CA1065517A - Thermoplastic moulding compositions consisting of organic cellulose esters and copolymers of olefinically unsaturated nitriles and conjugated diolefins - Google Patents
Thermoplastic moulding compositions consisting of organic cellulose esters and copolymers of olefinically unsaturated nitriles and conjugated diolefinsInfo
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- CA1065517A CA1065517A CA247,580A CA247580A CA1065517A CA 1065517 A CA1065517 A CA 1065517A CA 247580 A CA247580 A CA 247580A CA 1065517 A CA1065517 A CA 1065517A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/10—Esters of organic acids, i.e. acylates
- C08L1/14—Mixed esters, e.g. cellulose acetate-butyrate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/10—Esters of organic acids, i.e. acylates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
THERMOPLASTIC MOULDING COMPOSITIONS CONSISTING OF ORGANIC
CELLULOSE ESTERS AND COPOLYMERS OF OLEFINICALLY UNSATURATED
NITRILES AND CONJUGATED DIOLEFINS
Abstract of the Disclosure Thermoplastic moulding compositions comprising A) 1 to 99 % by weight of at least one cellulose ester of an aliphatic carboxylic acid, B) 99 to 1 % by weight of a copolymer of olefinically unsatu-rated nitriles and conjugated diolefins and which may optionally be modified with C) up to 35 % by weight of a low molecular weight plasticiser, the sum total of components A, B and C amounting to 100 % by weight.
CELLULOSE ESTERS AND COPOLYMERS OF OLEFINICALLY UNSATURATED
NITRILES AND CONJUGATED DIOLEFINS
Abstract of the Disclosure Thermoplastic moulding compositions comprising A) 1 to 99 % by weight of at least one cellulose ester of an aliphatic carboxylic acid, B) 99 to 1 % by weight of a copolymer of olefinically unsatu-rated nitriles and conjugated diolefins and which may optionally be modified with C) up to 35 % by weight of a low molecular weight plasticiser, the sum total of components A, B and C amounting to 100 % by weight.
Description
~365517 This invention relates to thermoplastic moulding compositions, of which the polymertc component conslsts of organic cellulose esters and copoly-mers of olefinically unsaturated ni~riles and con~ugated diolefins, the moulding compositions optionall~ being modified with low molecular weight plasticisers.
It is known tha~ cellulose can be thermoplasticall~ processed only after esterification with certain organic acids and, ln some cases, only after the addition of low molecular weight plasticisers. In principle, the three hydroxyl groups of the anhydroglucose units of the cellulose may be lQ esterlfied with a number of organic acids, of which the esters and mixed esters produced with acetic acid, proplonic acid and butyric acid, namely cellulose acetate, cellulose acetopropionate and cellulose acetobutyrate, have acquired particular commercial significance. Moulding compositions for thermoplastic processing and, for example acetate rayon, block acetate, film substrates for safety films, electrlcal insulating films and lacquers, are produced from esters of this kind.
In practice cellulose acetates cannot be processed ~hermoplastically without ~he addition of low molecular weight plasticisers, because the esters begin to decompose before soten~ng. In the case of cellulose acetopropionic and acetobutyrate, too, the softening and decomposition temperatures are ~fairly close to one another, so that in this case, as in the case of cellu-lose acetate, low molecular weight plasticisers have hitherto had to be worked in*o the e~ters before thermoplastic processing, reducing the process-ing temperature and processing viscosity of the cellulose esters. In some : :
cases, -the plasticise~s also imp.r~e the me~ anical properties ~or example, -the toughness and ~lexibility o~ articles produced there:~`rom. By g~adually adapting the additions of plasticisers to the cellulose esters, it .i.s possible specifically to adjust certain ~echanical properties for example, hardness, toughness, flexural and tensi~le streslgth, dimensional stability under heat and flow.
~he low molecular weight plasticisers used are primarily aliphatic esters oL phthalic acid, adipic acid, azelaic acid, sebacic acid and phosphoric acid, for example dimethyl phthalate, diethyl phthalate, dibutyl adipate, dioctyl adipate, dibutyl a~elate, trichloroethyl phosphate and tributyl phosphate. In ma.ny cases, it is also advantageous to use plast.iciser mixtures.
Although the cellulose ester moulding co~positions modified with low molecu].ar weight plasticisers show very good mechanical proparties, it would be desirable further to improve their dimensional stability under heat and their mechanical properties for oertain applications.
In addition, the plasticisers gradually migrate to the : surface of the mouldings, so that ~or example films of modi~ied cellulose esters cannot be used ~or packagillg certain foodstuffs.
:~: It has n~ surprisingly been fou~d that moulding compositions with extremely good thermoplastic processing properties can be obtained without any of the disadvantages referred to above by mixing cellulose esters with copolymers of olefinically unsaturated nitriles and conjugated diolefins.
