Note: Descriptions are shown in the official language in which they were submitted.
t3~l43
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IMPACT IMPROVEMENT OF RVBBER-MODIFIED
NIT~ILE ~RESINS
-- . :
This invention relates to improved impact resistance
in rubber modified nitrile resins and more particularly pertains
to the inclusion of certain naturally occurrlng oils, such as
clove,oil, eugenol, and the like, and other oils such as
2-ethyl hexanoic acid, tributyl phosphate, 2,6-di-t-butyl-4~
methyl phenol, triethyl phosphate, p-nonyl phenol, 4-hexyl ~,
resorcinol, and the like, in rubber modified high-nitrile `~
thermoplastic resins for the purpose of improving the process-
ability and impact resistance of said resins.
The naturally occurring oils most useful are commonly
called essential oils. Some derivatives of the essential oils ~ ,
are also useful in the present invention. A more complete ~ ;
description of the essential oils and their derivatives appears
in the Kirk-Othmer Encyclopedia of Chemical Technology, Second
Edition, Volume 14, pages 178-216. Most preferred in the
present invention are oils including clove oil, citral, eugenol,
veratrole, citronellal, iso-safrol, cinnamyl alcohol, safrole,
cineole, anisole, and the like, and 2-ethyl hexanoic acid,
tributyl phosphate, 2,6-di-t-butyl-4-methyl phenol, triethyl
phosphate, p-nonyl phenol, 4-hexyl resorcinol, and the like.
The oils are most useful when used in amounts within the range ;
of from about 1 to 30 parts by weight based on the total weight
of the oil and the rubber-modified high-nitrile resin~
The rubber-modified nitrile resins embodied herein
are those which result from the polymerization of a major
portion of an olefinically unsaturated nitrile, optionally ;
another monomer component, and in the presence of a preformed
rubber component by methods known to those skilled in the art.
~ 3~3
,.,, ~
The polymers which are most useful in the process of
this invention include those produced by polymerizing a major
proportion of a monounsaturated nitrile, such as acrylonitrile,
and optionally a minor proportion of another monovinyl monomer
component copolymerizable with said nitrile in an aqueous medium
in the presence of a preformed diene rubber which may be a
homopolymer or a copolymer of a conjugated diene monomer.
, ... .
The esters of olefinically unsaturated carboxylic ;~
acids include those having the structure CH2~-COOR2
Rl ~
wherein Rl is hydrogen, an alkyl group having from l to 4 x ,
carbon atoms, or a halogen, and R2 is an alkyl group having
from 1 to 6 carbon atoms. Compounds of this type include
methyl acrylate, ethyl acrylate, the propyl acrylates, the
butyl acrylates, the amyl acrylates, and the hexyl acrylates;
methyl methacrylate! ethyl methacrylate, the propyl metha- ~;~
crylates, the butyl methacrylates, the amyl methacrylates, and
the hexyl methacrylates; methyl alpha-chloroacrylate, ethyl ;;
alpha-chloroacrylate, and the like. Most preferred in the ~
20 present invention are methyl acrylate, ethyl acrylate, methyl ~ -
,:: .
methacrylate, and ethyl methacrylate.
The conjugated diene monomers useful in the present
.: .
invention include butadiene-1,3, isoprene, chloroprene, ;~ -
bromoprene, cyanoprene, 2,3-dimethylbutadiene-1,3, 2-ethyl-
butadiene-1,3, 2l3-diethyl-butadiene-1,3, and the like, and
others. Most preferred for the purpose of this invention are ;
butadiene-1,3 and isoprene because of their ready availability
and their excellent copolymerization properties. ;
The olefinically unsaturated nitriles useful in
the present invention are the alpha, beta-olefinically
-2-
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~3143
unsaturated mononitriles having the structure CH2aC-CN
wherein R is hydrogen, a lower alkyl group having from 1 to 4
carbon atoms, or a halogen. Such compounds include acryloni- ;
trile, alpha-chloroacrylonitrile, alpha~fluoro-acrylonitrile,
methacrylonitrile, ethacrylonitrile, and the like. The most
preerred olefinically unsaturated nitriles in the present
invention are acrylonitrile and methacrylonitrile and mixtures
thereof.
