CA1071786A - Thermoplastic moulding compound of cellulose esters and ethylene/vinyl ester copolymers - Google Patents
Thermoplastic moulding compound of cellulose esters and ethylene/vinyl ester copolymersInfo
- Publication number
- CA1071786A CA1071786A CA227,858A CA227858A CA1071786A CA 1071786 A CA1071786 A CA 1071786A CA 227858 A CA227858 A CA 227858A CA 1071786 A CA1071786 A CA 1071786A
- Authority
- CA
- Canada
- Prior art keywords
- weight
- percent
- moulding compound
- cellulose
- vinyl ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
- C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
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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)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Materials For Medical Uses (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
It is known that cellulose esters are difficult to use in thermo-plastic moulding applications as a result of their tendency to thermally degrade. The present invention seeks to overcome this drawback by providing thermoplastic moulding compounds consisting essentially of 1) at least one cellulose ester of an aliphatic carboxylic acid, 2) an ethylene/vinyl ester copolymer containing 30 to 98 percent by weight of vinyl esters and 3) optionally a low molecular weight plasticiser. Such compounds may be used in moulding transparent cellulosic articles.
Additionally, such compositions result in products which have superior physical and mechanical properties over those of the prior art.
It is known that cellulose esters are difficult to use in thermo-plastic moulding applications as a result of their tendency to thermally degrade. The present invention seeks to overcome this drawback by providing thermoplastic moulding compounds consisting essentially of 1) at least one cellulose ester of an aliphatic carboxylic acid, 2) an ethylene/vinyl ester copolymer containing 30 to 98 percent by weight of vinyl esters and 3) optionally a low molecular weight plasticiser. Such compounds may be used in moulding transparent cellulosic articles.
Additionally, such compositions result in products which have superior physical and mechanical properties over those of the prior art.
Description
107~786 This invention relates to transparent thermoplastic moulding compounds which comprise organic cellulose esters and ethylene/
vinyl ester copolymers and optionally low molecular weight plasti-cizers.
5~ It is well known that cellulose can be thermoplastically processed only after it has been esterified with certain organic acids, and even then, in many cases only after incorporation of low molecular weight plasticizers into the esterified product.
The three hydroxyl groups of the anhydroglucose units of cellulose I
are capable of being esterified with numerous organic acids but in practice only cellulose acetates, cellulose acetopropionates and cellulose acetobutyrates are used to any significant extent for this purpose. These esters are used to produce moulding com-¦ pounds which can be thermoplastically processed as well as pro-ducts such as acetate silk, block acetate, foil substrates forsafety films, electric lnsulating foils and lacquers.
Moulding compounds of cellulose acetate cannot be thermoplastically processed without the addition of low mole cular weight plasticizers because cellulose acetate begins to deco~pose before it softens. Cellulose acetopropionates and cellulose acetobutyrates also have their softening point and decomposition point fairly close together so tha-t moulding ccmpounds prepared from these esters must also be mixed with low molecular weight plasticizers before they are thermo-plastically processed. The addition of such plasticizers reduces the operating temperature and viscosity as required.
The plasticizers used for organic cellulose esters are mainly the aliphatic esters of phthalic acid, adipic acid, azelaic acid, sebacic acid and phosphoric acid~ for example dimethylphthalate, diethylphthalate, dibutyl adipate, dioctyla-Le A 15 757 ..
``" ` 107~786 dipate~ dibutylazelate~ trichloroethyl phosphate and tributylphosphate. It is also advantageous to use mixtures of plasticizers.
Although cellulose ester moulding compounds which have been modified with plasticizers are sufficiently transparent~ it would for many purposes be desirable to improve their dimensional stability under heat. Furthermore, the plasticizers migrate to the surface of the moulded articles over a period of time so that, for example, foils made of modified cellulose esters cannot be used for packaging certain foodstuffs.
Mixtures of organic cellulose esters~ low molecular weight plasti-cizers and olefine polymers have been described in German Auslegeschrift No.
1?303,219 = British patent specification No. 1,004,204. However, such mould-ing compounds are no longer transparent if they have a high olefine polymer content. Moreover, the plasticizers used in these mixtures are the conven- `
tional low molecular weight esters, which have the weIl known disadvantages.
It has now surprisingly been found that transparent moulding com-pounds which can be thermoplastically processed as required can be obtained without the disadvantages mentioned above if cellulose esters are mixed with copolymers of ethylene and vinyl esters.
This invention therefore relates to thermoplastic moulding com-pounds consisting essentially of 1) 1 to 99 percent by weight, preferably 50 to 98.99 percent by weight~ of at least one cellulose ester of an aliphatic carboxylic acid,
vinyl ester copolymers and optionally low molecular weight plasti-cizers.
5~ It is well known that cellulose can be thermoplastically processed only after it has been esterified with certain organic acids, and even then, in many cases only after incorporation of low molecular weight plasticizers into the esterified product.
The three hydroxyl groups of the anhydroglucose units of cellulose I
are capable of being esterified with numerous organic acids but in practice only cellulose acetates, cellulose acetopropionates and cellulose acetobutyrates are used to any significant extent for this purpose. These esters are used to produce moulding com-¦ pounds which can be thermoplastically processed as well as pro-ducts such as acetate silk, block acetate, foil substrates forsafety films, electric lnsulating foils and lacquers.
Moulding compounds of cellulose acetate cannot be thermoplastically processed without the addition of low mole cular weight plasticizers because cellulose acetate begins to deco~pose before it softens. Cellulose acetopropionates and cellulose acetobutyrates also have their softening point and decomposition point fairly close together so tha-t moulding ccmpounds prepared from these esters must also be mixed with low molecular weight plasticizers before they are thermo-plastically processed. The addition of such plasticizers reduces the operating temperature and viscosity as required.
The plasticizers used for organic cellulose esters are mainly the aliphatic esters of phthalic acid, adipic acid, azelaic acid, sebacic acid and phosphoric acid~ for example dimethylphthalate, diethylphthalate, dibutyl adipate, dioctyla-Le A 15 757 ..