Accordingly, the invention provides thermoplastic mouldin~ compositions o~ which the polymer component consists Le A 16 317 - 2 -,.~, 1C~6SS~
of:
1) l to 99% by weight, preferably 50 to 99% by weight of at least one cellulose ester of an aliphatic carboxylic acid; and
It is known tha~ cellulose can be thermoplasticall~ processed only after esterification with certain organic acids and, ln some cases, only after the addition of low molecular weight plasticisers. In principle, the three hydroxyl groups of the anhydroglucose units of the cellulose may be lQ esterlfied with a number of organic acids, of which the esters and mixed esters produced with acetic acid, proplonic acid and butyric acid, namely cellulose acetate, cellulose acetopropionate and cellulose acetobutyrate, have acquired particular commercial significance. Moulding compositions for thermoplastic processing and, for example acetate rayon, block acetate, film substrates for safety films, electrlcal insulating films and lacquers, are produced from esters of this kind.
In practice cellulose acetates cannot be processed ~hermoplastically without ~he addition of low molecular weight plasticisers, because the esters begin to decompose before soten~ng. In the case of cellulose acetopropionic and acetobutyrate, too, the softening and decomposition temperatures are ~fairly close to one another, so that in this case, as in the case of cellu-lose acetate, low molecular weight plasticisers have hitherto had to be worked in*o the e~ters before thermoplastic processing, reducing the process-ing temperature and processing viscosity of the cellulose esters. In some : :
cases, -the plasticise~s also imp.r~e the me~ anical properties ~or example, -the toughness and ~lexibility o~ articles produced there:~`rom. By g~adually adapting the additions of plasticisers to the cellulose esters, it .i.s possible specifically to adjust certain ~echanical properties for example, hardness, toughness, flexural and tensi~le streslgth, dimensional stability under heat and flow.
~he low molecular weight plasticisers used are primarily aliphatic esters oL phthalic acid, adipic acid, azelaic acid, sebacic acid and phosphoric acid, for example dimethyl phthalate, diethyl phthalate, dibutyl adipate, dioctyl adipate, dibutyl a~elate, trichloroethyl phosphate and tributyl phosphate. In ma.ny cases, it is also advantageous to use plast.iciser mixtures.
Although the cellulose ester moulding co~positions modified with low molecu].ar weight plasticisers show very good mechanical proparties, it would be desirable further to improve their dimensional stability under heat and their mechanical properties for oertain applications.
In addition, the plasticisers gradually migrate to the : surface of the mouldings, so that ~or example films of modi~ied cellulose esters cannot be used ~or packagillg certain foodstuffs.
:~: It has n~ surprisingly been fou~d that moulding compositions with extremely good thermoplastic processing properties can be obtained without any of the disadvantages referred to above by mixing cellulose esters with copolymers of olefinically unsaturated nitriles and conjugated diolefins.
Accordingly, the invention provides thermoplastic mouldin~ compositions o~ which the polymer component consists Le A 16 317 - 2 -,.~, 1C~6SS~
of:
1) l to 99% by weight, preferably 50 to 99% by weight of at least one cellulose ester of an aliphatic carboxylic acid; and
2) 99 to 1% by weight, preferably 50 to 1% by weight of a copolymer of olefinically unsaturated nitriles and conjungated diolefins with 10 to 60%
by weight, preferably 20 to 40% by weight of incorporated nitrile monomers.
In particular, the present invention provides a thermoplastic moulding composition comprising A) from 1 to 99% by weigh~ of at least one cellulose ester chosen from the group consisting of cellulose acetobutyrate and cellulose acetopropionate; and B) from 99 to 1~ by weigh~ of a copolymer of acrylonitrile and 1,3-butadiene, wherein the copolymer of component B com-prises from 10 to 60% by weight of acrylonitrile and 90 to 40% by weight of 1,3-butadiene and has a Mooney viscosity ~ML-4, 100C) in the range of from 20 to 100.
The thermoplastic moulding composition additionally contains 0 to 35% by weigh~ and pre~erably 0 to 20% by weight of a low molecular weight plasticiser. The sum total of components 1 and 2 together with the plasticiser amounts to 100% by weight.
The polymer component of the particularly preferred thermoplastic moulding compositions consists of:
1~ 95 to 70% by weight of a cellulose ester of an aliphatic acid and 2) ~ to 30% by weight of a copolymer of acrylonitrile and 1,3-butadiene with lO to 60% by weight of incorporated acrylonitrile.
The moulding composition additionally contains from 0 to 20% by weight of a low molecular weight plasticiser. The sum total of components 1 and 2 toge-ther with the plasticiser amounts to 100 per cent by weight.
Suitable cellulose esters for the production of the moulding com-positlons according to the invention are cellulose esters of aliphatic carboxylic acids containing 1 to 5 carbon atoms, preferably cellulose acetobutyrate and cellulose acetopropionate.
Processes for the production of organic cellulose
by weight, preferably 20 to 40% by weight of incorporated nitrile monomers.
In particular, the present invention provides a thermoplastic moulding composition comprising A) from 1 to 99% by weigh~ of at least one cellulose ester chosen from the group consisting of cellulose acetobutyrate and cellulose acetopropionate; and B) from 99 to 1~ by weigh~ of a copolymer of acrylonitrile and 1,3-butadiene, wherein the copolymer of component B com-prises from 10 to 60% by weight of acrylonitrile and 90 to 40% by weight of 1,3-butadiene and has a Mooney viscosity ~ML-4, 100C) in the range of from 20 to 100.
