US010364340B2

(12) United States Patent (10) Patent No.: US 10 , 364,340 B2

Pfaendner et al. (45) Date of Patent : Jul. 30 , 2019
(54 ) USE OF ORGANIC OXYIMIDES AS 21/12 (2013.01 ); B29K 2023/06 (2013.01);
RADICAL GENERATORS IN PLASTICS , B29K 2023 / 12 (2013 . 01 ); B29K 2105 /0005
METHOD FOR GENERATING RADICALS IN ( 2013.01)
PLASTICS AND USE OF SAID METHOD (58 ) Field of Classification Search
None
( 71 ) Applicant: FRAUNHOFER -GESELLSCHAFT See application file for complete search history.
ZUR FÖRDERUNG DER (56 ) References Cited
ANGEWANDTEN FORSCHUNG
E . V ., München (DE ) U . S. PATENT DOCUMENTS
4 ,267,084 A * 5 /1981 Mizutani ................ COSL 27/06
(72) Inventors : Rudolf Pfaendner, Rimbach (DE ); 524 /527
Markus Mazurowski, 4 ,409 , 367 A 10 / 1983 Beijleveld et al.
Ginsheim -Gustav (DE ) 9 ,428 ,692 B2 8/ 2016 Okada et al.
2008/0061270 A1 3 /2008 Tsuji et al.
(73 ) Assignee : Fraunhofer -Gesellschaft zur 2008/0269383 A1 * 10 /2008 Pauquet ................. C08K 5 /527
förderung der angewandten 524 / 120
2009 /0286060 A1* 11/2009 Sala ..................... CO7D 209 /48
Forschung e .V ., München (DE ) 428/220
2014 / 0225034 AL 8/2014 Okada et al.
(* ) Notice: Subject to any disclaimer, the term of this
patent is extended or adjusted under 35 FOREIGN PATENT DOCUMENTS
U . S .C . 154 (b ) by 0 days . CN 1968744 A 5 /2007
CN 101258194 A 9 /2008
(21) Appl. No.: 15 /511,471 CN 103764259 A 4 / 2014
WO WO 01/90113 AL 11/2001
(22 ) PCT Filed : Sep . 16 , 2015 WO WO 2006 / 106059 A 10 /2006
WO WO 2007 /028731 A1 3 / 2007
(86 ) PCT No.: PCT/EP2015 /071249 WO 2008 / 101845 A1 8/ 2008
(Continued )
$ 371 (c )( 1 ),
( 2 ) Date: Mar. 15 , 2017 OTHER PUBLICATIONS
(87) PCT Pub . No.: WO2016 /042038 Plastics Additives Handbook , 5th edition , Hans Zweifel, Editor,
Hanser Publishers, Munich, pp . 725 -811 (2001) .
PCT Pub . Date:Mar. 24 , 2016 Aubert et al., “ Azoalkanesnovel flame retardants and their structure
property relationship ,” Polym . Adv. Technol. 22 ( 11 ): 1529 - 1538
(65) Prior Publication Data (2011).
Aubert et al., “ Azoalkanes — A Novel Class of Additives for Cross
US 2017 /0260363 A1 Sep . 14 , 2017 Linking and Controlled Degradation of Polyolefins," Macromolecular
Materials and Engineering. 292 : 707 -714 (2007 ).
(30) Foreign Application Priority Data Pawelec et al., “ Triazene compounds as a novel and effective class
of flame retardants for polypropylene,” Polym . Degrad . Stab . 87(6 ):
Sep . 18 , 2014 (DE) ........................ 10 2014 218 811 948 -954 (2012 ).
European Patent Office , International Search Report and Written
Opinion issued in International Application No . PCT/ EP2015 /
(51) Int. Ci. 071249 (dated Nov. 27 , 2015 ).
C08K 5 /5373 ( 2006 .01) (Continued )
B29C 48 /00 (2019 .01) Primary Examiner - Robert T Butcher
C08K 5 / 3417 ( 2006 .01 )
CO7F 9 /572 (2006 .01) ( 74 ) Attorney , Agent, or Firm — Leydig , Voit & Mayer,
C08K 5 /5313 ( 2006 .01) Ltd .
C09D 5 / 18 ( 2006 .01) (57 ) ABSTRACT
CO9D 123/ 12 (2006 .01) The present invention relates to the use of phosphorus
COOK 15 /30 (2006 . 01) containing organic oxyimides according to the general for
COOK 15 /32 ( 2006 .01) mula I described below as flame retardant for plastic mate
COOK 21/ 12 ( 2006 .01) rials , as radical generators in plastic materials and /or as
B29C 45 /00 (2006 .01) stabilizers for plastic materials . The present invention relates
B29K 23 /00 ( 2006 .01 ) in addition to a flame- retardant plastic material molding
B29K 105 /00 ( 2006 .01) compound in which the previously described phosphorus
(52) U . S . CI. containing organic oxyimides are integrated, and also to a
CPC .. .... C08K 5 /5373 ( 2013 .01) ; B29C 45 /0001 method for the production of the previously mentioned
(2013 . 01) ; B29C 48 /022 (2019.02 ); CO7F plastic material composition . Furthermore , the present
9 /5728 (2013 .01 ); C08K 53417 (2013 .01); invention relates to a molded part, a paint or a coating made
C08K 5 /5313 ( 2013 .01) ; C09D 5 / 18 ( 2013.01); of the previously mentioned flame-retardant plastic material
C09D 123/ 12 (2013 .01 ); C09K 15 / 30 composition .
( 2013 .01) ; CO9K 15/322 ( 2013 .01) ; COOK 17 Claims, No Drawings
 US 10 ,Page
364,2340 B2

(56 ) References Cited

FOREIGN PATENT DOCUMENTS
WO WO 2012 /000022 AL 1 /2012
WO WO 2014 / 064064 A1 5 /2014
WO WO 2014/ 154636 AL 10 /2014
WO WO 2015 / 180888 A1 12 /2015
OTHER PUBLICATIONS
International Bureau of WIPO , International Preliminary Report of
Patentability issued in International Application No. PCT/ EP2015 /
071249 (dated Mar. 21, 2017).
State Intellectual Property Office of the People 's Republic of China ,
FirstOffice Action in Chinese Patent Application No. 201580050 105 .0
( dated Jun . 21 , 2018) .
European Patent Office , Communication Pursuant to Article 94 ( 3 )
EPC in European Patent Application No. 15 771 536 . 8 (dated Apr.
15 , 2019 ).
* cited by examiner
 US 10 , 364,340 B2
USE OF ORGANIC OXYIMIDES AS A further industrially important process is grafting of
RADICAL GENERATORS IN PLASTICS, monomers or unsaturated oligomers onto existing polymer
METHOD FOR GENERATING RADICALS IN chains in the presence of organic peroxides . These processes
PLASTICS AND USE OF SAID METHOD are important first and foremost for the production ofmaleic
anhydride - grafted or acrylic acid - grafted polyethylene or
CROSS -REFERENCE TO RELATED polypropylene , polyolefin co - and terpolymers, and also
APPLICATIONS maleic anhydride- grafted styrene -butadiene or styrene - buta
diene -styrene block copolymers and the hydrated subse
This patent application is the U .S . national phase of quent products thereof. Here also , as a consequence of the
International Application No. PCT/EP2015/071249 , filed on comparatively low decomposition temperatures of the per
Sep . 16 , 2015 , which claims the benefit of German Patent oxides, undesired secondary reactions, such as degradation ,
Application No. 10 2014 218 811. 3 , filed Sep . 18 , 2014 , the gel formation and / or discolouration , can occur.
disclosures ofwhich are incorporated herein by reference in There is therefore still a requirement for radical genera
their entireties for all purposes . 15 tors with improved control of the radical processes initiated
The present invention relates to the use of organic oxy herewith , an adjustable initiation temperature , high process
imides as radical generators in plastic materials . In addition , safety and simple synthetic accessibility, which in addition
the present invention relates to a method for the generation can be used as additives on normal processing machines ,
of radicals in plastic materials , in particular for degradation such as extruders .
and crosslinking - and grafting reactions of plastic materials 20 The object of the present invention is hence to indicate
or polymers and also to a use of this method . further radical generators for plastic materials which cir
The controlled production of different types of polymers, cumvent the previously mentioned problems.
in particular of types of polyolefins (different molecular This object is achieved by the features of the organic
weights , melting viscosities , molecular weight distributions , oxyimides used as radical generators in plastic materials
density ) can , on the one hand , be effected during synthesis , 25 described herein , by the features of the method for the
but also in a subsequent step , e.g . during processing by generation of radicals in plastic materials described herein ,
means of extrusion or injection moulding . An established and the advantageous developments thereof. Uses according
method is thereby addition of radical formers, which accord to the invention are also described .
ingly initiate radical reactions at the processing tempera The present invention therefore relates to the use of
tures, which then lead , as a function of the polymer struc - 30 organic oxyimides as radical generators in plastic materials.
ture, to a polymer degradation , i.e. to a reduction in the It is known
molecular weight, or to a polymer increase, i.e . to an oxyimides, according to the invention that the use of organic
increase in the molecular weight up to branching and subsequentlycomprising illustrated
at least one structural element of
formula I
crosslinking
A commercially important method is the degradation of 35
polypropylene (so -called " vis-breaking” ) to form a product Formula 1
with a lower molecular weight and narrower molecular
weight distribution (so -called “ controlled rheology PP” or
“ CR - PP ” ) . The resulting products are used e . g . for the
production of polypropylene fibres (“melt -blown” or “ spun - 40
bonded ” method ) or for easily - flowing thin -walled injection
moulded parts (“ thin -wall injection moulding” ). Conven
tional radical generators which are used for this method are
organic peroxides ( see e . g . D . Munteanu in H . Zweifel,
Plastics Additives Handbook , Munich 2001, p . 725 - 811 ). 45
Organic peroxides however require extensive safety devices is suitable as radical generators in plastic materials.
during handling, lead to undesired secondary reactions, and Formula I should thereby be understood such that the
the decomposition products from the peroxides can nega
tively influence the polymer properties, such as e.g . the illustrated structural element is contained in the organic
ide so50 oxyimide. The oxyimides used according to the invention
long-term stability . The use of aqueous hydrogen peroxide
(WO 2012 /000022) thereby represents an improvement, should not thereby be equated with isocyanurates or com
however here the handling with respect to technical safety is pounds or classes of compounds derived herefrom .
likewise challenging and cannot be effected in the com According to a preferred embodiment of the invention , in
monly available processing apparatus. Further known alter - particular oxyimides , comprising at least one structural
natives for radical generators in polypropylene degradation 55 element of following formula 1
processes are hydroxypiperidine esters (WO 0190113 ),
asymmetrical azo compounds (WO 2006 / 106059 ) or imi Formula II
noxytriazines (WO 2014 /064064). These compounds are
however frequently difficult to access synthetically so that
they are commercially unimportant . 60
A further industrially important process is crosslinking of w

polyethylene (e.g. LDPE , LLDPE , MDPE ) with radical N - 0 - R

formers . These processes with addition of peroxides are used
frequently in the production of pipes and cables. In addition ,
there applies in turn that the mentioned safety aspects must 65
be taken into account, here uncontrolled secondary reactions
in
lead to undesired gel formation and to processing problems.
 US 10 , 364 ,340 B2
are used as radical generators for plastic materials, R ! -continued
standing for hydrogen or a possibly substituted alkyl-,
cycloalkyl-, aryl-, heteroaryl- or acyl-radical.
Alternatively , or in combination with the previously men
tioned preferred variant, likewise bridged oxyimides, com - 5
prising at least one structural element of subsequent formula
III are used
[ 17
Formula III 10
In particular , the radicals R2 are thereby given by the
subsequent structural elements :
Wna N - 0 – R2 – 0 - N
wmian 15