``" ` 107~786 dipate~ dibutylazelate~ trichloroethyl phosphate and tributylphosphate. It is also advantageous to use mixtures of plasticizers.
Although cellulose ester moulding compounds which have been modified with plasticizers are sufficiently transparent~ it would for many purposes be desirable to improve their dimensional stability under heat. Furthermore, the plasticizers migrate to the surface of the moulded articles over a period of time so that, for example, foils made of modified cellulose esters cannot be used for packaging certain foodstuffs.
Mixtures of organic cellulose esters~ low molecular weight plasti-cizers and olefine polymers have been described in German Auslegeschrift No.
1?303,219 = British patent specification No. 1,004,204. However, such mould-ing compounds are no longer transparent if they have a high olefine polymer content. Moreover, the plasticizers used in these mixtures are the conven- `
tional low molecular weight esters, which have the weIl known disadvantages.
It has now surprisingly been found that transparent moulding com-pounds which can be thermoplastically processed as required can be obtained without the disadvantages mentioned above if cellulose esters are mixed with copolymers of ethylene and vinyl esters.
This invention therefore relates to thermoplastic moulding com-pounds consisting essentially of 1) 1 to 99 percent by weight, preferably 50 to 98.99 percent by weight~ of at least one cellulose ester of an aliphatic carboxylic acid,
2) 99 to 1 percent by weight, preferably 1 to 50 percent by weight of an ethylene/vinyl ester copolymer containing 30 to less than 72 percent by weight~ preferably 60 to 70 percent by weight of vinyl esters arld
3) o to 35 percent by weight, preferably 0.01 to 20 percent by weight of a low molecular weight plasticizer. The sum of components 1) ~.~
~,.
to 3) is 100 percent by weight.
Thermoplastic moulding compounds which are particularly preferred consist essentially of 1) 95 to 70 percent by weight, preferably 94.99 to 70 percent by weight of at least one cellulose ester of an aliphatic acid, 2~ 5 to 30 percent by weight of an ethylene/vinyl acetate copolymer containing 30 to less than 72 percent by weight, preferably 60 to 70 percent by weight of vinyl acetate and 3) 0 to 20 percent by weight~ preferably 0.01 to 20 percent by weight of a low molecular weight plasticizer. The sum of components 1) to 3) is 100 percent by weight.
One particularly surprising feature of the moulding compounds ac cording to the invention is their transparency and their very good mechanical properties.
Suitable cellulose esters for the preparation of the moulding com-pounds according to the invention are cellulose esters of aliphatic carboxylic ; acids containing 1 to 5 carbon atoms, particularly cellulose acetate, cellu-lose acetopropionate and cellulose acetobutyrate.
Processes for the preparation of organic cellulose esters have been known for a long time and have been described, for example, in Ullmanns Encyklop~die der technischen Chemie (Publishers Urban ~ Schwarzenberg, Munich-Berlin, 1963) in Volume 5 on pages 182 to 201.
Preferred cellulose acetobutyrates contain 40 to 50% of butyric acid, 15 to 26~ of acetic acid and ~.75 to 1.95~ of hydroxyl.
Cellulose acetobutyrates of the following composition are particularly suitable for the moulding compounds according to the invention: `
42 to 46% of butyric acid~
18 to 21~ of acetic acid and -~ 1.O to 1.7~ of hydroxyl.
~ Preferred cellulose acetopropionates generally contain -;10~ 50 to 63.5~ of propionic acid, 1 to 12~ of acetic acid and 1.2 to 1.95~ of hydroxyl and particularly preferred cellulose acetopropionates have the following comp~sition:
54 to 5~ of propionic acid, ; 5 to ~ of acetic acid and ' 1.5 to 1.8% of hydroxyl.
1~ i The c~llulose acetates used are preferably secondary ,, j cellulose acetates.
Th~ percentages given here and in the following are percentages by weight and parts are parts by weight.
' ! . , The relative viscosities (~ rel) of 2 % solutions of the aliphatic cellulose esters used in acetone at 25C are between ` 3.5 and 4.5 and preferably between 4.0 and 4.5.
~- 25 The vinyl esters used may be organic vinyl esters of satu-rated, optionally halogenated, in particular chlorinated, alipha-tic monocarboxylic acids containing 1 to 18 carbon atoms or aro-matic monocarboxylic acids containing 7 to 11 carbon atoms. The following are specific examples: Vinyl formate, vinyl acetate, vinyl propionate, vinyl chloropropionate, vinyl butyrate, -~ Le A 15 757 _ 4 _ vinylisobutyrate, vinyl caproate, vinyl laurate, vinyl myristate, vinyl stearate and vin~l benzoate. Vinyl acetate is preferred.
The ethylene/vinyl ester copolymers are prepared by the known methods of high or medium pressure synthesis, optionally in solve~ts such as tertiary butanol.
Ethylene/vinyl ester copolymers prepared by high pressure synthesis have melt index values (according to DIN 53 735 at 190C
and under a load of 2.16 kp) of between 0.1 and 100, preferably between 1.0 and 10 and more particularly between 4.5 and 6. Their intrinsic viscosities measured in tetralin at 120C are generally between 0.6 and 1.5. The molecular weights determined by the light diffusion method are preferably between 50,000 and 1,000,000. The non-uniformity U defined by the term /Mn ~ 1 (G.Schulz, Z. phys. Chem (B) 43 (1939) pages 25-34) is in the region of 5 to 30. These copolymers dissolved most easily ; in hot hydrocarbons.
Ethylene/vinyl ester copolymers prepared, for example, by the process of solution or emulsion polymerisation, which contain e.g. 30 to 98 % by weight and preferably 60 to 80 % by weight of vinyl esters, may have melt index values (190C 2.16 kp) greater than 100 and the melt index is preferably below 15 and in parti-cular between 0.5 and 5. The molecular weights determined by the method of light diffusion are preferably between 40,000 and 1,000,000. The non-uniformity U is 1 to 6. The copolymers are soluble in hydrocarbons and alcohols and preferably have intrin-sic viscosities of between 0.5 and 2.5, measured in toluene at 25C.
