##STR00017##
or a heterocyclic radical containing in the ring at least one
nitrogen atom which radical is linked to the triazine ring through
one of such nitrogen atoms, [0028] R.sub.2 is alkyl or cycloalkyl,
[0029] R.sub.1 is a divalent radical of piperazine of the
formula
##STR00018##
[0029] or R.sub.1 is divalent radical of the formula
##STR00019##
or R.sub.1 is divalent radical of the formula (Y)
##STR00020## [0030] n is an integer from 2 to 30, inclusive, [0031]
m is an integer from 2 to 6, inclusive, [0032] p is an integer from
2 to 12 inclusive, [0033] X.sub.2 is a hydrogen or a
C.sub.1-C.sub.4 alkyl group, and [0034] X.sub.1.dbd.OH, NH.sub.2 or
X, whereby X.sub.1 and X may be same or different, wherein the said
water-insoluble oligomer or polymer of a 1,3,5-triazine derivative
is formed by condensation of a cyanuric halogenide with one or more
appropriate amines and/or one or more heterocyclic compounds in two
or three steps.
[0035] In order to keep the reaction mixture as a smooth
suspension, it is preferable to add a surface active agent, also
referred to as a tenside or surfactant, such as
dodecylbenzenesulphonic acid.
[0036] The compounds according to formula I are obtained as white
powders with very high melting point and having a minimal content
of halogen, preferably are essentially free of halogens (namely
contains less than 0.1% wt. halogens based on the weight of the
said compounds) and most preferably include no halogens. They can
be comminuted into to small particles which are then ready for
incorporation, optionally with further flame retardant compounds,
like ammonium phosphate or amine phosphate, and/or other
conventional additives into synthetic polymers, especially
thermoplastic polymers. The compounds according to formula I, when
incorporated into or with one or more synthetic polymers to form a
synthetic polymer comprising composition, provide a
self-extinguishing benefit to said synthetic polymers and/or a
synthetic polymer comprising compositions.
[0037] A aspect of the invention is a solvent free-process for the
production of a water-insoluble oligomer or polymer of a
1,3,5-triazine derivative having the general formula:
##STR00021##
wherein X is selected from:
##STR00022##
or a heterocyclic radical containing in the ring at least one
nitrogen atom which radical is linked to the triazine ring through
one of such nitrogen atoms, [0038] R.sub.2 is alkyl or cycloalkyl,
[0039] R.sub.1 is a divalent radical of piperazine of the
formula
##STR00023##
[0039] or a divalent radical according to the formula
##STR00024## [0040] n is an integer from 10 to 30, inclusive,
[0041] m is an integer from 2 to 6, inclusive, wherein the process
comprises the the step of condensation of a cyanuric halogenide
with one or more amines and/or one or more heterocyclic compounds
in two steps of two stages, characterised by the fact that no
organic solvent is used in any of the two steps or stages
[0042] The compositions of the present invention can be made
according to known methods: for example, the ammonium phosphate or
the phosphate of an amine are first intimately mixed with the
finely ground triazine nitrogenous compound (preferably having
particles sized below 75 microns) and the mixture so obtained is
added to the thermoplastic polymer in a turbo-mixer to form a
homogeneous mix which is thereafter extruded and preferably also
granulated. The extrudate can be transformed into various articles
according to any of the known art molding techniques.
[0043] The flame retardant additives of this invention are suited
to be employed also in the field of fire retardant paints and fire
retardant coatings.
[0044] Generally it is preferable to employ from 0.01 to 5% by
weight of compounds of formula (I) or formula (A), more preferably
from 0.1 to 1%, based on the total weight of the synthetic polymer
comprising composition in which said compounds are included.
[0045] The compounds of formula (I) or formula (A) can be included
in a polymeric material composition, viz., synthetic polymer, by
various procedures, such as dry mixing in the form of powder, or by
a wet process in the form of a solution or slurry. In said
operation the synthetic polymer can be employed in the form of
powder, granulate, solution, slurry or emulsion.
