CA2087444C - Polymer mixture for producing films - Google Patents
Polymer mixture for producing films Download PDFInfo
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- CA2087444C CA2087444C CA002087444A CA2087444A CA2087444C CA 2087444 C CA2087444 C CA 2087444C CA 002087444 A CA002087444 A CA 002087444A CA 2087444 A CA2087444 A CA 2087444A CA 2087444 C CA2087444 C CA 2087444C
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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
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/04—Starch derivatives, e.g. crosslinked derivatives
- C08L3/06—Esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
Abstract
In order to produce a polymer mixture essentially consisting of starch and a polyolefine, up to 70 wt % of thermoplastically processable starch is mixed with 10 to 40 wt % polyolefine and to 35 wt % ethylene acrylate maleic anhydride copolymer.
During this mixing process an esterification reaction takes place between the maleic anhydride groups in the copolymer with free hydroxyl groups in the starch according to the general reaction process (T).
During this mixing process an esterification reaction takes place between the maleic anhydride groups in the copolymer with free hydroxyl groups in the starch according to the general reaction process (T).
Description
Polymer mixture for producing films The present invention relates to a polymer mixture essentially consisting of starch andl a polyolefin, a process to produce a polymer mixture, a film of at least a single ply, consisting essentially of a polymer mixture, along with the use of the process for the purpose of producing single or multi-ply films, as well as the use of the process to produce a foam-type film.
Polymer mixtures comprising starch are known, where starch l0 or other biopolymers are being used, preferably because of their biodegradability, their suitable price and their independence from petroleum products.
The use of biopolymers as technical material has been described in several patents. In EP-011 82 40, EP-28 24 51, EP
29 89 20, EP-30 44 01, EP-32 65 14, GB-22 14 919 and in EP-32 75 05, it is described how natural starch, gelatine or other biopolymers are modified or destructured respectively so that they can be used as technical polymers. This is accomplished by way of extrusion or by kneading of the starch or the biopolymer while utilizing the moisture content normally present in 'the biopolymer or in the starch, or by adding more water, in which case, however, just this relatively high water content for instance in the process of extrusion of the 'thus destructured biopolymers is extremely undesired. In contrast thereto, PCT-W090-05 161 proposes to take the water out of natural starch and by means of additives or plasticizing agents such as glycerine to convert it into a technically useful polymer, 'that is, a so-called thermoplastically processable starch. The workability as well as the moisture resistance of this starch polymer are of course considerably better than of those starch polymers that are produced in accordance with the above-mentioned processes.
However, the mechanical properties and in particular the moisture resistance are still unsatisfactory for many technical uses and in particular for the production of films.
For this reason, numerous patents, such as EP-040 28 26, EP-04047 23, EP-40 47 27, EP-40 27 28 and EP-40 73 50 propose to mix the starch with thermoplastic material such as polyolefins, polyalcohols, ABS copolymers, ethylene acrylic acid copolymers, copolymers of vinylpyrrolidines, copolymers having amino groups etc. respectively, to produce so-called polymer blends.
This creates, however, the problem of a poor compatibility between the starch and the further polymers, and results in a poor phase mixing of the individual polymers.
This can for instance be seen in films produced from these materials, where the non-starch proportion of polymer present in this mixture, when used by itself to produce a film, i.e. having a corresponding thinner sheet-thickness, exhibits better tensile strength than the thicker film produced from the total polymer mixture.
According to Patents EP-40 05 31 and EP-40 05 32 it is proposed to treat the starch analogous to W090-05 161 by means of a high boiling plasticizing agent, such as glycerine, urea, or sorbitol, in order to obtain thermoplastically processable starch in order to subsequently mix it with ethylene acrylic acid and/or polyvinyl alcohol copolymers. Films produced from these starch-polymer mixtures do exhibit a greater tensile strength; however, they are still not sufficiently moisture resistant.
The same applies to the starch-polymer mixtures prepared in accordance with W090-14 388, where polyethylene and ethylene acrylic acid copolymers are added to the glycerine starch.
It is, therefore, the purpose of this invention to propose a polymer mixture essentially consisting of starch, which is particularly well-suited to the production of films and which in moulds and extrudates, as for instance in films, exhibits good mechanical properties, as well as moisture resistance.
In accordance with the invention, this is achieved by means of a polymer mixture essentially consisting of starch i% a and a pol.yolefin, obtained by :=>ub.sv:arot.,, ai l y moistu:re--free mixing of thermoplastic<~11y pro~;es~aa~:~~l.e s,~~.~~z-~~:rwith at least one polyolefin and at 1_east. or:,e ~~tx~y lEoe a<~rylate malefic acid anhydride copolymer so trjat thcmixt~re cons:i.sts essentially at least of the added a~orry>oner~t»; as well. as of the esterification product st:arcuh rn.alei.c:: ac i<i ester-malefic acid anhydride et:hylerse acry:hate r~c>pcaiyrriex , k espectively by means of a polymer mixture prepa:eed suc'r. that the nati:rral starch and/or a derivative thereof i.s rruix<~d s~aa.t:.r:~ 15 o by weight to 40 0 by weight:. ot: at l.e~.st <>r~e ~:La;~>tici.~?_i.izc:3 agenr~, substantially anhydrous, for th.e prodnct~io::o g:~f_ t:he.r_~~~~op L aat:ically processable starch, whereafter the :~arr~e, at:. <~ tE~m~:~er~~ture of betw~sen 165°C
to 210°C, i.s mixed in the me_Lt with a po.Lyo:le:f:in and an ethylene acrylat~~ malei.c awi.~.:~ aro~yc~iride cod>olymE:r, whereby malefic acid anhydride groups fir: true pc>Lyrc~ers are esterified by means of free 1-rydx:oxy.i. grcoap:> ire y~he starch ir3 a manner similar analogous to the fol_l.ow.i.rag genera L reaction process 2 0 ~''~' ~ ~ ~"'~'''~ 'rte STARCH - OH +
~°/ ~ 1~''I
D
Starcr~ "~ ~l R
Starch' ~~ w ~ ~ -~
or p h ._ n ~ta.r. ch b ~: ~:?
