WO2009053836A2 - Homogenous copolymeric material and process for its preparation - Google Patents

Homogenous copolymeric material and process for its preparation Download PDF

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Publication number
WO2009053836A2
WO2009053836A2 PCT/IB2008/002886 IB2008002886W WO2009053836A2 WO 2009053836 A2 WO2009053836 A2 WO 2009053836A2 IB 2008002886 W IB2008002886 W IB 2008002886W WO 2009053836 A2 WO2009053836 A2 WO 2009053836A2
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Prior art keywords
fragments
copolymeric material
polyester
semi
homogenous
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PCT/IB2008/002886
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French (fr)
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WO2009053836A3 (en
Inventor
Zeev Ofer
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Zeev Ofer
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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
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
    • C08G63/6954—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from polxycarboxylic acids and polyhydroxy compounds
    • C08G63/6956—Dicarboxylic acids and dihydroxy compounds
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916—Dicarboxylic acids and dihydroxy compounds
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • C08G64/08—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen
    • C08G64/085—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen containing silicon
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/42—Chemical after-treatment
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/44—Polyester-amides
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/48—Polymers modified by chemical after-treatment
    • 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
    • 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
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond

Definitions

  • the present invention is directed to a homogenous copolymeric material and to a process for its preparation.
  • Nonpolar polymers such as PE or PP, have saturated and nonreactive stable hydrocarbon chains.
  • PET has a melting point from
  • PET and PC may be mixed together in a melded state to a mixture that can be used afterwards in the injection moulding technology, but not in the extru- sion technology.
  • LDPE has a melting range from 112 0 C to 135 0 C
  • PP has a melting range from 170 0 C to 19O 0 C.
  • this crystallized PET may be mixed in the sense of a plain mixture in any mixing ratio with any polymeric ma- terial, for example with PP or PC.
  • At least one further polymer that is not a polyester, and/or fragments thereof and at least one modifying agent, which contains silicon and which is able to connect together said polymer (s) and/or fragments thereof, are mixed and are allowed to react to give a second semi-modified polymeric material, and
  • At least one polyester and/or fragments thereof and at least one further polymer, that is not a polyester, and/or fragments thereof are mixed together in the desired ratio, then at least one modifying agent, which contains silicon and which is able to connect together said polyester (s) and/or fragments thereof and said polymer (s) and/or fragments thereof, is added to the mixture and is allowed to react to give a semi- modified copolymeric material, and
  • said extruded homogenous copolymeric material as received at the end of step c.) in the first version or said extruded homogenous copolymeric material as received at the end of step e.) in the second version is obtained.
  • inventive homogenous copolymeric material may be used as
  • a raw material for the preparation of products produced by an extrusion process for example tubes, pipes, cable insulation, sheets, films,
  • a raw material for the preparation of products produced by an injection molding process for example rigid massive items, such as outdoor furniture, parts used in automotive industry, sheets, capsules to be used as a starting material for packaging, for example blown bottles,
  • the obtained mixture was given into a mixing reactor and was heated up to a temperature of 120 0 C by means of blowing hot air there through for 1 hour.
  • the obtained first semi-modified polymeric material and the obtained second semi-modified polymeric material were loaded through two separate dosing systems into the hopper of a twin-screw extruder.
  • the obtained homogenous copolymeric melt was Strand pelletized (in German: Stranggranultechnik) by known standard technology.
  • pellets were loaded into a dryer of an injection moulding device. Herein these pellets were dried for 6 hours at a temperature o£ 160 0 C.
  • the obtained bottle pre- forms were suitable for bottle production by means of standard stretch- blowing technology.
  • the obtained mixture was given into a mixing reactor and was heated up to a temperature of 13O 0 C by means of blowing hot air there through for 1 hour.
  • the obtained mixture was given into a mixing reactor and was heated up to a temperature of 110 0 C by- means of blowing hot air there through for 1 hour.
  • the obtained first semi-modified polymeric material and the obtained second semi-modified polymeric material were loaded through two separate dosing systems into the hopper of a twin-screw extruder. .
  • the resulting mixture was heated to a temperature of 250°C to 260 0 C.
  • the residence time of the material inside the extruder was about 6 minutes.
  • the obtained homogenous c ⁇ polymeric melt was Strand pelletized (in German: Stranggranultechnik) by known standard technology.