[0046] The synthetic polymers stabilized by the products of formula
(I) or formula (A) can be used for the manufacture of molded
articles, films, tapes, fibers, monofilaments and the like.
[0047] A mixture of compounds of formula (I) or formula (A) and
synthetic polymers can optionally comprise further additives, such
as antioxidants, UV absorbers, nickel stabilizers, pigments,
charges, plastifying agents, antistatic agents, flame retardants,
lubricating agents, anticorrosive agents, metal inhibitors, and the
like.
[0048] Compounds of formula (I) or formula (A) are useful in
conjunction with synthetic polymers such as, for example, high and
low density polyethylene, polypropylene, ethylene-propylene
copolymers, ethylene-vinylacetate copolymers, polybutadiene,
polyisoprene, polystyrene, styrene-butadiene copolymers,
acrylonitrile-butadiene-styrene copolymers, vinyl- and vinylidene
chloride polymers and copolymers, polyoxymethylene,
polyethylene-terephthalate, polyamides such as nylon 66, nylon 6,
nylon 12, as well as polyurethanes, and also unsaturated
polyesters. The compounds according to formula A, when incorporated
into or with one or more synthetic polymers to form a synthetic
polymer comprising composition, provide a self-extinguishing
benefit to said synthetic polymers and/or a synthetic polymer
comprising compositions.
[0049] The self-extinguishing properties of polymeric compositions
containing the anti-flame additives may be evaluated as follows as
follows: a thermoplastic synthetic polymer containing compounds
according to formula I and/or formula A are is used to mold 3 mm
(1/8 inch) thick plates in a MOORE plate press, preferably by
operating the said press for about 7 minutes at a pressure of 40
kg/cm.sup.2 and at a suitable temperature. The plates are
subsequently removed, and allowed to cool to room temperature. Such
plates are then tested according to the UL-94 method.
[0050] The polytriazine compounds of formula (I) wherein
R.sub.1.dbd.Y are useful and valuable agents for improving the
stability to light, heat and oxidation of synthetic polymers such
as, for example, high and low density polyethylene, polypropylene,
ethylene-propylene copolymers, ethylene-vinylacetate copolymers,
polybutadiene, polyisoprene, polystyrene, styrene-butadiene
copolymers, acrylonitrile-butadiene-styrene copolymers, vinyl- and
vinylidene chloride polymers and copolymers, polyoxymethylene,
polyethylene-terephthalate, polyamides such as nylon 66, nylon 6,
nylon 12, as well as polyurethanes, and also unsaturated
polyesters.
[0051] The compounds of formula (I) wherein R.sub.1.dbd.Y are also
particularly useful as light stabilizers for synthetic polymers,
especially polyolefins and more particularly for polyolefin
articles of manufacture having a reduced thickness, such as fibers
and films. Surprisingly, said compounds are only poorly leachable
or extractable extracted from said thin articles, when such thin
articles, e.g. films, fibers and the like, are brought in contact
with water or an aqueous surfactant solution.
[0052] The compounds of formula (I) wherein R.sub.1.dbd.Y can be
employed as an additive for, or in a mixture with synthetic
polymers in various proportions, depending on the specific
synthetic polymer, the intended final use of the synthetic polymer
or article formed thereform, and the presence of additional
additives.
[0053] Generally it is preferable to employ from 0.01 to 5% by
weight of compounds of formula (I) wherein R.sub.1.dbd.Y referred
to the polymer weight, more preferably from 0.1 to 1%, based on the
total weight of the synthetic polymer comprising composition in
which said compounds are included
[0054] The compounds of formula (I) wherein R.sub.1.dbd.Y can be
included in a synthetic polymeric material containing composition
by various procedures, such as dry mixing in the form of powder, or
by a wet process in the form of a solution or slurry. In said
operation the synthetic polymer can be employed in the form of
powder, granulate, solution, slurry or emulsion.