The ethylene/vinyl acetate copolymers may be partly or completely 20 to 100 % saponified if desired.
Composition and melt indices of the ethylene/vinyl acetate copolymers used:
¦ Le A 15 757 - 5 -~' .
,.. . ,, . . , .. _ . __. _ ~
. . .
Name Vinyl acetate M~I
~ content [~]
-- , EVA - 800 78 0 ~15 E~A - 700 70 3 5 EVA - 600 60 10.4 EVA - ~l50 4~ 0 54 EVA ~ ~38 33 64 In tHe above table:
E~A: Ethylene/vinyl acetate copolymer MFI: Melt index [g/10 min] according to DIN 53 735 under a load of 2.16 kp and at a temperature of 190C.
Suitable low molecular weight plasticizers include dimethylphthalate; diethylphthalate; triphenylphosphate;
methyl phthalyl ethyl glycollate; di-n-butylsebacate;
ethylphthalyl ethyl glycollate; butyl phthalyl butyl glycollate; dibutylphthalate; dioctyladipate; dioctyl-I phthalate; butylbenzyl phthalate and triacetin.
Preparation of the moulding compounds according to the invention from organic cellulose esters and ethylene/vinyl ester copolymers which may, if desired, be modified with low molecular weight plasticizers is carried out by vigorously mixing the components. Any known mixing method may be used on rollers or in serew extruders, The mixtures may also be prepared via their solutions.
In that case, the components are dissolved in suitable solvents or solvent mixtures, and the polymer mixtures may be precipi-tated with suitable non-solvents or the solvents or solvent mixtures may be removed by evaporation. Methylene chloride Le A 15 757 - 6 -. ~ .
~ ' 107~786 and ~laciai acetic acid, for example, are suitable solvents for organic cellulose esters and ethylene/vinyl ester copolymers.
The mutual precipitating agent used may be hexane, for example, if the components have been dissolved in methylene chloride.
The mixtures according to the invention may also contain certain other additives to colour or pigment the polymer mixtures or improve their resistance to oxidation, light or combustion and the li~e.
The moulding compounds according to the invention prepared from ethylene/vinyl ester copolymers and organic cellulose esters show a remarkable increase in the notched impact strength measured according to DIN 53 453.
In addition, the moulding compounds according to the invention are distinguished by their improved dimensional ; 15 stability at elevated temperature determined e.g. as the Vicat softening temperature according to DIN 53 460.
The Vicat softening temperatures are up to 40C higher than the corresponding softening temperatures of cellulose esters which have been modified with low molecular weight - 20 plasticizers.
Compared with conventional cellulose ester moulding compounds which contain low molecular weight plasticizers, ~ the polymer mixtures according to the invention also show ; improved mechanical properties such as an increase in their ~` 25 hardness, tensile strength, flexural strength and modulus of elasticity.
The polymer mixtures of organic cellulose esters and ethylene/vinyl ester copolymers are virtually free from the well known effect of so-called plasticizer migration and 3o the moulding compounds are therefore also particularly Le A 15 757 _ 7 _ ~ suitable, for example, for purposes in which they come into con-: tact with foodstuffs.
~ I The improved resistance of the mixturesto hot air makes it ; possible for them to be used for outdoor garments, 5 I The moulding compounds according to ~the invention can be used for the production of shaped articles of any kind and for the production of acetate silk, block acetate, foil substrates for safety films, packaging material, electric insulating foils and lacquers.
Mixtures of organic cellulose esters and ethylene/vinyl ; ester copalymers can be processed contînuously or batchwise in ~: known extruders and injection moulding machines without any sub-:~ stantial difficulty and have good fluidity properties under these conditions.
l ~ ' :
~ ' , .
~ ~ Le A 15 757 - 8 -.
... .. . . _ .
~; ~ 1071786 ..
;~ Examples l_to 15 , I
"'`'`'`''''''` .. I
Cellulose acetobutyrate containing 42 to 46~ of butyric acid, 18 to 21~ of acetic acid and 1~0 to 1.7% o~ hydroxyl groups is vigorously mixed with ethylene/vinyl acetate co-polymers on rollers at 170C as indicated in the following Table.
¦ The rolled sheets are granulated and then extruded in an injection moulding apparatus at a mass te~perature of 230C
¦ 10 to form test samples.
In the examples marked L, the polymer mixtures are prepared as solutions and then precipitated. The appropriate -~; parts by volume of 10~ methylene chloride solutions of 'i~ cellulose acetobutyrate and of ethylene/vinyl acetate co-polymer are mixed and the polymer mixture is precipitated with hexane. The resulting mixtures are dried and then extrudéd to form test samples as mentioned above.
~ .
..., ,~ ~ """
i Le A 15 757 - ~ -, :
` ~`` ` 1071786 ~ I I I 1 1-1 ' ~i U~ O O Ll~ O O O O O Lt~ O O 1-~ 0 .- 2 ~ _ _ .
a ~
o I $ o ~ 1;
~ 1 _ _ i Lr~ (~ Lr~ 11~ ~U '-- . . (~ Lr~ LS'~
¦~ -- Ll~ Lt~ Lt\ LS~ r ~ ~ Lr~ ~ U~ =i ¦ h ~ ~ D Ll~ C' Lr~ L ~ 0 0 1~ ~ ID L~\ 1 ~ _ _ ~ i ~
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:
r~ ; X ~ ~ ~ D C~ 0 CS~ O O ~ ~ L
~ ' , ' - --___ ~,"q Le A 15 757 10 ~`~ 1071786 ~ 1 , I .
~ ~.
. ~egend to Table:
'' a~.~ Imp~ct strength accordin~ to DIN 5~ 453;
Dimension: ~kJ/m2].
ak: Notched impact strength accordinæ to DIN 53 453;
Dimension: [kJ/m2].
Vicat: Vicat softening temperature according to Method B .¦
(Force: 49.05 N) according to DIN 53 460;
Dimension: [C]. I
~b~: Bending yield stress according to DIN 53 452;
Dimension: [N/mm2~.
.. ~ . f : sagging at ~b~:
. Dimension; ~mm~.