The other monovinyl monomer component copo~ymerizable -
with the olefinically unsaturated nitriles which is useful in
this invention includes one or more of the esters of olefini-
cally unsaturated carboxylic acids.
Polymerizates of particular utility in this invention
and details of their method of preparation are described in ~ -
U. S. Paten-t Nos. 3,426,102 to Solak et al issued February
1969 and 3,586,737 to Duke et al issued June 1971.
Specific polymerizates useful in the process of
this invention include those prepared by the polymerization
of 100 parts by weight of (A) at least 50% by weight of at
least one nitrile having the structure CH2=CI-CN wharein
R ;~
R has the foregoing designation and (B) up to 50% by weight
based on the combined weights of (A) and (B) of an es-ter
having the struc-ture CH2eC-COOR2 wherein Rl and R2 have the
Rl ', `; '
foregoing respective designations in the presence of from 1
to 40 parts by weight of (C) a rubbery polymer of a conjugated
diene monomer selected from the group consisting of butadiene ;`
and isoprene and optionally a comonomer selected from the group
-3-
~ 3~3 .:
'
consisting of styrene, a nitrile monome~ ha~ing the stxuctuxe
OE12=C-CN wherein R has the ~oregoin~ designation, and a monomer
R
having the structure CH2=C-COOR wherein R]L and R2 have the
Rl
foregoing respective designations, said rubbery polymer con-
taining from 50 to 100~ by weight o~ polymerized conjuyated
diene and from 0 to 50~ by weight o.~ comonomer. ~
Pre~erably, component (A) should be present in -':
from about 60 to 90% by weight based on the combined weights `-~
of ~A) and (B~ and the rubbery pol~mer (C) should contain more.
.:. ~
than 50% by weight of conjugated diene and more preferably .
from 60 to 90~ by weight of conjugated diene. -:
Thus, in accordance with the present teachings,
an impact-resistant resin composition is provided which
comprises an intimate mixture of from 1 to 30 parts by .. I.
weight of an impact improver selected from the group consisting
of an essential oil, 2-ethyl hexanoic acid, tributyl phosphate t .~ -
2,6-di-t-butyl-4-methyl phenol, triethyl phosphate r p-nonyl
phenol, 4-hexyl resorcinol and lO0 parts by weight of a resin .~
; which results from the polymerization o 100 parts by weight of ` ::
(A~ at least 50% by weight of at least one nitrile
having the structure CH2=C-CN wherein R is hydrogen, a lower
R
alkyl group having from 1 to 4 carbon atoms, or a halogen, and
(B) up to 50~ by weight based on the combined
weigh-ts of (A) and (B) of an ester having the structure
CH2=C-COOR2 wherein Rl is hydrogen, an alkyl group having
Rl
from 1 to 4 carbon atoms, or a halogen, and R2 is an alkyl ;
group having from l to 6 carbon atoms, in the p.resence of from
~73~3
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1 to 40 parts by weight of
(C) ~rom 50% to 100~ by weight of a rubbery polymer
o~ a conjugated diene monomer selected from the group con-
sisting of butadiene and isoprene and from 0 to 50% by weight
of comonomer selected from the group consisting of styrene,
a nitrile monomer having the structure OEI2=C-CN wherein R
R -
has the foregoing designation, and a monomer having the
structure CH2=C-COOR2 wherein Rl and R2 have the Eoregoing
Rl
respective designations.
The polymerizates useful in the process of this
invention can contain compounding ingredients and additives,
pigments, colorants, stabilizers, etc., as is well known in
the art, so long as the balance between impact strength,
flexural strength, tensile strength, processability, heat-
distortion temperature, and the like, is not affected to such
a degree that the article is no longer useful for its intended
purpose.