[0055] The synthetic polymers stabilized by the products of formula
(I) wherein R.sub.1.dbd.Y can be used for the manufacture of molded
articles, films, tapes, fibers, monofilaments and the like.
[0056] A mixture of compounds of formula (I) wherein R.sub.1.dbd.Y
and synthetic polymers can optionally comprise further additives,
such as antioxidants, UV absorbers, nickel stabilizers, pigments,
charges, plastifying agents, antistatic agents, flame retardants,
lubricating agents, anticorrosive agents, metal inhibitors, and the
like.
[0057] The compounds of formula (I) wherein R.sub.1.dbd.Y are
useful in conjunction with synthetic polymers such as, for example,
high and low density polyethylene, polypropylene,
ethylene-propylene copolymers, ethylene-vinylacetate copolymers,
polybutadiene, polyisoprene, polystyrene, styrene-butadiene
copolymers, acrylonitrile-butadiene-styrene copolymers, vinyl- and
vinylidene chloride polymers and copolymers, polyoxymethylene,
polyethylene-terephthalate, polyamides such as nylon 66, nylon 6,
nylon 12, as well as polyurethanes, and also unsaturated
polyesters.
[0058] The synthetic polymers stabilized by the products of formula
(I) or formula (A) can be used for the manufacture of molded
articles, films, tapes, fibers, monofilaments and the like.
[0059] In the compounds according to formula (A) and formula (I),
R.sub.2 is preferably an alkyl radical containing from 1 to 20
carbon atoms or a cycloalkyl radical containing from 6 to 20 carbon
atoms, R.sub.1 is preferably a divalent radical of piperazine or a
divalent radical of a diamine wherein m is an integer ranging from
2 to 6, extremes included, n preferably is an integer ranging from
8 to 20, and p preferably is an integer from 4 to 10, extremes
included.
[0060] Examples of alkyl radicals are methyl, ethyl, propyl,
n-butyl, isobutyl, hexyl, octyl, decyl, dodecyl, cyclohexyl,
propyl-cyclohexyl, butyl-cyclohexyl, decylcyclohexyl. Examples of
heterocyclic groups defined as X are morpholine, piperidine and
piperazine. Examples of diamines for R.sub.1 are ethylenediamine,
tetramethylenediamine, pentamethylenediamine,
hexamethylenediamine.
[0061] The preferred compounds of formula I are those with
R.sub.1=hexamethylenediamine, piperazine and alkyl-substituted
piperazines as well as compounds of formula I in which X.sub.1 and
X are identical and have the meaning morpholino, piperidino or
piperazino.
[0062] Most preferably the compounds according to formula (A),
formula (I) and formula (I) wherein R.sub.1.dbd.Y are halogen free,
viz., do not include any halogen atoms, e.g., Br, Fl, Cl, I.
[0063] Most preferably the compounds according to formula (A),
formula (I) and formula (I) wherein R.sub.1.dbd.Y are water
insoluble.
[0064] The following examples illustrate the preparation of several
compounds according to formula A and I. All the parts indicated in
such preparation are to be considered, unless otherwise specified,
as parts by weight.
EXAMPLE 1
[0065] Into a reactor were charged 150 parts of water, 150 parts of
ice and 0.2 parts of dodecyl-benzenesulphonic acid. Then 74 parts
of cyanuric acid chloride were added under stirring over a period
of 15 minutes. The mixture was stirred for 15 minutes to obtain a
homogeneous suspension. After the formation of the suspension were
added simultaneously 34.9 parts of morpholine and 21.2 parts of
sodium carbonate (100% basis) dissolved in 150 parts of water,
while maintaining the pH value between 5 and 7 and a temperature of
0-5.degree. C. maximum. Addition time was 30 minutes. After the
addition was complete, the reaction mixture was stirred at
0-5.degree. C. for 30 minutes to form white suspension of the
compound II:
##STR00025##
[0066] To the resulting white suspension of the compound II were
added 34.9 parts of piperazine and the mixture heated to 40.degree.