Hk30: Ball pressure hardness after 30 s according to DIN 53 456; 2 Dimension: [rl/mm ].
~ ~ 3y~ ~ deno~es giass clear transparcncyr~ - denotes opaque.
.' ~ . . ' ,.
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~} .~, .-i^;~,'. ' .
J'~.,,, .
2 ~ .
'''' I Le A 15 757 _ 11 -.
i,;,,.~ ' ~, ,, ,,~' ' .
:
~ 1071786 `-` .. I
.-, Examples 16 to 29:
Cellulose acetopropionate containing 54 to 58~ of propionic acid, 5 to 8% of acetic acid and 1.5 to 1.8~ of free hydroxyl groups is vigorously mixed with ethylene/vinyl acetate copolymer on a roller at 180C as indicated in the following Table.
The rolled sheets are granulated and then extruded in ~j~ an injection moulding machine at a mass temperature of 240C
, - 10 to form test samples.
In the Examples marked L, the polymer mixtures are prepared. as solutions which are subsequently precipitated~
as described in Examples 1 to 15.
.~
~i,.b'. ,: ~ . . ~ . , .
'`
rc ~,,,,,,, ,`-','''.
: , .
~ . Le A 15 757 - 12 -'', ~ ~ ._ 107~786 r ~ ~ _ _ _ _ `~"
. ~ + + + I + + + + + ~ + + + +
~i i F.~ .
.5 _ _ . _ ~ O ~ ~ O ~ 0 0 o tr~ u~ O a~
, ~ CO ~ C~ D C- ~O ~ ~ C' , _ ~ C~ ~ ) 0 ~ J ~ .
~ . '- - . . - - . -~ , . q~ ~ 01~ u~ ~ U\ ;i;i .
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~ ~r '0 ~ g ~ ~ ~ ~00 ~9 ~ ~ ~D J ~D ~o ~ .
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:~ _ ~ ~ ~0 ~ J ~ ~ ~U ~ co ~ Ir~ Ct) ~' _ _. _ _ . ~ d d ~ d ; 1 ~ S~
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~ . _. _ ~ ~ u~ ~ 2 ~ ~ U' 2 u~ o ~ 2 ~
~ ~ ~ . , ~y ~, 0 CO ~ o o ~ ~ ~ ~ $
~ ~ o o o o o o o o o o o o o 0 0 ~ o o o o o o o o o ~ ~ ~ u~ ~ ~
0~) 0 0 ~) C~~ C~~ C~ ~ ~ ~ ;i- J
'" i ~1 _ _ _ ._ :g~i ~O ~ C' 0 Ci~ N ~\J N N J ~ N rN' ~0\J (U
, t~i ~, ; - . _ _ _ "." ` .
~ Le A 15 757 _ 13 _ 5~ When similar cellulose acetopropiDnates are mixed with ,the low molecular weight plasticizer dibutyladipate, the test samples obtained have much lower Vicat softening points.
'~
% DibutyladipateVicat C
~ 5 100 . . 15 68 ~ ,. 10 . ~ . Examples 30 to 33:
Secondary cellulose acetate is vigorously mixed with ethylene/vinyl acetate copolymer on a roller at 220C as indicated in the following Table~
The rolled sheets are granulated and then extruded in an injection moulding apparatus at a mass temperature of 230C to produce test samples.
In the examples marked L, the polymer mixtures are ~ prepared as solution which are then precipitated, as described in Examples 1 to 15~
''~ ' ' ~ `~i' , ,. j , `'''''' ` Le A 15 757 - 14 ~ .`` . 1071786 ~ 1`+~+++1 1~ ~ .. . ,., . I
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Le A 15 757 - 15 ~
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to 3) is 100 percent by weight.
Thermoplastic moulding compounds which are particularly preferred consist essentially of 1) 95 to 70 percent by weight, preferably 94.99 to 70 percent by weight of at least one cellulose ester of an aliphatic acid, 2~ 5 to 30 percent by weight of an ethylene/vinyl acetate copolymer containing 30 to less than 72 percent by weight, preferably 60 to 70 percent by weight of vinyl acetate and 3) 0 to 20 percent by weight~ preferably 0.01 to 20 percent by weight of a low molecular weight plasticizer. The sum of components 1) to 3) is 100 percent by weight.
One particularly surprising feature of the moulding compounds ac cording to the invention is their transparency and their very good mechanical properties.
Suitable cellulose esters for the preparation of the moulding com-pounds according to the invention are cellulose esters of aliphatic carboxylic ; acids containing 1 to 5 carbon atoms, particularly cellulose acetate, cellu-lose acetopropionate and cellulose acetobutyrate.
Processes for the preparation of organic cellulose esters have been known for a long time and have been described, for example, in Ullmanns Encyklop~die der technischen Chemie (Publishers Urban ~ Schwarzenberg, Munich-Berlin, 1963) in Volume 5 on pages 182 to 201.
Preferred cellulose acetobutyrates contain 40 to 50% of butyric acid, 15 to 26~ of acetic acid and ~.75 to 1.95~ of hydroxyl.
Cellulose acetobutyrates of the following composition are particularly suitable for the moulding compounds according to the invention: `
42 to 46% of butyric acid~
18 to 21~ of acetic acid and -~ 1.O to 1.7~ of hydroxyl.
~ Preferred cellulose acetopropionates generally contain -;10~ 50 to 63.5~ of propionic acid, 1 to 12~ of acetic acid and 1.2 to 1.95~ of hydroxyl and particularly preferred cellulose acetopropionates have the following comp~sition:
54 to 5~ of propionic acid, ; 5 to ~ of acetic acid and ' 1.5 to 1.8% of hydroxyl.
1~ i The c~llulose acetates used are preferably secondary ,, j cellulose acetates.
Th~ percentages given here and in the following are percentages by weight and parts are parts by weight.
' ! . , The relative viscosities (~ rel) of 2 % solutions of the aliphatic cellulose esters used in acetone at 25C are between ` 3.5 and 4.5 and preferably between 4.0 and 4.5.
