EP3538610A1 - Polyvinylchloride compositions comprising a fischer-tropsch wax - Google Patents

Polyvinylchloride compositions comprising a fischer-tropsch wax

Info

Publication number
EP3538610A1
EP3538610A1 EP17801646.5A EP17801646A EP3538610A1 EP 3538610 A1 EP3538610 A1 EP 3538610A1 EP 17801646 A EP17801646 A EP 17801646A EP 3538610 A1 EP3538610 A1 EP 3538610A1
Authority
EP
European Patent Office
Prior art keywords
fischer
wax
tropsch
polyvinylchloride
pvc
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP17801646.5A
Other languages
German (de)
French (fr)
Inventor
Cornelis Pieter Hamelink
Guy Lode Magda Maria Verbist
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Internationale Research Maatschappij BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Publication of EP3538610A1 publication Critical patent/EP3538610A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride

Definitions

  • the present invention relates to a polyvinylchloride composition comprising Fischer-Tropsch derived wax and the process for preparing said polyvinylchloride composition.
  • the present invention further relates to the use of Fischer- Tropsch derived wax as external lubricant in
  • WO2013/120792 discloses a composition comprising PVC as the substrate and a combination of a Fischer-Tropsch (FT) wax with oxidized polyethylene (PE) wax and high amounts of filling materials. It is known that fillers, such as calcium carbonate, talc, clay, etc. have negative effect on the mechanical properties of the PVC composition (Polymer
  • PVC polyvinylchloride composition
  • FT Fischer-Tropsch derived wax
  • the invention embraces a process to prepare a PVC composition.
  • Fischer-Tropsch derived wax is that the Fischer-Tropsch derived wax has very low levels of aromatics, sulphur, napthenics and impurities. In addition, the Fischer-Tropsch derived waxes have low kinematic viscosities.
  • the invention embraces a use of
  • FT waxes are almost uniquely composed of linear alkanes. Hence they have a very low viscosity as well as excellent separation from PVC. This result in the creation of a wax boundary layer between the PVC and the equipment (protecting the PVC from overheating and creating noxious CI containing vapors) ; while this boundary shows excellent low-viscosity rheology allowing high throughout and low energy demand thereto for PVC moulding.
  • a PVC composition comprises a Fischer-Tropsch derived wax.
  • the Fischer-Tropsch derived wax is derived from a
  • Fischer-Tropsch process Fischer-Tropsch product stream is known in the art.
  • Fischer-Tropsch derived wax is meant a paraffin wax is, or is derived from a Fischer- Tropsch process.
  • a Fischer-Tropsch derived paraffin wax may also be referred to a GTL (Gas-to-Liquids ) product.
  • GTL Gas-to-Liquids
  • the Fischer-Tropsch derived wax comprises paraffins, primarily n-paraffins .
  • the Fischer-Tropsch derived wax comprises more than 85 wt . % of n-paraffins, preferably more than 90 wt . % of n-paraffins .
  • the Fischer-Tropsch derived wax has a congealing point of at least 85°C.
  • the Fischer-Tropsch derived wax has a congealing point of at least 105°C.
  • the Fischer-Tropsch derived wax has a congealing point of at least 105°C and at most 120°C.
  • the Fischer-Tropsch derived wax has a
  • kinematic viscosity according to ASTMD-445 at 120°C between 15 and 30 Cst, more preferably between 15 and 26 Cst .
  • a Fischer-Tropsch wax with a congealing point of at least 105°C has kinematic viscosity according to ASTMD-445 at 120°C between 15 and 26 Cst.
  • the amount of the Fischer-Tropsch wax in the PVC is the amount of the Fischer-Tropsch wax in the PVC
  • composition according to the present invention is between 0.10 and 1.00 wt.%, preferably between 0.10 and 0.60 wt.%, more preferably between 0.10 and 0.15 wt.% and most
  • the PVC composition according to the present invention preferably further comprises fillers and additives.