Proposed is a po:Lyme~r mixt:u~:e ~-;~;ser-tial:.~y consisting of starch and polyolefi.rn, ol>fiain~cl t:~t~,- rczixing s~.zbstantially moisture-free therrr;c,plast.~~c~:~l_:1 ~ ~:yr:c>~;~f~>~:~;,.abi.e st:arc:h witwh at 1_east one polyolefin ana ~~t 1c1~.~t rare:=. et'.z~rlene acr5rl.ate malefic ac:i..d anhydride c~opc~l ymer ar~rl,.~,::~r c~rj.: ~Ti iu~;e.'a compound carrying an~ydride-f.unct:i.on as s.zbst:.:i.t~.aez~t~~ ~ "I'tie definition and production of thermoplast:ically processable starch is taught in WO-05 161.
The effect of the copolymer or the vinyl compound respectively is to be seen in the fact. that .it acts as a phasing agent between the starch phase and the polyolefin phase. The copolymer comprises hydrophobic particles, as well as hydrophillic particles and permeates, therefore, the boundaries between the starch and the polyolefin.
The polymer mixture propc.~sed :.n accordance with the present invention is obta.iruec. ~.yy .rna_x:inc~ :L:~bstantia.lls~ up to 70 0 by weight thermoplastically pzoc~essab:~.e starch containing at least one plastic:i~zing ageni~. w.it:~ .fJ; ay weight to 90% by we:~ght of polyolE:~f:~:L~~ anal ~°k:ay w~:i.a~~n.t: t:~::> 35 ~ by weight of ethylene acrylate malefic acid aanhydr.iaie copolymer.
In order to obtain on the one hand good mechanical properties, such as stability of moulds and extrudates such as films, and high moisture-resistance, it is, in accordance with the invention, proposed to mix 45~ by weight to 70% by weight, preferably 50 % by weight to 6~ ~ kay weight, oaf thermoplastically processable starch containing at least one plasticizing agent selected from the list of gLycera.ne, urea, an amino-alcohol, sorbitol and/or succinic acid anhydride comprising 10% by weight to 40% by weight, preferably 20% by weight to 35% by weight, of polyethylene or polypropylene with ~.~:~~5 by weight to 35% by weight, preferably 15% by weight to 25% by weight, of ethylene acrylate malefic acid anhydride copolymer. Moisture resistance, as well as high stability are :influen~:ed by the proportion of polyolefin and the copolymers, whereby on the other hand too high a proportion of these two <~omponents in the mixture: is, in particular for cost reasons, not desirable, In the case of films, too high a proportion of these components results furthermore irx an in~;reased gas permeability, whereas in the case of too high a proportion of starch, for instance, the oxygen permeability is decreased.
For the production of the aforementioned polymer mixtures in accordance with the invention, it is proposed that natural starch and/or a derivative there~>f, is mixed with 15~ by weight to 40~ by weight of at least one plasticizing agent such as glycerine, urea, an amine alcohol, sarbitoi and/or succinic acid anhydr~_<~e, substari'_:i<~l=L~y f re ,,.,;,: a~c:i ~ :~.r~~~, for f~rue purpose of producing thermoplastically processable :March, whereupon the starch thus produced is mixed in the melt at a temperature range of 165°C to 210°C with a polyolef.in, a:~ far instance preferably polyethylene and/'or polypropylene, and an ethylene acrylate malefic acid anhydride copolymer and a vinyl compound respectively, carrying anhydride funct:~_an as a substituent.
In this mixing process, mal.eic acid anhydride groups and generally all anhydride function in the capo.lymer is esterified in a mariner similar to the fal.lawing general progress of reaction:
STARCH -- OH +
r~
o S to ~ch Starch ~~ ' ~ ~ 1 ~ !
C7 ''~. ~ N
or ~,. o .~. / /' The polyolefin, as far instance the polyethylene or the polypropylene, forms a sort of a anatrix in which the :March will be enclosed. As mentioned before, the copolymer and the vinyl compound respectively, serve to achieve a strong bond between the polyethylene and polypropylene respectively, and the starch and the two phases respectively, so that in the case of 5 moulds and films accordingly produced from this polymer mixture good mechanical properties such as stability, are obtained.
This bonding at the phase boundary is achieved, as mentioned before, by means of the copolymer, for which, as already mentioned, in particular the esterification reaction is responsible. It can be proven by means of the infrared spectrum that the said reaction between the starch and the copolymer occurs during the mixing process. This detection by means of the infrared spectrum will be discussed later.
Preferred variations of execution of the process in accordance with the invention, as in particular also the production of thermoplastically processable starch and of the ethylene acrylate malefic acid anhydride copolymer are characterized in that:
- up to 70o by weight of thermoplastically processable starch is mixed in an extruder or kneader with 10o by weight to 40o by weight of polyethylene and/or polypropylene and 10%
by weight to 35o by weight of an ethylene acrylate malefic acid anhydride copolymer, whereby during the mixing process the total mechanical energy created amounts to approximately 0.4 kWh/kg and an adequate mixing action is achieved by means of kneading-blocks and appropriate backwash elements arranged in the extruder or kneader;
- natural starch and/or one derivative thereof having a moisture content of less than to is homogenized with the plasticizing agent at a temperature of 160°C to 190°C in an extruder or kneader, whereupon in a further extrusion or in 5a the same extruder in a further step, mixing with polyethylene and/or polypropylene and the copolymer takes place;
- the natural starch and/or a derivative thereof is pre mixed with the plasticizing agent essentially at room temperature or higher, whereupon the starch will swell, forming an essentially dry granulate which subsequently will be used for further working and for mixing with polyethylene and/or polypropylene, as well as with the copolymer; and - an ethylene acrylate malefic acid anhydride copolymer is being used which is obtained by working-up of 80o by weight to 95a by weight of ethylene, 1o by weight to 15o by weight of acrylic acid methyl ester and/or acrylic acid ethyl ester, as well as O.lo by weight to 15o by weight of malefic acid anhydride.