~- 25 The vinyl esters used may be organic vinyl esters of satu-rated, optionally halogenated, in particular chlorinated, alipha-tic monocarboxylic acids containing 1 to 18 carbon atoms or aro-matic monocarboxylic acids containing 7 to 11 carbon atoms. The following are specific examples: Vinyl formate, vinyl acetate, vinyl propionate, vinyl chloropropionate, vinyl butyrate, -~ Le A 15 757 _ 4 _ vinylisobutyrate, vinyl caproate, vinyl laurate, vinyl myristate, vinyl stearate and vin~l benzoate. Vinyl acetate is preferred.
The ethylene/vinyl ester copolymers are prepared by the known methods of high or medium pressure synthesis, optionally in solve~ts such as tertiary butanol.
Ethylene/vinyl ester copolymers prepared by high pressure synthesis have melt index values (according to DIN 53 735 at 190C
and under a load of 2.16 kp) of between 0.1 and 100, preferably between 1.0 and 10 and more particularly between 4.5 and 6. Their intrinsic viscosities measured in tetralin at 120C are generally between 0.6 and 1.5. The molecular weights determined by the light diffusion method are preferably between 50,000 and 1,000,000. The non-uniformity U defined by the term /Mn ~ 1 (G.Schulz, Z. phys. Chem (B) 43 (1939) pages 25-34) is in the region of 5 to 30. These copolymers dissolved most easily ; in hot hydrocarbons.
Ethylene/vinyl ester copolymers prepared, for example, by the process of solution or emulsion polymerisation, which contain e.g. 30 to 98 % by weight and preferably 60 to 80 % by weight of vinyl esters, may have melt index values (190C 2.16 kp) greater than 100 and the melt index is preferably below 15 and in parti-cular between 0.5 and 5. The molecular weights determined by the method of light diffusion are preferably between 40,000 and 1,000,000. The non-uniformity U is 1 to 6. The copolymers are soluble in hydrocarbons and alcohols and preferably have intrin-sic viscosities of between 0.5 and 2.5, measured in toluene at 25C.
The ethylene/vinyl acetate copolymers may be partly or completely 20 to 100 % saponified if desired.
Composition and melt indices of the ethylene/vinyl acetate copolymers used:
¦ Le A 15 757 - 5 -~' .
,.. . ,, . . , .. _ . __. _ ~
. . .
Name Vinyl acetate M~I
~ content [~]
-- , EVA - 800 78 0 ~15 E~A - 700 70 3 5 EVA - 600 60 10.4 EVA - ~l50 4~ 0 54 EVA ~ ~38 33 64 In tHe above table:
E~A: Ethylene/vinyl acetate copolymer MFI: Melt index [g/10 min] according to DIN 53 735 under a load of 2.16 kp and at a temperature of 190C.
Suitable low molecular weight plasticizers include dimethylphthalate; diethylphthalate; triphenylphosphate;
methyl phthalyl ethyl glycollate; di-n-butylsebacate;
ethylphthalyl ethyl glycollate; butyl phthalyl butyl glycollate; dibutylphthalate; dioctyladipate; dioctyl-I phthalate; butylbenzyl phthalate and triacetin.
Preparation of the moulding compounds according to the invention from organic cellulose esters and ethylene/vinyl ester copolymers which may, if desired, be modified with low molecular weight plasticizers is carried out by vigorously mixing the components. Any known mixing method may be used on rollers or in serew extruders, The mixtures may also be prepared via their solutions.
In that case, the components are dissolved in suitable solvents or solvent mixtures, and the polymer mixtures may be precipi-tated with suitable non-solvents or the solvents or solvent mixtures may be removed by evaporation. Methylene chloride Le A 15 757 - 6 -. ~ .
~ ' 107~786 and ~laciai acetic acid, for example, are suitable solvents for organic cellulose esters and ethylene/vinyl ester copolymers.
The mutual precipitating agent used may be hexane, for example, if the components have been dissolved in methylene chloride.
The mixtures according to the invention may also contain certain other additives to colour or pigment the polymer mixtures or improve their resistance to oxidation, light or combustion and the li~e.
The moulding compounds according to the invention prepared from ethylene/vinyl ester copolymers and organic cellulose esters show a remarkable increase in the notched impact strength measured according to DIN 53 453.
In addition, the moulding compounds according to the invention are distinguished by their improved dimensional ; 15 stability at elevated temperature determined e.g. as the Vicat softening temperature according to DIN 53 460.
The Vicat softening temperatures are up to 40C higher than the corresponding softening temperatures of cellulose esters which have been modified with low molecular weight - 20 plasticizers.
Compared with conventional cellulose ester moulding compounds which contain low molecular weight plasticizers, ~ the polymer mixtures according to the invention also show ; improved mechanical properties such as an increase in their ~` 25 hardness, tensile strength, flexural strength and modulus of elasticity.
The polymer mixtures of organic cellulose esters and ethylene/vinyl ester copolymers are virtually free from the well known effect of so-called plasticizer migration and 3o the moulding compounds are therefore also particularly Le A 15 757 _ 7 _ ~ suitable, for example, for purposes in which they come into con-: tact with foodstuffs.
~ I The improved resistance of the mixturesto hot air makes it ; possible for them to be used for outdoor garments, 5 I The moulding compounds according to ~the invention can be used for the production of shaped articles of any kind and for the production of acetate silk, block acetate, foil substrates for safety films, packaging material, electric insulating foils and lacquers.
Mixtures of organic cellulose esters and ethylene/vinyl ; ester copalymers can be processed contînuously or batchwise in ~: known extruders and injection moulding machines without any sub-:~ stantial difficulty and have good fluidity properties under these conditions.
l ~ ' :
~ ' , .
~ ~ Le A 15 757 - 8 -.
... .. . . _ .
~; ~ 1071786 ..
;~ Examples l_to 15 , I
"'`'`'`''''''` .. I
Cellulose acetobutyrate containing 42 to 46~ of butyric acid, 18 to 21~ of acetic acid and 1~0 to 1.7% o~ hydroxyl groups is vigorously mixed with ethylene/vinyl acetate co-polymers on rollers at 170C as indicated in the following Table.