  • the pipes were produced by means of standard extrusion process at a temperature of 245 0 C.
  • the diameter of the pipe was 16 mm, and the wall thickness of the pipe was 1.2 mm.
  • the modul factor and the break stress factor are increased significantly with regard to pipes made of PP.
  • the obtained mixture was given into a mixing reactor and was heated up to a temperature of 120 0 C by means of blowing hot air there through for 1 hour.
  • the semi -modified copoly- meric material was heated to a temperature of 250 0 C to 260 0 C.
  • the residence time of the material inside the extruder was about 6 minutes.
  • the obtained homogenous copolymeric melt was Strand pelletized (in German-. Stranggranulmaschine) by known standard technology.
  • pellets were loaded into a dryer of an injection moulding device. Herein these pellets were dried for 3 hours at a temperature of 160 0 C.
  • the obtained bottle pre-forms were suitable for bottle production by means of standard stretch- blowing technology.
  • the obtained mixture was given into a mixing reactor and was heated up to a temperature of HO 0 C by means of blowing hot air there through for 1 hour.
  • the obtained semi-modified copolymeric mate- rial was loaded into the hopper of a twin-screw extruder .
  • the semi-modified copolymeric material was heated to a temperature from 25O 0 C to 26O 0 C.
  • the residence time of the material inside the ex- truder was about 6 minutes.
  • the obtained homogenous copolymeric melt was Strand pelletized (in German: Stranggranulmaschine) by known standard technology.
  • the pipes were produced by means of standard extrusion process at a temperature of 245 0 C.
  • the diameter of the pipe was 20 mm, and the wall thickness of the pipe was 2 mm.
  • the modul factor and the break stress factor are increased significantly with regard to pipes made of PE.
  • pellets were loaded into a dryer of an injection moulding device. Herein these pellets were dried for 3 hours at a temperature of 160 0 C.
  • the obtained bottle pre-forms were suitable for bottle production by means of standard stretch- blowing technology. These bottles had an about 5 % better thermo resistance than conventional PET-botfcles.
  • the pipes were produced by means of Standard extrusion process at a temperature of 245°C.
  • the pipes were produced by means of standard extrusion process at a temperature of 245 0 C.

Abstract

The present invention is directed to a homogenous copolymeric material that is characterized in that it is built up of - at least one polyester and/ or fragments thereof, - at least one further polymer, that is not a polyester, and/or fragments thereof, and - silicon as an interconnecting element be- tween said polyester (s) and/ or fragments thereof and said further polymer (s) and/ or fragments thereof. There is also described a process for the preparation of this homogenous copolymeric material.

Description

Homogenous copσlymeric material and process for its preparation
The present invention is directed to a homogenous copolymeric material and to a process for its preparation.
In the prior art it is believed that it is complicate or even not possible to obtain from a mixture of polar polymers - for example polyesters, such as PET or PC, - with nonpolar polymers - for example polyole- fins, such as PE (LDPE and HDPE) , PP - a homogenous copolymeric material. This belief is based on the different molecular structures of the polar and nonpolar polymers. Nonpolar polymers, such as PE or PP, have saturated and nonreactive stable hydrocarbon chains.
It is a fact that PET has a melting point from
2530C to 2550C, whereas PC has a melting point of about 2550C. Thus, PET and PC may be mixed together in a melded state to a mixture that can be used afterwards in the injection moulding technology, but not in the extru- sion technology.
This means that neither PET nor PC nor their mixture may be used as a single component in the pipe production industry, despite the fact that their initial properties, such as their stiffness, would be much de- manded.
LDPE has a melting range from 1120C to 1350C, whereas PP has a melting range from 1700C to 19O0C.
In WO 03/104314 Al is described a process for processing of polyester wastes, for example waste-PET. Nothing is described in this reference about a mixing or further processing with any polymeric material.
In WO 2006/006064 Al is described crystallized PET, which contains silicon in a bounded and integrated into the molecular structure of PET form.
It is also described in this reference that this crystallized PET may be mixed in the sense of a plain mixture in any mixing ratio with any polymeric ma- terial, for example with PP or PC.
Thus, the resulting product is just a mechanical mixture of two different polymeric solids without any new chemical bond between them. Nothing is said in this reference about a further processing of this mix- ture .
It is an object of the present invention to provide a new homogenous copolymeric material with new properties and wide application possibilities.