The thermoplastic moulding composition additionally contains 0 to 35% by weigh~ and pre~erably 0 to 20% by weight of a low molecular weight plasticiser. The sum total of components 1 and 2 together with the plasticiser amounts to 100% by weight.
The polymer component of the particularly preferred thermoplastic moulding compositions consists of:
1~ 95 to 70% by weight of a cellulose ester of an aliphatic acid and 2) ~ to 30% by weight of a copolymer of acrylonitrile and 1,3-butadiene with lO to 60% by weight of incorporated acrylonitrile.
The moulding composition additionally contains from 0 to 20% by weight of a low molecular weight plasticiser. The sum total of components 1 and 2 toge-ther with the plasticiser amounts to 100 per cent by weight.
Suitable cellulose esters for the production of the moulding com-positlons according to the invention are cellulose esters of aliphatic carboxylic acids containing 1 to 5 carbon atoms, preferably cellulose acetobutyrate and cellulose acetopropionate.
Processes for the production of organic cellulose
- 3 -Yi ~06~
es-ters have been known for some time and are described, for example, in Ullmanns Enzyklopadie der technischen Chemie (Verlag Urban ~ Schwar~enberg, Munich-Berlin, 1963), Vol. 5, pages 182 to 201.
Preferred cellulQse acetobutyrates contain from 40 to 500/o of butyric acid, from 15 to 260/o of acetic acid and from n . 75 to l. 950/o of hydroxyl group.
Cellulose acetobutyrates with the ~ollowing composition are particularly preferrecl for the moulding compositions according to the invention: 42 to ~6~o of butyric acid~
18 to 21% of acetic acid and l.0 to l.7~ o-~ hydroxyl group.
Preferred cellulose acetopropionates generally contain from 50 to 63. 5% of propionic acid, from l to 12% of acetic acid and from 1.2 to 1.95% oi` hydroxyl group, and particularly preferred cellulose acetopropionates have the following composition: 54 to 58% of propionic acid, 5 to 8~/o of acetic acid and l.5 to l. 8% of hydroxyl group.
Of the cellulose acetates, it is preferred to use seoondary cellulose acetates.
Both here and in the ~ollowing, percentages represent per cent by weight and parts are parts by weight.
The cellulose esters used, in the form of 2% solutions in acetone, have relative viscosities ('~ r0l) at room temperature of from 3.5 to 4.5 and preferably from 4.0 to 4.5.
Elastomeric components of the moulding compositions according to the invention are binary copolymers, terpolymers or quater polymers, hereinafter referred to as copolymers, of .olefinically unsaturated nitriles and conjugated diolefins, copolymer mixtures also bsing suitable.
~0 The ~lefinically unsaturated nitrile compounds, preferably Le A 16 317 - 4 -S~7 acrylonitrile or its derivatives, correspond to the general ~ormula ~,CN
R - CH = C
in which R represents hydrogen and/or a hydrocarbon radical having 1 to 10 carbon atoms. Examples of hydrocarbon radicals are alkyl, cycloalkyl and aryl, such as methyl, ethyl, isopropyl, tert butyl, octyl, decyl 9 cyclopentyl, cyclohexyl, phenyl, tolyl, xylyl, ethylphenyl, ter-t-butylphenyl, etc.
Acrylonitrile and methacrylonitrile are preferably used.
The conjugated diolefins preferably contain from 4 to 8 carbon a-toms for example 1,3-butadiene, piperylene, isoprene~
1,3-hexadiene, 2,4-hexadiene, 1,3-heptadiene, etc. It is preferred to use 1,3-butadiene because the copolymers produced therefrom have particularly favourable proper-ties.
~ The copolymers are produced from the monomers in the ; presence of radical-forming initiators by known processes of the type described, for example, in Houben-Weyl, Methoden der organischen Chemie, Vol 14/1, ~eorg-Thi~me Verlag, Stuttgart(1961), and in W Hofmann, Nitrilkautschuk, Verlag Berliner Union, Stuttgart (1965). Suitable catalysts include oxides, peroxides, hydroperoxides and azo compounds, etc.
One of the possible polymerisation processes is, for example, emulsion polymerisation which is carried out in aqueous media in the presence of emulsifiers and which is described, for example, on pages 51 et se~ of the above-mentioned book by W.~ofmann.
In addition, the copolymers may be produced by polymerisation carried out in the absence of solvents or precipitants.
Le A 16 317 -- 5 -;S5~
Finally, -the monomers may also be copolymerlsed in solu-tion in the presence of inert organic solvents.
All the processes referred to above may be carried out either continuously or in batches.
The copolymers suitable in accordance with the invention for improving the technological properties of organic cellu-lose esters may contain a total of from 10 to 60 %, preferably from 20 to 40 % 9 of nitrile monomers. Accordingly, the suitable total conten-t of conjugated diolefins amounts to from 9~ to 40 % and preferably from 80 to 60 %.