R2 standing for a possibly substituted alkylene -, 20

- - -
cycloalkylene -, arylene-, heteroarylene - or bridging acyl
radical.
The oxyimide used according to the present invention is
thereby likewise preferably halogen - free , i.e. the corre oo
sponding compound does not comprise any halogen atoms. 25
According to a preferred variant, R2 is selected from
radicals of the group consisting of
( CH2) - with n = 1 to 18 , - CH (CH3) ,
- C ( CH3) 2 - , - , - S — , S02 - , - NHCO ,
Date of Jan
- CO , OC (O )O - and also the subsequently illustrated 30o caseAccording
of this
to a particularly preferred embodiment, in the
variant of the invention , the organic oxyimide
groups
has one of the subsequent structural formulae :

N - 0 - R1L N - 0 - R1

- T
N - 0 - R T- O - R
- 0 - 45

the cycloaliphatic or aromatic ring systems contained in the

previously illustrated groups being unsubstituted or substi - 50 RI - O - N N - 0— R
tuted by one or more alkyl- and/or alkoxy groups ,
Q upon each occurrence, being the same or different and
being selected from the group consisting of a chemical
bond and also the radicals (CH ), — with n = 1 to 18 ,
_ CH (CH3) , C (CH2)2 - , - 0 , S — , - SO , — ,
-NHCO , 0 - C (O ) O - , - CO — , and N - 0 – R2 — 0 ~ N
m being 0 or 1 to 18 .
For particular preference , the radicals R , are thereby
reproduced by the subsequently illustrated structural ele O

ments , Q having the above - indicated meaning:

R -0- N N - 0- R
65
 US 10 ,364,340 B2
-continued -continued

N - 0 – R2 — 0 N R10 - N N - OR ]

10 respectively R and R² having the above - indicated meaning

N - 0 – R2 — 0 - N - ORI and R ' and R or R2 and R , having the same meaning .
A particularly preferred radical R ' is thereby hydrogen , an
alkyl - or an acyl-radical.
As radical generators in plastic materials, the subse
15 quently illustrated compounds are suitable in particular
R10 - N

RO - N
ORI

N - ORI
mire20

25
HO — N
?? ??,

OSO
N - OH
ZOH

30 OH
N - 0 - R2 - 0 - N

Se
N
N - OH - OH

35 HO OH

R10 - N N - OR
R² having the above -indicated meaning .
40 The selection of the suitable radical generator is thereby
effected such that the formation of the radicals is effected at
the processing temperatures of the respective polymers
RO- N LOR within a sufficient range for the reaction and the respective
processing method . The temperatures at which a radical
45 formation is effected can be determined , for example , by
DSC (“ Differential Scanning Calorimetry ” ). A further crite
rion for selection is the formation of reaction products ,
which can for example be volatile and hence can easily be
removed from the product, or can be high -molecular and
RO - N N - OR 50 hence remain in the product without any disadvantages. The
respective processing processes and temperatures for plastic
material processing processes are known to the person
skilled in the art. Plastic material processing processes and
temperatures pertaining thereto can however also be
deduced from the expert literature , such as e . g . H . Domin
RI ORI inghaus, P. Elsner, P . Eyerer, T. Hirth , Kunststoffe (Plastic
Materials ), gth edition , Springer 2012 . In particular, for
degradation methods, the further addition of chain transfer
agents can be advantageous . Possible chain transfer agents
60 can be selected from the class of thiols , disulfides, phos
phoric acid esters , phosphines , organic halides, such as
iodides , bromides , chlorides , acid esters , aldehydes or ter
R10 - N ORI tiary amines . Preferably, the chain transfer agents have a
boiling point above the processing temperature of the
65 respective polymer. Particularly preferred are sulphur
derivatives, such as thiols and disulfides. Suitable chain
transfer agents are for example :
 US 10 ,364 ,340 B2
SH

Nat

NH HN :

O-
SH
SH H25C12 C12H25
C12
HS SH
SH

HS

In particular for molecular weight increase reactions and

for crosslinking reactions, the addition of further multifunc - 25 - continued
tional compounds, in addition to the radical generator and to
the polymer, can be advantageous. Suitable compounds
include the classes of
a ) repeatedly unsaturated oligomers and polymers based 30
on polybutadiene or polyisoprene
b ) di- and polyvinyl compounds, such as e.g. divinyl
benzene
c ) di- and polyallyl compounds , such as e.g . polyallyl
ether or polyallyl ester, trisallyl isocyanuranate , trisal- 35 Typical examples of di- and poly (methacrylesters of di
lyl cyanurate , diallyl bisphenol- A and polyols are:
d ) di- and polymaleimides
e ) di- and poly (meth Jacrylester of di- and polyalcohols ,
and /or 40
f) organofunctional silanes
Typical examples of organofunctional silanes are : - (CH2)n - 0
Y – (CH2)n — SiX ; 45

with n = 0 to 3 ; Y = CH2= CH - , CH2 = C (CH3)C00 — , with n = 2 - 5

NH , — , SH — , C1— ; X = OR (R = Me, Et), OCOCHZ.
Typical examples of di- and polymaleimides are :
50

with
with nn==15
1 -5
O
 US 10 , 364 ,340 B2
10
- continued A typical example of an allyl compound is:

10

Grafting reactions with initiation of the radical formers

according to the invention are implemented in the presence
of unsaturated monomers, which are bonded onto the poly
mer backbone by the reaction by means of a chemical bond .
Suitable unsaturated monomers are in particular maleic
anhydride , itaconic anhydride , N -alkylmaleimide , acrylic
acid , methacrylic acid , acrylic ester ,methacrylic ester, such
? N? as e .g . lauryl(methacrylate , stearyl (meth ) acrylate , glycidyl
20 (meth )acrylate, hydroxyethyl(meth )acrylate .
Furthermore, it can be advantageous to implement the
crosslinking - or grafting reaction in the presence of an
additional nitroxyl radical. By means of the addition of the
nitroxyl radical, the crosslinking - or grafting reaction can be
25 moderated , i. e . the reaction course can be controlled better,
which leads to fewer secondary reactions of the process .
Suitable nitroxyl radicals are for example :

30 - Ro Rio
O
:

35
'N

40
Rec
R3
C - R2
RA
Ó
R -R10 representing a possibly substituted alkyl group ,
phenyl, hydroxyl, alkoxy or ester group and being commer
cially available for example under the names TEMPO ,
45 Hydroxy - TEMPO or Oxo - TEMPO . The following nitroxyl
radicals are particularly preferred :

H3C CH ; H3C
H3CN CH3
-
H3C N
.
0

OH
OH
- (CH2)8

/ R H3C5 CH3
CNCH
H H2
-

with R = H or methyl .
0

and m = 0 - 10 , n = 2 - 10
 US 10 , 364 ,340 B2
12
-continued tert-butyl-perneodecanoate , tert-butylperpivalate, tert -am
ylperpivalate , bis ( 2 ,4 -dichlorobenzoyl) peroxide ,
diisononanoylperoxide , didecanoylperoxide , dioctanoylper
0 - N
oxide, dilauroylperoxide , bis( 2 -methylbenzoyl)peroxide ,
0
=
5 disuccinoylperoxide, diacetylperoxide, dibenzoylperoxide,
P tert -butylper- 2 -ethylhexanoate, bis( 4 -chlorobenzoyl) perox
ide, tert -butylperisobutyrate, tert-butylpermaleate , 1, 1-bis
(tert-butylperoxy )-3 , 5 ,5 -trimethylcyclohexane , 1, 1 -bis(tert
butylperhydroperoxide.
10 The at least one further radical former is thereby particu
larly preferably selected from the group consisting of
Furthermore , it can be advantageous that the degradation -, a ) N - alkoxyamines according to the subsequently illus
crosslinking - or grafting reactions of the oxyimides accord trated structural formula
ing to the invention are effected with the further addition of
catalytically acting compounds. Such compounds can be for R3 R3
example metal salts of transition metals, such as e. g . copper,
manganese or iron , for example in the form of acetates, such Vz
as Cu ( l)acetate . R4 - N Ñ

Furthermore , it can be advantageous that the radical 20 AZ

formers according to the invention are combined with at
least one further radical former, e .g . with different classes of R3 R3
radical formers and /or radical formers with different decom
position temperatures . The temperatures at which radicals R3 standing for hydrogen or a possibly substituted
are formed are chosen such that this formation is effected at 25 alkyl-, cycloalkyl -, aryl-, heteroaryl- or acyl -radical ,
the processing temperatures of the respective polymers. The in particular being a C1 to C4 alkyl radical,
combination of radical formers with differentdecomposition R4 standing for an alkoxy -, aryloxy -, cycloalkoxy -,
temperatures is advantageous in the case of multistage aralkoxy - or acyloxy - radical,
processes, thus for example in the case of low temperatures, Z standing for hydrogen or a possibly substituted
pre - crosslinking and , in the case of a higher temperature , 30 alkyl-, cycloalkyl-, aryl-, heteroaryl- or acyl -radical,
further crosslinking of polyethylene can be effected . the two radicals Z also being able to form a closed
Radical formers in the sense of the present invention are ring which can be substituted possibly by ester-,
compounds which can produce radicals by thermal and ether-, amine-, amide -, carboxy- or urethane groups,
light-induced cleavage . Suitable radical formers for the b ) azo compounds according to the subsequently illus
applications present here are those which , for the plastic 35 trated structural formulae
material- or coating processing processes in which degra
dation , crosslinking or grafting is effected , deliver a sufti
cient quantity of radicals for the reaction . R3 N = N - R $ or
The further radical former is thereby preferably selected
from the group consisting of peroxides, N -alkoxyamines, 40
— C — C — radical formers, radical formers with azo groups
N = N / ), radical formers with hydrazine groups R8 N NEN N - R8
( NH — HN — ), radical formers with hydrazone groups
( > C = N - NH - ), radical formers with azine groups
(> C = N — N — C < ), radical formers with triazene groups 45 RORO R7 R ROR
GN = N / N < ) and iminoxytriazines .
The production of suitable azo compounds is described R? meaning an alkyl-, cycloalkyl- or aryl- radical,
for example in M . Aubert et al. Macromol. Sci. Eng. 2007, Rºupon each occurrence , being the same or different
292 , 707 - 714 or in WO 2008101845, the production of and meaning a linear or branched alkyl-radical,
hydrazones and azines in M . Aubert et al., Pol. Adv . Technol. 50 R ' upon each occurrence , being the same or different
2011 , 22 , 1529- 1538 , the production of triazenes in W . and meaning hydrogen or a linear or branched alkyl
Pawelec et al., Pol. Degr. Stab . 2012, 97 , 948 - 954. The
synthesis of iminoxytriazines is described in WO 2014 / radical, and
064064 . R $ upon each occurrence , being the same or different
Peroxides are commercially available compounds , which 55 and meaning an alkyl-, alkoxy -, aryloxy -, cycloalky
can be obtained for example from United Initiators. Suitable loxy -, aralkoxy- or acyloxy -radical,
peroxides are for example : c ) dicumyl according to the subsequently illustrated struc
2 ,5 - dimethyl-2 ,5 -di?t -butylperoxylhexane, 2 ,5 - dimethyl tural formula
2 ,5 -di?t -butyl-peroxy)hexyne-3 ,3 ,6 ,6 , 9, 9 -pentamethyl-3
( ethylacetate ) -1 ,2 ,4 ,5 - tetraoxycyclononane , t-butylhydrop - 60

