Note: Descriptions are shown in the official language in which they were submitted.
33~3
The present invention rel~te6 to rubber mixtures ~nd more
particularly relates to rubber mixt.ures wh~rein a gra~t
polymer ~B) is added to a ~Ibber (A) :in qu~ntities of from
1 to 80~ by weight, the monomers Or (B) which ~re used ~or
grafting being identical or comp~tible with the ~ono~ers
of the rubber (A) used for mixing.
~ ixtures of rubber ~ith other rubbers vr the~mopl~sts
are known in many conceivable v~ri~-tions ~nd are described
in the relevant literature. See ~or ex~ple Rubber Chem.
Techn. 47 ~3) 481-50, 1974 and Rubber Chem. Techn, 49 (1),
93-104 (1976).
Such mixtures ~re gener~lly used to achie~e a balanced
r~tio between proc~ssing prop~rties, service properties and
costs. As far as the service propertie~ are concerned,
this means ior ex~mple that, in ~any cases, a specifio t~pe
of rubber is regarded as unsuitable for a cert~in ~pplioation,
whereas another property of the s~e ~Ibber is highly desirable.
Thus 9 cert~in rubbers are blended with one ~nother in order
to additionally obt~in desirable properties ~nd to reduee
undesir~ble properties.
Because of the well known serious incompAtibility o~
polymers wîth one ~nother, there are numerous limitations
in the production o~ polymer mixtures, see ~or ex~mple,.
Kolloid-Zeitschrift u. Zeitschrift ~. Polymere, VQ1~ 213,
1966, Lothar Bohn and J~ MQcro;nol. Sci.-Rev~. Macromol. Che~. 9
C7 (2), ~51-~14 ~1972).
As a result o~ incompatibilities, deteriorations gener~lly
occur in the technologic~l properties o~ rubber-ru~ber mi~tures
Le A 18 040 - 2
3''.~
(~or ex~mple reduct10n o~ the tensile ~trength of mixtures
of polybut~diene with polych10roprene or nitrile rubber)
or rubber-thermopl~st mi~ture~ ~for ex~DIple reduction in
the elong~tion at break o~ mixtures of polyethylene and
n~tur~l rubber or polystyrene ~nd polybut~diene). Considerable
reduction~ in tensi1e stren~th and te~r propagatlon resist~nce
are also observed ~or example in~t~ ease of mixtures of
thermopl~stic styrene~butadiene three~block po1ymers with
po1ybut~diene or polyethylene.
Gener~lly, it ~ay be s~id th~t, in the case of co~p~tîble
polymers~ the properties o~ the ~ixtures v~ry substanti~lly
line~rly with their composition. Th1s ~pplies only, howeYer,
to compatible mixtures~ Incomp~tible poIy~ers c~n on1y be
mixea ~ith one another when important properties o~ the polymer
to be mofli~ied ~re not too seriously a~ectea.
It has now been found that rubber ~A~; prefer~bly ~ diens
or olefin rubber or their copolymers, can be mixed with oth0r
polymers when certain gr~t polymers (B) are used ~or mixi~g
in qu~ntities of from 1 to 80~ by weight, $he base of the
graft polymer (B) being grafte~ with monomers which ~re
identical or compatible with the ~ono~er~ of the rubber (A)
and ~hich conveniently ~y be crosslinked together with th~
rubber (A) in the ~ixture. It is also possible to use
di~ferent mo~omers for gra~ting. In t~is way, ther~ is obt~ined
a new type o~ ~Ibber in which a regular~ locally fixed
distribution o~ graft po:ly~er particles i5 present.