  • Suitable fillers are based on minerals commonly found in nature, such as aluminium oxides, alumino silicates, calcium sulphate, barium sulphate, titanium oxide, calcium carbonate, dolomite, wollastonite, magnesium oxide, magnesium hydroxide, silicates, phosphates, talc, kaolin, chalk, mica, or other metal oxides and metal hydroxides. Preference is being given to calcium carbonate.
  • processing and stabilizing of PVC are selected from the group consisting of epoxides and epoxidized fatty acid esters, phosphites, thiophosphites and thiophosphates , polyols, 1,3- dicarbonyl compounds, mercapto-carboxylic esters,
  • Further additives which are customary for the processing and stabilizing of chlorine-containing polymers are selected from the group consisting of lubricants; plasticizers; impact modifiers; processing aids; blowing agents; antistats;
  • the present invention provides a process wherein the polyvinylchloride composition according to the present invention is prepared by mixing Fischer- Tropsch derived wax with a PVC compound.
  • the Fischer-Tropsch wax and the PVC compound are mixed at room temperature.
  • the Fischer-Tropsch wax used to prepare the PVC composition preferably has a congealing point of 105°C.
  • Process to prepare Fischer-Tropsch derived waxes are known in the art. The process to prepare a Fischer-Tropsch wax with a
  • the PVC compound used to prepare the PVC composition preferably comprises polyvinylchloride.
  • the PVC compound further comprises the additives as described above.
  • the present invention provides the use of Fischer-Tropsch derived wax as external lubricant in polyvinylchloride composition.
  • the Fischer- Tropsch was to be used as external lubricant is a Fischer- Tropsch derived wax with a congealing point of 105°C and a kinematic viscosity according to ASTMD-445 at 120°C between
  • polyvinylchloride composition compared to traditional waxes, such as PE wax.
  • the Fischer-Tropsch wax has very low viscosity as well as excellent separation from PVC. This result in the creation of a wax boundary layer between the PVC and the equipment (protecting the PVC from overheating and creating noxious CI containing vapors) ; while this boundary shows excellent low-viscosity rheology allowing high throughout and low energy demand thereto for PVC moulding.
  • Example 1 Determination of the fusion behaviour of the PVC compositions comprising a FT wax a .
  • PE520 wax from Clariant
  • SX50 Fischer-Tropsch wax with a congealing point of 50°C
  • SX105 Fischer-tropsch wax with a congealing point of 105°C
  • a certain amount of PVC composition (34 g PVC compound and an amount of wax as indicated in Table 1) was transferred into an heated mixing chamber (180 ⁇ 0.5°C), which chamber was a mixing chamber of a Plasticorder (Brabender Plasticorder PL2000 torque rheometer) .
  • the temperature ((180 ⁇ 0.5°C) of the mixing chamber was maintained by means of oil heating.
  • Friction was applied during the test by means of two kneaders (kneader speed was 90/60 ⁇ l r.p.m).
  • Table 1 shows the torque and the mass temperature measured during the test.
  • Table 1 shows that the PVC composition comprising SX105 has comparable fusion characteristics as the PVC composition comprising PE520 wax. Surprisingly, Table 1 also shows that by using SX105 in PVC compositions serious reduction in added wax of 75% can be reached because only 25% of SX105 based on the amount of PE520 was necessary in order to get comparable fusion characteristics. These observations indicate that the traditional PE wax can be replaced by a lower amount of Fischer-Tropsch derived wax as external lubricant for PVC processing .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to a polyvinylchloride composition comprising a Fischer-Tropsch derived wax. The present invention further relates to a process to prepare said composition and the use of Fischer-Tropsch wax as external lubricant in polyvinylchloride composition.