Olko
eroxide, hydrogen peroxide , dicumylperoxide , - ? ?
t-butylperoxyisopropylcarbonate , di-t-butylperoxide ,
p -chlorobenzoylperoxide, dibenzoyldiperoxide , t-butylcum R7 R7
ylperoxide , t-butylhydroxyethylperoxide, di-t- amylperox
ide, 2,5 -dimethylhexene -2 ,5 - diperisononanoate , acetylcy - 65
clohexanesulphonylperoxide, R7having the previously indicated meaning , preferably
diisopropylperoxydicarbonate , tert - amylperneodecanoate , being methyl,
 US 10 , 364 ,340 B2
13 14
d ) and /or polycumyl according to the subsequently illus ylpropoxy )-4 -hydroxy -2,2 ,6 ,6 -tetramethylpiperidine ; 1-( 2
trated structural formula hydroxy -2 -methylpropoxy)-4 -oxo - 2 ,2 ,6 ,6
tetramethylpiperidine ; 1 -(2 -hydroxy -2 -methylpropoxy )-4
octadecanoyloxy -2 ,2 ,6 ,6 - tetramethylpiperidine; bis( 1- (2

hol 5 hydroxy - 2 -methylpropoxy ) -2 ,2 ,6 ,6 - tetramethylpiperidin - 4

yl) sebacate ; bis ( 1- (2 -hydroxy -2 -methylpropoxy)- 2,2 ,6 ,6
tetramethylpiperidin -4 - yl )adipate ; 2,4 -bis {N -[1 -(2
hydroxy -2 -methylpropoxy)- 2, 2,6 ,6 - tetramethylpiperidin -4
R ’ having the previously indicated meaning , preferably yl ]-N -butylamino } -6 - (2 -hydroxyethylamino )- S - triazine );
being methyl, and 2 < n < 100 .
Typical examples of the previously mentioned 10 bonate 4 -piperidinol, 2, 2,6 ,6 -tetramethyl- 1 -(undecyloxy)-,4 ,4'-car
; the reaction product of 2 ,4 -bis[ (1 -cyclohexyloxy - 2 ,
N - alkoxyamines of the indicated structure are thereby : 2 , 6 ,6 - tetramethylpiperidin -4 -yl)butylamino )-6 -chloro - S -tri
1 -cyclohexyloxy -2 ,2,6 ,6 -tetramethyl-4 - octadecylamin azine with N ,N -bis ( 3 -aminopropylethylenediamine ); the
opiperidine ; bis ( 1 -octyloxy - 2 ,2 ,6 ,6 -tetramethylpiperidin -4 oligomer compound , which is the condensation product of
yl)sebacate; 2 ,4 -bis [ (1 -cyclohexyloxy - 2 ,2 ,6 ,6 -tetramethyl- 16 4 ,4'-hexamethylene -bis (amino -2 , 2 ,6 ,6 -tetramethylpiperi
piperidin -4 - yl )butylamino )-6 -(2 -hydroxyethylamino -S dine) and 2 ,4 - dichloro -6 -[ ( 1 -cyclohexyloxy- 2 ,2 ,6 ,6 - tetram
triazine; bis( 1 -cyclohexyloxy -2 ,2 ,6 ,6 -tetramethylpiperidin ethyl- 4 - yl)butylamino ] -S - triazine , closed at the ends with
4 -yl)adipate; 2 -chloro - 4 ,6 - bis ( dibutylamino ) -S -triazine; aliphatic hydrox
2,4 -bis [( 1 -cyclohexyloxy -2,2 ,6 ,6 -tetramethylpiperidin -4 ylamine, such as e .g . distearyl hydroxylamine ; and also
yl)butylamino ] -6 - chloro - S - triazine; 1 - (2 - hydroxy - 2 -meth compounds of the formulae