~lc~ ed ~bber
~ Aceordingly, the present invention pro~i~es a~ ixture
: of rubbers (A3 and gra~t polymers (B) in quantities of ~rom
Le A 18 040 - 3 ~
'~ '
~`
339
~9 to 20 parts by weight (A) and :I to 80 parts by welght {B), said grat
copolymer (~) having a parti.cle s:ize o:E from 0.1 to 2 ~m and having been
p:roduced by polymeri~atioll of grafting base and grafting monomer in the
presence of a radical ;.nit:i.ator; sai.d rubber (A) being selected from natural
rubber, polybutadi.ene, polyisoprene, polychloroprene, butadiene-styrene
copolymer, isoprene-styrene copolymer, butadiene-acrylonitrile copolymer,
butadiene-isobutylene copolymer, isoprene-isobutylene copolymer, ethylene-
propylene copolymer, polyisobutylene, ethylene-vinylacetate copolymer and
acrylate rubbers; the graft base of said graft copolymer (B) being at least
one member selected from polybutadiene, polyisoprene, polychloroprene, natural
rubber, styrene-butadiene copolymer, acrylonitri.le-butadiene copolymer,
styrene-isoprene copolymer, polystyrene, s~yrene-acrylonitrile copolymer,
ethylene-propylene copolymer, ethylene-propylene di.ene terpolymer, polyiso-
butylene, isobutylene-isoprene copolymer, polymethylacrylate, polyethylacrylate
polypropylacrylate, polybutylacrylate, polymethyl methacrylate, ethylene-vinyl-
acetate copolymer, polycarbonate, polyethylene, polypropylene, polyvinyl-
chloride and cellulose esters; and the grafting monomer of the graft copolymer
~B) being identical to or compatible with the monomer of rubber (A) and being
at least one monomer selected from butadiene, isoprene, chloroprene, isobutyl-
ene, butadiene/styrene, butadiene/acrylonitrile, isoprene/styrene, isoprene/isobutylene, methylacrylate, ethylacrylate, propylacrylate, butylacrylate,
isoprene/butadiene~ chloroprene/isoprene and isoprene/acrylonitrile. The
i.nvention also provides a process for producing said mixture.
In contrast to all hitherto known rubber mixtures, it is possible
with a rubber mixture of the present invention to establish a morphology of a
multiphase rubber system which is largely independent of the mixing conditions
~mixing rolls~ internal mixer, solution).
Preferred rubbers (A) are selected from polybutadienes, polyisoprenes,
butadi.ene-styrene copolymers butadiene-acrylonitrile copolymers, isoprene-
isobutylene copolymers, ethylene-propylene copolymers and polychloroprenes.
l~
il3~
~I;xtures of the above graEt polymers ~B) may also be used as the gra:Et base.
lhree or more of the ~raEt mollomers :Eor producing the graft
copolymer (B) may be grafted into the mixture to obtain better compatibility.
For the purposes of illustration, the following mixtures are
mentioned by way of e~ample:
For mi.xing with polychloroprene as rwbber ~A), the following polymers
may be gra~ted with chloroprene: po~ychloroprene, polybutadiene, styrene-
butadiene copolymers, acrylonitrile-butadiene copolymers, styrene-i.soprene .
copolymers, polystyrene, styrene-acrylonitrile copolymers, and ethylene~
propylene copolymers; the following polymers are preferably grafted with
butadi.ene and/or isoprene for mixing with polybutadiene, as rubber (A):
polystyrene, acrylonitrilebutadiene copolymers, polychloroprene, styrene-
acrylonitrile copolymers, and ethylene-propylene copolymers; the following
polymers are preferably grafted with isoprene or butadiene and acrylonitrile
for mixing with butadiene-acrylonitrile copolymers as rubber ~A): polybutadiene,
polyisoprene or polystyrene or their
'
~.
~l~3~3~3
copolymeTs, ~nd ethylene-propylene copolymers; -the following
polymers ~re preferably grafted with isobu-tylene ~or mixing
with polyisobutylene as rubber (A)~ pQlysl;yrene9 styrene-
~crylonitrile copolymers, and polychloroprene. the following
poly~ers are preferably grafted with isoprene and/or
butadiene and/or lsobutylene or chloroprene with i~oprene
~nd/or butadiene and/or butadiene and/or isobutylene for
mixing with ethylene-propylene copolymers as rubber (A)-
polystyrene,~polybutadiene, polyethylene, polycarbo~ate
~nd butadiene-~crylonitrile copolymers, and also styrene-
acrylonitrile copolymers~
Different rubbers (A) may also be made miscible with
one another by ~ixing in one or more graft copolymers.
Naturally the~examples given above only show some o~ the
nu'merous possibilities of producing co~patible ~ixtures.
The graft copolymers ~) which may consist of one or
~ore di~ferent graft copolymers ~re added to the rubber (A)
in quantities of from 1 to 80~ by weigh-t and pPe~erably
in quantities of ~ro~ ~ to 30% by weight. The graft monomer
of the gra~t polymer (B~ may be used i~ a quantity o~ ~rom
10 to 80~ by weight, preferably in a quantity o~ from
30 to 60~ by weight, based on the graft base.
The molecular weight of the chain o~ the graft br~ches
may be o~ the order o~ ~rom 5000 to 1,000,000 and preferably -
from 20,000 to 150,000 (~s measured by the light scattering
method).