Here again it has to be pointed out, that the production of thermoplastically processable starch is taught in W090-05 161.
The polymer mixtures produced in accordance with the present invention are especially well suited to the production of single or multi-ply films. The production of the polymer mixture can immediately be followed by the production of the film, in that the molten polymer mixture is extruded by means of a wide-mouth jet or a blow head. It is, however, also possible to first granulate the polymer mixture and to use the granulate later to produce a film.
It is in particular also possible to co-extrude the polymer mixture prepared in accordance with the present invention together with other polymers in order to produce multi-ply films, whereby for instance a three-ply film can be produced, where each outer ply contains the polymer mixture of the present invention, ~~fi'~~~~~
while the middle ply is produced from essentially thermoplastically processable starch.
It is also possible, prior to the extrusion of the polymer mixture produced in accordance with the invention, to mix in a propellant, for instance sodium carbonate or an organic acid, in which case the organic acid could for instance be citric acid.
It is, of course, also possible to produce moulds from the polymer mixture proposed by the invention, or extrudates such as hoses, where the composition of the ;polymer mixture, within the limits suggested by the invention, is dictated by the demands of the article to be produced.
Tre invention will now be explained by means of examples and by reference to 'the attached diagrams as follows:
Figure 1 shows infrared spectra of the polymer mixture at the beginning and at the end of the mixing process.
Figure 2 shows the heat flow diagram of natural starch with glycerin.
Figures 3 shows the heat flow diagram of thermoplastically processable starch.
Figure 4 shows the heat flow diagram when thermoplastically processable starch mixed with an ethylene acrylate malefic acid anhydride copolymer, and Figure 5 shows the heat flow diagram when natural starch and glycerine are mixed with an ethylene acrylate malefic acid anhydride copolymer.
1. Production of the thermoplastically ~~rocessable starch One starts with dried natural starch having a moisture content of preferably less than 1% by weight. The natural starch is hydrolysed by means of a suitable plasticizer, as for instance glycerine, whereby, in relation to the total mixture, preferably between 25~ by weight and 35% by weight of glycerine is added.
The starch/glycer:ine mixture is subseduently well mixed in an extruder at a temperature between 160'C and 190'C, preferably with high shearincJ action, or this mixing could also be done in a kneader.
2~~'"~~~~~
Suitable plasticizers are, of course, also other materials, such as urea, sorbitol, succinic acid anhydride, amino alcohols etc., and at this point attention should be drawn again to Wo90 05 161, where a series of further suitable plasticizers and additives are defined.
The subsequent treatment of the thermoplastically processable starch thus produced can be carried out directly in the same extruder or the starch can first be granulated.
2. Ethylene acrylate malefic acid anhydride copolymer Tt is not intended to elaborate at this point on the production of these copolymers since they are basic products and do not constitute a feature of the present invention.
The copolymers suitable for the present invention are copolymers preferably composed as follows:
Parts b~ Weiaht Ethylene: 80-95% by weight Acrylic acid methyl ester:
5--15% by weight Acrylic acid ethyl ester:
Malefic acid anhydride: 0.2-1% by weight In the following example of a polymer mixture produced in accordance with the present invention, a copolymer having the following parts by weight has been used:
Ethylene: 88.0% by weight Acrylic acid methyl ester: 9.0% by weight Acrylic acid ethyl ester: 2.5% by weight Malefic acid anhydride: 0.5% by weight 3. Production of a starch ethylene copolymer mixture Following the production of the thermoplastically processable starch in accordance with point 1), a homogeneous.
mixture consisting of polyethylene and the copolymer in accordance with point 2 ) was added to the starch melt at the beginning of the second mixing phase in the same extruder at a ~Uc~~'l ~~~~
temperature of 170°C as set at the extruder. The temperature of the melt was at this point about 190°C to 200°C. The starch, polyethylene, copolymer mixture was thereafter, during that second mixing step, mixed under strong shearing action created by means of kneading blocks arid backwash elements. Preferably a co-kneader or a twin-shaft extruder is used. The total mechanical energy created amounted to approximately 0.4 kWh/kg.
The quantities of the polyethylenes and copolymers that have been added are listed in the following Table, where in the abbreviation TPS = thermoplastically processable starch, P = proportion of copolymer, and K = proportion of polyethylene are used.
The polyethylene used was a high density polyethylene produced by BASF. Likewise listed in the Table i.s the proportion of plasticizes, ar glycerine present in the thermoplastically processable starch that was used.
The polymer mixtures that were produced in accordance with the present invention and listed in the following Table were used to produce films which were tested for their tensile strength and elongation properties. The measurements obtained are also shown in the Table below.
Starch Polyethylene Copolymer Mixtures Produced in Accordance with the Invention Moisture Plasti- TPS/P/K Tensile Strength Stretch Content cizer Strength at o (% by weight) (MPa) strain limit 2.8 18.6 50:20:30 18.2 - 95.0 0.5 25.7 50:10:40 15.9 - 43.0 0.5 25.7 50:25:25 12.2 - 168.0 0.5 25.7 65:21:14 12.0 - 75.0 0.5 25.7 50:15:35 16.6 - 59.0 0.5 25.7 55:32:13 16.2 - 53.0 0.8 19.1 55:13:32 17.5 - 30.0 0,8 17.3 50:15:35 16.7 - 26.5 0.8 17.3 60:12:28 15.7 - 14.0 0.5 12.0 50:15:35 20.5 21.0 290 (longitudinally) 0.5 12.0 50:15:35 20.5 21.0 290 (diagonally) With regard to tensile strength, it can be seen that the ratio between the individual components is of very little impact.
On the other hand, it can be seen, however, that the proportions of polyethylene and copolymers have a great effect on the stretchability, and that a relatively small proportion of polyethylene or a small proportion of copolymers result in a relatively poor stretchability.
_4. Esterification Reaction During the process of mixing the thermoplastically processable starch, the polyethylene and the ethylene acrylate malefic acid anhydride in the extruder, an esterification reaction occurs between the malefic acid anhydride groups in the copolymer and the hydroxyl groups of the starch. Such an esterification reaction is, by the way, also possible between malefic acid anhydride groups and the glycerine that has been added to the starch as a plasticizer; 'this reaction is, however, relatively insignificant.