0
-
i

N - ( CH2)6 - N N ( CH2)6 _ N
NN 2

N - C4H6 WA
ZO
DZ
in which n = 1 – 15 .
 US 10 , 364 ,340 B2
15 16
The above -mentioned compounds are partially commer Suitable 2 -hydroxybenzophenones are for example 4 -hy
cial products and are sold under the following trade names : droxy -, 4 -methoxy-, 4 -octyloxy -, 4 - decyloxy -4 -dodecyloxy ,
FLAMESTAB NOR 116® , TINUVIN NOR 371® , 4 -benzyloxy , 4,2',4 '- trihydroxy - and 2 -hydroxy -4 ,4 -dim
IRGATEC CR 76® by BASF SE , Hostavin NOW® by ethyoxy derivatives of 2 -hydroxybenzophenones .
Clariant or ADK Stab LA 81® by Adeka . Dicumyl and 5 Suitable acrylates are for example ethyl- a -cyano -ß ,ß
polycumyl are commercially available products which are diphenylacrylate, isooctyl-a - cyano- ß ,ß -diphenylacrylate ,
obtainable for example from United Initiators. methyl-a -carbomethoxycinnamate, methyl-a -cyano -B
niem
The plastic materials can comprise preferably normal methyl-p -methoxycinnamate , butyl-a -cyano -b -methyl-p
additives, e.g . additives selected from the group consisting methoxycinnamate , methyl-a -carbomethoxy -p -methoxy
of UV absorbers , light stabilisers , stabilisers, hydroxylam - 10 cinnamate and N - (ß -carbomethoxy -B - cyanovinyl)- 2
ines , benzofuranones , flame retardants , nucleation agents, methylindoline.
impact strength enhancers , plasticisers, lubricants , rheology Suitable esters of benzoic acids are for example 4 -tert
modifiers, processing aids, pigments, colourants, optical butylphenylsalicylate, phenylsalicylate , octylphenylsalicy
brighteners , antimicrobial active substances, antistatic 16 late , dibenzoylresorcinol, bis ( 4 - tert -butylbenzoyl resorci
agents , slip agents, antiblocking agents , coupling means, nol, benzoylresorcinol, 2,4 -di-tert -butylphenyl-3,5 -di- tert
chain lengtheners, dispersants , compatibilisers , oxygen col- butyl-4 -hydroxybenzoate, hexadecyl- 3,5 -di-tert-butyl-4
lectors, acid collectors , marking means or anti- fogging hydroxybenzoate , octadecyl-3 , 5 - di-tert-butyl-4
means. In a preferred embodiment, the compositions com - hydroxybenzoate, 2 -methyl-4 ,6 -di-tert-butylphenyl-3 ,5 - di
prise in particular acid collectors, e.g . based on salts of 20 tert -butyl-4 -hydroxybenzoate .
long -chain acids, such as e.g . calcium stearate , magnesium Suitable oxamides are for example 4 ,4 '- dioctyloxyoxa
stearate , zinc stearate , calcium lactate calciumstearoyl-2 - nilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy -5 ,5'-di-tert
lactylate , or of hydrotalcites and /or stabilisers from the butoxanilide , 2 ,2 -didodecyloxy - 5 ,5 - di-tert-butoxanilide,
group of phenolic antioxidants and phosphites and/or light 2 -ethoxy -2'-ethyloxanilide, N ,N -bis (3 -dimethylaminopro
stabilisers from the group of hindered amines (HALS) 25 pyl)oxamide , 2 -ethoxy -5 - tert -butyl-2'-ethoxanilide and the
and/ or dispersants . mixtures thereof with 2 - ethoxy- 2 '- ethyl-5 ,4 '-di- tert-butoxa
Suitable light stabilisers are for example compounds nilide, mixtures of o - and p -methoxy-disubstituted oxa
based on 2 -( 2 -hydroxyphenyl)benzotriazoles, 2 -hydroxy - nilides and mixtures of o - and p - ethoxy-disubstituted oxa
benzophenones, esters of benzoic acids, acrylates, oxamides nilides.
and 2 -( 2 -hydroxyphenyl) - 1,3 , 5 -triazines . Suitable 2 -(2 -hydroxyphenyl)-1, 3,5 - triazines are for
Suitable 2 -( 2" -hydroxyphenyl)benzotriazoles are for example 2 ,4 ,6 - tris(2 -hydroxy-4 -octyloxyphenyl) -1 ,3, 5 -tri
example 2 -(2'-hydroxy -5'-methylphenyl)benzotriazole , azine , 2 - (2 -hydroxy -4 -octyloxyphenyl)-4 ,6 -bis ( 2,4 -dimeth
2 -(3',5'-di-tert-butyl-2 -hydroxyphenyl)benzotriazole, 2 -(5 ' ylphenyl)- 1,3,5 -triazine, 2-(2,4 -dihydroxyphenyl) -4 ,6-bis
tert -butyl-2 -hydroxyphenyl)benzotriazole , 2 -( 2 -hydroxy- 35 (2,4 -dimethylphenyl)- 1,3 ,5 -triazine, 2 ,4 -bis (2 -hydroxy -4
5 -(1, 1,3,3 -tetramethylbutyl)phenyl)benzotriazole , 2 -(34, 58 propyloxyphenyl
2 - ( 2 - hydroxy - 4 -
)-6 -(2 ,4 -dimethylphenyl)- 1,3 ,5- triazine,
octyloxyphenyl )- 4 ,6 -bis (4 -methylphenyl-1 ,
di-tert -butyl-2 -hydroxyphenyl) -5 -chlorobenzotriazole ,
2 -( 3'-tert-butyl-2 -hydroxy -5 '-methylphenyl-5 -chlorobenzo 4 -dimethylphenyl)- 1,3 ,5 -triazine, 2-(2 -hydroxy)--44-,tridecy
3 , 5 - triazine, 2 - ( 2 -hydroxy - 4 -dodecyloxyphenyl 6 -bis (2 ,
triazole , 2 -(3 '- sec -butyl-5 '-tert-butyl-2 -hydroxyphenyl)ben - 20 loxyphenyl)- 4.6 -bis( 2 . 4 -dimethylphenyl)- 1,3 ,5 - triazine,
zotriazole, 2- (2 -hydroxy -4 '-octyloxyphenyl)benzotriazole, 2 - [ 2 -hydroxy -4 -( 2 -hydroxy - 3 -butyloxypropoxy) phenyl]- 4 ,
2 -( 3',5 '-di-tert-amyl-2'-hydroxyphenyl)benzotriazole , 2 -( 3', 6 -bis( 2 ,4 -dimethyl)- 1, 3, 5 - triazine , 2 -[2 -hydroxy -4 -(2 -hy
5 -bis (a ,a -dimethylbenzyl)-2 -hydroxyphenyl)benzotriaz droxy -3 -octyloxypropyloxy )phenyl]-4 ,6 -bis (2 ,4 -dimethyl)
ole, 2 -(3 '- tert-butyl- 2 -hydroxy -5 '-( 2 -octyloxycarbonyl- 1,3 ,5 -triazine, 2 -[4 -(dodecyloxy /tridecyloxy -2
ethyl)phenyl)-5 - chlorobenzotriazole , 2- (3'-tert-butyl-5 '-[2 - 45 hydroxypropoxy)-2 -hydroxyphenyl]-4 ,6 -bis(2 ,4
(2 -ethylhexyloxy )carbonylethyl )-2'-hydroxyphenyl)-5 dimethylphenyl )- 1,3 ,5 - triazine, 2 -[2 -hydroxy -4 -( 2
chlorobenzotriazole , 2 -(3 '-tert-butyl- 2 -hydroxy-5 '-( 2 - hydroxy -3 -dodecyloxypropoxy )phenyl]- 4 ,6 -bis( 2 ,4
methoxycarbonylethyl)phenyl) -5 -chlorobenzotriazole , dimethylphenyl- 1, 3 ,5 - triazine, 2 -(2 -hydroxy -4 -hexyloxy )
2 -( 3'-tert-butyl- 2 -hydroxy - 5'-( 2 -methoxycarbonylethyl) phenyl-4 ,6 -diphenyl- 1,3 ,5 -triazine, 2 -( 2-hydroxy-4
phenyl) benzotriazole , 2 -( 3'-tert-butyl-2 '-hydroxy -5'-(2 - oc - > methoxyphenyl)- 4,6 -diphenyl-1 ,3 ,5 - triazine , 2 ,4 ,6 -tris [2
tyloxycarbonylethyl)phenyl )benzotriazole , 2 -(3'- tert-butyl h ydroxy -4 -( 3 -butoxy- 2 -hydroxypropoxy )phenyl]- 1,3 ,5
5'-[2 - (2 -ethylhexyloxy ) carbonylethyl)-2'-hydroxyphenyl) triazine, 2 -( 2 -hydroxyphenyl)-4 -(4 -methoxyphenyl)-6
benzotriazole, 2 -(3 '-dodecyl- 2 -hydroxy -5 '-methylphenyl) phenyl-1 ,3 ,5 - triazine , 2 - { 2 -hydroxy-4 - [3 -( 2 -ethylhexyl-1
benzotriazole , 2 -(3 '-tert-butyl- 2 -hydroxy-5 '-( 2 - 55 oxy)- 2-hydroxypropyloxylphenyl} -4 ,6 -bis(2 ,4
isooctyloxycarbonylethyl)phenylbenzotriazole , 2,2i dimethylphenyl- 1,3 ,5 -triazine .
methylenebis [4 -( 1, 1, 3,3 -tetramethylbutyl)-6 -benzotriazol Suitable metal deactivators are for example N ,N - diphe
2 -ylphenol]; the product of reesterification of 2 -[3'- tert nyloxamide (salicyloyl)
, N - salicylal-N '-salicyloylhydrazine, N , N - bis
hydrazine , N ,N '-bis (3 ,5 -di- tert-butyl-4 -hydroxy
butyl-5 '-(2 -methoxycarbonylethyl)-2 -hydroxyphenyl]-2H . 60 phenylpropionyl)hydrazine
benzotriazole with polyethylene glycol 300 ; triazole, bis (benzylidene ,)oxalyldihydrazide 3 -salicyloylamino -1,2 ,4
, oxanilide ,
[R - CH2CH2 - COO CH2CH2 + 2, wherein R = 3 '-tert -bu isophthaloyldihydrazide, sebacoylbisphenylhydrazide,
tyl-4 -hydroxy -54-2H -benzotriazol-2 -ylphenyl, 2-[ 2'-hy N ,N -diacetyladipoyldihydrazide, N ,N '-bis ( salicyloyl)oxy
droxy - 3'-(a ,a -dimethylbenzyl) -5 -(1 ,1 ,3, 3 -tetramethylbu lyldihydrazide, N ,N -bis(salicyloyl)thiopropionyldihydraz
tyl)phenyl]benzotriazole , 2- [2 -hydroxy- 3'-(1 ,1, 3,3 - 65 ide .
tetramethylbutyl) -5 '-( a ,a -dimethylbenzyl) phenyl] In particular, the following structures are suitable asmetal
benzotriazole . deactivators :
 US 10 , 364 ,340 B2
17 18
cyclohexylphenol), 2 ,2'-methylenebis (6 -nonyl-4
OH methylphenol) , 2 , 2 -methylenebis ( 4 ,6 - di- tert-butylphenol),
2 ,2 -ethylidenebis( 4 ,6 -di- tert-butylphenol), 2 ,2'- ethyliden
ebis(6 -tert-butyl-4 -isobutylphenol), 2, 2'-methylenebis[6 -la
5 methylbenzyl) -4 - nonylphenol], 2 ,2'-methylenebis[6 - a , a
dimethylbenzyl)-4 -nonylphenol ], 4 ,4 '-methylenebis (2 ,6 -di
tert -butylphenol, 4 ,4 '-methylenebis (6 - tert- butyl- 2
methylphenol), 1, 1 -bis( 5 - tert-butyl- 4 -hydroxy - 2
methylphenyl) butane , 2 ,6 -bis ( 3 - tert-butyl-5 -methyl- 2
N 10 hydroxybenzyl) -4 -methylphenol, 1, 1, 3 - tris ( 5 -tert - butyl- 4
hydroxy - 2 -methylphenyl)butane , 1, 1 -bis (5 -tert-butyl-4
hydroxy - 2 -methylphenyl) -3 -n - dodecylmercaptobutane ,
ethylene glycol-bis[ 3,3 -bis ( 3'-tert-butyl-4'-hydroxyphenyl)
butyrate ), bis (3 - tert-butyl-4 -hydroxy -5 -methylphenyl)dicy
clopentadiene, bis [2 -(3 '-tert-butyl-2 -hydroxy- 5 '-methylben
OH zyl)- 6 -tert- butyl- 4 -methylphenyl ]terephthalate , 1 , 1 - bis -( 3 ,
5 -dimethyl-2 -hydroxyphenyl) butane , 2 ,2 -bis(3 ,5 - di- tert
butyl-4 -hydroxyphenyl)propane , 2 ,2 - bis -(5 -tert-butyl-4
hydroxy- 2 -methylphenyl) -4 - n -dodecylmercaptobutane , 1 ,1 ,
5 ,5 -tetra (5 -tert -butyl-4 -hydroxy -2 -methylphenyl) pentane;
20 0 -, N - and S -benzyl compounds , such as e. g . 3 , 5 , 3 ,5
OH tetra -tert-butyl-4 ,4'-dihydroxydibenzylether, octadecyl-4
hydroxy - 3 ,5 -dimethylbenzylmercaptoacetate , tridecyl-4 -hy
droxy - 3, 5 -di-tert-butylbenzylmercaptoacetate, tris (3 ,5 -di
tert -butyl - 4 -hydroxybenzyl)amine, bis ( 4 -tert-butyl- 3
25 hydroxy -2 ,6 -dimethylbenzyl)dithioterephthalate , bis (3 ,5 - di