C. and stirred at 40.degree. C. for 30 minutes. Thereafter was
added slowly over a period of 15 minutes 16 parts of sodium
hydroxide (100% basis) dissolved in 100 parts of water, thereby
keeping the temperature at 40.degree. C. After stirring for 15
minutes at 40.degree. C., the mixture was heated to 95.degree. C.
After reaching the temperature of 95.degree. C., a second portion
of 16 parts of sodium hydroxide (100% basis) dissolved in 100 parts
of water was added over a period of two hours. The resulting
suspension was heated for 24 hours at 130.degree. C. under pressure
and the pH at the end was basic (pH>7). The suspension was
filtered at 90.degree. C. and the product washed thoroughly with
hot water till the pH was neutral. The product was dried at
100.degree. C. for 24 hours till the weight was constant. The
process yielded 109 parts of the compound of the formula
##STR00026##
wherein n=10 with the following characteristics: [0067] Appearance:
White powder [0068] Melting Point: Above 290.degree. C. [0069]
Organic chlorine content (Elemental analysis and hydrolysis
method): 1.42%
EXAMPLE 2
[0070] Into a reactor were charged 150 parts of water, 150 parts of
ice and 0.2 parts of dodecyl-benzenesulphonic acid. Then 74 parts
of cyanuric acid chloride were added under stirring over a period
of 15 minutes. The mixture was stirred for 15 minutes to obtain a
homogeneous suspension. After the formation of the suspension were
added simultaneously 34.9 parts of morpholine and 21.2 parts of
sodium carbonate (100% basis) dissolved in 150 parts of water,
while maintaining the pH value between 5 and 7 and a temperature of
0-5.degree. C. maximum. Addition time was 30 minutes. After the
addition was complete, the reaction mixture was stirred at
0-5.degree. C. for 30 minutes, filtered, washed with water to
obtain 387 parts of press cake with 23.5% solid content,
corresponding to 91 parts and 96.8% of the theoretical yield of the
compound of formula II. A small sample of II dried at 50.degree. C.
under vacuum has a melting point of 88.5-89.degree. C. and an
organic chlorine content of 29.8% as per elemental analysis and
hydrolysis methods.
[0071] Into a 2-liter reactor equipped with stirrer, thermometer,
reflux cooler and heating bath, there were introduced 1200 parts of
water and 0.5 parts of dodecylbenzenesulphonic acid. Then 387 parts
of the press cake of II obtained as above were added at 20.degree.
C. To the resulting white suspension were added 33.4 parts of
piperazine, the mixture was heated to 40.degree. C. and stirred at
40.degree. C. for 30 minutes. Over a period of 15 minutes 15.5
parts of sodium hydroxide (100% basis) dissolved in 100 parts of
water were added slowly, thereby keeping the temperature at
40.degree. C. After stirring for 15 minutes at 40.degree. C. the
mixture was heated to 100.degree. C. After reaching the temperature
of 95.degree. C., the second portion of 15.5 parts of sodium
hydroxide (100% basis) dissolved in 100 parts of water was added
over a period of two hours. The resulting suspension was heated for
24 hours at 125.degree. C., the pH at the end should be basic. The
suspension was filtered at 95.degree. C. and washed thoroughly with
hot water till the pH was neutral. The product was dried at
100.degree. C. for 24 hours till the weight was constant. One
obtained 97.5 parts of the compound of the formula III wherein n=10
with the following characteristics: [0072] Appearance: White powder
[0073] Melting Point: Above 290 degree C. [0074] Organic chlorine
Content (Elemental analysis and hydrolysis method): 1.52%
EXAMPLE 3
[0075] 400 parts of morpholine at room temperature were placed in a
reactor with a condenser, a stirrer and a thermometer. 200 parts of
