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Title:
PROCESS FOR PRODUCING POLYMER BLEND
Document Type and Number:
WIPO Patent Application WO/2018/219845
Kind Code:
A1
Abstract:
The invention relates to a process for producing a blend of a thermoplastic starch and a polyolefin using a first extruder comprising successive zones comprising a first zone, a second zone, a third zone and a fourth zone and a second extruder comprising successive zones comprising a first zone, a second zone, a third zone and a fourth zone, the process comprising the steps of: 1 a) introducing a polyolefin and a compatibilizer in the first zone of the first extruder, 1 b) melt mixing the polyolefin and the compatibilizer in the second zone of the first extruder, 1 c) adding a thermoplastic starch to the mixture of step 1 b) in the third zone of the first extruder and 1 d) melt-mixing the mixture of step 1 c) in the fourth zone of the first extruder to obtain the blend, wherein the thermoplastic starch is produced in the second extruder by a process comprising the steps of: 2a) introducing starch in the first zone of the second extruder, 2b) adding a plasticiser to the mixture of step 2a) in the second zone of the second extruder to obtain the thermoplastic starch, 2c) degassing the thermoplastic starch of step 2b) in the third zone of the second extruder and 2d) pressurizing the degassed thermoplastic starch of step 2c) in the fourth zone of the second extruder to be moved to the third zone of the first extruder.

Inventors:
MARTENS JOHANNES (NL)
SCHIPPER RONALD (NL)
Application Number:
PCT/EP2018/063879
Publication Date:
December 06, 2018
Filing Date:
May 28, 2018
Export Citation:
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Assignee:
SABIC GLOBAL TECHNOLOGIES BV (NL)
International Classes:
B01F15/02; B32B27/08; B65D65/40; B65D81/24; C08F10/00; C08J3/20; C08J5/18
Domestic Patent References:
WO2013178746A12013-12-05
WO2015071396A12015-05-21
WO2011020170A12011-02-24
WO2016109196A12016-07-07
WO2013178746A12013-12-05
Foreign References:
US20140272370A12014-09-18
US20110118390A12011-05-19
US20130154151A12013-06-20
US9045625B22015-06-02
Attorney, Agent or Firm:
SABIC INTELLECTUAL PROPERTY GROUP (NL)
Download PDF:
Claims:
CLAIMS

A process for producing a blend of a thermoplastic starch and a polyolefin using a first extruder comprising successive zones comprising a first zone, a second zone, a third zone and a fourth zone and a second extruder comprising successive zones comprising a first zone, a second zone, a third zone and a fourth zone, the process comprising the steps of:

1 a) introducing a polyolefin and a compatibilizer in the first zone of the first extruder,

1 b) melt mixing the polyolefin and the compatibilizer in the second zone of the first extruder,

1 c) adding a thermoplastic starch to the mixture of step 1 b) in the third zone of the first extruder and

1 d) melt-mixing the mixture of step 1 c) in the fourth zone of the first extruder to obtain the blend,

wherein the thermoplastic starch is produced in the second extruder by a process comprising the steps of:

2a) introducing starch in the first zone of the second extruder,

2b) adding a plasticiser to the mixture of step 2a) in the second zone of the second extruder to obtain the thermoplastic starch,

2c) degassing the thermoplastic starch of step 2b) in the third zone of the second extruder and

2d) pressurizing the degassed thermoplastic starch of step 2c) in the fourth zone of the second extruder to be moved to the third zone of the first extruder.

The process according to claim 1 , wherein the amount of the polyolefin is 10 to 70 wt% based on the blend, the amount of the compatibiliser is 3 to 30 wt% based on the blend and/or the amount of the thermoplastic starch is 10 to 70 wt% based on the blend.

The process according to any one of the preceding claims, wherein the polyolefin is selected from the group consisting of propylene homopolymers, ethylene propylene copolymers, polyethylene such as high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene and mixtures of at least two of the foregoing polyolefins.

4. The process according to any one of the preceding claims, wherein the

compatibiliser is selected from ethylene acrylic acid copolymers, ethylene vinyl acetate copolymers, polyolefins having at least 1 wt% maleic anhydride grafted thereon, ethylene vinyl alcohol copolymers, block saponified polyvinyl acetate, random terpolymers of ethylene, butylacrylate and maleic anhydride, random, partially hydrolised and saponified polyvinylacetate and mixtures of at least two of these compatibilisers.