The Mooney viscosities (ML-4, 100C) determined in accordance with DIN 53 523 o~ acrylonitrile-bu~adiene copoly-mers particularly suitable ~or admixture with organic cellulose esters are in the range from 20 to 100 and pre~erably in the range from 20 to 65.
The low molecular weight plasticisers used are primarily aliphatic esters of phthalic acid, adipic acid, azelaic acid, sebacic aoid and phosphoric acid, for example dlmethyl phtha-late, diethyl phthalate~ dibutyl adipate, dioctyl adipate, dibutyl azelate, trichloroethyl phosphate and tributyl phos-phate. In many cases, it is also ad~antageous to use plasti-ciser mixtures.
Production of the moulding compositions according to the invention from organic cellulose esters and copolymers of olefinioally unsatura-ted nitriles and conjugated diole~ins, which may optionally be modified with low molecular weight plasticisers, is carried out by intensively mixing the components by any known mixing process, for example on miæing rolls or in sclew e~truders.
The mi~tures may also be prepared from solutions. To Le A 16 317 - 6 -~L~6S5~
this end, the components are dissolved ln sui-table solvsnts or solvent mixtures and the polymer mixtures are precipitated with suitable non-solvents. The solvents or solvent mixtures may also be rernoved by e~aporation. Suitable solvents are, for example 7 methylene chloride or acetone; hexane for example may be used as common precipitant.
The mixtures according to the invention may be compounded with certain additives ~or colouring and pigm~nting the polymer mixtures and for improving their resistance to oxidation, light or fire and the like. In addition, fillers and strengthe-ners may be worked into the mixtures.
Given a suitable copolymer content, the mixtures may be crosslinked in the same way as rubber It is also possible to use crosslinked rubbers for producing the mixtures according to the invention.
The moulding compositions according to the invention of organic cellulose esters and copolymers of olefinically unsaturated nitriles and conjugated diolefins show a remarkable increase in notched impact strength as measured in accordance with DIN 53 453.
In addition, the moulding compositions according to the invention are distinguished by improved dimensional stability under heat as measured, for example, in accordance witll DIN 53 460 (Vicat softening temperature).
The Vica-t softening temperatures are up to 25C above the softening temperatures of the cellulose esters modified with corresponding quantities o~ low molecular weight plasticisers.
By comparison with conventional cellulose ester moulding compositions containing low molecular weight plasticisers, Le A 16 317 - 7 -~.
~655~L7 the polymer mix~ures according to the invention additionally show improved mechanical properties, for example, an i.ncrease in hardness, tensile strength, flexural strength and elast.i.city modulus The known effect of so-called plasticiser migration does not occur in the polymer mixtures of organic cellulose esters and copolymers of olefinically ~msa-turated nitriles and conjugated diolefins, so that moulding compositions of this kind are also particularly suitable for e~amp].e for applications involving contact with foodstuffs.
Shaped articles of any kind and also acetate rayon, block acetate, film substrates for safety films, electrical insulating films and lacquers, may be produced from the moulding compositions according to the invention.
.~
, Le A 16 317 - 8 -l~iS~
EXAMPI.ES 1 to 9 Cellulose acetobutyrate conta:ining 42 to 460/o of butyric acid, 18 to 21% o~ acetic acid an~ 1.0 to 107% of hydro~yl groups, was interlsively mixed on m:ixing ro].ls at 180C with 5 5~ 10 and 15%~ respectively, of an acrylonitrile-butadiene copolymer of the -following composition:
.
Acrylonitrile- Acrylonitrile Mooney-visosity butadiene content[ ~ ~ ML-4, 100 C
copolymer .
NBR-2~07 28 + 1 45 ~ 5 NBR-3307 34 + 1 k5 + 5 NBR-3807 39 + 1 45 + 5 The rough sheets were granulated and subsequently injection-moulded into test specimens at a melt temperature of 22~C.
~` The moulding compositions of Examples 1, 4 and 7 were transparent, the rest opaque.
.~ .
~ - 9 i5~7 o V u~
.
:~ o o o o o o o o o C5~ 0 ~ oo u~
~D ~ ~ r~
~ oo ~ ~ o ~ ~ o Z; "~
O ~ co O
V ~ ., ~ oo :~
..-...-.-h h D P ,~ ~ ,D ~ ,D
~ .~
SY
Z o U~ o ~ o U~
~ o o o o o o o o o a: c~ ~ ~ ~ 0 0 oo c~
~a ___ ~ ~6 55 ~
The abbreviations used in the Table have the following meanings:
a : impact strength according to DIN 53 453;
n . dimension: [kJ/m2]
unbr: unbroken ~: not~hed impact s~rength according to DIN 53 453;
- dimension: [kJ/m ]
Vicat: Vicat sot~ning temperature according to method B
(Force: 49.05 N) according to DIN 53 460;
dimension: ~C]
bF' bending flow stress according to DIN 53 452;
. dimension: ~Nlmm2]
: B-E-M: bending elasticity modulus measured under three-point load;
dimension: [N/mm2]
HC30: ball indentation hardness after 30 seconds according : to DIN 53 456;
dimension: [N/mm Le A 16 317 ~o~s~
EXAMPLES 1 to 18 Cellulose acetopropionate containing 54 to 58% of propionic acid, 5 to 8% of acetic acid and 1.5 to 1.8% of llyd.roxyl groups was int0nsively mixe~ on a mixing roll at 185C with 5, 10 and 15 /0, respectively~ of an acrylonitrile-butadiene copolymer of the same composition as in Examples 1 to 9.