the compound of Formula III (containing 1.5% chlorine) were added
and the mixture heated to 120.degree. C. The mixture was stirred
for 12 hours. After cooling down to room temperature, the mixture
was poured out on 1000 parts of ice and 1000 parts of water
containing 3.5 parts of sodium hydroxide 100%. The resulting
suspension was filtered and washed thoroughly with water at room
temperature till the pH was neutral. The obtained product was dried
at 100.degree. C. for 24 hours till the weight was constant. One
obtained 230 parts of the compound of the formula IIIa
##STR00027##
wherein n=10, with the following characteristics: [0076] Cl content
(AOX): <0.01% [0077] Colour: White [0078] Melting point: Above
290 C
EXAMPLE 4
[0079] 40 parts of morpholine, 0.5 parts of sodium
dodecylbenzenesulphonate and 1000 parts of water were placed at
room temperature in a reactor with a stirrer and a thermometer. 200
parts of the compound of Formula III (containing 1.42% chlorine)
were added and the mixture heated to 130.degree. C. After stirring
for 4 hours at 130.degree. C. 3.2 parts of sodium hydroxide (100%
basis) dissolved in 20 parts of water were added. The resulting
suspension was heated for 8 hours at 130.degree. C., the pH at the
end should be basic. The suspension was filtered at 95.degree. C.
and washed thoroughly with hot water till the pH was neutral. The
product was dried at 100.degree. C. for 24 hours till the weight
was constant. One obtained 214 parts of the compound of the formula
IIIa with the following characteristics: [0080] Cl content (AOX):
<0.01% [0081] Colour: Off white [0082] Melting point: Above 290
C
EXAMPLE 5
[0083] 400 parts of piperazine were placed at room temperature in a
reactor with a condenser, a stirrer and a thermometer. 200 parts of
the compound of formula III (containing 1.72% chlorine) prepared
according to example 3 of the U.S. Pat. No. 4,504,610 were added
and the mixture heated to 100 C. The mixture was stirred for 12
hours. After cooling down to room temperature, the mixture was
poured out on 1000 parts of ice and 1000 parts of water containing
3.2 parts of sodium hydroxide 100%.The resulting suspensionwas
filtered and washed thoroughly with water at room temperature till
the pH was neutral. The product was dried at 100 C for 24 hours
till the weight was constant. One obtained 203 parts of the
compound of the formula IIIb
##STR00028##
wherein n=10, with the following characteristics: [0084] Cl content
(aox): <0.01% [0085] Colour:=Off white [0086] Melting point:
Above 290 C
EXAMPLE 6
[0087] 40 parts of piperazine, 0.5 parts of dodecylbenzenesulphonic
acid and 1000 parts of water were placed at room temperature in a
reactor with a stirrer and a thermometer. 200 parts of the compound
of Formula III (containing 1.5% chlorine) was added and the mixture
heated to 130.degree.C. After stirring for 4 hours at 130.degree.
C. 3.2 parts of sodium hydroxide (100% basis) dissolved in 20 parts
of water were added. The resulting suspension was then heated for 8
hours at 130.degree. C., the pH at the end should be basic. The
suspension was filtered at 95.degree. C. and washed thoroughly with
hot water till the pH was neutral. The product was dried at
100.degree. C. for 24 hours till the weight was constant. One
obtained 237 parts of the compound of the formula IIIb
EXAMPLE 7
[0088] Using commercially available compound of Formula III
[PPM-Triazine, poly-2,4-piperazinyl-6-morpholinyl-1,3,5-triazine;
CAS Nr.: 93058-67-4, obtained from Degussa AG and now AlzChem,
Germany, containing 1.48% organic chlorine (AOX)] in place of the
compound of formula III of the Example 2 of this patent
application, in example 4, the product IIIa with a yield of 97% was
obtained.