The polymers useful in the prcoess of this
invention are thermoplastic materials which are easily pro-
cessed and can be thermoformed into a wide variety o~ useful
articles in any of the conventional ways employed with well
known thermoplastic polymeric materials such as by extrusion,
milling, molding, drawing, blowing, etc. The polymers re-
sulting from the~process of this invention have excellent
solvent resistance, including water-frost resistance, and
their impact strength (when rubber modified) and low
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~73~43
permeability to gases and vapors make them very useful in
the packaging industry, and they are particularly useful in
the manufacture of bottles, films, envelopes, boxes, and other
types of containers for liquids and solids.
In the following examples, which will further illus- ~ r
trate this inven~Ion~ the amounts of various ingredients are
given in parts by weight unless otherwise specified.
Example l ; ,~
A. A rubber latex was prepared by polymerizing with
continuous agitation at 45C in the substantial absence of
oxygen a mixture of the following ingredients;
Ingredient Parts
acrylonitrile 30
butadiene-1,3 60 ~ ;
emulsifier (Gafac~ RE-610)*2.4
azobisisobutyronitrile 0.3
t-dodecyl mercaptan 0.5 ~-
water 200
. . .
*A mixture of R-O-(CH2CH2~) PO3M2
and ~R-o-(CH2CH2O-)n]2PO2M wherein
n is an number from 1 to 40, R is an
alkyl or alkaryl group and preferably
a nonyl phenyl group, and M is hydrogen,
ammonia or an alkali metal, which
composition is sold by GAF Corporation. --
Before reaction was started, the pH of the mixture
was adjusted to about 8 wikh KOH. The polymerization was ~ ;
carried out for 22 and l/2 hours to a conversion of about 92% ~ -
and a total solids of about 33.1%.
B. An impact-resistant, gas barrier resin was
prepared by polymerization of a mixture of the following
ingredients:
-5-
,~, ! ;
3~43 . ~
Ingredient Parts r
acrylonitrile 75
methyl acrylate 25
rubber s~ids in the form :
of latex A (above) 9 : :~
potassium persulate OD 06
emulsifier (Gafac RE-610) 3
modifier (n-dodecyl mercaptan)
ethylene diamine tetra 0.05 ~ -
acetic acid ;
water 200 .
The pH was adjusted to about 7 with NH40H. The polymerization
was carried out in the substantial absence of oxygen at 60C .:
for 5 hours so as to produce a conversion of 91% of a latex.
The latex obtained from the polymerization was then coagulated ;.:
and the resin was dried and compression molded into a bar at .. .;
150C. The molded bar was transparent and found to have a :`:
notched Izod impact strength of 1.2 foot pounds per inch of
notch and ASTM heat-distortion temperatures of 69C at 264 psi
and 75C at 66 psi by ASTM test D-648-56. The polymer was
easily blended in a Brabender~ plasticorder and at the end
of 10 minutes in the plasticorder at 230C and 35 rpm, a
torque reading of 1150 meter grams was obtained for the polymer.
A sample of this polymer was compression molded into a sheet
and this sheet was found to have a water vapor transmission :~
of ~.51 grams/mil/100 inches2/24 hours at 90~ relative
humidity and 100F by ASTM procedure E-96~ The sheet was
found to have an oxygen transmission of 0.6 cc/mil/lOQ inches2/ ~
24 hours/atmosphere by ASTM procedure D-1434. The sheet was ;
also found to have a frosting index of 6.4 haze units~
~0 Frosting index was obtained by measuring the haze or refracted
; -6-
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31~
.,~.` ,
light off the piece of the sheet. The sheet was then subjected ,
to a temperature of 50C and 100% relative humidity for 16
hours at which time the haze was redetermined. The difference
in the haze readings is the frost index. The haze readings ~ ;
were done on a Hunter Laboratories color difference meter
model D-25-P. :`
Example 2
Samples of the resin described in Example l were
blended with various amounts of clove oil in an efficient ~,
10 mixer such as a rubber mill, Banbur~, extruder or ko-kneader~. '
The blends were compression molded into test bars and the notched
: - .;
Izod impact values were determined on the bars including a
control bar containing no clove oil. The following results
were obtained:
: ''.