¦ The rolled sheets are granulated and then extruded in an injection moulding apparatus at a mass te~perature of 230C
¦ 10 to form test samples.
In the examples marked L, the polymer mixtures are prepared as solutions and then precipitated. The appropriate -~; parts by volume of 10~ methylene chloride solutions of 'i~ cellulose acetobutyrate and of ethylene/vinyl acetate co-polymer are mixed and the polymer mixture is precipitated with hexane. The resulting mixtures are dried and then extrudéd to form test samples as mentioned above.
~ .
..., ,~ ~ """
i Le A 15 757 - ~ -, :
` ~`` ` 1071786 ~ I I I 1 1-1 ' ~i U~ O O Ll~ O O O O O Lt~ O O 1-~ 0 .- 2 ~ _ _ .
a ~
o I $ o ~ 1;
~ 1 _ _ i Lr~ (~ Lr~ 11~ ~U '-- . . (~ Lr~ LS'~
¦~ -- Ll~ Lt~ Lt\ LS~ r ~ ~ Lr~ ~ U~ =i ¦ h ~ ~ D Ll~ C' Lr~ L ~ 0 0 1~ ~ ID L~\ 1 ~ _ _ ~ i ~
. ~ ¦ ~1 <~ ~j ~ O 11~ a~ L O O ~ a) :;1 O ~ Lr~
_' ~ _ ~
N~ O ~ ~ t N ~ N O (~ ~ O ~ ¦_ ~i , ~ ' ~ j ~ a ~a ¦~a ~ 'a ;~ ~ a~ 0 0 O o ~ ~o ~ t ~ ~ ~ oo :~ -~ . ~i O O O Oo o o ~ LD r~ r~
:
:
r~ ; X ~ ~ ~ D C~ 0 CS~ O O ~ ~ L
~ ' , ' - --___ ~,"q Le A 15 757 10 ~`~ 1071786 ~ 1 , I .
~ ~.
. ~egend to Table:
'' a~.~ Imp~ct strength accordin~ to DIN 5~ 453;
Dimension: ~kJ/m2].
ak: Notched impact strength accordinæ to DIN 53 453;
Dimension: [kJ/m2].
Vicat: Vicat softening temperature according to Method B .¦
(Force: 49.05 N) according to DIN 53 460;
Dimension: [C]. I
~b~: Bending yield stress according to DIN 53 452;
Dimension: [N/mm2~.
.. ~ . f : sagging at ~b~:
. Dimension; ~mm~.
Hk30: Ball pressure hardness after 30 s according to DIN 53 456; 2 Dimension: [rl/mm ].
~ ~ 3y~ ~ deno~es giass clear transparcncyr~ - denotes opaque.
.' ~ . . ' ,.
,.,,f .
~} .~, .-i^;~,'. ' .
J'~.,,, .
2 ~ .
'''' I Le A 15 757 _ 11 -.
i,;,,.~ ' ~, ,, ,,~' ' .
:
~ 1071786 `-` .. I
.-, Examples 16 to 29:
Cellulose acetopropionate containing 54 to 58~ of propionic acid, 5 to 8% of acetic acid and 1.5 to 1.8~ of free hydroxyl groups is vigorously mixed with ethylene/vinyl acetate copolymer on a roller at 180C as indicated in the following Table.
The rolled sheets are granulated and then extruded in ~j~ an injection moulding machine at a mass temperature of 240C
, - 10 to form test samples.
In the Examples marked L, the polymer mixtures are prepared. as solutions which are subsequently precipitated~
as described in Examples 1 to 15.
.~
~i,.b'. ,: ~ . . ~ . , .
'`
rc ~,,,,,,, ,`-','''.
: , .
~ . Le A 15 757 - 12 -'', ~ ~ ._ 107~786 r ~ ~ _ _ _ _ `~"
. ~ + + + I + + + + + ~ + + + +
~i i F.~ .
.5 _ _ . _ ~ O ~ ~ O ~ 0 0 o tr~ u~ O a~
, ~ CO ~ C~ D C- ~O ~ ~ C' , _ ~ C~ ~ ) 0 ~ J ~ .
~ . '- - . . - - . -~ , . q~ ~ 01~ u~ ~ U\ ;i;i .
~ _ , _ .
~ ~r '0 ~ g ~ ~ ~ ~00 ~9 ~ ~ ~D J ~D ~o ~ .
_ I
~ ~ O ~ O O ~ J O N ~ o i~ ~ ~
:~ _ ~ ~ ~0 ~ J ~ ~ ~U ~ co ~ Ir~ Ct) ~' _ _. _ _ . ~ d d ~ d ; 1 ~ S~
. ~ h h h ~ h ~ ~0 J ~ ~ :i J
~ . _. _ ~ ~ u~ ~ 2 ~ ~ U' 2 u~ o ~ 2 ~
~ ~ ~ . , ~y ~, 0 CO ~ o o ~ ~ ~ ~ $
~ ~ o o o o o o o o o o o o o 0 0 ~ o o o o o o o o o ~ ~ ~ u~ ~ ~
0~) 0 0 ~) C~~ C~~ C~ ~ ~ ~ ;i- J
'" i ~1 _ _ _ ._ :g~i ~O ~ C' 0 Ci~ N ~\J N N J ~ N rN' ~0\J (U
, t~i ~, ; - . _ _ _ "." ` .
~ Le A 15 757 _ 13 _ 5~ When similar cellulose acetopropiDnates are mixed with ,the low molecular weight plasticizer dibutyladipate, the test samples obtained have much lower Vicat softening points.
'~
% DibutyladipateVicat C
~ 5 100 . . 15 68 ~ ,. 10 . ~ . Examples 30 to 33:
Secondary cellulose acetate is vigorously mixed with ethylene/vinyl acetate copolymer on a roller at 220C as indicated in the following Table~
The rolled sheets are granulated and then extruded in an injection moulding apparatus at a mass temperature of 230C to produce test samples.