Description

POLYVINYLCHLORIDE COMPOSITIONS COMPRISING
A FISCHER-TROPSCH WAX
Field of the Invention
The present invention relates to a polyvinylchloride composition comprising Fischer-Tropsch derived wax and the process for preparing said polyvinylchloride composition. The present invention further relates to the use of Fischer- Tropsch derived wax as external lubricant in
polyvinylchloride composition.
Background of the Invention
It is known in the art to use wax as external lubricant for polyvinylchloride (PVC) processing.
WO2013/120792 discloses a composition comprising PVC as the substrate and a combination of a Fischer-Tropsch (FT) wax with oxidized polyethylene (PE) wax and high amounts of filling materials. It is known that fillers, such as calcium carbonate, talc, clay, etc. have negative effect on the mechanical properties of the PVC composition (Polymer
Handbook, Eds. C. E. Wilkes , J. W. Summers, C. Daniels,
Verlag, Carl Hanser Verlag 2005, page 499) . Although in
WO2013/120792 the amount of fillers does not effectively reduce the desirable mechanical properties of the
composition, the addition of expensive PE wax is necessary to obtain desirable mechanical properties.
It is an object of the invention to use a low amount of wax as external lubricant for PVC processing.
It is a further object of the present invention to provide a cheaper PVC composition with desirable mechanical properties.
Summary of the invention From a first aspect, above and other objects may be achieved according to the present invention by providing an polyvinylchloride composition (PVC) composition comprising a Fischer-Tropsch derived (FT) wax.
It has been found according to the present invention that a lower amount of FT wax can replace the traditional PE wax in PVC compositions without affecting the lubricant properties of the PVC composition.
From a second aspect, the invention embraces a process to prepare a PVC composition. An advantage of the use of
Fischer-Tropsch derived wax is that the Fischer-Tropsch derived wax has very low levels of aromatics, sulphur, napthenics and impurities. In addition, the Fischer-Tropsch derived waxes have low kinematic viscosities.
From a third aspect, the invention embraces a use of
Fischer-Tropsch derived wax as external lubricant in
polyvinylchloride composition.
FT waxes are almost uniquely composed of linear alkanes. Hence they have a very low viscosity as well as excellent separation from PVC. This result in the creation of a wax boundary layer between the PVC and the equipment (protecting the PVC from overheating and creating noxious CI containing vapors) ; while this boundary shows excellent low-viscosity rheology allowing high throughout and low energy demand thereto for PVC moulding.
Detailed description of the invention
According to the present invention a PVC composition comprises a Fischer-Tropsch derived wax.
The Fischer-Tropsch derived wax is derived from a
Fischer-Tropsch process. Fischer-Tropsch product stream is known in the art. By the term "Fischer-Tropsch derived wax" is meant a paraffin wax is, or is derived from a Fischer- Tropsch process. A Fischer-Tropsch derived paraffin wax may also be referred to a GTL (Gas-to-Liquids ) product. An example of a Fischer-Tropsch process is given in
WO2002/102941, EP 1 498 469 and WO2004/009739, the teaching of which is incorporated by reference.
The Fischer-Tropsch derived wax comprises paraffins, primarily n-paraffins . Preferably, the Fischer-Tropsch derived wax comprises more than 85 wt . % of n-paraffins, preferably more than 90 wt . % of n-paraffins .
Preferably, the Fischer-Tropsch derived wax has a congealing point of at least 85°C. Also, the Fischer-Tropsch derived wax has a congealing point of at least 105°C. In addition, the Fischer-Tropsch derived wax has a congealing point of at least 105°C and at most 120°C.
Suitably, the Fischer-Tropsch derived wax has a
kinematic viscosity according to ASTMD-445 at 120°C between 15 and 30 Cst, more preferably between 15 and 26 Cst .
Preferably, a Fischer-Tropsch wax with a congealing point of at least 105°C has kinematic viscosity according to ASTMD-445 at 120°C between 15 and 26 Cst.
The amount of the Fischer-Tropsch wax in the PVC
composition according to the present invention is between 0.10 and 1.00 wt.%, preferably between 0.10 and 0.60 wt.%, more preferably between 0.10 and 0.15 wt.% and most
preferably 0.15 wt.% based on the total amount of the PVC composition .
The PVC composition according to the present invention preferably further comprises fillers and additives.
Examples of suitable fillers or reinforcing agents are listed in Handbook of PVC-Formulating edited by E. J.
Wickson, John Wiley & Sons, New York 1993, pp. 393-449 or in Taschenbuch der Kunststoff additive", Editors R. Gachter and H. Muller, Carl Hanser Verlag, 3rd Edition, 1989,
pages 549-615.