To confirm 'this reaction, samples of the polymer mixture ware taken from the extruder at the beginning and at the end of the mixing step, and corresponding infrared spectra were established as shown in Figure 1. It can be seen in Figure 1 that infrared active molecular vibrations of anhydride groups occur at 1780 cm.''. By comparison, infrared active molecular vibrations of the ester-groups are detectable at 1740 cm~.
Graph 1 shows the infrared spectrum at.the beginning of the mixing process, and Graph 2 shows the infrared spectrum at the end of the mixing process.
It has furthermore been found by means of infrared spectra of samples taken during the mixing process that the intensity of the "peaks" of the anhydride group decreases as the mixing process continues, whereas the intensity of the ester vibrations increases.
Figures 2 and 3 show heat flow diagrams of natural starch and glycerine respectively of thermoplastically processable starch.
~~3~'l ~~~
In Figures 4 and 5, the esterification reaction has been monitored by means of a thermal flux calorimeter having a heat rate of 10 ° /min. It shows the progress of an exothermic reaction at a temperature range from 165°C to 207°C, where a maximum peak 5 is visible at 190°C. Figure ~ is based on a thermoplastically processable starch to which an ethylene acrylate malefic acid anhydride copolymer has been added, and Figure 5 is based on natural starch and glycerine.
The polymer mixtures defined above in accordance with the 10 present invention and consisting of thermoplastically processable starch and a polyolefin, as for instance the polyethylene mentioned, and of the ethylene acrylate malefic acid anhydride copolymer, are suitable for the production of any kind of moulded body or extrudate. Particularly suitable for the production of films are polymer mixtures as defined in accordance with the invention, where these could be a single ply film as well as a multi-ply film, whereby, for their production, the polymer mixture as defined in the invention can be co-extruded together with thermoplastically processable starch.
It must furthermore be mentioned that instead of the ethylene acrylate malefic acid anhydride-copolymer, any vinyl combinations carrying anhydride functions as substituents can be used as well.
Polymer mixtures comprising starch are known, where starch l0 or other biopolymers are being used, preferably because of their biodegradability, their suitable price and their independence from petroleum products.
The use of biopolymers as technical material has been described in several patents. In EP-011 82 40, EP-28 24 51, EP
29 89 20, EP-30 44 01, EP-32 65 14, GB-22 14 919 and in EP-32 75 05, it is described how natural starch, gelatine or other biopolymers are modified or destructured respectively so that they can be used as technical polymers. This is accomplished by way of extrusion or by kneading of the starch or the biopolymer while utilizing the moisture content normally present in 'the biopolymer or in the starch, or by adding more water, in which case, however, just this relatively high water content for instance in the process of extrusion of the 'thus destructured biopolymers is extremely undesired. In contrast thereto, PCT-W090-05 161 proposes to take the water out of natural starch and by means of additives or plasticizing agents such as glycerine to convert it into a technically useful polymer, 'that is, a so-called thermoplastically processable starch. The workability as well as the moisture resistance of this starch polymer are of course considerably better than of those starch polymers that are produced in accordance with the above-mentioned processes.
However, the mechanical properties and in particular the moisture resistance are still unsatisfactory for many technical uses and in particular for the production of films.
For this reason, numerous patents, such as EP-040 28 26, EP-04047 23, EP-40 47 27, EP-40 27 28 and EP-40 73 50 propose to mix the starch with thermoplastic material such as polyolefins, polyalcohols, ABS copolymers, ethylene acrylic acid copolymers, copolymers of vinylpyrrolidines, copolymers having amino groups etc. respectively, to produce so-called polymer blends.
This creates, however, the problem of a poor compatibility between the starch and the further polymers, and results in a poor phase mixing of the individual polymers.
This can for instance be seen in films produced from these materials, where the non-starch proportion of polymer present in this mixture, when used by itself to produce a film, i.e. having a corresponding thinner sheet-thickness, exhibits better tensile strength than the thicker film produced from the total polymer mixture.
According to Patents EP-40 05 31 and EP-40 05 32 it is proposed to treat the starch analogous to W090-05 161 by means of a high boiling plasticizing agent, such as glycerine, urea, or sorbitol, in order to obtain thermoplastically processable starch in order to subsequently mix it with ethylene acrylic acid and/or polyvinyl alcohol copolymers. Films produced from these starch-polymer mixtures do exhibit a greater tensile strength; however, they are still not sufficiently moisture resistant.
The same applies to the starch-polymer mixtures prepared in accordance with W090-14 388, where polyethylene and ethylene acrylic acid copolymers are added to the glycerine starch.
It is, therefore, the purpose of this invention to propose a polymer mixture essentially consisting of starch, which is particularly well-suited to the production of films and which in moulds and extrudates, as for instance in films, exhibits good mechanical properties, as well as moisture resistance.
In accordance with the invention, this is achieved by means of a polymer mixture essentially consisting of starch i% a and a pol.yolefin, obtained by :=>ub.sv:arot.,, ai l y moistu:re--free mixing of thermoplastic<~11y pro~;es~aa~:~~l.e s,~~.~~z-~~:rwith at least one polyolefin and at 1_east. or:,e ~~tx~y lEoe a<~rylate malefic acid anhydride copolymer so trjat thcmixt~re cons:i.sts essentially at least of the added a~orry>oner~t»; as well. as of the esterification product st:arcuh rn.alei.c:: ac i<i ester-malefic acid anhydride et:hylerse acry:hate r~c>pcaiyrriex , k espectively by means of a polymer mixture prepa:eed suc'r. that the nati:rral starch and/or a derivative thereof i.s rruix<~d s~aa.t:.r:~ 15 o by weight to 40 0 by weight:. ot: at l.e~.st <>r~e ~:La;~>tici.~?_i.izc:3 agenr~, substantially anhydrous, for th.e prodnct~io::o g:~f_ t:he.r_~~~~op L aat:ically processable starch, whereafter the :~arr~e, at:. <~ tE~m~:~er~~ture of betw~sen 165°C
to 210°C, i.s mixed in the me_Lt with a po.Lyo:le:f:in and an ethylene acrylat~~ malei.c awi.~.:~ aro~yc~iride cod>olymE:r, whereby malefic acid anhydride groups fir: true pc>Lyrc~ers are esterified by means of free 1-rydx:oxy.i. grcoap:> ire y~he starch ir3 a manner similar analogous to the fol_l.ow.i.rag genera L reaction process 2 0 ~''~' ~ ~ ~"'~'''~ 'rte STARCH - OH +
~°/ ~ 1~''I
D
Starcr~ "~ ~l R
Starch' ~~ w ~ ~ -~
or p h ._ n ~ta.r. ch b ~: ~:?