[0089] The product showed the following characteristics: [0090] Cl
content: <0.01% [0091] Colour: Off white [0092] Melting point:
Above 290 C
EXAMPLE 8
[0093] 4 parts of sodium hydroxide (100% basis), 0.5 parts of
dodecylbenzenesulphonic acid and 1000 parts of water were placed at
room temperature in a reactor with a condenser, a stirrer and a
thermometer. 200 parts of the compound of Formula III (containing
1.5% chlorine) were added and the mixture heated to 98.degree. C.
The resulting suspension was heated for 12 hours at 130.degree. C.,
the pH at the end should be basic. The suspension was filtered at
95.degree. C. and washed thoroughly with hot water till the pH was
neutral. The product was dried at 100.degree. C. for 24 hours till
the weight was constant. One obtained 237 parts of the compound of
the formula IIIc
##STR00029##
wherein n=10 , with the following characteristics: [0094] Cl
content: <0.01% [0095] Colour: White [0096] Melting point: Above
290 C
EXAMPLE 9
[0097] Using 12 parts of ammonium hydroxide (approx 30%) in place
of 4 parts of sodium hydroxide (100% basis) in EXAMPLE 8 and
carrying out the reaction in a closed reactor, the compound of
formula IIId was obtained
##STR00030##
wherein n=10, with the following characteristics: [0098] Cl
content: <0.01% [0099] Colour: Off white [0100] Melting point:
Above 290 C
EXAMPLE 10
[0101] Into a reactor were charged 150 parts of water, 150 parts of
ice and 0.2 parts of dodecyl-benzenesulphonic acid. Then 74 parts
of cyanuric acid chloride were added under stirring over a period
of 15 minutes. The mixture was stirred for 15 minutes to obtain a
homogeneous suspension. After the formation of the suspension were
added simultaneously 34.9 parts of morpholine and 21.2 parts of
sodium carbonate (100% basis) dissolved in 150 parts of water,
while maintaining the pH value between 5 and 7 and a temperature of
0-5.degree. C. maximum. Addition time 30 minutes. After the
addition was complete, the reaction mixture was stirred at
0-5.degree. C. for 30 minutes.
[0102] To the resulting white suspension of II were added 34.9
parts of piperazine and the mixture heated to 40.degree. C. and
stirred at 40.degree. C. for 30 minutes. Thereafter was added
slowly over a period of 15 minutes 16 parts of sodium hydroxide
(100% basis) dissolved in 100 parts of water, thereby keeping the
temperature at 40.degree. C. After stirring for 15 minutes at
40.degree. C., the mixture was heated to 95.degree. C. After
reaching the temperature of 95.degree. C., a second portion of 16
parts of sodium hydroxide (100% basis) dissolved in 100 parts of
water was added over a period of two hours. The resulting
suspension was heated for 24 hours at 98.degree. C. Thereafter 5
parts of morpholine were added and the mixture was stirred for 4
hours at 120.degree. C. (under pressure). The suspension was
treated with 3.2 parts of sodium hydroxide (100% basis) dissolved
in 20 parts of water at 90.degree. C., filtered at 90.degree. C.
and the product washed thoroughly with hot water till the pH was
neutral. The product was dried at 100.degree. C. for 24 hours till
the weight was constant. One obtained 101 parts of the compound of
the formula IIIa with <0.1% chlorine (AOX) content.
EXAMPLE 11
[0103] Into a reactor were charged 150 parts of water, 150 parts of
ice and 0.2 parts of dodecyl-benzenesulphonic acid. Then 74 parts
of cyanuric acid chloride were added under stirring over a period
of 15 minutes. The mixture was stirred for 15 minutes to obtain a
homogeneous suspension. After the formation of the suspension were
added simultaneously 34.9 parts of morpholine and 21.2 parts of
sodium carbonate (100% basis) dissolved in 150 parts of water,
while maintaining the pH value between 5 and 7 and a temperature of
0-5.degree. C. maximum. Addition time 30 minutes. After the
addition was complete, the reaction mixture was stirred at
0-5.degree. C. for 30 minutes.