~he graft monomer may be crosslinked, but a low degree
of crosslinki~g is preferred. The graft base may be crosslinked
ke A 18 040 ~ 6 ~
33~3
or uncrossL:inked, althou~ll i-t is pre.eerably crosslink~d.
The graI't polymer (B~ has a pArtic:l~ size of Irom
0.1 to 2~m, preferably ~rom Ool -to 0.8 ~m.
The gra~t po.lymcrs (B) may be prc,duced by radical
solut~on, or by bulk, suspension or emulsion polymerisation5
irrespectiv~ of the~ tor used~ at t,empe~a-tures of from
~2VC to 120C. It is preferred to adopt a process in which .
the graft polymer is obtalne~ in a form in which it can be
favourably mixed with the r~bber (A). For e:~ample, in cases
where a rubb~r (A) produced by solution polymerisation, such
as for c~alDple cis-194~olybutadiene or an ethylene-propylene
copolymer, is, to be mixed with a graft polymer (B), the
graft polymer (B) used will be a graft polymer which has been
produced in ~1 solution which is identical or miscible with
the solvent used in the production o~ the rubber (A)~
If for example a rub~er ~A) produced by emulsion
polymerisation, such as an emulsion st~rene butadiene copolymer
or polychloroprene or a butadiene acrylonitrile copolymer,
is to be mixed with a graft polymer (B) 9 it is preferable
to use an emulsion process ~or producing the graft polymer (B)~
Bases having an aver~ge particle size of from 0.05 to 1 ~,
pre~erably from 0.1 to 0.4 ~, ~re used for the production
of graft latices.
If it is desired to produce gra~t polymers ~) haYing
~ base which normally contains no doublc bonds, hydrogen
atoms or heterogenous groups which are suitable ~or gra~ting,
bases are synthesised by copolymerisation with certain
Le A 1~ 0ll0 - 7
eomc)rlomcl~ sllitR`ble for gl~nIt polymerisation (for exarnplo
styl~ene is copolymeri~c(l ~ith isoprene or butadiene in
quantities O:e from 5 to 2~
A number o-L` desir~ble technological ~roperties can be
o`btainecl by suitable mixtures of rubber (A) and gr~Et
polymer (B). For example, the strength9 moduli and processi-
bili~y of polychloroprene rubbers can be improved accordingly
by ch~oroprene-gra~ted polystyrene or styrene/acrylonitrile
copolymer. By mixing chloroprene-grafted polybutadiene with
polychloropre~e, its low-temper~ture flexibility is increased.
By mixing chloropr~ne-gra~ted butadie~e/acrylonitrile copolymer
with polychloroprene, its resistance to oil is ~lproved~
By mixing butadLene- or isoprene-grafted polys~yrene with
polybutadiene or ethylene-propylene rubbers, their strength
and processibility are improved. By mixing isoprene- or
butadiene/acrylonitrile~grafted butadiene or i~oprene,
the low-temperature flexibility o~ butadiene/acrylonitrile
copolymers is increased. o
These examples may be continued ad in~initun and the
aboYe are by way o~ illustration only The important ~actor
in every case is that~ by virtue of the grafting-induced
compa~ibility of the graft copolymers with the rubbers, it
ia possible to obtain a controlled modi~ication of certain
technological properties without the characteristic properties
~5 of the base rubber (A) being undesirably in:Eluenced to any
significant extent.
The rubber (A) may be mi~ed with the gra~t polymer (B)
~e ~ lB 040 - 8 -
~3~
in diIferent ways:
For ex~mple, it is possible to mix the corresponding
latices at room temper~tllre or at el~vated temperature ~nd
then to congulate the resulti~g mixtures by adding salts~
acids or alcohols, or to precipita-te the rubber mi~ture
by low-temperature coagulatio~. It i~ also possible to mix
the dissol~ved pol~mers (A) and (B) ~nd to work up the
solution by stripping, spray d~ying or precipitation~ for
example with alcohol. For the sake of comp1eteness, re~e.rence
is ~lso made to the possibility of mixing latex with solution.
Mixing may also be carried out mechanic~lly o~ mixing rolls,
in internnl mixers or in screw extruders at temperatures
in the range ~rom 20 to 120C.
Fillers, extenders and vulcanisation aids may also be
incorporated duri~g the mixing oper~tio~s.
The mixtures of rubber ~A) and graft polymer (B) may be
vulcanised ln the usual way in the presence of sulphur or
peroxides.