The granul.ated rough sheets were injection-moulded in-to test specimens at a melt temperature of 230C.
`; 10 The mouldlng compositions of Examples 13 and 16 were transparent, the rest opaque.
: .
Le A 16 317 - 12 -~Ot;S~ 7 o ooooooooo ,~ ~ o U~ ~ o o o a~ o~ ~ O oo c~
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~:: G o O o o O ~ ~ G
Z o ~ o ~ o U~
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.
Le A 16 317 - 13 -.
5~
EXA~IPLES 19 to 24 The cellulose acetobutyrate previously ~escribed was used in Examples 19 to 21. On this occasion, however, i-t contailled th~ low molecular weight plasticiser (nm-WM) dibu-tyl adipate.
Acrylonitrile-butadien~ rubber of the type described above was worked into these moulding compositions by int;ensive mixing on a mixing roll in thc~same way as in Examples 1 to 9, and further processing was also carried out in the same way as described above.
The same applies as regards Examples 22 to 247 except that in their case the cellulose acetopropionate described above was used as the starting material. The mixtures were prepared and processed in the same way as in Examples 10 to l~.
Le A 16 317 - 14 -~L0655~iL'7 o . ~ U~ ~ ~o ~ U) r~ ~ ~
X o o o ~ o o .
o~ ~ I
U~ .
., ~. ., ., ~ ,, ) ~ ~ oo C~l ~ o o ~ U~ ~
.~ 1 ,~ ~ O r~
oo r~ o~ cr~
'C~ ~D ~ ~ O
' ~ ~ ~ ~ ~
o o ~ U~ U~
.
r~ ,~ ,~ r~ I~ r~
IY O O O O O O
a~ ~ a~ ~ ~ ~ ~
Z .
~ ~ +1 +1 u~ ~ 0~ ~ ~D O
.
CJ~ O -~ c~ .
C~ ~ ~ C~ l .
Le A 16 317 - 15 -
es-ters have been known for some time and are described, for example, in Ullmanns Enzyklopadie der technischen Chemie (Verlag Urban ~ Schwar~enberg, Munich-Berlin, 1963), Vol. 5, pages 182 to 201.
Preferred cellulQse acetobutyrates contain from 40 to 500/o of butyric acid, from 15 to 260/o of acetic acid and from n . 75 to l. 950/o of hydroxyl group.
Cellulose acetobutyrates with the ~ollowing composition are particularly preferrecl for the moulding compositions according to the invention: 42 to ~6~o of butyric acid~
18 to 21% of acetic acid and l.0 to l.7~ o-~ hydroxyl group.
Preferred cellulose acetopropionates generally contain from 50 to 63. 5% of propionic acid, from l to 12% of acetic acid and from 1.2 to 1.95% oi` hydroxyl group, and particularly preferred cellulose acetopropionates have the following composition: 54 to 58% of propionic acid, 5 to 8~/o of acetic acid and l.5 to l. 8% of hydroxyl group.
Of the cellulose acetates, it is preferred to use seoondary cellulose acetates.
Both here and in the ~ollowing, percentages represent per cent by weight and parts are parts by weight.
The cellulose esters used, in the form of 2% solutions in acetone, have relative viscosities ('~ r0l) at room temperature of from 3.5 to 4.5 and preferably from 4.0 to 4.5.
Elastomeric components of the moulding compositions according to the invention are binary copolymers, terpolymers or quater polymers, hereinafter referred to as copolymers, of .olefinically unsaturated nitriles and conjugated diolefins, copolymer mixtures also bsing suitable.
~0 The ~lefinically unsaturated nitrile compounds, preferably Le A 16 317 - 4 -S~7 acrylonitrile or its derivatives, correspond to the general ~ormula ~,CN
R - CH = C
in which R represents hydrogen and/or a hydrocarbon radical having 1 to 10 carbon atoms. Examples of hydrocarbon radicals are alkyl, cycloalkyl and aryl, such as methyl, ethyl, isopropyl, tert butyl, octyl, decyl 9 cyclopentyl, cyclohexyl, phenyl, tolyl, xylyl, ethylphenyl, ter-t-butylphenyl, etc.
Acrylonitrile and methacrylonitrile are preferably used.
The conjugated diolefins preferably contain from 4 to 8 carbon a-toms for example 1,3-butadiene, piperylene, isoprene~
1,3-hexadiene, 2,4-hexadiene, 1,3-heptadiene, etc. It is preferred to use 1,3-butadiene because the copolymers produced therefrom have particularly favourable proper-ties.