Clove Oil, % Notched Izod Impact Strength ~ .: .
1.2 foot pounds per inch of notch
2.2 foot pounds per inch of notch
3.6 foot pounds per inch of notch
2.8 foot pounds per inch of notch
Example 3
The procedure of Example 2 was repeated using 10% of
eugenol in place of 10% of clove oil with the following ~ ~
results: ~ -
Euge~ol, % Notched Izod Impact Stren~th -
0 1.2 foot pounds per inch of notch
3.4 foot pounds per inch of notch
Example 4 ;
~:. :'`
The procedure of Example 3 was repeated using citral
in place of eugenol. The notched Izod impact for the citral-
containing resin was 5.1 foot pounds per inch of notch compared
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~ ~'73~143 :
to 1.2 foot pounds per inch of notch for the control~
Example 5 ~;
,
The procedure of Example 4 was repeated using
veratrole in place of citral. The notched Izod impact strength
for the veratrole-containing resin was 2.1 Eoot pounds per ;
inch of notch compared to 1.2 foot pounds per inch of notch
for the control.
Example 6
The procedure of Example 5 was repeated using ~ -
10 citronellal in place of veratrole. The not~hed Izod impact `
strength for the citronellal-containing resin was 2.8 foot -
pounds per inch of notch compared to 1.2 foot pounds per inch ~ ;~
of notch for the control.
Example 7
The procedure of Example 6 was repeated using cinnamyl '
alcohol in place of citronellal. The notched Izod impact
strength for the cinnamyl alcohol-containing resin was 2.1
foot pounds per inch o-f notch compared to 1.2 foot pounds per
inch of notch for the control. ~`
~xample 8
The procedure of Example 7 was repeated using
iso-safrol instead of cinnamyl alcohol. The notched Izod
impact strength for the iso-safrol-containing resin was 1.9
foot pounds per inch of notch compared to 1.2 foot pounds per
inch of notch for the controlO
Example 9
,
The procedure of Example 8 was repeated using iso- -
eugenol instead of iso-safrol. The notched Izod impact strength `~
for the iso-eugenol-containing resin was 2.1 foot pounds per
30 inch of notch compared to 1.2 foot pounds per in¢h of notch ~-
for the control.
-8-
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Example 10 -
The procedure of Example 9 was repeated using trans
cinnamaldehyde instead of iso-eugenol. The notched Izod
impact strength for the trans cinnamaldehyde-containing resin ~ -
was 1.6 foot pounds per inch of notch compared to 1.2 foot pounds ;
per inch of notch for the control.
Example 11 ; ;~
The procedure of Example 10 was repeated using
safrole instead of -trans cinnamaldehyde. The notched Izod
impact strength for the safrole-containing resin was 1.6 foot
pounds per inch of notch compared to 1.2 foot pounds per inch
of notch for the control.
Example 12
The procedure of Example 11 was repeated using 4
parts of cineole instead of 10 parts of safrole. The notched
Izod impact strength for the cineole-containing resin was 2.3
foot pounds per inch of notch compared to 1.2 foot pounds per
inch of notch for the control.
Example 13
The procedure of Example 11 was repeated using 8 parts
of anisole instead of 10 parts of safrole. The notched Izod
impact strength for the anisole-containing resin was 2O9 foot
pounds per inch of notch compared to 1.2 foot pounds per inch
of notch for the control.