The process accordlng to the invention is illustrated
by the following Examples:
A~ Production o~ gra~t polymers
B. Production o~ graft polrmer/rubber mixtures~
Ad A: The graft polymers used ~or ml~i~g with rubber are
produced i~ emulsion, suspension or solution by means
o-f radical initiators,
EX~MPLE A 1
1600 g of polybutadi~ne latex ~solids content 540 4~,
average particle size 0.4 ~) and 1640 ~1 o~ desalted water
Le A 18 040 ~ 9 -
are introduced in-to ~ (i litre fl.ask. The ~lask ls then
purged with nitrogen an~ lts contents heated to 63-65C.
After heating, a solutlon o:f 4.5 g of potassium persulph~ke
ln 200 ml of water ls added.
At 63 to 65C~ 540 g of chloroprene and a mixture of
375 g of water and 12 g of an emulsifier of the alkyl
sulphonate type are separately and sl~ultaneously added
dropwise over a period oI 4 hours, followed by stirring
for 4 to 6 hours at 63-65C.
After degassing, the latex is filtered and directly
u~ed for mixing test~ with rubber lat~ces or solutions,
EX~PLE A 2
1600 g o butadiene-acrylonitrile copolymer latex
~ o~ acrylonitrîle, DeYo hardne~s 1000, solids co~centration
49 5~ particle size 0.2 ~) and 1640 ml of desalted water
are introduced into a 6 litre flask.
The flask is then purged wi-th nitrogen and its contents
heated to 63 - 65C. A~ter heati~g9 ~ solution o~ 4.5 g o~ !:
potassium persulphate in 200 ml of desalted water is added.
At 63 to 650~, 540 g of chloroprene and a ~ixture o~
375 g of water and 12 g of an emulsi~ier o~ the alkyl sulphonate
type.are simultaneously and separately added dropwise over
a period of 4 hours, followed by stirri~g for 4 to 6 hours
at 63 to 65C. A~ter degas~ing, the ~atex is filtered.
EX~MPLE A 7
2260 g of polychloroprene latex (solids conc~n-tration
35.2 %, av~rage particle size 0~ /u) and 1000 ml
of desalted water are introduced into a 6 litre flask,
~he fla.~k is t~en purged with nit~o~en and its con~ents
heated to 63 - 65C. After heating7 a solution of 405 g o~
Le A 18 040 - 10 -
__ .
~13~31~
potassium persulphate in 200 ml of water i~ added.
At 63 to 65C, 540 g of chloroprene and a mixture of
375 g of water and 12 g of an emulsifier of the alkyl sulphonate
type are simultaneously and sep~rately added dropwise over
a period of ~ hoursy ~ollowed b~ stirring for 4 to 6 hours,
at 63 to 65C. After degas~ing, the latex i5 ~iltered.
EXAMPIIE A 1~
___
1600 g of polybutadiene latex (solids content 54.4%,
average particle size 0.4 ~) and 1640 ml of desalted w~ter
are introduc~d into a 6 litre flask.
The flask is then purged with nitro~en and its contents
heated to 63 - 650C. After hea-ti~g~ a solution of 4,5 g of
potassium persulphate in 200 ml of water is added.
At 63 - 65C, a mixture of 378 g of isoprene and 162 g
f acrylonitrile together with 375 ml of water and 12 g of
an emulsifier of the alkyl sulphon~te type ~re simultaneously
and separately added drop~ise over ~ period of 4 hours,
fol'Lowed ~y stirring for 4 to 6 hours at 63 - 65C. After
degassing, the latex is filtered.
EXAMPLE A 5
1600 g of a butadiene-acrylonitrile copolymer latex
(33% of acrylonitrile, Defo hardnese 1000, so:Lids concentration
49.3%, average partic:le size 0,19 ~) and 1640 ml of des~lted
water are introduced into a 6 litre flask.
The flask is then purged with nitrogen and its contents
heated to 63 ~ 65Co At 63- 65C, ~ mixture of 475 g of
styrene and 65 g of acrylonitrile together with 375 ml of
Le A 18 040 1'1 ~-
.3~
wa-ter ~nd 12 g of an emulsi~ier of the alkyl sulphonats
type nre simult~neously and separately added dropwise over
a period of 4 hours, follQwed by stirring ~or 4 to 6 hours
at 63 - 65C. After degassing~ the latex is filtere~
r EX~SPl.E A ~i
___
1970 g o-f ~tyrene-~soprene copolymer latex (10~ o~
isoprene, solids content 40 8~, ~ver~ge particles size 0.15
and 1260 g of des~lted wa-ter are initially intru~ced
into a 6 litre flas~.