5. The process according to any one of the preceding claims, wherein the amount of the starch is about 30 to 90 wt%, for example 35 to 80 wt%, 35 to 70 wt%, 35 to 60 wt% or 40 to 50 wt%, relative to the total weight of the starch and the plasticiser.

6. The process according to any one of the preceding claims, wherein the plasticiser is glycerol and/or sorbitol plasticiser.

7. The process according to any one of the preceding claims, wherein step 2c) is performed at a temperature of 1 10 to 140 5C.

8. The process according to any one of the preceding claims, wherein the first

extruder is a twin screw extruder and the second extruder is a twin screw extruder.

9. A process for producing a biaxially stretched film, comprising the process for

producing the blend according to any one of claims 1 -8 and stretching the blend at elevated temperatures in a machine direction and a transverse direction.

10. The blend of the thermoplastic starch and the polyolefin obtainable by or obtained by the process according to any one of claims 1 -8.

1 1 . The biaxially stretched film obtainable by or obtained by the process according to claim 9.

12. The biaxially stretched film obtainable by or obtained by the process according to claim 9 wherein the film has a clarity of at least 60%, preferably 70%, more preferably 75%.

13. A multi-layer film comprising the biaxially stretched film according to claims 1 1 -12 and a polymer film provided on each side of the biaxially stretched film.

14. A multi-layer film comprising the biaxially stretched film according to claims 1 1 -12 and a polymer film provided on each side of the biaxially stretched film, wherein the film has a clarity of at least 60%, preferably 70%, more preferably 75%.

Description:
PROCESS FOR PRODUCING POLYMER BLEND

The present invention relates to a process for producing a blend of a thermoplastic starch and a polyolefin. The invention further relates to the blend obtained thereby and its use.

Blending highly viscous and low viscous polymer into a well-dispersed polymer/polymer compound is most commonly executed on one twin screw extruder with suitable screw design under suitable compound conditions. One example is the production of a blend of polyethylene (PE) and thermoplastic starch (TPS). The ingredients for the formation of the thermoplastic starch as well as polyethylene and compatibilizer are fed into the throat of a twin screw extruder. In the first part of the extruder TPS is formed by the gelatinization process of native starch, glycerol and additives, while the PE and the compatibilizer are still solid. In the second part of the twin screw extruder the barrel temperature is raised. The PE and the compatibilizer become molten and the TPS phase and the PE phase are mixed intensively into a homogeneous material.

If the viscosity difference between the low molecular weight polymer and the high molecular weight polymer becomes too great, it may not be possible to produce a well- dispersed blend of these polymers. The resulting blend may comprise gels and/or may have inhomogeneous appearance.

This problem becomes more pronounced for the production of a blend on a large scale. High temperature spots tend to appear in a large scale production system, which leads to an inhomogeneous blend.

Adjustment of the screw design of the twin screw extruder is not always sufficient for producing a well-dispersed blend of these polymers, especially for the production on a large scale.

It is an objective of the invention to solve the above-mentioned and/or other problems.

The present invention provides a process for producing a blend of a thermoplastic starch and a polyolefin using a first extruder comprising successive zones comprising a first zone, a second zone, a third zone and a fourth zone and a second extruder comprising successive zones comprising a first zone, a second zone, a third zone and a fourth zone, the process comprising the steps of:

1 a) introducing a polyolefin and a compatibilizer in the first zone of the first extruder, 1 b) melt mixing the polyolefin and the compatibilizer in the second zone of the first extruder,

1 c) adding a thermoplastic starch to the mixture of step 1 b) in the third zone of the first extruder and

1 d) melt-mixing the mixture in the fourth zone of the first extruder to obtain the blend, wherein the thermoplastic starch is produced in the second extruder by a process comprising the steps of:

2a) introducing starch in the first zone of the second extruder,

2b) adding a plasticiser to the mixture of step 2a) in the second zone of the second extruder to obtain the thermoplastic starch,

2c) degassing the thermoplastic starch of step 2b) in the third zone of the second extruder and

2d) pressurizing the degassed thermoplastic starch of step 2c) in the fourth zone of the second extruder to be added to the third zone of the first extruder.