One of the intended fields of application for this new homogenous copolymeric material shall be the pipe production.
It is a further object of the present invention to provide a so called "tailor made" new homogenous copolymeric material that meets requested values of cer- tain characteristics.
It is a further object of the present inven- ■ tion to reduce the year-to-year increasing amount of post-consumer polymeric waste by transforming it into a convertible and demanded new homogenous copolymeric material that shall have a high market value.
It is a further object of the present invention to provide a simple and cost advantageous process for the preparation of this new homogenous copolymeric material .
With the present invention these objects are achieved.
The present invention is directed to a homoge- nous copolymeric material that is characterized in that it is built up of
- at least one polyester and/or fragments thereof ,
- at least one further polymer, that is not a polyester, and/or fragments thereof, and
- silicon as an interconnecting element between said polyester (s) and/or fragments thereof and said further polymer (s) and/or fragments thereof.
The inventive process for the preparation of the homogenous copolymeric material is characterized in that
- according to a first version
a.) at least one polyester and/or fragments thereof and at least one modifying agent, which contains silicon and which is able to connect together said polyester (s) and/or fragments thereof, are mixed and are al- lowed to react to give a first semi-modified polymeric material ,
b.) at least one further polymer, that is not a polyester, and/or fragments thereof and at least one modifying agent, which contains silicon and which is able to connect together said polymer (s) and/or fragments thereof, are mixed and are allowed to react to give a second semi-modified polymeric material, and
c.) said first semi-modified polymeric mate- rial and said second semi-modified polymeric material are mixed together in the desired ratio and are extruded to a homogenous copolymeric material ,-
- according to a second version
d.) at least one polyester and/or fragments thereof and at least one further polymer, that is not a polyester, and/or fragments thereof are mixed together in the desired ratio, then at least one modifying agent, which contains silicon and which is able to connect together said polyester (s) and/or fragments thereof and said polymer (s) and/or fragments thereof, is added to the mixture and is allowed to react to give a semi- modified copolymeric material, and
e.) said semi-modified copolymeric material is extruded to a homogenous copolymeric material; and
f.) said extruded homogenous copolymeric material as received at the end of step c.) in the first version or said extruded homogenous copolymeric material as received at the end of step e.) in the second version is obtained. The inventive homogenous copolymeric material may be used as
- a raw material for the preparation of products produced by an extrusion process, for example tubes, pipes, cable insulation, sheets, films,
- a raw material for the preparation of products produced by an injection molding process, for example rigid massive items, such as outdoor furniture, parts used in automotive industry, sheets, capsules to be used as a starting material for packaging, for example blown bottles,
- a raw material for the preparation of fibers.
Preferred embodiments of this invention are defined in the dependent claims.
In the following part are described possible embodiments of the present invention.
The following examples shall illustrate the present invention.
Example 1 (first version of the process)
54 kg of crushed, washed and dried flakes from waste-PET bottles, whereby these flakes had a size from 2 mm to 10 mm, and 1.35 kg of a mixture of 0.81 kg TOS (tetra ortho silicate) [Si (OC2H5) J and of 0.54 kg HMDS (Hexamethyl-disilazane) were mixed at room temperature in a mixing screw. The obtained mixture was given into a mixing reactor and was heated up to a temperature of 13O0C by means of blowing hot air there through for 1 hour.
There results a first semi-modified polymeric material .
6 kg of PP in the form of new and fresh, so- called "virgin" , pellets having a size from 2 mm to 4 mm and 0.12 kg of polyethylhydrosiloxane were mixed at room temperature in a mixing screw.
The obtained mixture was given into a mixing reactor and was heated up to a temperature of 1200C by means of blowing hot air there through for 1 hour.
There results a second semi-modified polymeric material .
The obtained first semi-modified polymeric material and the obtained second semi-modified polymeric material were loaded through two separate dosing systems into the hopper of a twin-screw extruder.
Thereby was used a ratio of 90 parts per weight of semi-modified PET and 10 parts per weight of semi-modified PP.
Inside the extruder the resulting mixture was heated to a temperature of 2500C to 2600C. The residence time of the material inside the extruder was about 6 minutes. The obtained homogenous copolymeric melt was Strand pelletized (in German: Stranggranulierung) by known standard technology.
There were obtained 58 kg of a new homogenous copolymeric material in the form of pellets having a size from 2 mm to 4 mm.