[0104] To the resulting white suspension of II were added 34.9
parts of piperazine and the mixture heated to 40.degree. C. and
stirred at 40.degree. C. for 30 minutes. Thereafter was added
slowly over a period of 15 minutes 16 parts of sodium hydroxide
(100% basis) dissolved in 100 parts of water, thereby keeping the
temperature at 40.degree. C. After stirring for 15 minutes at
40.degree. C., the mixture was heated to 95.degree. C. After
reaching the temperature of 95.degree. C., a second portion of 16
parts of sodium hydroxide (100% basis) dissolved in 100 parts of
water was added over a period of two hours. The resulting
suspension was heated for 24 hours at 98.degree. C. Thereafter 5
parts of piperazine were added and the mixture was stirred for 4
hours at 120.degree. C. (under pressure). The suspension was
treated with 3.2 parts of sodium hydroxide (100% basis) dissolved
in 20 parts of water at 90.degree. C., filtered at 90.degree. C.
and the product washed thoroughly with hot water till the pH was
neutral. The product was dried at 100.degree. C. for 24 hours till
the weight was constant. One obtained 101 parts of the compound of
the formula IIIb with <0.1% chlorine (AOX) content.
EXAMPLE 12
[0105] 400 parts of water at 2.degree. C., 400 parts of crushed ice
and 0.5 parts of dodecylbenzenesulphonic acid were introduced into
a 2-liter flask equipped with stirrer, thermometer, dropping funnel
and cooling bath, followed by the introduction of 110.6 parts of
cyanuric acid chloride over a period of 30 minutes. The mixture was
stirred for 15 minutes till a homogeneous suspension was obtained.
While externally cooling and maintaining the pH value between 5 and
7 and the temperature from -2.degree. C. to +2.degree. C., 51.6
parts of piperidine in 200 parts of water and 31.8 parts of sodium
carbonate (100% basis) in 200 parts of water were simultaneously
fed. The mixture was stirred for 15 minutes at 2.degree. C. The
white product thus obtained was filtered and then washed with
water. There were obtained 525 parts of press cake with a solid
content of 25.5% corresponding to 134 parts of the dry material
corresponding to the theoretical yield of 96%.
[0106] After drying a sample of 10 parts at 50.degree. C. under
vacuum, there were obtained 2.55 parts of
2.6-dichloro-4-piperidine-1,3,5-triazine (IV) (melting point
88-88.5.degree. C.)
##STR00031##
[0107] The structure of such compound was proved by elemental
analysis and NMR.
[0108] Into a 1-liter reactor equipped with stirrer, thermometer
and heating bath, there were introduced 400 parts of water and 0.1
part of dodecylbenzenesulphonic acid. Then 46.6 parts of the
product IV and 17.2 parts of piperazine were added thereto at
20.degree. C. and letting the temperature to rise up to 30.degree.
C. due to the exothermic reaction. The mixture was heated to and
stirred at 40.degree. C. for 1 hour. Thereafter, it was heated to
130.degree. C. under pressure and maintained at such temperature
during 10 hours. 16 parts of solid sodium hydroxide 100% were
successively charged and the mixture stirred at 130.degree. C.
during 10 hours. The product obtained was filtered hot, thoroughly
washed with boiling water and dried. 49.2 parts of product V with a
yield of 98% were obtained.
[0109] The product was insoluble in the common organic solvents and
in water, its solubility values at room temperature being lower
than 0.1%. It exhibited a melting point higher than 290.degree. C.
and has the following formula:
##STR00032##
wherein n is 10.
EXAMPLE 13
[0110] Compound Va was made by using piperidine in place of
morpholine and compound V in place of compound III in example 3. It
is a white powder with <0.01% chlorine (AOX) content.