Proposed is a po:Lyme~r mixt:u~:e ~-;~;ser-tial:.~y consisting of starch and polyolefi.rn, ol>fiain~cl t:~t~,- rczixing s~.zbstantially moisture-free therrr;c,plast.~~c~:~l_:1 ~ ~:yr:c>~;~f~>~:~;,.abi.e st:arc:h witwh at 1_east one polyolefin ana ~~t 1c1~.~t rare:=. et'.z~rlene acr5rl.ate malefic ac:i..d anhydride c~opc~l ymer ar~rl,.~,::~r c~rj.: ~Ti iu~;e.'a compound carrying an~ydride-f.unct:i.on as s.zbst:.:i.t~.aez~t~~ ~ "I'tie definition and production of thermoplast:ically processable starch is taught in WO-05 161.
The effect of the copolymer or the vinyl compound respectively is to be seen in the fact. that .it acts as a phasing agent between the starch phase and the polyolefin phase. The copolymer comprises hydrophobic particles, as well as hydrophillic particles and permeates, therefore, the boundaries between the starch and the polyolefin.
The polymer mixture propc.~sed :.n accordance with the present invention is obta.iruec. ~.yy .rna_x:inc~ :L:~bstantia.lls~ up to 70 0 by weight thermoplastically pzoc~essab:~.e starch containing at least one plastic:i~zing ageni~. w.it:~ .fJ; ay weight to 90% by we:~ght of polyolE:~f:~:L~~ anal ~°k:ay w~:i.a~~n.t: t:~::> 35 ~ by weight of ethylene acrylate malefic acid aanhydr.iaie copolymer.
In order to obtain on the one hand good mechanical properties, such as stability of moulds and extrudates such as films, and high moisture-resistance, it is, in accordance with the invention, proposed to mix 45~ by weight to 70% by weight, preferably 50 % by weight to 6~ ~ kay weight, oaf thermoplastically processable starch containing at least one plasticizing agent selected from the list of gLycera.ne, urea, an amino-alcohol, sorbitol and/or succinic acid anhydride comprising 10% by weight to 40% by weight, preferably 20% by weight to 35% by weight, of polyethylene or polypropylene with ~.~:~~5 by weight to 35% by weight, preferably 15% by weight to 25% by weight, of ethylene acrylate malefic acid anhydride copolymer. Moisture resistance, as well as high stability are :influen~:ed by the proportion of polyolefin and the copolymers, whereby on the other hand too high a proportion of these two <~omponents in the mixture: is, in particular for cost reasons, not desirable, In the case of films, too high a proportion of these components results furthermore irx an in~;reased gas permeability, whereas in the case of too high a proportion of starch, for instance, the oxygen permeability is decreased.
For the production of the aforementioned polymer mixtures in accordance with the invention, it is proposed that natural starch and/or a derivative there~>f, is mixed with 15~ by weight to 40~ by weight of at least one plasticizing agent such as glycerine, urea, an amine alcohol, sarbitoi and/or succinic acid anhydr~_<~e, substari'_:i<~l=L~y f re ,,.,;,: a~c:i ~ :~.r~~~, for f~rue purpose of producing thermoplastically processable :March, whereupon the starch thus produced is mixed in the melt at a temperature range of 165°C to 210°C with a polyolef.in, a:~ far instance preferably polyethylene and/'or polypropylene, and an ethylene acrylate malefic acid anhydride copolymer and a vinyl compound respectively, carrying anhydride funct:~_an as a substituent.
In this mixing process, mal.eic acid anhydride groups and generally all anhydride function in the capo.lymer is esterified in a mariner similar to the fal.lawing general progress of reaction:
STARCH -- OH +
r~
o S to ~ch Starch ~~ ' ~ ~ 1 ~ !
C7 ''~. ~ N
or ~,. o .~. / /' The polyolefin, as far instance the polyethylene or the polypropylene, forms a sort of a anatrix in which the :March will be enclosed. As mentioned before, the copolymer and the vinyl compound respectively, serve to achieve a strong bond between the polyethylene and polypropylene respectively, and the starch and the two phases respectively, so that in the case of 5 moulds and films accordingly produced from this polymer mixture good mechanical properties such as stability, are obtained.
This bonding at the phase boundary is achieved, as mentioned before, by means of the copolymer, for which, as already mentioned, in particular the esterification reaction is responsible. It can be proven by means of the infrared spectrum that the said reaction between the starch and the copolymer occurs during the mixing process. This detection by means of the infrared spectrum will be discussed later.
Preferred variations of execution of the process in accordance with the invention, as in particular also the production of thermoplastically processable starch and of the ethylene acrylate malefic acid anhydride copolymer are characterized in that:
- up to 70o by weight of thermoplastically processable starch is mixed in an extruder or kneader with 10o by weight to 40o by weight of polyethylene and/or polypropylene and 10%
by weight to 35o by weight of an ethylene acrylate malefic acid anhydride copolymer, whereby during the mixing process the total mechanical energy created amounts to approximately 0.4 kWh/kg and an adequate mixing action is achieved by means of kneading-blocks and appropriate backwash elements arranged in the extruder or kneader;
- natural starch and/or one derivative thereof having a moisture content of less than to is homogenized with the plasticizing agent at a temperature of 160°C to 190°C in an extruder or kneader, whereupon in a further extrusion or in 5a the same extruder in a further step, mixing with polyethylene and/or polypropylene and the copolymer takes place;
- the natural starch and/or a derivative thereof is pre mixed with the plasticizing agent essentially at room temperature or higher, whereupon the starch will swell, forming an essentially dry granulate which subsequently will be used for further working and for mixing with polyethylene and/or polypropylene, as well as with the copolymer; and - an ethylene acrylate malefic acid anhydride copolymer is being used which is obtained by working-up of 80o by weight to 95a by weight of ethylene, 1o by weight to 15o by weight of acrylic acid methyl ester and/or acrylic acid ethyl ester, as well as O.lo by weight to 15o by weight of malefic acid anhydride.