These pellets were loaded into a dryer of an injection moulding device. Herein these pellets were dried for 6 hours at a temperature o£ 1600C.
Afterwards they were transformed into bottle pre-forms by means of standard injection moulding techniques .
The obtained bottle pre- forms were suitable for bottle production by means of standard stretch- blowing technology.
Example 2 (first version of the process)
9 kg of PC in the form of parts of crushed compact discs (CD) , which were separated from impurities, such as aluminum, mechanical dirt and colorants, in the form of chips having a size from 4 mm to 10 mm and 0.225 kg of HMDS (Hexamethyl-disilazane) were mixed at room temperature in a mixing screw.
The obtained mixture was given into a mixing reactor and was heated up to a temperature of 13O0C by means of blowing hot air there through for 1 hour.
There results a first semi-modified polymeric material . 21 kg of PP in the form of new and fresh, so- called "virgin" , pellets having a size from 2 mm to 4 mm and 0.42 kg of TOS (tetra ortho silicate) CSi (OC2H5) J were mixed at room temperature in a mixing screw.
The obtained mixture was given into a mixing reactor and was heated up to a temperature of 1100C by- means of blowing hot air there through for 1 hour.
There results a second semi-modified polymeric material .
The obtained first semi-modified polymeric material and the obtained second semi-modified polymeric material were loaded through two separate dosing systems into the hopper of a twin-screw extruder. .
Thereby was used a ratio of 30 parts per weight of semi-modified PC and 70 parts per weight of semi-modified PP.
Inside the extruder the resulting mixture was heated to a temperature of 250°C to 2600C. The residence time of the material inside the extruder was about 6 minutes.
The obtained homogenous cσpolymeric melt was Strand pelletized (in German: Stranggranulierung) by known standard technology.
There were obtained 27 kg of a new homogenous copolymeric material in the form of pellets having a size from 2 mm to 4 mm. These pellets were loaded into a pipe production device.
The pipes were produced by means of standard extrusion process at a temperature of 2450C.
The diameter of the pipe was 16 mm, and the wall thickness of the pipe was 1.2 mm.
The modul factor and the break stress factor are increased significantly with regard to pipes made of PP.
Example 3 (second version of the process)
45 kg of crushed, washed and dried flakes from waste-PET bottles, whereby these flakes had a size from 2 mm to 10 mm, 5 kg of PP in the form of new and fresh, so-called "virgin", pellets having a size from 2 mm to 4 mm, 1.5 kg of PA-6 in the form of new and fresh, so- called "virgin" , pellets having a size from 2 mm to 4 mm and 1.25 kg of a mixture of 0.75 kg of TOS (tetra ortho silicate) [Si(OC2H5)J and 0.5 kg of HMDS (Hexamethyl- disilazane) were mixed at room temperature in a mixing screw.
The obtained mixture was given into a mixing reactor and was heated up to a temperature of 1200C by means of blowing hot air there through for 1 hour.
There results a semi-modified copolymeric ma- terial. The obtained semi -modified copolymeric material was loaded into the hopper of a twin-screw extruder.
Inside the extruder the semi -modified copoly- meric material was heated to a temperature of 2500C to 2600C. The residence time of the material inside the extruder was about 6 minutes.
The obtained homogenous copolymeric melt was Strand pelletized (in German-. Stranggranulierung) by known standard technology.
There were obtained 50 kg of a new homogenous copolymeric material in the form of pellets having a size from 2 mm to 4 mm.
These pellets were loaded into a dryer of an injection moulding device. Herein these pellets were dried for 3 hours at a temperature of 1600C.
Afterwards they were transformed into bottle pre-forms by means of standard injection moulding techniques.
The obtained bottle pre-forms were suitable for bottle production by means of standard stretch- blowing technology.
These bottles had about 10 % better barrier properties than conventional PET-bottles. Example 4 (second version of the process)
30 kg of crushed, washed and dried flakes from waste-PET bottles, whereby these flakes had a size from 2 mm to 10 mm, 30 kg of LDPE in the form of crushed, washed and dried flakes from post-consumer bottle caps, whereby these flakes had a size from 2 mm to 10 mm, and 1.20 kg of polyethylhydrosiloxane were mixed at room temperature in a mixing screw.
The obtained mixture was given into a mixing reactor and was heated up to a temperature of HO0C by means of blowing hot air there through for 1 hour.