tert -butyl-4 - hydroxybenzyl) sulfide, isooctyl-3 ,5 - di- tert
butyl- 4 -hydroxybenzylmercaptoacetate ;
hydroxybenzylated malonates, such as e .g. dioctadecyl
2 ,2 -bis(3 ,5 - di-tert-butyl- 2 -hydroxybenzyl)malonate , diocta
OH Ö 30 decyl-2 - (3 -tert-butyl-4 -hydroxy -5 -methylbenzyl)malonate ,
didodecylmercaptoethyl- 2 ,2 -bis (3 ,5 -di-tert- butyl- 4 -hy
Suitable phenolic antioxidants are for example : droxybenzyl)malonate, bis [4 -( 1 , 1,3 , 3 - tetramethylbutyl) phe
alkylated monophenols, such as e. g . 2,6 - di-tert -butyl-4 nyl]-2 ,2 -bis(3 ,5 -di- tert -butyl-4 -hydroxybenzyl)malonate ;
methylphenol, 2 -tert-butyl-4 ,6 -dimethylphenol, 2 ,6 -di-tert 35 aromatic hydroxybenzyl compounds, such as e.g . 1,3 ,5
butyl-4 -ethylphenol, 2 ,6 -di- tert-butyl-4 -n -butylphenol, 2 ,6 tris (3 ,5 -di-tert-butyl- 4 -hydroxybenzyl)-2 ,4 ,6 -trimethylben
di-tert-butyl-4 -isobutylphenol, 2 ,6 -dicyclopentyl-4 zene , 1,4 -bis(3 ,5 -di-tert -butyl-4 -hydroxybenzyl)-2 ,3,5 ,6 - te
tramethylbenzene, 2 ,4 ,6 -tris( 3, 5 - di- tert-butyl-4
methylphenol, 2 -( a -methylcyclohexyl)-4 ,6 hydroxybenzyl) phenol;
dimethylphenol, 2 ,6 - dioctadecyl-4 -methylphenol, 2 ,4 ,6 - triazine compounds, such as e.g . 2.4 -bis( octylmercapto )
tricyclohexylphenol, 2 ,6 -di-tert- butyl -4 - 40 6 -( 3, 5 - di-tert -butyl-4 -hydroxyanilino )- 1,3 , 5 -triazine , 2 -oc
methoxymethylphenol, linear or branched nonylphenols, tylmercapto -4 ,6 -bis (3 ,5 -di- tert -butyl-4 -hydroxyanilino )- 1,
such as e. g . 2 ,6 -dinonyl -4 -methylphenol, 2 ,4 - dimethyl-6 - 3 ,5 - triazine, 2 -octylmercapto -4 ,6 -bis (3 ,5 - di-tert-butyl-4
( 1'-methylundec -1'-yl)phenol, 2,4 -dimethyl-6 -( 1'-methyl- hydroxyphenoxy )- 1,3 ,5- triazine, 2,4 ,6 -tris (3,5 - di- tert -butyl
heptadec - 1'-yl) phenol, 2 ,4 -dimethyl-6 -( 1'-methyltridec - 1' 4 -hydroxyphenoxy) - 1,2 , 3 - triazine , 1, 3, 5 -tris ( 3 ,5 -di- tert
yl) phenol and mixtures hereof; 45 butyl -4 - hydroxybenzyl) isocyanurate , 1, 3 ,5 - tris (4 - tert-butyl
alkylthiomethylphenols , such as e. g . 2 ,4 -dioctylthiom - 3 -hydroxy -2 ,6 -dimethylbenzyl) isocyanurate , 2 ,4 ,6 -tris ( 3 ,5
ethyl-6 - tert -butylphenol, 2 ,4 -dioctylthiomethyl-6 -methyl di-tert-butyl-4 -hydroxphenylethyl) - 1,3 ,5 - triazine , 1, 3 ,5 - tris
phenol, 2,4 - dioctylthiomethyl-6 - ethylphenol, 2 ,6 -didode - (3,5 -di-tert-butyl-4 -hydroyphenylpropionyl)hexahydro - 1,3 ,
cylthiomethyl-4 -nonylphenol; 5 - triazine , 1,3,5 -tris (3 ,5 -dicyclohexyl-4 -hydroxybenzyl)
hydroquinones and alkylated hydroquinones, such as e. g . 50 isocyanurate;
2 ,6 -di-tert-butyl-4 -methyoxyphenol, 2 ,5 -di-tert -butylhydro benzylphosphonates, such as e.g. dimethyl -2 ,5 -di-tert
quinone, 2 ,5 -di-tert- amylhydroquinone, 2 ,6 - diphenyl-4 - oc butyl -4 -hydroxybenzylphosphonate , diethyl-3,5 -di- tert-bu
tadecyloxyphenol, 2 ,6 - di-tert -butylhydroquinone, 2 , 5 - di - tyl- 4 -hydroxybenzylphosphonate , dioctadecyl-3 ,5 - di-tert
tert-butyl-4 -hydroxyanisole , 3 ,5 - di-tert- butyl-4 butyl-4 -hydroxybenzylphosphonate , dioctadecyl- 5 - tert
hydroxyanisole, 3 ,5 - di-tert -butyl-4 -hydroxyphenylstearate , 55 butyl-4 -hydroxy -3 -methylbenzylphosphonate , the calcium
bis (3 ,5 -di-tert-butyl- 4 -hydroxylphenyl)adipate ; salt of the monoethylester of 3 ,5 -di-tert-butyl-4 -hydroxy
tocopherols, such as e. g . a -, B -, y-, d - tocopherol and benzylphosphonic acid ;
mixtures of these ( vitamin E ); acylaminophenols, such as e .g . 4 -hydroxylauranilide,
hydroxylated thiodiphenylethers, such as e .g . 2 ,2'-thiobis 4 -hydroxystearanilide, octyl- N - (3 ,5 -di-tert -butyl- 4 -hy
(6 -tert -butyl-4 -methylphenol), 2 ,2 - thiobis(4 -octylphenol), 60 droxyphenyl)carbamate;
4 ,4 '- thiobis(6 -tert- butyl- 3 -methylphenol), 4 ,4 '-thiobis (6 esters of B -(3, 5 -di-tert-butyl-4 - hydroxyphenyl)propionic
tert-butyl- 2 -methylphenol), 4, 4'-thiobis( 3 ,6 - di- sec -amyl- acid with mono - or multivalent alcohols , e .g . methanol,
phenol), 4 ,4 '-bis(2 ,6 - dimethyl-4 -hydroxyphenyl)disulfide; ethanol, n - octanol, i-octanol, octadecanol, 1 ,6 - hexanediol,
alkylidene bisphenols , such as e . g. 2 . 2 -methylenebis (6 - 1, 9 - nonanediol, ethylene glycol, 1, 2 - propanediol, neopentyl
tert-butyl- 4 -methylphenol), 2 ,2 -methylenebis (6 -tert -butyl- 65 glycol, thiodiethylene glycol, diethylene glycol, triethylene
4 -ethylphenol), 2,2"-methylenebis [4 -methyl-6 -( a -methylcy - glycol, pentaerythritol, tris (hydroxyethyl)isocyanurate ,
clohexyl) phenol], 2 ,2'-methylenebis (4 -methyl-6 - N ,N '-bis (hydroxyethyl) oxamide, 3 - thiaundecanol, 3 -thia
 US 10 , 364 ,340 B2
19 20
pentadecanol, trimethylhexanediol, trimethylolpropane , (3,5 -di-tert -butyl-4 -hydroxyphenylpropionyl)hydrazide,
4 -hydroxymethyl-1 -phospha-2 ,6 ,7 - trioxabicyclo [ 2.2 .2 ]oc - N .N '-bis( 2 -(3 -(3 ,5 - di-tert -butyl- 4 -hydroxyphenyl]propiony
tane,
esters of B - (5 -tert-butyl -4 -hydroxy -3 -methylphenyl)pro loxy )ethyl]oxamide (Naugard®XL - 1, marketed by
pionic acid with mono - or multivalent alcohols , e. g. metha - 5
nol, ethanol, n -octanol, i-octanol, octadecanol, 1,6 -hexane ascorbic acid (vitamin C ).
diol, 1,9 -nonanediol, ethylene glycol, 1,2 -propanediol, Particularly preferred phenolic antioxidants are :
neopentyl glycol, thiodiethylene glycol, diethylene glycol, octadecyl-3 -(3 ,5 -di-tert-butyl-4 -hydroxyphenyl)propi
triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocya - 10 onate , pentaerythritol-tetrakis (3 -( 3,5 - di- tert -butyl-4 -hy
nurate , N ,N '-bis(hydroxyethyl)oxamide, 3 - thiaundecanol, droxyphenyl)propionate , tris (3,5 - di -tert-butyl -4 -hydroxy
3 -thiapentadecanol, trimethylhexanediol, trimethylolpro - phenyl)isocyanurate, 1,3 ,5 -trimethyl-2 ,4 ,6 - tris (3 ,5 -di- tert
pane, 4 -hydroxymethyl-1 -phospha - 2,6,7 - trioxabicyclo b utyl-4 -hydroxyphenyl) isocyanurate , 1,3 ,5-trimethyl- 2,4,6
[2.2.2 ]octane, 3,9 -bis [ 2- (3 -(3 - tert-butyl-4-hydroxy -5 -meth - 15 tris (3,5 -di-tert-butyl-4-hydroxybenzyl)benzene, triethylene
ylphenyl)propionyloxy } - 1,1-dimethylethyl)-2,4,8 ,10 - glycol-bis[3 -(3 -tert -butyl-4 -hydroxy -5 -methylphenyl)propi
tetraoxaspiro [5 .5 ]undecane; onate , N , Nº-hexan -1,6 - diyl-bis [3 -(3 ,5 -di-tert-butyl-4 -hy
esters of ß -(3, 5- dicyclohexyl-4 -hydroxyphenyl)propionic droxyphenyl)propionic acid amide .
acid with mono - or multivalent alcohols, e. g. methanol, 20 Suitable phosphites/phosphonites are for example:
ethanol, octanol, octadecaneol, 1,6 -hexanediol, 1,9- nonane - triphenylphosphite, diphenylalkylphosphites , phenyl
diol, ethylene glycol, 1,2 -propanediol, neopentyl glycol, dialkylphosphites, tri(nonylphenyl)phosphite , trilaurylphos
thiodiethylene glycol, diethylene glycol, triethylene glycol, phites, trioctadecylphosphite , distearylpentaerythritol
pentaerythritol, tris(hydroxyethyl) isocyanurate, N ,N '-bis diphosphite, tris -(2 ,4 -di-tert-butylphenyl)phosphite ,
(hydroxyethyl)oxamide, 3-thiaundecanol, 3 -thiapentadeca diisodecylpentaerythritoldiphosphite , bis (2 ,4 -di-tert-butyl
nol, trimethylhexanediol, trimethylolpropane, 4 -hydroxym - phenyl)pentaerythritoldiphosphite, bis (2 ,4 -di-cumylphenyl)
ethyl-1 -phospha-2 ,6 ,7 -trioxabicyclo [ 2.2 .2 ]octane ; pentaerythritoldiphosphite , bis(2 ,6 -di-tert -butyl-4 -methyl
esters of 3,5 - di -tert-butyl -4-hydroxyphenyl)acetic acid phenyl)pentaerythritoldiphosphite ,
with mono - or multivalent alcohols, e.g. methanol, ethanol, 30 diisodecyloxypentaerythritoldiphosphite, bis (2,4 -di-tert-bu
octanol, octadecanol, 1,6 -hexanediol, 1,9 -nonanediol, eth - tyl-6 -methylphenyl)pentaerythritoldiphosphite, bis(2 ,4,6
ylene glycol , 1,2- propanediol, neopentyl glycol, thiodieth tris(tert-butylphenyl)pentaerythritoldiphosphite , tristearyl
ylene glycol, diethylene glycol, triethylene glycol, pen sorbitoltriphosphite , tetrakis (2 ,4 - di-tert- butylphenyl)-4 ,4 '
taerythritol, tris (hydroxyethyl) isocyanurate , N , N '-bis 35 biphenylenediphosphonite, 6 - isooctyloxy-2,4 ,8 , 10 -tetra
(hydroxyethyl)oxamide , 3 - thiaundecanol, tert -butyl- 12H -dibenzo [d ,g )- 1, 3,2 -dioxaphosphocine, bis (2 ,
3 -thiapentadecanol, trimethylhexanediol, trimethylolpro - 4 -di- tert-butyl-6 -methylphenyl)methylphosphite , bis ( 2,4 -di
pane, 4 -hydroxymethyl-1 -phospha -2 ,6 ,7 - trioxabicyclo tert -butyl-6 -methylphenyl) ethylphosphite , 6 -fluoro -2 ,4 ,8 ,
[2 . 2 .2 ] octane; 40 10 -tetra- tert-butyl-12-methyldibenzo [d,g ]-1,3 ,2
amides of B -(3,5 -di- tert -butyl-4 -hydroxyphenyl)propi- dioxaphosphocine, 2, 2'2" -nitrilo [ triethyltris (3,3" ,5 ,5'-tetra
onic acid , such as e.g . N ,N '-bis(3 ,5 -di-tert -butyl-4 -hydroxy -tert -butyl- 1, 1'-biphenyl-2 ,2'-diyl) phosphite ), 2 - ethylhexyl
phenylpropionyl)hexamethylenediamide, N , N -bis( 3,5 - di- (3 ,3 ',5 , 5'-tetra - tert-butyl- 1, 1'-biphenyl-2 ,2'-diyl))phosphite,
tert-butyl-4 -hydroxyphenylpropionyl) 45 5 -butyl-5 - ethyl- 2-( 2,4 ,6 -tri-tert-butylphenoxy )- 1,3 ,2 -dioxa
hexamethylenediamide , N , N '-bis(3 ,5 -di-tert -butyl-4 - phosphirane .
hydroxyphenylpropionyl)hexamethylenediamide , N , N -bis Particularly preferred phosphites/phosphonites are :