In the examples marked L, the polymer mixtures are ~ prepared as solution which are then precipitated, as described in Examples 1 to 15~
''~ ' ' ~ `~i' , ,. j , `'''''' ` Le A 15 757 - 14 ~ .`` . 1071786 ~ 1`+~+++1 1~ ~ .. . ,., . I
'~ o00~ .
I ~9 ~ 0 . .
.
.~ ~ o~ , I
~r. . __ . ~
',~ . ~ ~ ' ~, I i~ .~
I
I! cu ~ (U
_ . _ . ~ Lr~O~O
~ . , _ . . .
~ ~ ~ 0 0~Q0 0~0 . t:l.
~ ~ r i _ _ ~
~j ~ O ~U
_ ¢ O O O O O
~ ~i 0 ~ 0 ~
j ~ ., I O O ~
~5 ~
' . ~ _ _ ' . .
..
.
Le A 15 757 - 15 ~
, ~ ~
, - .... ........ ~
Claims (18)
1. A thermoplastic moulding compound consisting essentially of 1) 1 to 99 percent by weight of at least one cellulose ester of an aliphatic carboxylic acid, 2) 99 to 1 percent by weight of an ethylene/vinyl ester copoly-mer containing 30 to less than 72 percent by weight of vinyl esters and 3) 0 to 35 percent by weight of a low molecular weight plasti-cizer, the sum of components 1) to 3) being 100 percent by weight.
2. A moulding compound as claimed in claim 1 which consists essentially of 50 to 98,99 percent by weight of component 1), 1 to 50 percent by weight of component 2) and 0,01 to 20 percent by weight of component 3), the sum of components 1) to 3) being 100 percent by weight.
3. A moulding compound as claimed in claim 1 which consists essentially of 95 to 70 percent by weight of component 1), 5 to 30 percent by weight of component 2) and 0 to 20 percent by weight of component 3).
4. A moulding compound as claimed in claim 1, in which compo-nent 2) contains 60 to 70 percent by weight of vinyl ester.
5. A moulding compound as claimed in claim 1 in which compo-nent 1) comprises a cellulose ester of an aliphatic carboxylic acid containing 1 to 5 carbon atoms.
6. A moulding compound as claimed in claim 5 in which compo-nent 1) comprises cellulose acetate, cellulose acetopropionate or cellulose acetobutyrate.
7. A moulding compound as claimed in claim 6 in which compo-nent 1) comprises cellulose acetobutyrate containing 40 to 50 %
of butyric acid, 15 to 26 % of acetic acid and 0.75 to 1.95 %
of hydroxyl.
Le A 15 757 - 16 -
of butyric acid, 15 to 26 % of acetic acid and 0.75 to 1.95 %
of hydroxyl.
Le A 15 757 - 16 -
8. A moulding compound as claimed in claim 7 in which the cellu-lose acetobutyrate contains 42 to 46 % of butyric acid, 18 to 21 %
of acetic acid and 1.0 to 1.7% of hydroxyl.
of acetic acid and 1.0 to 1.7% of hydroxyl.
9. A moulding compound as claimed in claim 6 in which compo-nent 1) comprises cellulose acetopropionate containing 50 to 63.5 %
of propionic acid, 1 to 12 % of acetic acid and 1.2 to 1.95 % of hydroxyl.
of propionic acid, 1 to 12 % of acetic acid and 1.2 to 1.95 % of hydroxyl.
10. A moulding compound as claimed in claim 9 in which the cellu-lose acetopropionate contains 54 to 58 % of propionic acid, 5 to 8 % of acetic acid and 1.5 to 1.8 % of hydroxyl.
11. A moulding compound as claimed in claim 6 in which compo-nent 1) comprises a secondary cellulose acetate.
12. A moulding compound as claimed in claim 1 in which compo-nent 2) comprises, as vinyl ester component, an organic vinyl ester of a saturated aliphatic monocarboxylic acid containing 1 to 18 carbon atoms or an aromatic monocarboxylic acid containing 7 to 11 carbon atoms.
13. A moulding compound as claimed in claim 12 in which the vinyl ester is the vinyl ester of a saturated aliphatic haloge-nated monocarboxylic acid.
14. A moulding compound as claimed in claim 12, in which the vinyl ester component is vinyl formate, acetate, propionate, chloropropionate, butyrate, isobutyrate, caproate, laurate, myri-state, stearate and benzoate.
15. A moulding component as claimed in claim 1 in which compo-nent 3) comprises dimethylphthalate; diethylphthalate; triphenyl phosphate; methyl phthalyl ethyl glycollate; di-n-butylsebacate;
ethyl phthalyl ethyl glycollate; butyl phthalyl butyl glycollate;
dibutylphthalate; dioctyladipate; dioctylphthalate, butylbenzyl-phthalate or triacetin.
Le A 15 757 - 17 -
ethyl phthalyl ethyl glycollate; butyl phthalyl butyl glycollate;
dibutylphthalate; dioctyladipate; dioctylphthalate, butylbenzyl-phthalate or triacetin.
Le A 15 757 - 17 -
16. A shaped article when produced from a moulding compound as claimed in claim 1.
17. A shaped article as claimed in claim 16, which comprises also ace-tate silk, block acetate, a foil substrate for a safety film or packaging, an electric insulating foil or lacquer.