Suitable fillers are based on minerals commonly found in nature, such as aluminium oxides, alumino silicates, calcium sulphate, barium sulphate, titanium oxide, calcium carbonate, dolomite, wollastonite, magnesium oxide, magnesium hydroxide, silicates, phosphates, talc, kaolin, chalk, mica, or other metal oxides and metal hydroxides. Preference is being given to calcium carbonate.
Suitable additives which are customary for the
processing and stabilizing of PVC are selected from the group consisting of epoxides and epoxidized fatty acid esters, phosphites, thiophosphites and thiophosphates , polyols, 1,3- dicarbonyl compounds, mercapto-carboxylic esters,
dihydropyridines and polydihydropyridines , antioxidants;
light stabilizers and UV absorbers, alkali metal and alkaline earth metal compounds, perchlorate salts, zeolites,
hydrotalcites and dawnsonites.
Further additives which are customary for the processing and stabilizing of chlorine-containing polymers are selected from the group consisting of lubricants; plasticizers; impact modifiers; processing aids; blowing agents; antistats;
biocides; antifogging agents; pigments and dyes; metal deactivators and flame proofing agents, cf. in this respect the above-mentioned Handbook of PVC Formulating.
In another aspect, the present invention provides a process wherein the polyvinylchloride composition according to the present invention is prepared by mixing Fischer- Tropsch derived wax with a PVC compound.
Preferably, the Fischer-Tropsch wax and the PVC compound are mixed at room temperature. The Fischer-Tropsch wax used to prepare the PVC composition preferably has a congealing point of 105°C. Process to prepare Fischer-Tropsch derived waxes are known in the art. The process to prepare a Fischer-Tropsch wax with a
congealing point of 105°C is for example described in
WO2016107864.
The PVC compound used to prepare the PVC composition preferably comprises polyvinylchloride. Optionally the PVC compound further comprises the additives as described above.
In a further aspect, the present invention provides the use of Fischer-Tropsch derived wax as external lubricant in polyvinylchloride composition. Preferably, the Fischer- Tropsch was to be used as external lubricant is a Fischer- Tropsch derived wax with a congealing point of 105°C and a kinematic viscosity according to ASTMD-445 at 120°C between
15 and 30 Cst, more preferably between 15 and 26 Cst .
It was surprisingly found that less Fischer-Tropsch is necessary to be used as external lubricant in
polyvinylchloride composition compared to traditional waxes, such as PE wax. Furthermore, the Fischer-Tropsch wax has very low viscosity as well as excellent separation from PVC. This result in the creation of a wax boundary layer between the PVC and the equipment (protecting the PVC from overheating and creating noxious CI containing vapors) ; while this boundary shows excellent low-viscosity rheology allowing high throughout and low energy demand thereto for PVC moulding.
The present invention is described below with reference to the following Examples, which are not intended to limit the scope of the present invention in any way.
Examples
Example 1: Determination of the fusion behaviour of the PVC compositions comprising a FT wax a . Sample preparation
An amount of PE520 wax (from Clariant) , a Fischer-Tropsch wax with a congealing point of 50°C (SX50) or a Fischer-tropsch wax with a congealing point of 105°C (SX105) was cold mixed into 34 g PVC compound comprising (A Ca/Zn stabilised
compound from Wavin Netherlands) . SX50 and SX105 were
prepared as described in the Example of WO2016107864. The amounts of PE520 wax, SX50 and SX105 have been indicated in Table 1. b . Measurement of torque and mass temperature
A certain amount of PVC composition (34 g PVC compound and an amount of wax as indicated in Table 1) was transferred into an heated mixing chamber (180±0.5°C), which chamber was a mixing chamber of a Plasticorder (Brabender Plasticorder PL2000 torque rheometer) . The temperature ((180±0.5°C) of the mixing chamber was maintained by means of oil heating.
Friction was applied during the test by means of two kneaders (kneader speed was 90/60±l r.p.m).
Table 1 shows the torque and the mass temperature measured during the test.
Table 1.
1. M: Mass: the amount of wax
2. B: point of minimum fusion with the corresponding measured parameters: time t, torque M and mass temperature T;
3. X: point of maximum fusion with the corresponding measured parameters: time t, torque M and mass temperature T;
4. E: endpoint of the fusion test with the corresponding measured parameters: time t, torque M and mass
Discussion
Table 1 shows that the PVC composition comprising SX105 has comparable fusion characteristics as the PVC composition comprising PE520 wax. Surprisingly, Table 1 also shows that by using SX105 in PVC compositions serious reduction in added wax of 75% can be reached because only 25% of SX105 based on the amount of PE520 was necessary in order to get comparable fusion characteristics. These observations indicate that the traditional PE wax can be replaced by a lower amount of Fischer-Tropsch derived wax as external lubricant for PVC processing .