Here again it has to be pointed out, that the production of thermoplastically processable starch is taught in W090-05 161.
The polymer mixtures produced in accordance with the present invention are especially well suited to the production of single or multi-ply films. The production of the polymer mixture can immediately be followed by the production of the film, in that the molten polymer mixture is extruded by means of a wide-mouth jet or a blow head. It is, however, also possible to first granulate the polymer mixture and to use the granulate later to produce a film.
It is in particular also possible to co-extrude the polymer mixture prepared in accordance with the present invention together with other polymers in order to produce multi-ply films, whereby for instance a three-ply film can be produced, where each outer ply contains the polymer mixture of the present invention, ~~fi'~~~~~
while the middle ply is produced from essentially thermoplastically processable starch.
It is also possible, prior to the extrusion of the polymer mixture produced in accordance with the invention, to mix in a propellant, for instance sodium carbonate or an organic acid, in which case the organic acid could for instance be citric acid.
It is, of course, also possible to produce moulds from the polymer mixture proposed by the invention, or extrudates such as hoses, where the composition of the ;polymer mixture, within the limits suggested by the invention, is dictated by the demands of the article to be produced.
Tre invention will now be explained by means of examples and by reference to 'the attached diagrams as follows:
Figure 1 shows infrared spectra of the polymer mixture at the beginning and at the end of the mixing process.
Figure 2 shows the heat flow diagram of natural starch with glycerin.
Figures 3 shows the heat flow diagram of thermoplastically processable starch.
Figure 4 shows the heat flow diagram when thermoplastically processable starch mixed with an ethylene acrylate malefic acid anhydride copolymer, and Figure 5 shows the heat flow diagram when natural starch and glycerine are mixed with an ethylene acrylate malefic acid anhydride copolymer.
1. Production of the thermoplastically ~~rocessable starch One starts with dried natural starch having a moisture content of preferably less than 1% by weight. The natural starch is hydrolysed by means of a suitable plasticizer, as for instance glycerine, whereby, in relation to the total mixture, preferably between 25~ by weight and 35% by weight of glycerine is added.
The starch/glycer:ine mixture is subseduently well mixed in an extruder at a temperature between 160'C and 190'C, preferably with high shearincJ action, or this mixing could also be done in a kneader.
2~~'"~~~~~
Suitable plasticizers are, of course, also other materials, such as urea, sorbitol, succinic acid anhydride, amino alcohols etc., and at this point attention should be drawn again to Wo90 05 161, where a series of further suitable plasticizers and additives are defined.
The subsequent treatment of the thermoplastically processable starch thus produced can be carried out directly in the same extruder or the starch can first be granulated.
2. Ethylene acrylate malefic acid anhydride copolymer Tt is not intended to elaborate at this point on the production of these copolymers since they are basic products and do not constitute a feature of the present invention.
The copolymers suitable for the present invention are copolymers preferably composed as follows:
Parts b~ Weiaht Ethylene: 80-95% by weight Acrylic acid methyl ester:
5--15% by weight Acrylic acid ethyl ester:
Malefic acid anhydride: 0.2-1% by weight In the following example of a polymer mixture produced in accordance with the present invention, a copolymer having the following parts by weight has been used:
Ethylene: 88.0% by weight Acrylic acid methyl ester: 9.0% by weight Acrylic acid ethyl ester: 2.5% by weight Malefic acid anhydride: 0.5% by weight 3. Production of a starch ethylene copolymer mixture Following the production of the thermoplastically processable starch in accordance with point 1), a homogeneous.
mixture consisting of polyethylene and the copolymer in accordance with point 2 ) was added to the starch melt at the beginning of the second mixing phase in the same extruder at a ~Uc~~'l ~~~~
temperature of 170°C as set at the extruder. The temperature of the melt was at this point about 190°C to 200°C. The starch, polyethylene, copolymer mixture was thereafter, during that second mixing step, mixed under strong shearing action created by means of kneading blocks arid backwash elements. Preferably a co-kneader or a twin-shaft extruder is used. The total mechanical energy created amounted to approximately 0.4 kWh/kg.
The quantities of the polyethylenes and copolymers that have been added are listed in the following Table, where in the abbreviation TPS = thermoplastically processable starch, P = proportion of copolymer, and K = proportion of polyethylene are used.
The polyethylene used was a high density polyethylene produced by BASF. Likewise listed in the Table i.s the proportion of plasticizes, ar glycerine present in the thermoplastically processable starch that was used.
The polymer mixtures that were produced in accordance with the present invention and listed in the following Table were used to produce films which were tested for their tensile strength and elongation properties. The measurements obtained are also shown in the Table below.
Starch Polyethylene Copolymer Mixtures Produced in Accordance with the Invention Moisture Plasti- TPS/P/K Tensile Strength Stretch Content cizer Strength at o (% by weight) (MPa) strain limit 2.8 18.6 50:20:30 18.2 - 95.0 0.5 25.7 50:10:40 15.9 - 43.0 0.5 25.7 50:25:25 12.2 - 168.0 0.5 25.7 65:21:14 12.0 - 75.0 0.5 25.7 50:15:35 16.6 - 59.0 0.5 25.7 55:32:13 16.2 - 53.0 0.8 19.1 55:13:32 17.5 - 30.0 0,8 17.3 50:15:35 16.7 - 26.5 0.8 17.3 60:12:28 15.7 - 14.0 0.5 12.0 50:15:35 20.5 21.0 290 (longitudinally) 0.5 12.0 50:15:35 20.5 21.0 290 (diagonally) With regard to tensile strength, it can be seen that the ratio between the individual components is of very little impact.