( H3C )C3 - C (CH3)3

C (CH3) 3 (H3C )3C

C (CH3)3 [ (HzC);
(H3C )3C - O - P + 04 C (CH3)3
 US 10 ,364,340 B2
21
- continued

(CH3) 3C .
C (CH3)3

H3C - CH PF

C (CH3)3
( CH3)3C

C (CH3)3
(CH3)3C
C( CH3)3 ( CH3)3C

P — 0 - CH2CH2 + N H3C -0 -0 % Ich

C (CH3)3 (CH3)3C
(CH3)3C
C (CH3)3
CH3
H3C — C — CH3
04P - OCH2CH3
H37C18 — 0 P - 0 – C18H37
H3C
- CH3
H?C ? CH ; CH3
J;
C ( CH3)3
(CH3) 3C

P — 0 - CH2CH ( C4H9)CH2CH3

(CH3)3C
C (CH3)3

ofootto
Further suitable stabilisators are aminic antioxidants. phenylenediamine ,
Suitable aminic antioxidants are for example :
N ,N -bis ( 1 -methylheptyl)-p
phenylenediamine, N , N°-dicyclohexyl-p -phenylenediamine ,
N , Nº-di-isopropyl-p - phenylenediamine , N ,N -di-sec -bu - 65 N ,N -diphenyl-p -phenylenediamine , N ,N '-bis(2 -naphthyl)
tyl-p -phenylenediamine, N ,N '-bis(1 ,4 -dimethylpentyl)-p - p -phenylenediamine, N - isopropyl-N -phenyl-p -phenylene
phenylenediamine , N ,N -bis ( 1 -ethyl-3 -methylpentyl)-p diamine, N -( 1,3 -dimethylbutyl)-N '-phenyl-p -phenylenedi
 US 10 , 364 ,340 B2
23 24
amine, N - (1 -methylheptyl) -N '- phenyl-p -phenylenediamine , Further suitable stabilisers, in particular for polyamides ,
N - cyclohexyl-N '-phenyl-p -phenylenediamine , 4 -(p -toluene are copper salts, such as e .g . copper (I)iodide , copper(I)
sulphamoyl) diphenylamine, N ,N -dimethyl-N , N '- di-sec -bu bromide or copper complexes, such as e. g. triphenylphos
tyl-p -phenylenediamine, diphenylamine, N - allyldiphe phine -copper (I) complexes.
nylamine, 4 -isopropoxydiphenylamine, N -phenyl- 1 - 5 Suitable hindered amines are for example 1,1 -bis (2 ,2 ,6 ,
naphthylamine, N - (4 -tert -octylphenyl)- 1 -naphthylamine , 6 - tetramethyl-4 -piperidyl) succinate , bis ( 1,2 ,2,6 ,6 -pentam
N - phenyl-2 -naphthylamine, octylated diphenylamine, e.g . ethyl - 4 -piperidyl) sebacate , bis( 1 - octyloxy- 2 ,2 ,6 ,6 -tetram
p ,p '-di- tert-octyldiphenylamine , 4 -n -butylaminophenol, ethyl-4 -piperidyl)sebacate , bis (1 ,2 ,2 ,6 ,6 - pentamethyl-4
4 -butyrylaminophenol, 4 -nonanoylaminophenol, 4 -dode piperidyl)-n -butyl- 3, 5 -di-tert-butyl-4
canoylaminophenol, 4 -octadecanoylaminophenol, bis (4 - 10 hydroxybenzylmalonate, the condensation product of 1-(2
methoxyphenyl)amine, 2 ,6 - di-tert -butyl- 4 -dimethylamin - hydroxyethyl)-2 ,2 ,6 ,6 -tetramethyl-4 -hydroxypiperidine und
omethylphenol, 2 ,4 '-diaminodiphenylmethane , 4 ,4' succinic acid , linear or cyclic condensation products of
diaminodiphenylmethane, N , N , N ',N '-tetramethyl-4 ,4 N ,N -bis ( 2 ,2,6 ,6 -tetramethyl-4 -piperidyl)hexamethylenedi
diaminodiphenylmethane , 1, 2 -bis[ (2 -methylphenyl) amino ] amine and 4 -tert-octylamino - 2,6 - di- chloro - 1,3 ,5 -triazine,
ethane , 1,2 - bis(phenylamino )propane , (o -tolyl)biguanide , 15 tris( 2, 2,6 ,6 -tetramethyl-4 -piperidyl)nitrilotriacetate, tetrakis
bis [4 -( 1', 3'- dimethylbutyl)phenyljamine, tert -octylated (2 ,2 ,6 ,6 -tetramethyl- 4 -piperidyl)- 1,2 ,3 ,4 -butanetetracar
N -phenyl-1 -naphthylamine, a mixture of mono - and dialky- boxylate , 1, 1'-( 1,2 - ethandiyl)-bis ( 3 ,3,5 ,5 - tetramethylpiper
lated tert-butyl/tert-octyldiphenylamines, a mixture of azinone ), 4 -benzoyl-2 ,2 ,6 ,6 - tetramethylpiperidine ,
mono - and dialkylated nonyldiphenylamines, a mixture of 4 -stearyloxy - 2, 2,6 ,6 -tetramethylpiperidine , linear or cyclic
mono- and dialkylated dodecyldiphenylamines, a mixture of 20 condensation products of N ,N -bis (2 , 2 ,6 ,6 - tetramethyl-4 - pi
mono- and dialkylated isopropyl/ isohexyldiphenylamines, a peridyl)hexamethylenediamine and 4 -morpholino - 2 ,6 - di
mixture ofmono - and dialkylated tert -butyldiphenylamines, chloro - 1 , 3 ,5 -triazine , the reaction product of 7 , 7 , 9 , 9 -tetram
2 ,3 -dihydro - 3 ,3 -dimethyl- 4H -1 ,4 -benzothiazine, phenothi- ethyl-2 -cycloundecyl- 1- oxa -3 ,8 -diaza - 4 -oxospiro -[4 ,5 ]
azine , a mixture of mono - and dialkylated tert- butyl/tert - decane and epichlorhydrin .
octylphenothiazines, a mixture of mono - and dialkylated 25 Suitable flame retardants are for example :
tert -octylphenothiazines , N -allylphenothiazine, N ,N , N ',N '- a ) inorganic flame retardants , such as e . g . Al(OH ) 3 ,
tetraphenyl - 1 , 4 - diaminobut- 2 -ene and also mixtures or com Mg (OH )2, AlO (OH ), MgCO3, layer silicates, such as
binations hereof. e . g . montmorillonite or sepiolite , non - or organically
Further suitable aminic antioxidants are hydroxylamine , modified double salts , such as e . g . Mg — Al-silicates ,
or N -oxides (nitrons), such as e .g . N ,N -dialkylhydroxylam - 30 POSS -(Polyhedral Oligomeric Silsesquioxane ) com
ines, N , N - dibenzylhydroxylamine , N , N -dilaurylhydrox pounds , huntite , hydromagnesite or halloysite and also
ylamine, N , N -distearylhydroxylamine , N -benzyl-a -phenyl Sb2O3, Sb2O5,MoO3, zinc stannate , zinc hydroxystan
nitron , N -octadecyl-a -hexadecylnitron , and also Genox EP nate ,
(Addivant) according to the formula : b ) nitrogen -containing flame retardants , such as e .g .
35 melamine, melem , melam , melon , melamine deriva
tives , melamine condensation products or melamine
CH3 salts, benzoguanamine , polyisocyanurates , allantoin ,
N- 0 (polyphosphacenes , in particular melamine cyanurate ,
R melamine phosphate , dimelamine phosphate ,
R2 40 melamine pyrophosphate , melamine polyphosphate,
R1, R2 = C24 -C24 alkyl melamine -methane phosphonate , melamine -metal
Genox EP phosphates, such as e .g. melamine aluminium phos
phate , melamine zinc phosphate , melaminemagnesium
phosphate , and also the corresponding pyrophosphates
Further suitable stabilisers are thiosynergists . Suitable 45 and polyphosphates , ethylene diamine-methane phos
thiosynergists are , for example, distearylthiodipropionate , phonate, poly -[2 ,4 - piperazin - 1,4 -yl)-6 -(morpholin -4
dilauryldipropionate or the compound according to the fol yl)- 1, 3,5 -triazine ], ammonium polyphosphate,
lowing formula : melamine borate, melamine hydrobromide ,
 US 10 , 364 ,340 B2
25 26
c ) phosphorus -containing flame retardants, such as e.g .
inorganic or organic phosphonates, such as e. g. alu
minium phosphonate , phosphonate ester, oligomeric (H3C )3C C (CH3)3
and polymeric derivatives ofmethane phosphonic acid ,
red phosphorus, phosphates, such as e.g . resorcin 5
diphosphate, bisphenol- A - diphosphate and the oligom
ers thereof, triphenylphosphate , ethylene diamine
diphosphate , phosphinates, such as e.g . salts of hypo
phosphorous acid and the derivatives thereof, such as
alkyl phosphinate salts e. g . diethylphosphinate alu
.
C (CH3) 3
minium or diethylphosphinate zinc or aluminium phos
phinate , aluminium phosphite , aluminium phosphate ,
9 , 10 - dihydro - 9 - oxa - 10 -phosphorylphenanthrene- 10
oxide (DOPO ) and the substituted compounds thereof, 15
d ) halogen - containing flame retardants based on chlorine NH
and bromine, such as e.g polybrominated diphenyl
oxides, such as e.g . decabromodiphenyl oxide , tris (3 HN
bromo- 2,2 -bis (bromomethyl) propyl phosphate, tris( tri
bromoneopentyl)phosphate , tetrabromophthalic acid , 20
1 ,2 - bis ( tribromophenoxy )ethane, hexabromocyclodo
decane , brominated diphenylethane , tris -(2 , 3 - dibro
mopropyl)isocyanurate , ethylene-bis (tetrabro N