~ The copolymers are produced from the monomers in the ; presence of radical-forming initiators by known processes of the type described, for example, in Houben-Weyl, Methoden der organischen Chemie, Vol 14/1, ~eorg-Thi~me Verlag, Stuttgart(1961), and in W Hofmann, Nitrilkautschuk, Verlag Berliner Union, Stuttgart (1965). Suitable catalysts include oxides, peroxides, hydroperoxides and azo compounds, etc.
One of the possible polymerisation processes is, for example, emulsion polymerisation which is carried out in aqueous media in the presence of emulsifiers and which is described, for example, on pages 51 et se~ of the above-mentioned book by W.~ofmann.
In addition, the copolymers may be produced by polymerisation carried out in the absence of solvents or precipitants.
Le A 16 317 -- 5 -;S5~
Finally, -the monomers may also be copolymerlsed in solu-tion in the presence of inert organic solvents.
All the processes referred to above may be carried out either continuously or in batches.
The copolymers suitable in accordance with the invention for improving the technological properties of organic cellu-lose esters may contain a total of from 10 to 60 %, preferably from 20 to 40 % 9 of nitrile monomers. Accordingly, the suitable total conten-t of conjugated diolefins amounts to from 9~ to 40 % and preferably from 80 to 60 %.
The Mooney viscosities (ML-4, 100C) determined in accordance with DIN 53 523 o~ acrylonitrile-bu~adiene copoly-mers particularly suitable ~or admixture with organic cellulose esters are in the range from 20 to 100 and pre~erably in the range from 20 to 65.
The low molecular weight plasticisers used are primarily aliphatic esters of phthalic acid, adipic acid, azelaic acid, sebacic aoid and phosphoric acid, for example dlmethyl phtha-late, diethyl phthalate~ dibutyl adipate, dioctyl adipate, dibutyl azelate, trichloroethyl phosphate and tributyl phos-phate. In many cases, it is also ad~antageous to use plasti-ciser mixtures.
Production of the moulding compositions according to the invention from organic cellulose esters and copolymers of olefinioally unsatura-ted nitriles and conjugated diole~ins, which may optionally be modified with low molecular weight plasticisers, is carried out by intensively mixing the components by any known mixing process, for example on miæing rolls or in sclew e~truders.
The mi~tures may also be prepared from solutions. To Le A 16 317 - 6 -~L~6S5~
this end, the components are dissolved ln sui-table solvsnts or solvent mixtures and the polymer mixtures are precipitated with suitable non-solvents. The solvents or solvent mixtures may also be rernoved by e~aporation. Suitable solvents are, for example 7 methylene chloride or acetone; hexane for example may be used as common precipitant.
The mixtures according to the invention may be compounded with certain additives ~or colouring and pigm~nting the polymer mixtures and for improving their resistance to oxidation, light or fire and the like. In addition, fillers and strengthe-ners may be worked into the mixtures.
Given a suitable copolymer content, the mixtures may be crosslinked in the same way as rubber It is also possible to use crosslinked rubbers for producing the mixtures according to the invention.
The moulding compositions according to the invention of organic cellulose esters and copolymers of olefinically unsaturated nitriles and conjugated diolefins show a remarkable increase in notched impact strength as measured in accordance with DIN 53 453.
In addition, the moulding compositions according to the invention are distinguished by improved dimensional stability under heat as measured, for example, in accordance witll DIN 53 460 (Vicat softening temperature).
The Vica-t softening temperatures are up to 25C above the softening temperatures of the cellulose esters modified with corresponding quantities o~ low molecular weight plasticisers.
By comparison with conventional cellulose ester moulding compositions containing low molecular weight plasticisers, Le A 16 317 - 7 -~.
~655~L7 the polymer mix~ures according to the invention additionally show improved mechanical properties, for example, an i.ncrease in hardness, tensile strength, flexural strength and elast.i.city modulus The known effect of so-called plasticiser migration does not occur in the polymer mixtures of organic cellulose esters and copolymers of olefinically ~msa-turated nitriles and conjugated diolefins, so that moulding compositions of this kind are also particularly suitable for e~amp].e for applications involving contact with foodstuffs.
Shaped articles of any kind and also acetate rayon, block acetate, film substrates for safety films, electrical insulating films and lacquers, may be produced from the moulding compositions according to the invention.
.~
, Le A 16 317 - 8 -l~iS~
EXAMPI.ES 1 to 9 Cellulose acetobutyrate conta:ining 42 to 460/o of butyric acid, 18 to 21% o~ acetic acid an~ 1.0 to 107% of hydro~yl groups, was interlsively mixed on m:ixing ro].ls at 180C with 5 5~ 10 and 15%~ respectively, of an acrylonitrile-butadiene copolymer of the -following composition:
.
Acrylonitrile- Acrylonitrile Mooney-visosity butadiene content[ ~ ~ ML-4, 100 C
copolymer .
NBR-2~07 28 + 1 45 ~ 5 NBR-3307 34 + 1 k5 + 5 NBR-3807 39 + 1 45 + 5 The rough sheets were granulated and subsequently injection-moulded into test specimens at a melt temperature of 22~C.
~` The moulding compositions of Examples 1, 4 and 7 were transparent, the rest opaque.