On the other hand, it can be seen, however, that the proportions of polyethylene and copolymers have a great effect on the stretchability, and that a relatively small proportion of polyethylene or a small proportion of copolymers result in a relatively poor stretchability.
_4. Esterification Reaction During the process of mixing the thermoplastically processable starch, the polyethylene and the ethylene acrylate malefic acid anhydride in the extruder, an esterification reaction occurs between the malefic acid anhydride groups in the copolymer and the hydroxyl groups of the starch. Such an esterification reaction is, by the way, also possible between malefic acid anhydride groups and the glycerine that has been added to the starch as a plasticizer; 'this reaction is, however, relatively insignificant.
To confirm 'this reaction, samples of the polymer mixture ware taken from the extruder at the beginning and at the end of the mixing step, and corresponding infrared spectra were established as shown in Figure 1. It can be seen in Figure 1 that infrared active molecular vibrations of anhydride groups occur at 1780 cm.''. By comparison, infrared active molecular vibrations of the ester-groups are detectable at 1740 cm~.
Graph 1 shows the infrared spectrum at.the beginning of the mixing process, and Graph 2 shows the infrared spectrum at the end of the mixing process.
It has furthermore been found by means of infrared spectra of samples taken during the mixing process that the intensity of the "peaks" of the anhydride group decreases as the mixing process continues, whereas the intensity of the ester vibrations increases.
Figures 2 and 3 show heat flow diagrams of natural starch and glycerine respectively of thermoplastically processable starch.
~~3~'l ~~~
In Figures 4 and 5, the esterification reaction has been monitored by means of a thermal flux calorimeter having a heat rate of 10 ° /min. It shows the progress of an exothermic reaction at a temperature range from 165°C to 207°C, where a maximum peak 5 is visible at 190°C. Figure ~ is based on a thermoplastically processable starch to which an ethylene acrylate malefic acid anhydride copolymer has been added, and Figure 5 is based on natural starch and glycerine.
The polymer mixtures defined above in accordance with the 10 present invention and consisting of thermoplastically processable starch and a polyolefin, as for instance the polyethylene mentioned, and of the ethylene acrylate malefic acid anhydride copolymer, are suitable for the production of any kind of moulded body or extrudate. Particularly suitable for the production of films are polymer mixtures as defined in accordance with the invention, where these could be a single ply film as well as a multi-ply film, whereby, for their production, the polymer mixture as defined in the invention can be co-extruded together with thermoplastically processable starch.
It must furthermore be mentioned that instead of the ethylene acrylate malefic acid anhydride-copolymer, any vinyl combinations carrying anhydride functions as substituents can be used as well.
Claims (18)
1. A composition, essentially consisting of starch and a polyolefin, obtained by mixing substantially moisture-free thermoplastically processable starch with at least one polyolefin and at least one ethylene acrylate maleic acid anhydride copolymer so that the mixture consists essentially of the added components as well as of the esterification product starch maleic acid ester-maleic acid anhydride ethylene acrylate copolymer.
2. A composition, in accordance with Claim 1, obtained by mixing thermoplastically processable starch containing at least one plasticizing agent in a quantity of substantially up to 70% by weight of the composition with polyolefin in a quantity of 10% by weight to 90% by weight of the composition and an ethylene acrylate maleic acid anhydride copolymer in a quantity of 1% by weight to 35% by weight of the composition so that the mixture consists essentially at least of the added components as well as of the esterification product from the starch and the copolymer.
3. A composition, in accordance with any one of Claims 1 or 2, obtained by mixing thermoplastically processable starch containing at least one plasticizing agent in a quantity of 45% by weight to 70% by weight of the composition from the list of glycerine, urea, an amino alcohol, sorbitol, and/or succinic acid anhydride; polyethylene or polypropylene in a quantity of 10% by weight to 40% by weight of the composition and an ethylene acrylate maleic acid anhydride copolymer in a quantity of 10% by weight to 35% by weight of the composition.~
4. A process for the production of a composition, essentially consisting of starch and a polyolefin, characterized in that the natural starch and/or a derivative thereof is mixed with at least one plasticizing agent, substantially anhydrous, in a quantity of 15% by weight to 40%
by weight of the composition, for the production of thermoplastically processable starch, whereafter the same, at a temperature of between 165°C to 210°C, is mixed in the melt with a polyolefin and an ethylene acrylate maleic acid anhydride copolymer, whereby maleic acid anhydride groups in the polymers are esterified by means of free hydroxyl groups in the starch in a manner similar analogous to the following general reaction process:
by weight of the composition, for the production of thermoplastically processable starch, whereafter the same, at a temperature of between 165°C to 210°C, is mixed in the melt with a polyolefin and an ethylene acrylate maleic acid anhydride copolymer, whereby maleic acid anhydride groups in the polymers are esterified by means of free hydroxyl groups in the starch in a manner similar analogous to the following general reaction process:
5. A process, in accordance with Claim 4, characterized in that thermoplastically processable starch in a quantity of up to 70% by weight of the composition is mixed in an extruder or kneader with polyethylene and/or polypropylene in a quantity of 10% by weight to 40% by weight of the composition and an ethylene acrylate maleic acid anhydride copolymer in a quantity of 10% by weight to 35% by weight of the composition, whereby during the mixing process the total mechanical energy created amounts to approximately 0.4 kWh/kg and an adequate mixing action is achieved by means of kneading-blocks and appropriate backwash elements arranged in the extruder or kneader.
6. A process, in accordance with any one of Claims 4 or 5, characterized in that natural starch and/or one derivative thereof having a moisture content of less than 1% is homogenized with the plasticizing agent at a temperature of 160°C to 190°C in an extruder or kneader, whereupon in a further extrusion or in the same extruder in a further step, mixing with polyethylene and/or polypropylene and the copolymer takes place.