Claims

C L A I M S
1. Polyvinylchloride composition comprising a Fischer-Tropsch derived wax.
2. Polyvinylchloride composition according to claim 1,
wherein the Fischer-Tropsch derived wax has a congealing point of at least 85°C.
3. Polyvinylchloride composition according to claim 1 or 2, wherein the Fischer-Tropsch derived wax has a congealing point of at least 105°C.
4. Polyvinylchloride composition according to any one of
claims 1 to 3, wherein the Fischer-Tropsch derived wax has a congealing point of at least 105°C and at most 120°C.
5. Polyvinylchloride composition according to any one of
claims 1 to 4, wherein the Fischer-Tropsch derived wax has a kinematic viscosity according to ASTMD-445 at 120°C between 15 and 30 Cst, more preferably between 15 and 26 Cst .
6. Polyvinylchloride composition according to any one of
claims 1 to 5, wherein the amount of the Fischer-Tropsch wax is between 0.10 and 1.0 wt . % based on the total amount of the polyvinylchloride composition.
7. Polyvinylchloride composition according to any one of
claims 1 to 6, wherein the amount of the Fischer-Tropsch wax is between 0.10 and 0.15 wt . % based on the total amount of the polyvinylchloride composition.
8. Polyvinylchloride composition according to any one of
claims 1 to 7, wherein the composition further comprises fillers and additives.
9. Process to prepare a polyvinylchloride composition as
defined according to one or more of the preceding claims 1 to 8, wherein the Fischer-Tropsch derived wax is mixed with a polyvinylchloride compound.
Use of Fischer-Tropsch derived wax as external lubricant in polyvinylchloride composition.
EP17801646.5A 2016-11-11 2017-11-10 Polyvinylchloride compositions comprising a fischer-tropsch wax Withdrawn EP3538610A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP16198505 2016-11-11
PCT/EP2017/078858 WO2018087277A1 (en) 2016-11-11 2017-11-10 Polyvinylchloride compositions comprising a fischer-tropsch wax

Publications (1)

Publication Number Publication Date
EP3538610A1 true EP3538610A1 (en) 2019-09-18

Family

ID=57321147

Family Applications (1)

Application Number Title Priority Date Filing Date
EP17801646.5A Withdrawn EP3538610A1 (en) 2016-11-11 2017-11-10 Polyvinylchloride compositions comprising a fischer-tropsch wax

Country Status (2)

Country Link
EP (1) EP3538610A1 (en)
WO (1) WO2018087277A1 (en)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4002706A (en) * 1974-02-25 1977-01-11 Dirk Jacobus Pretorius Wax and wax blends
WO2002102941A2 (en) 2001-06-15 2002-12-27 Shell Internationale Research Maatschappij B.V. Process for preparing a microcrystalline wax
AU2003255058A1 (en) 2002-07-18 2004-02-09 Shell Internationale Research Maatschappij B.V. Process to prepare a microcrystalline wax and a middle distillate fuel
WO2013120792A1 (en) 2012-02-15 2013-08-22 Basf Se Pvc compositions of high impact strength
EP3240874A1 (en) * 2014-12-31 2017-11-08 Shell Internationale Research Maatschappij B.V. Process to prepare a heavy paraffin wax
SG10201907001WA (en) 2014-12-31 2019-09-27 Shell Int Research Process to prepare paraffin wax

Also Published As

Publication number Publication date
WO2018087277A1 (en) 2018-05-17

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