Example 14
A. A rubber latex was prepared by polymerizing wi-th
continuous agitation at 45C in the substantial absence of
oxygen a mixture of the following ingredients:
' '
~
_g_
.
l~q~3
Ingredient Pa_ s
acrylonitrile 30 ' .
butadiene-1,3 60
emulsifier (Gafac RE-610)* 2.4
azobisisobutyronitrile 0.3 :
~-dodecyl mercaptan 0.5
water 200 ;-~
-
~A mixture of R-o-(cH2cH2otnpo2M2 :
and ER-o-(cH2cH2o~n32po2M whe
n is a number from l to 40, R is
an alkyl or alkaryl group and
preferably a nonyl phenyl group, ~ -
and M is hydrogen, ammonia or an
alkali metal) which aompQsition :
is sold by GAF Corporation. -~
Before reaction was started, the pH of the mixture was adjusted `~
to about 8 with KOH. The polymerization was carried out for ~:
22 and l/2 hours to a conversion of about 92% and a total solids
of about 33.1%.
B. An impact-resistant, gas barrier resin was
prepared by polymeriza-tion of a mixtùre of the following
ingredients:
Ingrèdient Parts
acrylonitrile 75
methyl acrylate 25
rubber solids in the .
form of latex A (above) 9 :~
potassium persulfate 0.06
emulsifier (Gafac RE-610) 3
modifier (n-dodecyl
mercaptan)
-10- ~,
~73~l4~
Ingredient Parts
ethylene diamine 0.05
tetra acetic acid
water 200
The pH adjusted to about 7 with NH40H. The polymerization was
carried out in the substantial absence of oxygen at 60C for 5
hours so as to produce a conversion of 91% of a latex. The -~
latex obtained from the polymerization was then coagulated and
the resin was dried and compression molded into a bar at 150C.
The molded bar was transparent and found to have a notched Izod
impact strength of 1.2 foot pounds per inch of notch and ASTM
heat-distortion temperatures of 69C at 264 psi and 75C at 66
psi by AS1'M test D-648-56. The polymer was easily blended in a
Brabender plasticorder and at the end of 10 minutes in the
plasticorder at 230C and 35 rmp, a torque reading of 1150 meter :
grams was obtained for the polymer. A sample of this polymer
was compression molded into a sheet and this sheet was found
to have a water vapor transmission of 4.51 grams/mil/lOOinches /
24 hours at 90~ relative humidity and 100F by ASTM procedure
E-96. The sheet was found to have an oxygen transmission of 0.6
cc/mil/100 inches /2~ hours/atmosphere by ASTM procedure D-1434.
The sheet was also found to have a frosting index of 6~4 haze t
units. Fros~ing index was obtained by measuring the haze or
refracted light off the piece of the sheet. The sheet was then
subjected to a temperature of 50C and 100~ relative humidity
for 16 hours at which time the haze was redetermined. The
difference in the ha~e readings is the frost index. The haze
readings were done on a Hunter Laboratories color difference
meter model D-25-P.
Example 15
Samples of the resin described in Example 14 we.re
1~3~3 :~
blended with various amounts of triethyl phosphate in an ;
efficient mixer such as a rubber mill, Banbury, extruder or
ko-kneader. The blends were compression molded into test bars
and the notched Izol impact values were determined on the bars
including a control bar containing no oil. The following
results were obtained:
Triethyl
Phosphate, % Notched Izod Impact Strength :-
0 1.2 foot pounds per inch of notch ~ ~.
8 3.2 foot pounds per inch of notch ~ .
5.3 foot pounds per inch of notch
7.8 foot pounds per inch of notch `
Example 16 ~:
The procedure of ~xample 15 was repeated using 10%
of 2-ethyl hexanoic acid in place of 10% of triethyl phosphate
with the following results:
2-Ethyl
Hexanoic .:
Acid, % Notched Izod Impact Strength
0 1.2 foot pounds per inch of notch
3.1 foot pounds per inch of notch
Example 17
The procedure of Example 16 was repeated using
2,4-di-t-butyl phenol in place of 2-ethyl hexanoic acid.
The notched Izod impact strength for the 2,4-di-t-butyl
phenol-containing resin was 1.5 foot pounds per inch of
notch compared to 1.2 foot pounds per inch of notch for
the control. .