According to the process of the invention, the thermoplastic starch is produced in a separate extruder (second extruder) from the first extruder, and the first extruder is used for melting the polyolefin and making the blend of the thermoplastic starch and the polyolefin. The formation of the thermoplastic starch has already been completed when it is mixed with the blend of the polyolefin and the compatibilizer. This ensures that a homogeneous composition is obtained.

The production of the thermoplastic starch requires sufficient residence time. The second extruder can advantageously be adjusted independently from the first extruder to ensure sufficient residence time, when the process conditions for producing the thermoplastic starch are to be changed.

The degassing step 2c) reduces the water content in the thermoplastic starch.

Performing the degassing step at this stage is more advantageous than performing degassing on a composition comprising both the thermoplastic starch and the polyolefin, such as done in a single extruder. According to the invention, degassing can be performed at a lower temperature in the absence of the polyolefin. In a single extruder, the degassing can only be performed in the presence of all components including polyolefin. The presence of the polyolefin melt requires the temperature of the degassing step to be high, which leads to the risk of the decomposition of the starch. Furthermore, when the temperature is high, the degassing leads to a large amount of vapor to exit from the extruder, which has a risk of the produced blend being pushed out from the extruder. This would block the venting path and the system. According to the process of the invention, this process instability is avoided.

It is noted that US9045625 discloses a continuous process of producing a

thermoplastic starch/polymer blend by introducing starch and a plasticizer into a twin- screw extruder to form thermoplastic starch and thereafter introducing dry solid polymer to form the thermoplastic starch/polymer blend. In this process, a

thermoplastic starch is first produced in a twin-screw extruder, after which dry solid polymer is introduced. The time for the thermoplastic starch to be formed is limited by the design of the twin-screw extruder. If the formation of the thermoplastic starch has not been completed before the introduction of the solid polymer, the resulting composition may not be homogeneous.

First extruder

The blend of the polyolefin and the thermoplastic starch is formed in the first extruder. The first extruder comprises successive zones comprising a first zone, a second zone, a third zone and a fourth zone.

A polyolefin and a compatibilizer are introduced in the first zone of the first extruder. The polyolefin and the compatibilizer are melt mixed in the second zone of the first extruder. A thermoplastic starch is added to the melt-mixture of the polyolefin and the compatibilizer in the third zone of the first extruder. The mixture of the polyolefin, the compatibilizer and the thermoplastic starch is melt-mixed in the fourth zone of the first extruder to obtain the thermoplastic starch/polymer blend.

Typical temperatures ranges of the zones during compounding are:

- 1 st zone [°C]: 120-130, e.g. 121 -129

- 2 nd zone [°C]: 130-161 , e.g. 138-161

- 3 rd zone [°C]: 130-160, e.g. 135-160

- 4 th zone [°C]: 130-160, 140-154 The residence time in the first extruder may e.g. be around 1 minute. Second extruder The thermoplastic starch to be mixed with the polyolefin is formed in the second extruder. The second extruder comprises successive zones comprising a first zone, a second zone, a third zone and a fourth zone. Starch and optional additives are introduced in the first zone of the second extruder. The starch and the optional additives can be introduced separately or as a mixture. Plasticiser is added in the second zone of the second extruder. The conditions of the second zone are selected such that the formation of the thermoplastic starch is completed. For example, the second zone has a temperature of at least 1 10 Q C and the residence time is at least 30 seconds. In the third zone, the formed thermoplastic starch is degassed. In the fourth zone, the degassed thermoplastic starch is moved to the third zone of the first extruder.

Typical temperatures ranges of the zones during compounding are:

- 1 st zone [°C]: 70 - 90

- 2 nd zone [°C]: 1 10 - 140

- 3 rd zone [°C]: 1 10 -140

- 4 th zone [°C]: 100 - 140 The residence time in the second extruder may e.g. be around 1 -2 minutes. Polyolefin

The polyolefin is preferably selected from the group consisting of propylene

homopolymers, ethylene propylene copolymers, polyethylene such as high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene and mixtures of at least two of the preceding polyolefins.