The flask is then purged with ni~rogen and its contents
heated to 63 - 65C. A-t 63 - 65C9 540 g o~ chloroprene ~nd
a mixture of 375 g of water and 12 g o~ an emulsifier of the
alkyl su:Lphonate type are simultaneously and separately
added dropwise over ~ period o~ 4 hours) followed by s~irring
for 4 to 6 hours at 63 - 65~o A~ter degassing, the latex
is filtered.
' :
250 g o~ cis-1,4-polybutadiene ~ ~ 240 ml~g~ is
added to 4 litres o~ toluene, followed by stirrlng until a
solution is formed. 200 g of chlorophene, 200 g o~ isoprene
and 12 g o~ benzoyl peroxide are then added, followed by
stirrlng ~or 18 hours at 60C
EXAMPLE A 8
5.2 litres o~ n-hexane and 320 g of ethylene-propylene
:2S terpolymer (EN-type~ Mooney ML 4-100 90, 12 C=C-d~uble bonds
per 1000 carbon atoms) are introduced into a 10 litre autocla~e,
followed by stirring until the rubber has completely dissolved.
Le A 18 040 - 12 ~
__
~L~3~L~33~
~l80 g o~ chloroprenc and a so`lution of 15.'~ g o~ dibenzoyl
pero~ide in 100 ml o~ benzene are then added, followed b~r
stirring for 18 hourc at 60C~
Ad B: The rubber ~nd gra~t polymer are mi~ed with each other
in latex form, in solution or in solid form on mixing
rolls or in all internal mixer. The latex mixtures ~nd
the solutlon are worked up in kno~ manner ~y
precipitation and stripping, respectively.
St~ndard c~rbon black mi~tures are initially produced
-from the graft polymer mixtures in accordance with
IS0 Speci~ic~tioll 2475-1975 ~E), ~ter which ~ouldings
are produced ~rom the resulting mixtures and then
pressvulcanised for 20, 40 and 60 minutes at a
temperature of 150C. The necessary test specimens ~re
cut ~rom the sheets obtained. Strength (F~l elong~tion
(D) and strain values (S; at 100/300~ elongation)
are tested on the Standard ~est Ring I according to
DIN 53 504, whilst Shore hardness A ~H; a-t 20 and 70C~
is -tested in accordance with DIN 53~05 and resilience
2V (E) in accordance with DIN 53512. The compression set
is measured in accordance with DIN 53517~ The crude
graft polymer m-ixtures employed are used for measuring
the polymer viscosity and the difference in viscosity
between the one minute and the ~our minute value in
a Mooney Tester at 100C (Ml-4) i~ accord~nce with
DIN 53523 and De~o plasticity in accordance with former
DIN 53514. The gel content is determined by centri~uging
Le A 18 040 ~ 13
~3~3~
a toluenc ~olutiorl,
A selection of prepared and tested graft poly~er
mixl;ures (I~.~X) is given and fully characterised
in 'l'ables la ~nd lb. The test dat~ of the vulcanisates
nre shown ln Table II.
F~MPLE B 1 (Table 1~)
Polymer mixtures of 90 (I) and 80 (II) parts by weight
o~ a chloroprene homopolymer with 10 and 20 parts by weight,
respectiv~ly, of a chloroprene-grafted polystyrene have
a distinctly higher gel content and viscos:ity trencl value,
re~lected in better prccessing properties, in comparison
with the pure chloroprene ho~opolymer (V).
The products also show high streng-th, strength and
hardness ~alues in the vulc~nis~tes.
~ (Table la)
Pol~mer mixtures of 90 (III) and 80 (IY) parts by weight
of a chloroprene homopolymer with 10 and 20 parts by weight,
respectively, of ~ chloroprene-grafted butadiene-~crylonitrile
copolymer containing 38~ of acrylonitrile ~l~o show a
higher gel content and viscosity trend value ~nd, hence,
better processing properties ~y comp~rison with the pure
chloroprene homopolymer (V). In the ext~usio~ of strln~sg
output is higher axld the level o~ extrusion swelling lower.
A~ter agein~ in hot air (21 days/100C)~ the i~crease
in the hardness and strain values ~ the vulcanisates containing
the polymers according to the inve~tion is lower, i.e. they
are more resistant to ageing. In addition, the ~ulcaxlisates
~e A 18 040 - 14 -
~3~33~
cont~ining the polymers accordlng to the l~vention ars muoh
more resistant -to ASTM oils~ ~s shown by storage test~ at
1.00C.