18. A process for producing shaped articles as claimed in claim 16 which process comprises subjecting to injection moulding or extrusion a moulding compound as claimed in claim 1.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2426178A DE2426178C3 (en) | 1974-05-29 | 1974-05-29 | Thermoplastic molding compounds made from cellulose esters and ethylene-vinyl ester copolymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1071786A true CA1071786A (en) | 1980-02-12 |
Family
ID=5916861
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA227,858A Expired CA1071786A (en) | 1974-05-29 | 1975-05-27 | Thermoplastic moulding compound of cellulose esters and ethylene/vinyl ester copolymers |
Country Status (17)
| Country | Link |
|---|---|
| JP (1) | JPS5845458B2 (en) |
| AT (1) | AT343918B (en) |
| BE (1) | BE829578A (en) |
| BR (1) | BR7503381A (en) |
| CA (1) | CA1071786A (en) |
| CH (1) | CH617948A5 (en) |
| DD (1) | DD119249A5 (en) |
| DE (1) | DE2426178C3 (en) |
| DK (1) | DK238275A (en) |
| ES (1) | ES438015A1 (en) |
| FR (1) | FR2275514A1 (en) |
| GB (1) | GB1501414A (en) |
| IT (1) | IT1035896B (en) |
| NL (1) | NL183241C (en) |
| NO (1) | NO143911C (en) |
| SE (1) | SE411354B (en) |
| SU (1) | SU828976A3 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2807663A1 (en) * | 1978-02-23 | 1979-08-30 | Bayer Ag | USE OF MIXTURES OF CELLULOSE STARS AND ETHYLENE-VINYL ACETATE COPOLYMERS IN CONTACT EYE OPTICS |
| CA1163739A (en) * | 1980-07-12 | 1984-03-13 | Dietrich J. Bahr | Process for producing a polymerized, heat-resistant lacquer |
| JPH0741056B2 (en) * | 1986-03-14 | 1995-05-10 | 松下電工株式会社 | Matsusage machine |
| JPS6326462A (en) * | 1986-07-16 | 1988-02-04 | Sumitomo Heavy Ind Ltd | Support mechanism for pulley of grinding stone driving motor |
| JP5182778B2 (en) * | 2006-06-12 | 2013-04-17 | 太平化学製品株式会社 | Resin composition and transparent sheet |
| JP5258233B2 (en) * | 2006-09-07 | 2013-08-07 | 太平化学製品株式会社 | Resin composition and molded body |
| JP6511754B2 (en) * | 2014-09-26 | 2019-05-15 | 富士ゼロックス株式会社 | Resin composition and resin molded body |
| JP6897196B2 (en) * | 2016-08-31 | 2021-06-30 | 富士フイルムビジネスイノベーション株式会社 | Resin composition and resin molded product |
| WO2018089610A1 (en) * | 2016-11-11 | 2018-05-17 | Eastman Chemical Company | Polymer-based resin compositions derived from cellulose and articles made using these compositions |
| WO2018089575A1 (en) * | 2016-11-11 | 2018-05-17 | Eastman Chemical Company | Cellulose ester and ethylene vinyl acetate compositions and articles made using these compositions |
| JP6930232B2 (en) * | 2017-02-17 | 2021-09-01 | Dic株式会社 | Cellulose ester compositions, moldings and films |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2186454A (en) * | 1937-06-24 | 1940-01-09 | Hercules Powder Co Ltd | Lacquers containing cellulose acetobutyrate and cellulose acetopropionate |
| US3454349A (en) * | 1965-12-28 | 1969-07-08 | Celanese Corp | Cellulose ester shaped articles of improved dyeability |
| DE1745565A1 (en) * | 1967-10-23 | 1971-10-28 | Wacker Chemie Gmbh | Process for the production of copolymers from ethylene and vinyl esters |
| JPS50759B1 (en) * | 1969-03-20 | 1975-01-11 | ||
| US3682850A (en) * | 1970-07-30 | 1972-08-08 | Du Pont | Cellulosic esters of two organic acids blended with a copolymer of ethylene and at least one ethylenically unsaturated ester of a saturated fatty acid |
| JPS5343978B2 (en) * | 1973-12-04 | 1978-11-24 |
-
1974
- 1974-05-29 DE DE2426178A patent/DE2426178C3/en not_active Expired
-
1975
- 1975-05-15 NO NO751730A patent/NO143911C/en unknown
- 1975-05-20 GB GB21455/75A patent/GB1501414A/en not_active Expired
- 1975-05-27 CA CA227,858A patent/CA1071786A/en not_active Expired
- 1975-05-27 AT AT402175A patent/AT343918B/en not_active IP Right Cessation
- 1975-05-27 JP JP50062610A patent/JPS5845458B2/en not_active Expired
- 1975-05-27 CH CH678375A patent/CH617948A5/en not_active IP Right Cessation
- 1975-05-27 DD DD186280A patent/DD119249A5/xx unknown
- 1975-05-27 IT IT49794/75A patent/IT1035896B/en active
- 1975-05-28 BR BR4324/75D patent/BR7503381A/en unknown
- 1975-05-28 BE BE156781A patent/BE829578A/en not_active IP Right Cessation
- 1975-05-28 ES ES438015A patent/ES438015A1/en not_active Expired
- 1975-05-28 DK DK238275A patent/DK238275A/en unknown
- 1975-05-28 SE SE7506095A patent/SE411354B/en not_active IP Right Cessation
- 1975-05-29 FR FR7516869A patent/FR2275514A1/en active Granted
- 1975-05-29 SU SU752140025A patent/SU828976A3/en active
- 1975-05-29 NL NLAANVRAGE7506381,A patent/NL183241C/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| SU828976A3 (en) | 1981-05-07 |
| IT1035896B (en) | 1979-10-20 |
| NL7506381A (en) | 1975-12-02 |
| NO143911C (en) | 1981-05-06 |
| DE2426178A1 (en) | 1975-12-18 |
| AU8157375A (en) | 1976-12-02 |
| SE411354B (en) | 1979-12-17 |
| DD119249A5 (en) | 1976-04-12 |
| NO751730L (en) | 1975-12-02 |
| GB1501414A (en) | 1978-02-15 |
| NL183241C (en) | 1988-09-01 |
| BR7503381A (en) | 1976-04-27 |
| NO143911B (en) | 1981-01-26 |
| FR2275514A1 (en) | 1976-01-16 |
| ATA402175A (en) | 1977-10-15 |
| DE2426178C3 (en) | 1981-12-03 |
| SE7506095L (en) | 1975-12-01 |
| DE2426178B2 (en) | 1980-10-30 |
| BE829578A (en) | 1975-11-28 |
| AT343918B (en) | 1978-06-26 |
| FR2275514B1 (en) | 1979-04-13 |
| JPS5845458B2 (en) | 1983-10-11 |
| JPS512756A (en) | 1976-01-10 |
| ES438015A1 (en) | 1977-05-16 |
| CH617948A5 (en) | 1980-06-30 |
| DK238275A (en) | 1975-11-30 |
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