Preferably the density of the polyolefin is at least 0.910 g/cm 3 . In a preferred embodiment the polyolefin is polyethylene, in particular low density polyethylene (LDPE).

The amount of the polyolefin is preferably in the range of 10-70 wt%, e.g. 15-50 wt%, based on the blend.

Compatibilizer

The term "compatibiliser" as used herein is defined as a material having affinity with both the starch phase and the polyolefin phase and which material is able to improve the adhesion of the two phases at the interface so that the thermoplastic phase and the polyolefin phase can co-exist in the same article without the phases becoming physically separated. A compatibiliser suitable for use in the present invention consists of a molecular part which has high affinity and/or miscibility with the thermoplastic starch and a further molecular part which has high affinity and/or miscibility with the polyolefin.

Due to the non-polar nature of the polyolefin phase and the polar nature of the starch phase compatibilisers may be polymer materials having a non-polar backbone and a polar group incorporated in the backbone or grafted thereon. Such polar group may be reactive with respect to the starch and react with at least a part of the starch.

Compatibilisers may also be block copolymers having blocks of non-polar and polar monomers.

Examples of suitable compatibilisers include ethylene acrylic acid copolymers, ethylene vinyl acetate copolymers, polyolefins having at least 1 wt% maleic anhydride grafted thereon, ethylene vinyl alcohol copolymers, block saponified polyvinyl acetate, random terpolymers of ethylene, butylacrylate and maleic anhydride, random, partially hydrolised and saponified polyvinylacetate or mixtures of at least two of these compatibilisers.

Preferably, the compatibiliser is selected from the group consisting of ethylene vinyl alcohol copolymers, block saponified polyvinyl acetate and random terpolymers of ethylene, butylacrylate and maleic anhydride and mixtures thereof. The amount of the compatibiliser is preferably in the range of 3-30 wt% based on the blend. Preferably, the amount of the compatibiliser is 4-15 wt%, more preferably 5-10 wt%, even more preferably 5-7.5 wt% based on the blend.

Thermoplastic starch

Those skilled in the art will appreciate that thermoplastic starch is a de-structured form of starch comprising one or more plasticisers. Hence, for the avoidance of doubt it should be understood that processing aids, such as plasticisers, required for making thermoplastic starch from starch are considered as part of the thermoplastic starch.

The amount of the thermoplastic starch is preferably in the range of 10-70 wt%, e.g. 50-70 wt%, based on the blend. Starch

Starch is found mainly in seeds, fruits, tubers, roots and stem pith of plants, and is a naturally derived polymer made up of repeating glucose groups linked by glucosidic linkages in the 1 -4 carbon positions. Starch predominantly consists of amylose, a substantially linear polymer with molecular weight of about 1 x 10 5 and amylopectin, a highly branched polymer with very high molecular weight of the order 1 x 10 7 .

The starch may be from any suitable starch source such as corn, tapioca, maize, wheat, rice, potato, soy bean or any combination of at least two of these starch sources, potato starch being preferred because of its availability.

Each repeating glucose unit typically has three free hydroxyl groups, thereby providing the polymer with hydrophilic properties and reactive functional groups. Most starches contain 20 to 30% amylose and 70 to 80% amylopectin. However, depending on the origin of the starch the ratio of amylose to amylopectin can vary significantly. For example, some corn hybrids provide starch with 100% amylopectin (waxy corn starch), or progressively higher amylose content ranging from 50 to 95%.

Besides the native form of starch, a chemically modified starch may also be used in the present invention. Chemically modified starch includes, but is not limited to, oxidised starch, etherificated starch, esterified starch or a combination of such chemical modifications (e.g. etherificated and esterified starch). Suitable etherificated starch includes, but is not limited to starch that is substituted with ethyl and/or propyl groups. Suitable esterified starch includes, but is not limited to starch that is substituted with actyl, propanoyl and/or butanoyl groups.