There results a semi-modified copolymeric material.
The obtained semi-modified copolymeric mate- rial was loaded into the hopper of a twin-screw extruder .
Inside the extruder the semi-modified copolymeric material was heated to a temperature from 25O0C to 26O0C. The residence time of the material inside the ex- truder was about 6 minutes.
The obtained homogenous copolymeric melt was Strand pelletized (in German: Stranggranulierung) by known standard technology.
There were obtained 56 kg of a new homogenous copolymeric material in the form of pellets having a size from 2 mm to 4 mm. These pellets were loaded into a pipe production device.
The pipes were produced by means of standard extrusion process at a temperature of 2450C.
The diameter of the pipe was 20 mm, and the wall thickness of the pipe was 2 mm.
The modul factor and the break stress factor are increased significantly with regard to pipes made of PE.
Example 5 (second version of the process)
There were processed as described in example 3 40 kg of waste~PET bottles, 6 kg of "virgin" PS and 1.150 kg of TOS (tetra ortho silicate) [Si(OC2H5)J .
There were obtained 46 kg of a new homogenous copolymeric material in the form of pellets having a size from 2 mm to 4 mm.
These pellets were loaded into a dryer of an injection moulding device. Herein these pellets were dried for 3 hours at a temperature of 1600C.
Afterwards they were transformed into bottle pre- forms by means of standard injection moulding techniques .
The obtained bottle pre-forms were suitable for bottle production by means of standard stretch- blowing technology. These bottles had an about 5 % better thermo resistance than conventional PET-botfcles.
Example S (second version of the process)
There were processed as described in example 4 28 kg of PP, 12 kg of PET, modified as described in
WO 03/104314 Al7 and 600 g of TOS (tetra ortho silicate) [Si(OC2H5)J .
There were obtained 40 kg of a new homogenous copolymeric material in the form of pellets having a size from 2 mm to 4 mm.
These pellets were loaded into a pipe production device .
The pipes were produced by means of Standard extrusion process at a temperature of 245°C.
There were produced pipes having a diameter of
20 mm and 16 mm.
Example 7 (second version of the process)
There were processed as described in example 4 15 kg of LDPE in the form of crushed, washed and dried flakes from post-consumer bottle caps, 35 kg of waste- PET bottles and 1 kg of polymethylhydrosiloxane .
There were obtained 50 kg of a new homogenous copolymeric material in the form of pellets having a size from 2 mm to 4 mm. These pellets were loaded into a pipe production device.
The pipes were produced by means of standard extrusion process at a temperature of 2450C.
There were produced pipes having a diameter of
20 mm and 16 mm.
In the following table are mentioned some properties of "virgin" materials and of the products as obtained in the above examples 1 to 7. In this table are mentioned in examples 1 to 7 the percentage numbers of the used starting polymers .
Table
Figure imgf000015_0001
Figure imgf000016_0001

Claims

Patent Claims
1. Homogenous copolymeric material, characterized in that it is built up of
- at least one polyester and/or fragments thereof ,
- at least one further polymer, that is not a polyester, and/or fragments thereof, and
- silicon as an interconnecting element between said polyester (s) and/or fragments thereof and said further polymer (s) and/or fragments thereof.
2. Homogenous copolymeric material according to claim 1, characterized in that the silicon is present in a bounded and integrated into the molecular structure of the copolymeric material form.
3. Homogenous copolymeric material according to one of claims 1 to 2, characterized in that the copolymeric material is in the form of a granulate, that can especially be processed by means of standard injection moulding technologies or by means of standard ex- trusion technologies.
4. Homogenous copolymeric material according to one of claims 1 to 3, characterized in that the copolymeric material has such a melt flow index that allows the transformation to a product by an extrusion process, for example a melt flow index in the range from 0.5 g/10 minutes to 50 g/lθ minutes at a temperature from 1600C to 2600C.
5. Homogenous copolymeric material according to one of claims 1 to 4, characterized in that the copolymeric material has a silicon content from 15 ppm to 150 ppm, preferably from 50 ppm to 150 ppm.
6. Homogenous copolymeric material according to one of claims 1 to 5, characterized in that the polyesters are selected from the group consisting of polyethylene terephthalate, PET, and polycarbonate, PC7 especially waste PET and waste PC.