EXAMPLE ~ 3 (Tnble la)
Pol~r mixtures of 85 (~ nd 70 (VII) pnrts by weight
o~ a chloroprene homopolymer wi th 15 arld 30 parts by we:ight
respectively~ of a chloroprene-grafted polybutadiene also
show a much higher gel content and viscosity trend value and,
hence, extre~ely good processing properties in comparison
with the pure ho~opolymer (V)~
The vulc~nisates of the polymer mi~tures show hlgher
hardness, strain and elastic~-ty values in compariso~ with the
re-ference material.
EXAMPLE B ~ (Table la)
. Polymer mixtures of 90 (VII13 and 80 (IX) parts by
weight of a chloroprene homopoly~er with lO and 20 parts by
weight, respectively, o~ ~ ehloroprene-gr~ed styrene~isoprene
copolymer show higher gel contents and viscosi*y trend values
and, hence, better processing properties in co~parison wit~
the pure chloroprene homopolymer (Y).
EXAMPLE B 5 (Table la)
In comparlson with the ungrafted re~erence material (V)g
a polymer ~ixture o~ 80 parts by weight of a chloroprene
homopolymer with 20 parts by weight o~ a chloropre~e-gra~ted
polychloroprene (X) also 3hQws higher gel contents and viscosity
trend values ~nd9 hence9 better proce3sing properties. Higher
strain, hardnes~ ~nd elasticity v~Lues are ob-tained in the
Le A 18 040 lc~ _
~ L3
vulc~ni sate .
EXAMPLE ~ 6 ~Table la)
In compArison with the ungrafted re~erence material (XIII),
polymer mixtures of 90 (XI) and 80 (XII) parts by weight
of a sulphur-modified polychloroprene with l0 and 20 parts
by weight, respectively, of ~ chloroprene-grafte~ polybutadiene
si~ilarly to the product6 of the preceding Examples - show
higher gel contents and ~iscosity trend values which enable
rolled sheets to be rapidly ~ormed. In the carbon bl~ck mixtures,
the products are less lnclined to become tacky on the rolls
and pro~ote more rapid vulcanisation which leads to a higher
crosslinking density with higher strain, hardness, el~sticity
and compression set values.
~ tTable la)
The polymer mixture of 80 parts by weight of a chl~ropr~ne
homopolymer with 20 parts by weight of a chloroprene-grafted
butadiene-acrylonitrile copolymer containing 38~ of acrylonitrile
(IV b) shows ~ Mooney vi8c06ity ML-4~100C o~ 58 ME and a
gel content of 16%.
In this respect, it is comparable with a so-called pre-
crosslinked polychloroprene (IV a) which is obtained by mixing
benzene-soluble homopolymers or copolymers of chloroprene
with ben~ene-insoluble copolymers of chloroprene generally
produced by known methods, e.g. British Patent No. 1,158,970,
using diesterst and which is used in particular for applications
requiring good processing properties. Howe~er, ~or e~uivalent
processing properties of IV b and IV a, the polymer mixture
according to the invention produces higher strength valuesf
Le A 18 040 - 16
___
33~
better co~pression set and be-tter agei~g b0haviour.
EXAMPLE L 8 lTable lb)
A pol~er mixtllre o~ 90 (XI~) and 80 (XV) parts by
welght of a ch].oroprene homopolymer with 10 an~ 20 parts by
weight, respectively, of a ehloroprene-grn~ed cis-1,4-poly~
butadiene has Mooney viscosities ML-4/100C ol 58 ~nd 68, and
gel contents of 8 and 20% respoctively.
In the vulcanisa-tes9 the mixture ~hows excellent
strengths ~nd elongations, good low-temperature flexibility
and a low compression se~c
EXAMP~E B 9 ~Table lb)
In comparison with the pure homopolymer (V), a poly~er
mixt~re of 80 parts by weight of a chloroprene homopolymer
with 20 parts by weigh-t of a chloroprene-grafted ethylene-
propylene terpolymer (XVI) shows a higher gel content and
viscos.ity trend ~alue and, hence9 extremely good processing
properties, An increased resistance to ageing is obtained in
the vulcanisates.
EXAMPLE ~ 10 (Table lb)
A polymer mixture of 85 (XVII) and 70 (XVIII) parts by
weight of ~ nitrile rubber with 15 and 30 parts by weight,
re:spectively, of an isoprene/acrylonitrile-gr~tea polybutadiene
shows good strength and elongation values, incre~sed low-
temperature flexibility and r~duced co~pression set.