.~ .
~ - 9 i5~7 o V u~
.
:~ o o o o o o o o o C5~ 0 ~ oo u~
~D ~ ~ r~
~ oo ~ ~ o ~ ~ o Z; "~
O ~ co O
V ~ ., ~ oo :~
..-...-.-h h D P ,~ ~ ,D ~ ,D
~ .~
SY
Z o U~ o ~ o U~
~ o o o o o o o o o a: c~ ~ ~ ~ 0 0 oo c~
~a ___ ~ ~6 55 ~
The abbreviations used in the Table have the following meanings:
a : impact strength according to DIN 53 453;
n . dimension: [kJ/m2]
unbr: unbroken ~: not~hed impact s~rength according to DIN 53 453;
- dimension: [kJ/m ]
Vicat: Vicat sot~ning temperature according to method B
(Force: 49.05 N) according to DIN 53 460;
dimension: ~C]
bF' bending flow stress according to DIN 53 452;
. dimension: ~Nlmm2]
: B-E-M: bending elasticity modulus measured under three-point load;
dimension: [N/mm2]
HC30: ball indentation hardness after 30 seconds according : to DIN 53 456;
dimension: [N/mm Le A 16 317 ~o~s~
EXAMPLES 1 to 18 Cellulose acetopropionate containing 54 to 58% of propionic acid, 5 to 8% of acetic acid and 1.5 to 1.8% of llyd.roxyl groups was int0nsively mixe~ on a mixing roll at 185C with 5, 10 and 15 /0, respectively~ of an acrylonitrile-butadiene copolymer of the same composition as in Examples 1 to 9.
The granul.ated rough sheets were injection-moulded in-to test specimens at a melt temperature of 230C.
`; 10 The mouldlng compositions of Examples 13 and 16 were transparent, the rest opaque.
: .
Le A 16 317 - 12 -~Ot;S~ 7 o ooooooooo ,~ ~ o U~ ~ o o o a~ o~ ~ O oo c~
~ ~ ~0 0 ~1 ' ~ ~0 ~`1~ O ~ C~ ~ ~1 0 ~D
~i i ~, ~
~:~ ~o ~d J _I ~') ~t) .1 ~ r~ ~ ~
~:: G o O o o O ~ ~ G
Z o ~ o ~ o U~
~ ooooooooo æ c~ c~ c~ ~ ~ ~ tY7 ~ O ~
.
Le A 16 317 - 13 -.
5~
EXA~IPLES 19 to 24 The cellulose acetobutyrate previously ~escribed was used in Examples 19 to 21. On this occasion, however, i-t contailled th~ low molecular weight plasticiser (nm-WM) dibu-tyl adipate.
Acrylonitrile-butadien~ rubber of the type described above was worked into these moulding compositions by int;ensive mixing on a mixing roll in thc~same way as in Examples 1 to 9, and further processing was also carried out in the same way as described above.
The same applies as regards Examples 22 to 247 except that in their case the cellulose acetopropionate described above was used as the starting material. The mixtures were prepared and processed in the same way as in Examples 10 to l~.
Le A 16 317 - 14 -~L0655~iL'7 o . ~ U~ ~ ~o ~ U) r~ ~ ~
X o o o ~ o o .
o~ ~ I
U~ .
., ~. ., ., ~ ,, ) ~ ~ oo C~l ~ o o ~ U~ ~
.~ 1 ,~ ~ O r~
oo r~ o~ cr~
'C~ ~D ~ ~ O
' ~ ~ ~ ~ ~
o o ~ U~ U~
.
r~ ,~ ,~ r~ I~ r~
IY O O O O O O
a~ ~ a~ ~ ~ ~ ~
Z .
~ ~ +1 +1 u~ ~ 0~ ~ ~D O
.
CJ~ O -~ c~ .
C~ ~ ~ C~ l .
Le A 16 317 - 15 -
Claims (14)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A thermoplastic moulding composition comprising A) from 1 to 99%
by weight of at least one cellulose ester chosen from the group consisting of cellulose acetobutyrate and cellulose acetopropionate; and B) from 99 to 1%
by weight of a copolymer of acrylonitrile and 1,3-butadiene, wherein the co-polymer of component B comprises from 10 to 60% by weight of acrylonitrile and 90 to 40% by weight of 1,3-butadiene and has a Mooney viscosity (ML-4, 100°C) in the range of from 20 to 100.
by weight of at least one cellulose ester chosen from the group consisting of cellulose acetobutyrate and cellulose acetopropionate; and B) from 99 to 1%
by weight of a copolymer of acrylonitrile and 1,3-butadiene, wherein the co-polymer of component B comprises from 10 to 60% by weight of acrylonitrile and 90 to 40% by weight of 1,3-butadiene and has a Mooney viscosity (ML-4, 100°C) in the range of from 20 to 100.
2. A thermoplastic moulding composition as claimed in claim 1, which also comprises C) up to 35% by weight of a low molecular weight plasticiser, the sum total of components A, B and C amounting to 100% by weight.