7. A process, in accordance with one of Claims 4 or 5, characterized in that the natural starch and/or a derivative thereof is pre-mixed with the plasticizing agent substantially at room temperature or higher, whereupon the starch will swell, forming an essentially dry granulate which subsequently will be used for further working and for mixing with polyethylene and/or polypropylene, as well as with the copolymer.
8. A process, in accordance with any one of Claims 4 through 7, characterized in that an ethylene acrylate maleic acid anhydride copolymer is being used which is obtained by working-up of ethylene in a quantity of 80% by weight to 95 %
by weight of the composition, acrylic acid methyl ester and / or acrylic acid ethyl ester in a quantity of 1% by weight to 15%
by weight of the composition, as well as maleic acid anhydride in a quantity of 0.1% by weight to 15% by weight of the composition.
by weight of the composition, acrylic acid methyl ester and / or acrylic acid ethyl ester in a quantity of 1% by weight to 15%
by weight of the composition, as well as maleic acid anhydride in a quantity of 0.1% by weight to 15% by weight of the composition.
9. A film, consisting of at least one single ply, consisting essentially of a polymer mixture in accordance with any one of Claims 1 through 3.
10. A single or multi-ply film produced by the process as defined in any one of Claims 4 to 8 comprising at least one ply consisting of a polymer mixture in accordance with one of Claims 1 through 3, characterized in that the polymer mixture produced in accordance with any one of Claims 4 through 8 is processed into a film.
11. A single or multi-ply film in accordance with Claim 10, characterized in that the mixture by means of an substantially pure thermoplastically processable starch comprising a plasticizing agent is co-extruded to produce a two-ply or multi-ply film.
12. A foam-like film produced by the process as defined in any one of Claims 4 to 8, comprising a polymer mixture in accordance with any one of Claims 1 through 3, characterized 14a in that prior to its extrusion a propelling agent such as sodium carbonate or an organic acid, is added to the polymer mixture.
13. A moulded body or extrudate, essentially consisting of a polymer mixture in accordance with any one of Claims 1 through 3.
14. A composition in accordance with Claim 3, wherein the composition comprises 50% by weight to 65% by weight thermoplastically processable starch, 20% by weight to 35% by weight polyethylene or polypropylene and 15% by weight to 25%
by weight ethylene acrylate maleic acid anhydride copolymer.
by weight ethylene acrylate maleic acid anhydride copolymer.
15. A process in accordance with Claim 4, wherein the plasticizing agent can be glycerine, urea, an amino alcohol, sorbitol or succinic acid anhydride and the polyolefin can be polyethylene.
16. A process in accordance with Claim 6, wherein the process takes place under strong shearing action.
17. A single or multi-ply film in accordance with Claim 10, wherein the polymer mixture is processed into a film by means of wide-mouth extrusion, blow extrusion or co-extrusion.
18. A foam-like film in accordance with Claim 12 wherein the organic acid is citric acid.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4116404.0 | 1991-05-18 | ||
| DE4116404A DE4116404A1 (en) | 1991-05-18 | 1991-05-18 | POLYMERMISCHUNG FOR THE MANUFACTURE OF FOILS |
| PCT/CH1992/000091 WO1992020740A1 (en) | 1991-05-18 | 1992-05-12 | Polymer mixture for producing foils |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2087444A1 CA2087444A1 (en) | 1992-11-19 |
| CA2087444C true CA2087444C (en) | 2005-11-29 |
Family
ID=6432013
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002087444A Expired - Lifetime CA2087444C (en) | 1991-05-18 | 1992-05-12 | Polymer mixture for producing films |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5314934A (en) |
| EP (1) | EP0539544B1 (en) |
| JP (1) | JP3137198B2 (en) |
| AT (1) | ATE113635T1 (en) |
| AU (1) | AU1670592A (en) |
| CA (1) | CA2087444C (en) |
| DE (2) | DE4116404A1 (en) |
| HK (1) | HK1006847A1 (en) |
| HU (1) | HU211429B (en) |
| WO (1) | WO1992020740A1 (en) |
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-
1991
- 1991-05-18 DE DE4116404A patent/DE4116404A1/en not_active Withdrawn
-
1992
- 1992-05-12 US US07/975,923 patent/US5314934A/en not_active Expired - Fee Related
- 1992-05-12 WO PCT/CH1992/000091 patent/WO1992020740A1/en active IP Right Grant
- 1992-05-12 DE DE59200729T patent/DE59200729D1/en not_active Expired - Lifetime
- 1992-05-12 HU HU9300119A patent/HU211429B/en not_active IP Right Cessation
- 1992-05-12 AU AU16705/92A patent/AU1670592A/en not_active Abandoned
- 1992-05-12 AT AT92909525T patent/ATE113635T1/en not_active IP Right Cessation
- 1992-05-12 EP EP92909525A patent/EP0539544B1/en not_active Expired - Lifetime
- 1992-05-12 CA CA002087444A patent/CA2087444C/en not_active Expired - Lifetime
- 1992-05-12 JP JP04508422A patent/JP3137198B2/en not_active Expired - Lifetime
-
1998
- 1998-06-22 HK HK98105977A patent/HK1006847A1/en not_active IP Right Cessation
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|---|---|
| HUT68437A (en) | 1995-06-28 |
| HU9300119D0 (en) | 1993-04-28 |
| EP0539544A1 (en) | 1993-05-05 |
| JP3137198B2 (en) | 2001-02-19 |
| WO1992020740A1 (en) | 1992-11-26 |
| US5314934A (en) | 1994-05-24 |
| AU1670592A (en) | 1992-12-30 |
| ATE113635T1 (en) | 1994-11-15 |
| JPH06500149A (en) | 1994-01-06 |
| CA2087444A1 (en) | 1992-11-19 |
| HU211429B (en) | 1995-11-28 |
| DE59200729D1 (en) | 1994-12-08 |
| EP0539544B1 (en) | 1994-11-02 |
| DE4116404A1 (en) | 1992-11-19 |
| HK1006847A1 (en) | 1999-03-19 |
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