Chemically modified starch is generally prepared by reacting the hydroxyl groups of starch with one or more reagents. The degree of reaction, often referred to as the degree of substitution (DS), can significantly alter the physiochemical properties of the modified starch compared with the corresponding native starch. The DS for a native starch is designated as 0 and can range up to 3 for a fully substituted modified starch. Depending upon the type of substituent and the DS, a chemically modified starch can exhibit considerably different hydrophilic/hydrophobic character relative to native starch. The amount of the starch may typically be from about 30 to 90 wt%, for example 35 to 80 wt%, 35 to 70 wt%, 35 to 60 wt% or 40 to 50 wt%, relative to the total weight of the starch and the plasticiser. Plasticiser

Preferably, the plasticiser is a polyhydric alcohol plasticiser. Suitable examples of the polyhydric alcohols include glycerol, ethylene glycol, propylene glycol, ethylene di- glycol, propylene di-glycol, ethylene tri-glycol, propylene tri-glycol, polyethylene glycol, polypropylene glycol, 1 ,2-propanediol, 1 ,3-propanediol, 1 ,2-butanediol, 1 ,3-butanediol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, 1 ,5-hexanediol, 1 ,2,6-hexanetriol, 1 ,3,5-hexanetriol, neo-pentyl glycol, trimethylol propane, pentaerythritol, mannitol, sorbitol, and the acetate, ethoxylate, and propoxylate derivatives thereof.

Preferably, the plasticiser is glycerol and/or sorbitol plasticisers.

The amount of the starch may typically be from about 10 to 70 wt%, for example 20 to 65 wt%, 30 to 65 wt%, 40 to 65 wt% or 50 to 60 wt%, relative to the total weight of the starch and the plasticiser. Additives

When present, the amount of the additives may typically be 0.1 to 5 wt% with respect to the blend. Typical additives include fatty acids and stearates, which act as processing aids and viscosity regulators for the thermoplastic starch. Blend

Preferably, the amount of the polyolefin is 20 to 80 wt%, for example 25 to 75 wt% or 30 to 70 wt% with respect to the total of the polyolefin and the thermoplastic starch in the blend. The blend according to the invention mainly consists of polyolefin, thermoplastic starch and compatibiliser, i.e. at least 80 wt% of the blend is polyolefin, thermoplastic starch and compatibiliser. Preferably, at least 90 wt% or at least 95 wt% of the blend is polyolefin, thermoplastic starch and compatibiliser. The invention further relates to the blend of the thermoplastic starch and the polyolefin obtainable by or obtained by the process according to the invention. The invention further relates to the blend of the thermoplastic starch and the polyolefin obtainable by or obtained by the process according to the invention, wherein the film produced from the blend may have a clarity of at least 60%, preferably 70%, more preferably 75%.

The invention further relates to an article comprising the blend according to the invention.

The article may be a biaxially stretched film made from the blend.

The invention further relates to a process for producing a biaxially stretched film comprising stretching the blend according to the invention at elevated temperatures in a machine direction and a transverse direction. Such process is described in detail e.g. in WO2013/178746, incorporated herein by reference. The film so-obtained has a multi-layered structure comprising layers of starch and polyolefin. The film according to the invention has the combination of both low oxygen permeability and low water vapour permeability. Accordingly, suitable examples of the article of the invention include food packaging. The biaxially stretched film according to the invention may have a thickness e.g. of 2 μηι to 250 μπι, more typically 5 μπι to 100 μηι, 20 to 80 μηι or 40 to 60 μηι.

The biaxially stretched film obtainable by or obtained by the process may have a clarity of at least 60%, preferably 70%, more preferably 75%.

The multi-layer film comprising the biaxially stretched film and a polymer film provided on each side of the biaxially stretched film may have a clarity of at least 60%, preferably 70%, more preferably 75%. In view of the starch phase, the temperature of the thermoplastic composition while being stretched may not be too high, because a too high temperature will cause yellowing or browning of the thermoplastic starch. The thermoplastic starch may also become brittle at too high temperatures, which is undesirable. A practical upper limit is 130°C. The lower temperature limit for the stretching depends to some extent on the blend, but in general it can be said that the lower limit is determined by the melting and crystallization temperature of the polyolefin phase. A practical lower limit may be 00°C, although a skilled person may easily find the practical lower limit by routine experimentation. Preferably, the stretching of the blend is performed at a temperature above the melting points of both the thermoplastic starch and the polyolefin.