7. Homogenous copolymeric material according to one of claims 1 to 6, characterized in that the further polymers are selected from the group consisting of
- polyolefins, especially polyethylene, PE, and polypropylene, PP,
- polyamides, PA, and
- polystyrene, PS,
preferably the wastes of all these polymers or fragments of these polymers.
8. A process for the preparation of the ho- mogenous copolymeric material according to one of claims 1 to 7, characterized in that
- according to a first version
a.) at least one polyester and/or fragments thereof and at least one modifying agent, which contains silicon and which is able to connect together said polyester (s) and/or fragments thereof, are mixed and are al- lowed to react to give a first semi-modified polymeric material,
b.) at least one further polymer, that is not a polyester, and/or fragments thereof and at least one modifying agent, which contains silicon and which is able to connect together said polymer (s) and/or fragments thereof, are mixed and are allowed to react to give a second semi-modified polymeric material, and
c.) said first semi-modified polymeric mate- rial, and said second semi-modified polymeric material are mixed together in the desired ratio and are extruded to a homogenous copolymeric material ;
- according to a second version
d.) at least one polyester and/or fragments thereof and at least one further polymer, that is not a polyester, and/or fragments thereof are mixed together in the desired ratio, then at least one modifying agent, which contains silicon and which is able to connect together said polyester (s) and/or fragments thereof and said polymer (s) and/or fragments thereof, is added to the mixture and is allowed to react to give a semi- modified copolymeric material, and
e.) said semi-modified copolymeric material is extruded to a homogenous copolymeric material ; and
f.) said extruded homogenous copolymeric material as received at the end of step c . ) in the first version or said extruded homogenous copolymeric material as received at the end of step e.) in the second version is obtained.
9. The process according to claim 8, characterized in that the copolymeric material is extruded to granules or shaped products, for example tubes, cable insulation, films, fibers.
10. The process according to one of claims 8 to 9, characterized in that the polyesters are selected from the group consisting of polyethylene terephthalate, PET, and polycarbonate, PC, especially waste PET and waste PC.
11. The process according to one of claims 8 to 10, characterized in that the further polymers are selected from the group consisting of
- polyolefins, especially polyethylene, PE, and polypropylene, PP,
- polyamides, PA, and
- polystyrene, PS,
preferably the wastes of all these polymers or fragments of these polymers .
12. The process according to one of claims 8 to 11, characterized in that the modifying agent is added in the form of a powder, a liquid or a solution, whereby a possible solvent is isopropanol, and that it is especially selected from the group consisting of
- silazanes of the general formula I
R^NH-Si-(R1), (I) wherein the residues R1 und R2 are, independent from each other, a C1 to C6 containing straight or branched alkyl group,
- disilazanes of the general formula II
(R1) 3-Si-NH-Si-(R1) 3 (II)
wherein the residues R1 are a C1 to C6 containing straight or branched alkyl group,
- dioxysilanes of the general formula III
R1O-Si- (OR2) (R3) (R4) (III)
- trioxysilanes of the general formula IV
R^Si-(OR2) (OR3) (OR4) (IV)
- tetraoxysilanes of the general formula V
Si-(OR1) (OR2) (OR3) (OR4) (V)
wherein in the formulas III to V the residues R1 to R4 are, independent from each other, a C1 to C6 containing straight or branched alkyl group or an aryl group, for example a phenyl group,
- siloxanes of the general formula VI
(R1) (R2) (R3) -Si-O-Si- (R4) (R5) (R6) (VI)
wherein the residues R1 to R6 are, independent from each other, hydrogen, a C1 to C6 containing straight or branched alkyl group or an aryl group, for example a phenyl group,
- diphenylsilandiol,
- polymethylhydrosiloxane, and
- polyethylhydrosiloxane.
13. The process according to one of claims 8 to 12, characterized in that
- in the first version
the modifying agent is added in dependency of the used type(s) of polyester (s) and in dependency of the used type(s) of further polymer (s) in an amount of not more than 4 % by weight and not less than 0.5 % by weight, preferably in an amount of 1.5 % by weight, referred to the weight of the polymeric starting compo- nents,
- in the second version
the modifying agent is added in dependency of the used type(s) of polyester (s) , in dependency of the used type(s) of further polymer (s) and in dependency of the mixing ratio of these polymeric starting components in an amount of not more than 4 % by weight and not less than 0.5 % by weight, preferably in an amount of 1.5 % by weight, referred to the weight of the polymeric starting components.