Example 18
The procedure of Example 17 was repeated using
trimethyl phosphate in place of 2,4-di-t-butyl phenol.
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;:
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~3143
, '
~he notched Izod impact strength for the trimethyl phosphate-
containing resin was 2.1 foot pounds per inch of notch compared
to 1.2 foot pounds per inch of notch for the control.
Example 19
The procedure of Example 18 was repeated usiny
tributyl phosphate in place o trimethyl phosphate. The ;;~
notched Izod impact strength for the tributyl phosphate-
containing resin was 2.3 foot pounds per inch of notch compared
, - .
to 1.2 foot pounds per inch of notch for the control.
Example 20
The procedure of Example 19 was repeated using
2,6-di-t-butyl-4-methyl phenol in place of tributyl phosphate.
The notched Izod impact strength for the 2,6-di-t-butyl~4-
methyl phenol-containing resin was 2.9 foot pounds per inch
of notch compared to 1.2 foot pounds per inch of notch for the
control.
Example 21 , ,-
,,~.,.:. ",
The procedure of Example 20 was repeated using p-nonyl
phenol instead of 2,6-di-t-butyl-4-methyl phenol. The notched
Izod impact strength for the p-nonyl phenol-containing resin
was 3.1 foot pounds per inch of notch compared to 1.2 foot -
pounds per inch of notch for the control.
Example 22
The procedure of Example 21 was repeated using
4-hexyl resorcinol instead of p-nonyl phenol. The notched
IzQd impact strength for the 4-hexyl resorcinol-containing
resin was 2.1 foot pounds per inch of notch compared to 1.2
foot pounds per inch of notch for the control. ~-~
-13-
:::
1~3~3 ~-
.:
Example 23
The procedure of Example 22 was repeated using
p~butoxy phenol instead of 4-hexyl resorcinol. The notched
Izod impact strength for the p-butoxy phenol-containing resin
was 2.1 foot pounds per inch of notch compared to 1.2 foot
pounds per inch of notch for the control.
Example 24
The procedure of Example 23 was repeated using an ~
epoxidized soybean oil instead of p-butoxy phenol. The notched ` -
I~od impact strength for the epoxidized soybean oil-containing
resin was 7.9 foot pounds per inch of notch compared to 1.2
foot pounds per inch of notch for the control.
Example 25
The procedure of Example 24 was repeated uslng
benzaldehyde instead of epoxidized soybean oil. The notched
Izod impact strength for the benzaldehyde-containing resin waS
2.0 foot pounds per inch of notch compared to 1O2 foot pounds `
per inch of notch for the control. ;~
Example 26
The procedure of Example 25 was repeated using benzil
instead of benzaldehyde. The notched Iæod impact strength for
the benzil-containing resin was 1.7 foot pounds per inch of
notch compared to 1.2 foot pounds per inch of notch for the
control.
Example 27
The procedure of Example 2~ was repeated using benzyl
alcohol instead of benzil. The notched Izod impact strength --
for the benzyl alcohol-containing resin was 2.0 foot pounds per
inch of notch compared to 1.2 foot pounds per inch of notch
for the control.
-14-
''
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~31~3
'.:', '
Example 28 ;~
The procedure of Example 27 was repeated using benzyl
ether instead o benzyl alcohol. The notched Izod impact ;
strength for the benzyl ether-containing resin was 2.8 foot
pounds per inch of notch compared to 1.2 foot pounds per inch
. ~ ~
of notch for the control.
,.;
Example 29
The procedure of Example 28 was repeated using 5% ~ -
of 2,4,6-tri(t-butyl) phenol instead of 10% of benzyl ether.
lO The notched Izod impact strength for the 2,4,6-tri(t-butyl) ~ ~`
phenol~containing resin was 2.9 foot pounds per inch of notch
compared to 1.2 foot pounds per inch of notch for the control.
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