EXAMPLE B 11 (Table lb)
____.
A polymer mixture of 90 (XIX~ and 80 (XX) parts by weight
of a lithium polybutadiene with 10 and 20 parts by weight,
respeetively, of an isoprene~grafted polystyrene shows good
Le A 1~ 040 - 17 -
3~3
~tren~th An~l elo;l~ation vnlues and n very considerable
improvement :in proces~:Lbllity over lt,he pure polybut~diene.
~e A l ~ 0 4(3
~_1 J ~L~l3~ 3
.~ o
_ _. . _ _
U~ ~ o
~ ~ `D ~ ~ O . c;~
:> oo ~- ~ ~ X ~_ O ~:r
_ ---~ - ~ ~ --
O ~D~ ~ ~
o .~ ~ o o ~o
or~ X ~ C~J~
--l -----I - ~--
~,o ,~
::~ O O O ) C~l H O O O 00
W 00 ~ ~ ~O ~' r- C~ ~ ~
._ . . __ _ ._ _ _
. o - '~"-1 ~ .
~ c~ ~O O~ ~C o~ ~ 00 ~ o~ ~ ~In
- ~_ _ l __ _.
1_~ ~7~1 O~ X oo~ ~)~o ~ O u~
._ _. l __ _ _____ . __
O I_~ O
~ 1-~ ~
O O Q ~ 1_1 O O O 1--
~1 C5~ ~ ~ ~ > ~ ~ CJ~ )
_h . _ ~ ¢ _ h
¢ o I bl) O
~1 b~ O ~ rI
bO ~r~ ~ ~ ~ O ,~
~-rl ~ O ~ t) ,~
O ~0 0 ~ ~0 0 G) ~0
. :~ ta ~ 0 ~ ,~ ,~ ~
~ _ aJ ~ p~ ~0 -' GJ ~d ~_
_ ~a a~ ~ o ~ ~ aJ ~
~ ~ ~ ~,o ~ ~ ~ ~: C~
~-r~ ~ o ~ o P.,-~ o
v) a ~ o D u) o ~ O o~a o
r~ V~ ~ ~ ~r~r~rO V~ ~_ ~ o ~ V~
o ~ o ~ a) o o o c- ~ . ~ aJ
~ ~ ~ o~ ~v ~ ~ ~
O ~ a a h ~i ,o .rJ ~a ~a ~o ~ ~ O ,:>~ a h
p~ V ~ p~ Ll P P. O ~Ll P
o ~ ~ ~ ~ o :~ 0 4~ a o ~ o L~ ~ ~ o
E3 ~ 5h ~ ~ c~ O ~ ~ J_l ~ F~ ) 5 1 ~ V
0 h 1~ d h ~ .,;O h h h rl Q ~ rl J_) O ~U h ~ P ~ rl
.S:~ bO OO b~ r~ ~ u) ,~ bO bO bO ~J rJ ~ u) r ~ I O r-l _~
.) a~ a ta ~ a~
. ~ U~ ~ O rl ~ U~ J- ~-rl ~ rl ~ U~
o a~ aJ bQ aJ o rl ~ ~1 ~J rl U~ a) r-l 9.J ~r s~
1~ U~ ~I h ~ ~ ~ h ~ U) h ~ h I ~I) J~ td U~ ~ U~ a~ J~~ ~ P. ~ p,-,l ~ ~ ~ P. ~ P~ P. h J t:: r~ al p, (n ~:~,-,1 Ll ~:
, ::1 s~ ~ t) ~ ~ ~ o o o ~ E 1: P ~ ~ h ~ ~a ~ ~o~
~ X rlr~Jr-l O r-l ~~~ O X ~-~ r-l r-l r-l rl 3 r-l O ~ ~ r-l a\ r-l O ~3 r-~ O
X ~ a~ O ,1 ~ ,c~ ~ a~ ,1 rC rl P~ $
Le A 18 040 - 19 -
33~9
QO 0~
~ ~ ~0~-
_ ~ ____-.
X
~ O O O
X ~ 1
_ _ __ ..
~ U~
~ ~ 1'~
_ _ _ . __ .__
~ o~
~ U) U~ O O
X ~ o~ ~- ~
_ ..... ~ I _ ._
~ O
~ O O ~ It~
~C oO
~ '
__ _ . .. . __ ,
O 'O COO
oo C~
_ ...... _.. _____ -
:~
X O O U~ o~
._ __ , .