14. The process according to one of claims 8 to 13, characterized in that - in the first version the reaction to the two semi-modified polymeric materials is realized in dependency of the used polymeric starting components at a temperature from about 1100C to about 1300C during about 1 hour,
- in the second version the reaction to the semi-modified copolymeric material is realized in dependency of the used polymeric starting components at a temperature from about 1100C to about 1300C during about 1 hour.
15. The process according to one of claims 8 to 14, characterized in that the extrusion to the homogenous copolymeric material, preferably in the form of a granulate, is realized in a twin-screw extruder, also named co-extruder, in dependency of the semi-modified polymeric material preferably at a temperature from 1600C to 2600C.
16. Homogenous copolymeric material, obtainable in that
- according to a first version
a.) at least one polyester and/or fragments thereof and at least one modifying agent, which contains silicon and which is able to connect together said polyester (s) and/or fragments thereof, are mixed and are al- lowed to react to give a first semi-modified polymeric material,
b.) at least one further polymer, that is not a polyester, and/or fragments thereof and at least one modifying agent, which contains silicon and which is able to connect together said polymer (s) and/or fragments thereof, are mixed and are allowed to react to give a second semi-modified polymeric material, and
c.) said first semi-modified polymeric mate- rial and said second semi-modified polymeric material are mixed together in the desired ratio and are extruded to a homogenous copolymeric material;
- according to a second version
d.) at least one polyester and/or fragments thereof and at least one further polymer, that is not a polyester, and/or fragments thereof are mixed together in the desired ratio, then at least one modifying agent, which contains silicon and which is able to connect together said polyester (s) and/or fragments thereof and said polymer (s) and/or fragments thereof, is added to the mixture and is allowed to react to give a semi- modified copolymeric material, and
e.) said semi-modified copolymeric material is extruded to a homogenous copolymeric material ; and
f.) said extruded homogenous copolymeric material as received at the end of step c.) in the first version or said extruded homogenous copolymeric material as received at the end of step e.) in the second version is obtained.
17. Homogenous copolymeric material according to claim 16, obtainable in that the process according to one of claims 9 to 15 is carried out.
18. Use of the homogenous copolymeric material according to one of claims 1 to 7 as
- a raw material for the preparation of products produced by an extrusion process, for example tubes, pipes, cable insulation, sheets, films,
- a raw material for the preparation of products produced by an injection molding process, for example rigid massive items, such as outdoor furniture, parts used in automotive industry, sheets, capsules to be used as a starting material for packaging, for example blown bottles,
- a raw material for the preparation of fibers.
19. Use according to claim 18, characterized in that the homogenous copolymeric material is prepared according to the process according to one of claims 8 to 15.
20. Use of a silicon containing compound as an interconnecting element between at least one polyester and at least one further polymer, that is not a polyester, whereby this silicon containing compound is especially selected from the group consisting of
- silazanes of the general formula I
R^NH-Si-(R1) 3 (I)
wherein the residues R1 und R2 are, independent from each other, a C1 to C6 containing straight or branched alkyl group, - disilazanes of the general formula II
(R1) 3-Si-NH-Si-(R1) 3 (II)
wherein the residues R1 are a C1 to C6 containing straight or branched alkyl group,
- dioxysilanes of the general formula III
R1O-Si- (OR2) (R3) (R4) (III)
- trioxysilanes of the general formula IV
R^Si-(OR2HOR3MOR4) (IV)
- tetraoxysilanes of the general formula V
Si- (OR1) (OR2) (OR3) (OR4) (V)
wherein in the formulas III to V the residues R1 to R4 are, independent from each other, a C1 to C6 containing straight or branched alkyl group or an aryl group, for example a phenyl group,
- siloxanes of the general formula VI
(R1) (R2) (R3) -Si-O-Si- (R4) (R5) (Rβ) (VI)
wherein the residues R1 to R6 are, independent from each other, hydrogen, a C1 to C6 containing straight or branched alkyl group or an aryl group, for example a phenyl group,
- diphenylsilandiol, - polymethylhydrosiloxane, and
- polyethylhydrosiloxane.
PCT/IB2008/002886 2007-10-25 2008-10-27 Homogenous copolymeric material and process for its preparation WO2009053836A2 (en)

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