aolo
mophthalimide ), tetrabromobisphenol A , brominated
polystyrene , brominated polybutadiene or polystyrene
brominated polybutadiene copolymers , brominated
epoxy resin , polypentabromobenzyl acrylate , possibly
in combination with Sb2O3 and /or Sb2O5,
e ) borates , such as e .g . zinc borate or calcium borate , 30
possibly on carrier materials such as silica , A ZH
f) sulphur- containing compounds such as e.g . elementary
sulphur, disulfides, and polysulfides, thiuram sulfide ,
dithiocarbamates, mercaptobenzathiozol and sulphena
mides ,
g ) antidrip agents, such as e.g. polytetrafluorethylene ,
h ) silicon -containing compounds, such as e .g . polyphe
nylsiloxanes, 40
i) carbon modifications such as e.g . carbon nanotubes HN
(CNT) or graphene
and also combinations or mixtures hereof.
Suitable dispersants are for example : 45
polyacrylates, e.g. copolymers with long -chain side
groups , polyacrylate -block copolymers, alkylamides : e.g .
N ,N '-1,2 -ethanediylbisoctadecanamide sorbitan ester, e.g . Suitable fillers and reinforcing materials are for example
monostearylsorbitan ester, titanates and zirconates, reactive synthetic or natural materials , such as e . g . calcium carbon
copolymers with functional groups e. g . polypropylene -co - 30 ate , silicates, glass fibres , glass balls ( solid or hollow ), talc ,
acrylic acid , polypropylene-co -maleic anhydride, polyethyl mica, kaolin ,barium sulfate , metaloxides and metal hydrox
ides, carbon black , graphite, carbon nanotubes, graphene,
ene -co -glycidylmethacrylate, polystyrene-alt -maleic anhy sawdust
dride -polysiloxanes: e.g . dimethylsilanediolethylene oxide syntheticorfibresfibres of natural products, such as e. g . cellulose ,
or metal fibres. Further suitable fillers are
copolymer, polyphenylsiloxane copolymer, amphiphilic 55 hydrotalcites or zeolites or layer silicates, such as e . g .
copolymers : e.g . polyethylene -block -polyethylene oxide , montmorillonite , bentonite , beidellite , mica , hectorite ,
dendrimers, e .g . hydroxyl group -containing dendrimers. saponite, vermiculite, ledikite, magadiite , illite, kaolinite ,
wollastonite , attapulgite .
WOT
Suitable nucleation agents are for example talc, alkali or Suitable chain -lengtheners for the linearmolecular weight
alkaline earth salts of mono - and polyfunctional carboxylic 60 increase of polycondensation polymers , such as polyesters
acids, such as e.g . benzoic acid , succinic acid , adipic acid , or polyamides are for example diepoxides, bis -oxazolines ,
e . g . sodium benzoate , zinc glycerolate , aluminium hydroxy - bis -oxazolones, bis -oxazines , diisocyanates, dianhydrides ,
bis (4 -tert-butyl)benzoate , benzylidene sorbitols, such as e. g . bis -acyllactams, bis -maleimides, dicyanates , carbodiimides .
1,3 :2 ,4 -bis(benzylidene) sorbitol or 1,3 :2 ,4 - bis(4 -methyl- Further suitable chain -lengtheners are polymeric com
benzylidene )sorbitol, 2 , 2" -methylene -bis -(4 ,6 -di-tert-butyl- 65 pounds, such as e .g . polystyrene-polyacrylate -polyglycidyl
phenyl) phosphate, and also trisamides , such as e. g . accord (methacrylate copolymers , polystyrene -maleic anhydride
ing to the following structures copolymers and polyethylene-maleic anhydride copolymers.
 US 10 , 364 ,340 B2
28
Suitable pigments can be of an inorganic or organic and vinylidene chloride or made of vinyl chloride and
nature . Suitable inorganic pigments are for example titanium vinyl acetate , chlorinated polyethylene, polyvinylidene
dioxide , zinc oxide, zinc sulfide, iron oxide , ultramarine, fluoride,
carbon black . Suitable organic pigments are for example d ) polymers of unsaturated esters, such as e.g polyacry
anthraquinones, anthanthrones, benzimidazolones, quinac - 5 lates and polymethacrylates, such as polymethylmeth
ridones, diketopyrrolopyrroles, dioxazines, indanthrones, acrylate (PMMA), polybutylacrylate , polylaurylacry
isoindolinones , azo compounds, perylenes , phthalocyanines late , polystearylacrylate , polyglycidylacrylate ,
or pyranthrones . Further suitable pigments are effect pig polyglycidylmethacrylate , polyacrylonitrile, polyacry
ments based on metal or pearlescent pigments based on 10
lamides, copolymers, such as e.g . polyacrylonitrile
metal oxide . polyalkylacrylate , polymethacrylimide,
Optical brighteners are for example bisbenzoxazoles, e ) polymers made of unsaturated alcohols and derivates ,
phenylcoumarins or bis( styryl)biphenyls and in particular such as e.g . polyvinyl alcohol, polyvinyl acetate, poly
optical brighteners of the formulae : vinyl butyral,
15 f) polyacetals, such as e .g . polyoxymethylene ( POM ) or
t -Bu Bu - t copolymers with e. g. butanal,
AE g ) polyphenylene oxides and blends with polystyrene or
polyamides,
h ) polymers of cyclic ethers, such as e.g . polyethylene
20 glycol, polypropylene glycol, polyethylene oxide ,
polypropylene oxide,
Suitable filler deactivators are for example glycidyl- based i) polyurethanes made of hydroxy -terminated polyethers
epoxides, such as e .g. bis-phenol- A -diglycidylethers, or or polyesters and aromatic or aliphatic isocyanates, in
bisphenol-F -diglycidylethers, and the oligomers thereof or particular linear polyurethanes, polyureas,
polymer resins , polysiloxanes, polyacrylates, in particular 25 j) polyamides , such as e. g . polyamide 6 , 6 .6 , 6 . 10 , 4 .6 ,
block copolymers, such as polymethacrylic acid -polyalky 4 .10 , 6 . 12 , 12 .12 , polyamide 11, polyamide 12 and also
lene oxide or polystyrene -polyacrylate -polyglycidy (meth ) (partially ) aromatic polyamides , such as e.g. polyphtha
acrylate copolymers . lamides , e.g . produced from terephthalic acid and /or
Suitable antistatic agents are for example ethoxylated isophthalic acid and aliphatic diamines or from ali
alkylamines , fatty acid esters , akylsulphonates and poly - 30 phatic dicarboxylic acids, such as e . g. adipic acid or
mers , such as e . g . polyether amides or copolymers , which sebacic acid and aromatic diamines, such as e.g . 1,4 - or
comprise salts of acrylic acid , such as e .g . polyethylene 1,3 -diaminobenzene, blends of different polyamides,
polyacrylate - polyacrylate -Na copolymers .
According to the present invention , the previously illus such as e .g . PA -6 and PA 6 .6 or blends of polyamides
trated organic oxyimides can be used for modification (deg - 35 k ) and polyolefins, such as e .g . PA /PP ,
polyimides , polyamide imides, polyether imides, poly
radation , crosslinking, grafting ) of the following plastic
materials: ester imides , poly ( ether)ketones , polysulphones,
a ) polymers made of olefins or diolefins, such as e .g . polyethersulphones, polyarylsulphones, polyphenylene
polyethylene (LDPE , LLDPE , VLDPE , ULDPE , sulphide , polybenzimidazoles, polyhydantoins,
MDPE , HDPE , UHMWPE ), metallocene-PE (m - PE ), 40 1) polyesters made of aliphatic or aromatic dicarboxylic
polypropylene , polyisobutylene , poly -4 -methylpen acids and diols or made of hydroxycarboxylic acids ,
tene- 1 , polybutadiene, polyisoprene , polycyclooctene , such as e .g . polyethylene terephthalate (PET), polybu
polyalkylene- carbon monoxide copolymers , and also tylene terephthalate (PBT), polypropylene terephtha
copolymers in the form of statistical or block struc late , polyethylene naphthylate , poly - 1,4 -dimethylolcy
tures, such as e .g . polypropylene -polyethylene (EP ), 45 clohexane terephthalate , polyhydroxybenzoate ,
EPM or EPDM , ethylene-vinyl acetate (EVA ), ethyl polyhydroxynaphthalate, polylactic acid (PLA ), poly
ene-acrylic ester, such as e. g . ethylene-butyl acrylate , hydroxybutyrate (PHB ), polyhydroxyvalerate ( PHV ),
ethylene-acrylic acid and the salts thereof ( ionomers ), m ) polycarbonates , polyester carbonates, and also blends,
and also terpolymers, such as e .g . ethylene- acrylic such as e. g. PC /ABS, PC /PBT, PC /PET/ PBT, PC /PA ,
acid -glycidylacrylate , graft polymers , such as e.g. poly - 50 n ) cellulose derivatives, such as e.g. cellulose nitrate,
propylene - graft -maleic anhydride , polypropylene cellulose acetate, cellulose propionate, cellulose
graft-acrylic acid , polyethylene- graft-acrylic acid , butyrate ,
polyethylene-polybutacrylate- graft -maleic anhydride, 0 ) and also mixtures, combinations or blends made of two
b ) polystyrene, polymethylstyrene , polyvinyl naphtha or more of the previously mentioned polymers.
lene , styrene-butadiene (SB ), styrene -butadiene-sty - 55 Provided that the polymers indicated under a ) to n )
rene (SBS ), styrene - ethylene -butylene -styrene (SEBS ), concern copolymers , these can be present in the form of
styrene -ethylene -propylene-styrene , styrene - isoprene, statistical (“ random ” ), block - or “ tapered ” structures .
styrene - isoprene - styrene (SIS ), styrene -butadiene - Provided that the polymers indicated under a ) to n )
acrylonitrile (ABS ), styrene-acrylonitrile -acrylate concern stereo - regular polymers, these can be present in the
(ASA ), styrene- ethylene, styrene -maleic anhydride 60 form of isotactic , stereotactic , but also in atactic forms or in
polymers incl. corresponding graft copolymers , such as stereoblock structures.
e . g . styrene on butadiene, maleic anhydride on SBS or Furthermore , the polymers indicated under a ) to o ) can
SEBS , and also graft copolymers made of methylmeth have both amorphous and (partially ) crystalline morpholo
acrylate, styrene-butadiene and ABS (MABS ), gies.
c ) halogen -containing polymers, such as e .g polyvinyl 65 The mentioned polymers a ) to n ) can thereby not only be
chloride (PVC ), polychloroprene and polyvinylidene present as virgin material, but also in the form of recyclates ,
chloride (PVDC ), copolymers made of vinyl chloride e.g . as production waste or as post-consumer recyclates .
 US 10 , 364 ,340 B2
29 30
According to the invention , the oxyimides of the initially The invention relates in addition to the use of the previ
mentioned formula I can be used in the following duromeric ously mentioned method for modification of the plastic
or elastomeric , non - thermoplastic plastic materials as radical materials .
generators : Particularly preferably , the oxyimides according to the
a ) epoxy resins , consisting of di- or polyfunctional epoxy 5 present invention are used as radical generators for con
compounds in combination with e.g . hardeners based trolled degradation of the polymers, in particular polyole
on amines, anhydrides, dicyanodiamide, mercaptans, fins, in particular polypropylene or for crosslinking of the
isocyanates or catalytically -acting hardeners, polymers, in particular polyolefins or unsaturated polyesters,
b ) phenol resins, such as e. g. phenol-formaldehyde resins, 10 as radical formers for grafting of unsaturated compounds
urea - formaldehyde resins , melamine -formaldehyde onto the polymers , in particular polyolefins.
resins, With respect to the specific details of the organic oxyim
c ) unsaturated polyester resins made of unsaturated dicar ides , which can be used in the method according to the
boxlic acids and diols , invention or in the purposes ofuse of the method , reference
d ) silicones, 15 is made to the previously given embodiments . All of the
e ) polyurethanes as reaction products made of di- or above- described , preferred embodiments likewise apply,
polyfunctional isocyanates and polyols , polyureas, without restriction , also for the above -described method
f) alkyd resins , allyl resins . according to the invention or the use according to the
For very particular preference , the radical generators
according to the invention are used for modification in the 20 invention of the method according to the invention .
case of polyolefins, preferably polypropylene and /or poly The present invention is described in more detail with
ethylene and the copolymers and blends thereof and also for reference to the subsequent embodiments , without restrict
unsaturated polyester resins . ing the invention to the examples.
For very particular preference, the radical generators
according to the invention are used preferably for the 25 EXAMPLE 1
molecular weight reduction of polypropylene and/or for the
crosslinking of polyethylene or unsaturated polyester resins
and the copolymers and blends thereof and also for the Molecular Weight Decrease of Polypropylene
grafting of unsaturated monomers on polypropylene or
polyethylene . For the crosslinking reaction , the hydroxyim - 0 The extrusions of the polypropylene samples (Moplen HP
ides and the hydroxyimide ethers are particularly preferred . 500N ) with addition of the radical generators are effected at
In particular in the case of combinations of the oxyimide the indicated temperature and with a screw speed of rotation
used according to the invention with at least one additional of 400 rpm on an 11 mm twin -screw extruder (Process 11 of
radical former, synergistic effects are produced . The addi- 35 Thermo Scientific ). The desired ratio of polymer and addi
tional radical former is thereby preferably selected from the tives is firstly homogenised by mixing and supplied for
group consisting of the radical formers which are described extrusion via volumetric metering . The MVR (melt volume
further back and preferably to be used . In order to avoid rate ) of the granulated extruded samples was determined
repetitions, reference is made to the previous embodiments subsequently at 230° C ./2 . 16 kg according to ISO 1133 and
with respect to the additional radical formers. 40 the average weight of the molecular weight was determined
In the case of a combined use of the oxyimide used by means of high -temperature gel permeation chromatogra
according to the invention with at least one further radical phy.
former, it is preferred in the case of the present invention if
the previously mentioned compounds are used in a weight TABLE 1
ratio (oxyimide : further radical formers ) of 99 : 1 to 1 : 99, 45 –
preferably of 5: 95 to 95 :5 , particularly preferably of 10 : 90 Compositions in polypropylene and results of the analyses
to 90 : 10 . of the melt volume flow rates and of the molecular weight
Furthermore , it is advantageous in the invention if the
organic oxyimides, relative to the plastic materials, are used Test Extrusion
at 0.01 to 30 % by weight, preferably at 0 .1 to 10 % by 50 number Additive temperature [° ] MVR MW
weight, particularly preferably at 0 .5 to 5 % by weight.
In addition , the present invention relates to a method for Comparative Without 240 14 400 ,000
generating radicals in plastic materials, in which at least one example 1
organic oxyimide , comprising at least one structural element Comparative Without 260 381 ,000
of the previously described formula I is mixed with a plastic 55 example 2
material or with at least one moulding compound compris Comparative Without 280
280 22 362,000
ing at least one plastic material and activated . During example 3
activation , radicals are thereby released . In particular, the Comparative Without 300 n .d .
activation is effected thermally or by irradiation . Particularly example 4
preferably , the activation is undertaken simultaneously dur- 60 Example 1 0 . 1 % oxyimide 1 280 45 n.d.
ing a shaping method of the plastic material or of the according to
moulding compound comprising the plastic material, in the
particular by injection moulding or extrusion . In these invention
methods, the plastic materials are heated above their plas - Example 2 0 .2 % oxyimide 1 280 61 244,000
ticising temperature from which the plastic material or the 65 Example 3 0 .5 % oxyimide 1 280 84 n .d .
moulding compound comprising the plastic material is pres Example 4 0 .2 % oxyimide 1 240 25 346 ,000
ent in the plasticised state.
 US 10 , 364 ,340 B2
31 32
TABLE 1 -continued Surprisingly, it is shown that the compositions with the
Compositions in polypropylene and results of the analyses
oxyimides according to the invention have a higher
of the melt volume flow rates and of the molecular weight MVR (= lower molecular weight) and , likewise , in the GPC
5 measurement, a lower molecular weight than the compara
Test
number Additive
Extrusion
temperature [°] MVR Mw tive examples. With increasing concentration of oxyimide
and increasing processing temperature , the molecular weight
Example 5 0 .2 % oxyimide 1 260 30 317 ,000 reduces furthermore.
Example 6 0 . 2 % oxyimide 1 300 > 200 n .d .
Example 7 0 .1 % oxyimide 2 280 27 n . d. 10
EXAMPLE 2
n . d . = not determined