##STR00033##
EXAMPLE 14
[0111] Using 158 parts of
N,N'-bis-(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine (CAS
Nr: 61260-56-7) in place of 34.9 parts of piperazine in example 1,
one obtained the compound of formula VI as a white powder
##STR00034##
EXAMPLE 15
[0112] Using 4-amino-2,2,6,6-tetramethylpiperidine instead of
piperazine and the compound of Formula VI instead of the compound
of formula III in Example 5 one obtained the compound of the
formula VIa
##STR00035##
EXAMPLE 16
[0113] Using the compound of Formula VI instead of the compound of
formula III in Example 3 one obtained the compound of the formula
VIb
##STR00036##
EXAMPLE 17
[0114] Using 168.8 parts of
N,N'-bis-(1,2,2,6,6-pentamethyl-4-piperidinyl)-1,6-hexanediamine in
place of 34.9 parts of piperazine in example 1, one obtained the
compound of formula VII as a white powder
##STR00037##
EXAMPLE 18
[0115] Using the compound of Formula VII instead of the compound of
formula III in Example 3 one obtained the compound of the formula
VIIa
##STR00038##
EXAMPLE 19
[0116] Using 4-amino-2,2,6,6-tetramethylpiperidine instead of
piperazine and the compound of Formula VII instead of the compound
of formula III in Example 5 one obtained the compound of the
formula VIIb
##STR00039##
EXAMPLE 20
[0117] Using tert.octylamine in place of morpholine in example 1,
the product of the formula VIII with a yield of 97% was obtained.
The product was insoluble in water and in the usual organic
solvents and has the formula
##STR00040##
wherein n is 15.
EXAMPLE 21
[0118] Using the product of the formula VIII instead of the product
of the formula III and piperidine instead of morpholine in example
4, the product of the formula VIIIa with a yield of 97% was
obtained. The product was insoluble in water and in the usual
organic solvents and has the formula
##STR00041##
EXAMPLE 22
[0119] Using hexamethylenediamine in place of piperazine in example
12, the product of the formula IX which was insoluble in water and
in the common organic solvents and wherein n is 15 was
obtained.
##STR00042##
EXAMPLE 23
[0120] The product of the formula IXa was obtained by using the
compound of Formula IX instead of the compound of the formula III
in Example 3
##STR00043##
[0121] The self-extinguishing power degree can be determined by
measuring the oxygen index (according to ASTM D-2863) in a Stanton
Redcroft apparatus or by applying the UL-94 standards (published by
"Underwriters Laboratories" USA) which provide an evaluation of the
plastic materials' self-extinguishing power degree.
[0122] In the tests recorded on the following Table, for
compositions containing the oligomers or polymer of formula (III),
(V), (VI) and (VII) prepared according to the preceding examples,
the Vertical Burning Test was employed, which permits to classify
the materials at the following three levels: 94 V-0, 94 V-1 and 94
V-2, which express, in the decreasing order, the uninflammability
degree. An isotactic polypropylene in flakes having a melt flow
index equal to 12 was used as thermoplastic polymer.
Table
[0123] Self-extinguishing compositions based on polypropylene
(parts of weight)
TABLE-US-00001 Ex. Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8
Ex. 9 10 Polypropylene 78 78 78 78 77.5 78 77 78 77.5 77.0
Antioxidant* 1 1 1 1 1 1 1 1 1 1 Ammonium 14 15 15 15 14 14 14 15
14 14 Polyphosphate (Exolit AP 423, Clariant) Compound III 7 7 7
Compound IIIa 7 Compound IIIb 7 Compound IIIc 6 Compound IIId 7
Compound V 7 Compound Va 7 Compound VIIIa 6 Pigment Red 254 0.5
Pigment Yellow 180 0.5 Pigment White 6 1 1.0 Oxygen Index 27.5 28
29 28 27 28 29 28 28 27 UL-94 at 0.8 mm V2 V1 V0 V0 V2 V2 V1 V2 V2
V1 *This is a mixture of 0.5 parts of
Tris(2,4-di-tert-butylphenyl)phosphite (CAS: 31570-04-4) and 0.5
parts of
Pentaerythritol-tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)
(CAS: 6683-19-8)
* * * * *