3. A thermoplastic moulding composition as claimed in claim 2 in which the low molecular weight plasticiser is a member of the group consisting of aliphatic esters of phthalic acid, adipic acid, acelaic acid, sebacic acid and phosphoric acid.
4. A thermoplastic moulding composition as claimed in claim 1 com-prising A) from 50 to 99% by weight of at least one cellulose ester chosen from the group consisting of cellulose acetobutyrate and cellulose aceto-propionate; and B) from 1 to 50% by weight of a copolymer of acrylonitrile and 1,3-butadiene, wherein the copolymer of component B comprises from 10 to 60% by weight of acrylonitrile and 90 to 40% by weight of 1,3-butadiene and has a Mooney viscosity in the range from 20 to 100.
5. A thermoplastic moulding composition as claimed in claim 4, which also comprises C) up to 20% by weight of a low molecular weight plasticiser, the sum total of components A, B and C amounting to 100% by weight.
6. A thermoplastic moulding composition as claimed in claim 1 com-prising A) from 95 to 70% by weight of a least one cellulose ester chosen from the group consisting of cellulose acetobutyrate and cellulose aceto-propionate; and B) from 5 to 30% by weight of a copolymer of acrylonitrile and 1,3-butadiene wherein the copolymer of component B comprises from 10 to 60% by weight of acrylonitrile and 90 to 40% by weight of 1,3-butadiene and has a Mooney viscosity in the range of from 20 to 100.
7. A thermoplastic moulding composition as claimed in claim 6, which also comprises up to 20% by weight of a low molecular weight plasticiser, the sum total of components A, B and C amounting to 100% by weight.
8. A thermoplastic moulding composition as claimed in claim 1, com-prising as component B from 20 to 40% by weight of acrylonitrile and 80 to 60% of 1,3-butadiene.
9. A thermoplastic moulding composition as claimed in claim 1 wherein the cellulose ester of component A is cellulose acetobutyrate.
10. A thermoplastic moulding composition as claimed in claim 1 wherein the cellulose ester of component A is cellulose acetopropionate.
11. A thermoplastic composition as defined in either of claims 1, 2 or 3 wherein the copolymer of component B has a Mooney viscosity in the range of 20 to 65.
12. A thermoplastic composition as defined in either of claims 4, 5 or 6 wherein the copolymer of component B has a Mooney viscosity in the range of 20 to 65.
13. A thermoplastic composition as defined in either of claims 7 or 8 wherein the copolymer of component B has a Mooney viscosity in the range of 20 to 65.
14. A thermoplastic composition as defined in either of claims 9 or 10 wherein the copolymer of component B has a Mooney viscosity in the range of 20 to 65.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19752510763 DE2510763C2 (en) | 1975-03-12 | 1975-03-12 | Thermoplastic molding compounds, consisting of cellulose esters of an aliphatic carboxylic acid, copolymers of olefinically unsaturated nitriles and conjugated diolefins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1065517A true CA1065517A (en) | 1979-10-30 |
Family
ID=5941160
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA247,580A Expired CA1065517A (en) | 1975-03-12 | 1976-03-10 | Thermoplastic moulding compositions consisting of organic cellulose esters and copolymers of olefinically unsaturated nitriles and conjugated diolefins |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS51112868A (en) |
| BE (1) | BE839432A (en) |
| CA (1) | CA1065517A (en) |
| DE (1) | DE2510763C2 (en) |
| FR (1) | FR2303829A1 (en) |
| GB (1) | GB1527527A (en) |
| IT (1) | IT1057947B (en) |
| NL (1) | NL7602571A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2573519C1 (en) * | 2014-07-30 | 2016-01-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Московский государственный университет дизайна и технологии" (ФГБОУ ВПО "МГУДТ") | Elastic thermoplastic ether-cellulose composition |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1004204A (en) * | 1962-11-09 | 1965-09-15 | Teijin Ltd | A cellulose ester-polyolefin thermoplastic composition for producing shaped articles |
-
1975
- 1975-03-12 DE DE19752510763 patent/DE2510763C2/en not_active Expired
-
1976
- 1976-03-08 GB GB913076A patent/GB1527527A/en not_active Expired
- 1976-03-10 JP JP2518576A patent/JPS51112868A/en active Pending
- 1976-03-10 CA CA247,580A patent/CA1065517A/en not_active Expired
- 1976-03-10 IT IT4849576A patent/IT1057947B/en active
- 1976-03-11 BE BE165050A patent/BE839432A/en not_active IP Right Cessation
- 1976-03-11 NL NL7602571A patent/NL7602571A/en not_active Application Discontinuation
- 1976-03-12 FR FR7607225A patent/FR2303829A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| BE839432A (en) | 1976-09-13 |
| FR2303829A1 (en) | 1976-10-08 |
| DE2510763C2 (en) | 1984-01-05 |
| IT1057947B (en) | 1982-03-30 |
| NL7602571A (en) | 1976-09-14 |
| DE2510763A1 (en) | 1976-09-23 |
| GB1527527A (en) | 1978-10-04 |
| JPS51112868A (en) | 1976-10-05 |
| FR2303829B1 (en) | 1979-05-18 |
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