Oxyimide 1 = N -hydroxyphthalimide Molecular Weight Increase of Polyethylene

15
The molecular weight increase of the PE types (obtainable
at ExxonMobil) via reactive extrusion with N -hy
droxyphthalimide (NHPI) was effected at 200° C ., with a
OH
20 screw speed of rotation of 300 rpm on an 11 mm twin -screw
extruder (Process 11 of Thermo Scientific ). The analyses of
the melt volume flow rates (MVR ) were effected according
to ISO 1133 at a temperature of 190° C . and a weight of 5
kg or 10 kg .
TABLE 2
Compositions in polyethylene and results of the
analyses of the melt volume flow rates

MVR MVR
(5 kg, 190° C .)/ ( 10 kg, 190° C .)/
Example Composition cm3 * min - 1 cm3 * min -1
Comparative example 1 LDPE (LD 185 BW ) 100 % 10 . 2 31. 7
NHPI 0%
Example 1 according LDPE (LD 185 BW ) 99 . 80 % 9 .9
to the invention NHPI 0 . 20 %
Example 2 according LDPE (LD 185 BW ) 99 .60 % 9. 7
to the invention ???? 0 .40 %
Example 3 according LDPE (LD 185 BW ) 99. 20 % 31. 2
to the invention NHPI 0 . 80 %
Comparative example 2 HDPE (HTA 108 ) 100 % 12 .9
NHPI 0%
Example 4 according HDPE (HTA 108 ) 99 . 20 % 12 . 5
to the invention NHPI 0 .80 %

Oxyimide 2 (produced according to WO 2014154636 ) 45 With reference to the significant reduction in MVR values
of the examples according to the invention relative to the
comparative examples, an increase in melt viscosity is
shown , which can be attributed to an increase in the molecu
lar weight. Hence , a controlled increase in the molecular
50 weightby means of the method described within the present
application can be established .
The invention claimed is:
1 . A method of incorporating a radical generator into a
plastic material comprising incorporating into said plastic
N - O 55 material an organic oxyimide having the structural element
of formula I
U

Formula I

: #+ - 0
 US 10 ,364 ,340 B2
33 34
wherein the radical generator is activated thermally or by -continued
irradiation ,
wherein the activation is accomplished during shaping of
the plastic material or shaping of a moulding compound -Q
comprising the plastic material,
wherein the thermal activation is accomplished at a tem
perature of 240° C . or more ,
said method resulting in a modification of the plastic wherein the cycloaliphatic or aromatic ring systems con
material, wherein the modification is increasing the tained in the above groups is unsubstituted or substi
molecular weight of the plastic material, branching or 10 tuted by one or more alkyl- and /or alkoxy- groups,
crosslinking of the plastic material, molecular weight Q upon each occurrence , is the same or different and is
decrease of the plastic material, influencing a molecular selected from the group consisting of a chemical bond ,
weight distribution of the plastic material, and/or graft (CH2)n - with n = 1 to 18 , - CH (CH3)
ing of an unsaturated monomer onto the plastic mate - C (CH3) 2 - , - , - S — , - S0 , - , - NHCO — ,
rial. 15
2 . The method according to claim 1, wherein the oxyimide CO — , OC ( O ) O - and
is selected from the group consisting of m is 0 or 1 to 18 .
a ) oxyimides comprising at leastone structural element of 4 . The method according to claim 1 , wherein the organic
formula II tyin has one of the following formulae ,
oxyimide
20
Formula II

vra re N – 0 - R1 25 N- 0- R N- 0— R

wherein R ! is hydrogen or an optionally substituted 30

alkyl-, cycloalkyl-, aryl-, heteroaryl- or acyl-radical, N – 0 - R1 1– 0 - R
and
b ) bridged oxyimides comprising at least one structural
element of formula III, 35

Formula III
R1 - 0 - N N– 0- R
40

N - 0 – R2 – 0 - N
R1 - 0 - N N - 0- R
45

wherein R2 is an optionally substituted akylene -,

cycloalkylene -, arylene -, heteroarylene - or bridging
acyl-radical.
3 . The method according to claim 2, wherein R2 is 50so 'N - 0 – R2 — 0 N
selected from the group consisting of
( CH2). — with n = 1 to 18 , CH (CH3) ,
C (CH3) 2 - , - O - , - S — , - S02— , - NHCO ,
- CO
55

N - 0 – R2 – 0 - N
- -

N - 0 - R2 – 0 - N N - OR ]
65
, and
 US 10 ,364,340 B2
35 36
- continued

R10 - N — OR 5
- { le

10
RO - N N - ORI
? and

15

N - 0 – R2 - 0 - N

20
wherein the cycloaliphatic or aromatic ring systems con
tained in the above groups is unsubstituted or substi
RIO - N — OR1
tuted by one or more alkyl- and /or alkoxy -groups,
Q upon each occurrence, is the same or different and is
25 selected from the group consisting of a chemical bond ,
( CH )n - with n = 1 to 18 , - CH (CH3) ,
- C (CH3) 2, 0 % , - S - , - S02 — , - NHCO — ,
- C0 — , OC (O ) - 0 — and
RON OR1
30 m is 0 or 1 to 18 .
5 . The method according to claim 2 , wherein R ? = H ,
R '= alkyl or R '- acyl.
6 . The method according to claim 1 , which further
35 includes incorporating at least one chain transfer agent.
RO - N N - OR 7 . The method according to claim 1 , which further
includes incorporating at least one multifunctional com
pound selected from the group consisting of
a ) repeatedly unsaturated oligomers and polymers based
40 on polybutadiene or polyisoprene ,
Ril OR1 b ) di- and polyvinyl compounds,
c ) di- and polyallyl compounds,
45
d ) di- and polymaleimides,
e) di- and poly (meth )acrylesters of di- and polyalcohols ,
and
R10 - N OR f) organofunctional silanes, and combinations thereof.
8 . The method according to claim 1, which further
º includes incorporating at least one nitroxyl radical.
9 . The method according to claim 1, which further
includes incorporating at least one catalytic compound .
RO - N N - OR 10 . The method according to claim 1 , which includes
55 incorporating at least one further radical former.
11 . Themethod according to claim 10 , wherein the further
radical former is selected from the group consisting of
N -alkoxyamines, C - C — radical formers , radical form
60 ers with azo groups ( N = N — ), radical formers with
wherein R ! is hydrogen or an optionally substituted 60 hydrazine
alkyl-, cycloalkyl-, aryl-, heteroaryl- or acyl-radical, hydrazone groups ( NH — HN — ), radical formers with
groups (> C = N - NH — ), radical formers with
and azine groups ( > C = N — N = C < ), radical formers with triaz
R2 is selected from the group consisting of ene groups ( N = N — N < ), radical formers with disulfide
- ( CH2). — with n = 1 to 18 , CH (CH3) , 65 or polysulfide groups ( S _ S — ), radical formers with thiol
C ( CH3)2 — , 04 , S4 , S02— , - NHCO , groups ( S - H ), thiuram sulfide, dithiocarbamates, mer
CO — , captobenzothiazole , and sulphenamides.
 US 10 ,364,340 B2
37 38
12 . Themethod according to claim 11 , wherein the further wherein R ' has the previously indicated meaning, and
radical former is selected from the group consisting of d ) polycumylenes according to the structural formula
a ) N - alkoxyamines according to the structural formula

- R²
N

R4 - N
N 10
wherein R ' has the previously indicated meaning and
R3 R3 2 < n < 100 .
13 . The method according to claim 1, wherein the plastic
wherein materials are thermoplastic , elastomeric or duroplastic poly
R is hydrogen or an optionally substituted alkyl-, 15 mers m 14.. Themethod according to claim 13 , wherein the plastic
cycloalkyl-, aryl-, heteroaryl - or acyl- radical,
R * is an alkoxy -, aryloxy -, cycloalkoxy -, aralkoxy - or materials
15 . The
are thermoplastic polymers.
method according to claim 14 , wherein the
acyloxy -radical, thermoplastic polymers are selected from the group consist
Z is hydrogen or an optionally substituted alkyl-, ing of
cycloalkyl-, aryl-, heteroaryl- or acyl-radical, or two 20 a ) polymers made of olefins or diolefins.
Z radicals form a closed ring which is optionally b ) polystyrene, polymethylstyrene , polyvinyl naphtha
substituted with an ester -, ether -, amine -, amide-, lene , styrene-butadiene (SB ) , styrene -butadiene-sty
carboxy- or urethane -group , rene (SBS), styrene -ethylene -butylene - styrene (SEBS ),
b ) azo compounds according to the structural formulae styrene-ethylene -propylene - styrene, styrene -isoprene,
25 styrene - isoprene - styrene (SIS ), styrene -butadiene
RS— N N — R5 acrylonitrile (ABS), styrene -acrylonitrile -acrylate
or (ASA ), styrene-ethylene, and styrene -maleic anhydride
polymers ,
c ) halogen - containing polymers,
R6 R7 R7 RO 30 d ) polymers of unsaturated esters ,
R6 e ) polymers made of unsaturated alcohols and derivatives,
f) polyacetals,
R8JN N =N
N = N N - RY g ) polyphenylene oxides and blends with polystyrene or
polyamides,
R6 R6 35 h ) polymers of cyclic ethers,
R6 R7 R RO i) polyurethanes made of hydroxy -terminated polyethers
or polyesters and aromatic or aliphatic isocyanates ,
wherein j) polyamides,
R is an alkyl-, cycloalkyl- or aryl-radical, k ) polyimides , polyamide imides, polyether imides, poly
Rupon each occurrence , is the same or different and 40 ester imides, poly ( ether)ketones , polysulphones,
is a linear or branched alkyl-radical, polyethersulphones, polyarylsulphones, polyphenylene
R ? upon each occurrence , is the same or different and sulphide, polybenzimidazoles , and polyhydantoins ,
is hydrogen or a linear or branched alkyl- radical, and 1) polyesters made of aliphatic or aromatic dicarboxylic
Rºupon each occurrence , is the same or different and acids and diols or made of hydroxycarboxylic acids,
is an alkyl-, alkoxy-, aryloxy -, cycloalkyloxy -, m ) polycarbonates, polyester carbonates, and blends
aralkoxy or acyloxy -radical, thereof,
c) dicumylenes according to the structural formula n ) cellulose derivatives ,
o ) non -thermoplastic or duroplastic plastic materials, and
p ) mixtures , combinations, or blends thereof.
R ? R? 16 . The method according to claim 1, wherein the organic

Ollo R7 R7
oxyimide is incorporated at a concentration of 0 .01 to 30 %
by weight, relative to the plastic material.
17 . The method according to claim 1 , wherein the shaping
is carried out by injection moulding or by extrusion .