.~
C)'~:
I ~ ~
aJ ~ ~ O O
.,~ ~ ~
~a ~ P ~ o
~ ~.~
O ~ ~ O
;
O ~ ~ ;~
Cl, I O ~ O
I Q~ 1~ 0 a~ o t~
O ~ O
~_ ~ h ~) ~ ~ O
, ~a) ~o :~
u) .5 1 a~ ~ ~ ~ v
~ .rl IJ ¢ W ~ ~ O aJ
F () Q~ ~ O ~ O ^ ,~
~O~ ~ O )~
,~ a ~ ~ h ~ ~ o ~ 1 s~
o ~ o a~ o I ~ X
~.~.1L) ~rl J- O O r~
o ~ r~ co ~ ~ ~ O
1 o
o h ~: h ~ r~ '~ I L) ~; ~ .r
bO ~0 h ~ J u~ ~u ~ o u) _~
I O I o h o r~ u~ ~ ~ ,~ o
O Q~ 0 a) --~a v Ll
t~ o ~ ~,~ V) ,c~
~J ~o o ta~ ~o~ a ~ .,~ o
h 1~ h
P~ 1
h O O ~O O ~ a o ,1~ ~ ~ O
a) ~) ~ h ~ E h ~ ~ ~ U) ~ E~
L) O O O O ~ Q, O :~ O ~ ~ i
P ~ ~ ~ o ~ ~ O ~ ~ ~: O ~
~O .,~ .~ ~ ~) ~ o U~ U) o o ~ o V
~ ;~: ~ r_
Le A 18 040 20 -
~ ~ ~3~33~
~ o
~ ~ ~ o o o In Ir~ o ~'~ co
~ ~ r~ ~ ~ r~ ) r~ r~
,1'.~ I I I I t I ~ t I I
~J O
.
~0
~ r~
o o
O O ~ r~ ~ i~ C~ ~ r~ C~ r~
t~ o r~) r~ r~ r~ ~ r~ ~ r~ r,~ ~ I I r~l I I I ~ r~l
~'1 i3 ~ ~ ~-- ~ r~) G~ ) a~ o r~
V~ r,~ r~ ~ ~ r.~ ~ ~ ~ r,~ r~J ~ C~l
h
L~
D c~ ~ O O O `~
Z ~ ~D ~ ~ ~ O a' ~ `~
~)
~3
- -------I -- - -- - - ---
r.
U~ U~
o ~ o ~ a' o ~ co
¢
~7
~ o
O O u~ ro ~ r~J ~ ~ r~ co r~ r.~ 1 r~ r~ r~ 1~ r~ ~ ~ co ~ co
I~ ~ ~O ~ ~ ~O ~O ~ ~O ~ ~O ~ ~ ~ ~ O ~ ~O ~O ~O ~O Ul
o C7~ ~o ~ u~ r.~l u) co o ~o ~ ~ ~ ~.~ ~ ~ c~ ~ 1~ r~ o ~ r.
:r: c~l ~o 1~ ~0 ~O ~O ~O ~0 ~ r~ O ~O ~ O ~O ~ ~O ~ O
.
0~
O ^
O (~ N ~ r~ `J ~`3 ll'l ~ r~l r~) ~ O t~) r~ ~ ~ ~n co C~ u~ o t~ .
.~ ............. ~........... ~.
_~ ~ r~ l r.~ ~ ~ r~ r~ ~ ~ ~ C~l ~ ~ ~ C~ r,~l ~ r.
0~
." ~, . o o o o o o o o o o o o o o o o n n o o O ~t
JJ ~ O r~ I~ ~ r~ o ~ o ~ ~o ~- ~ o ~ '1 o c~ a~
~ ~ ~ ~ r~ ~ ~ r~ r) r~ r~ r7 ~ ~ r~
Q
a~
J
.,~.C. ~ o In o co ~ O U~ O ~o o In o c~ U~ O r~l r~
~: ~, co r~ 1~ r~ ~ In r~ r~ r~ r~ 1~ u~ In r~ ~ ~0 o r~ r~ u~ ~ 1
,~ r"
. I
~ _ ~
.~
~Ir,~J
) 1 1--I 1--1 ~1 ~ ~ I--I H ~1 ,~ ' H ~ H ~ ~ ~ ~ ~ ~ C r~ ,C
r X ~ ~ 1~ ~ ~ ~/ ~1 ~ X ~I r" X ?" ~ ~ r< 1--1
r~
Le A 18 040 - 21 -