The stretching process for obtaining the film of the present invention is not limited to a specific stretching process, yet it is preferred to use a film blowing technique, as such techniques are very suitable for making thin films. However, other stretching techniques such as calendaring may also be applied.

The article may also be a multi-layer film comprising the biaxially stretched film according to the invention and polymer films provided on each side of the biaxially stretched film according to the invention, wherein the polymer films preferably comprise a polyolefin such as polyethylene and a compatibiliser. Suitable examples include the compatibilisers described in relation to the blend according to the invention. Such polymer films may be provided on the biaxially stretched film according to the invention by means of lamination or co-extrusion prior or after stretching in machine direction and transverse direction.

The multi-layer film according to the invention may have a thickness e.g. of 2 μηι to 250 μιη, more typically 5 μιη to 100 μηη, 20 to 80 μιη or 40 to 60 μιτι. The ratio of the thickness between the biaxially stretched film and the remaining films in the multi-layer film may e.g. be 5:95 to 95:5, for example 40:60 to 60:40. In some embodiments, the multi-layer film according to the invention has a thickness of 40 to 60 μηι and the biaxially stretched film has a thickness of 2 to 25 μηι. It is noted that the invention relates to all possible combinations of features described herein, preferred in particular are those combinations of features that are present in the claims. It will therefore be appreciated that all combinations of features relating to the blend according to the invention; all combinations of features relating to the process according to the invention and all combinations of features relating to the blend according to the invention and features relating to the process according to the invention are described herein.

It is further noted that the term 'comprising' does not exclude the presence of other elements. However, it is also to be understood that a description on a product/blend comprising certain components also discloses a product/blend consisting of these components. The product/blend consisting of these components may be advantageous in that it offers a simpler, more economical process for the preparation of the product/composition. Similarly, it is also to be understood that a description on a process comprising certain steps also discloses a process consisting of these steps. The process consisting of these steps may be advantageous in that it offers a simpler, more economical process.

When values are mentioned for a lower limit and an upper limit for a parameter, ranges made by the combinations of the values of the lower limit and the values of the upper limit are also understood to be disclosed. The invention is now elucidated by way of the following examples, without however being limited thereto.

Experiments

Blends of an LDPE and a thermoplastic starch were prepared by a twin-screw extruder from components as shown in Table 1 .

A three layer blown film was prepared using this blend as the middle layer. The outer layers of the three layer blown film consist of a dry blend of LDPE and a compatibilizer which is a random terpolymer of ethylene, bytylarcylate and maleic anhydride (Lotader 3410). The temperature of the extruders (feeding the separate materials to the blow extruder) was 125-140-135-130-130°C at a screw speed of 50 rpm, line speed of 9 m/min and throughput rate of about 20 kg/hr. The blow up rate (BUR) of all the three layer materials was 3. In comparative experiments A-D and E-G, the blend of LDPE and thermoplastic starch was produced on a single twin screw extruder. The screw type, the ratio between the length and the diameter of the extruder and throughput were varied in comparative experiments A-D and in comparative experiments E-G. In comparative experiments A-D, the melt index was 1 .1 dg/min to 3.2 dg/min. Visual inspection of the film revealed that the obtained blend in the middle layer was clear, but inhomogeneous and had a coarse morphology structure for all experiments.

In comparative experiments E-G, the melt index was 25.5 dg/min to 33.3 dg/min. Visual inspection of the film revealed that the clarity and homogeneity of the obtained blend in the middle layer was better than in comparative experiments A-D but still the obtained blend was not sufficiently homogeneous for all cases. In the examples 1 -6 according to the invention, the blend was produced on a double twin screw extruder system according to the invention. In all examples, the middle layer was clear and had a well-dispersed homogeneous structure.

Table 1

Clarity measurements were performed on the films at 23°C and 50% RH. The measurements were done on equipment from BYK-Gardner GmbH. The method is based on ASTM D1746. In contrast to ASTM D1746, BYK defines small angle scattering as the amount of light which scatters (after passing through a film sample) by no more than 2,5°, while ASTM D1767 uses an angle of 0,1 °. However, all other features are as described in ASTM D1746.

Table 2

From Table 2 it can clearly be seen that the inventive examples 1 -6 show a much higher clarity compared to the comparative examples A-C.