CA2372121A1 - Acceleration of the phase separation of liquid phases which contain polymers - Google Patents
Acceleration of the phase separation of liquid phases which contain polymers Download PDFInfo
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- CA2372121A1 CA2372121A1 CA 2372121 CA2372121A CA2372121A1 CA 2372121 A1 CA2372121 A1 CA 2372121A1 CA 2372121 CA2372121 CA 2372121 CA 2372121 A CA2372121 A CA 2372121A CA 2372121 A1 CA2372121 A1 CA 2372121A1
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- solvent
- polymers
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- acceleration
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
- C08J11/08—Recovery or working-up of waste materials of polymers without chemical reactions using selective solvents for polymer components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/02—Separating plastics from other materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/092—Hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/02—Separating plastics from other materials
- B29B2017/0203—Separating plastics from plastics
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/02—Separating plastics from other materials
- B29B2017/0213—Specific separating techniques
- B29B2017/0293—Dissolving the materials in gases or liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/06—PE, i.e. polyethylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/06—PE, i.e. polyethylene
- B29K2023/0608—PE, i.e. polyethylene characterised by its density
- B29K2023/0633—LDPE, i.e. low density polyethylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/06—PE, i.e. polyethylene
- B29K2023/0608—PE, i.e. polyethylene characterised by its density
- B29K2023/065—HDPE, i.e. high density polyethylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/10—Polymers of propylene
- B29K2023/12—PP, i.e. polypropylene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Extraction Or Liquid Replacement (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention relates to the acceleration of the separation of liquid phases which contain polymers by using branched instead of linear solvents.
Description
ACCELERATION OF THE PHASE SEPARATION OF LIQUID PHASES
WHICH CONTAIN POLYMERS
Mixed polymers may be separated by a liquid-liquid phase separation [1].
Thereby, polymers are present in all phases, but selectively separated. Liquid phases with no insignificant poly-mer contents have high viscosities. Polymers are understood to be technically or biologically produced macromolecules having a molar weight of 1000 Daltons or more.
Polymers of dif ferent kind are understood to be chemically or structurally different polymers, such as HDPE, l0 LDPE, PP or PVC.
For the economic of such a thermal separation process, the times of sedimentation in the separation steps are decisive, since space-time-yields are determined thereby.
Further, long residence times contribute that decomposition reactions take place.
Liquid systems having two or more phases include a continuous phase (KP) and one or more discontinuous - -phases (DP) in a dispersed state. The literature [2]_ subdivides coalescence and sedimentation of the discontinuous phase into several stages:
WHICH CONTAIN POLYMERS
Mixed polymers may be separated by a liquid-liquid phase separation [1].
Thereby, polymers are present in all phases, but selectively separated. Liquid phases with no insignificant poly-mer contents have high viscosities. Polymers are understood to be technically or biologically produced macromolecules having a molar weight of 1000 Daltons or more.
Polymers of dif ferent kind are understood to be chemically or structurally different polymers, such as HDPE, l0 LDPE, PP or PVC.
For the economic of such a thermal separation process, the times of sedimentation in the separation steps are decisive, since space-time-yields are determined thereby.
Further, long residence times contribute that decomposition reactions take place.
Liquid systems having two or more phases include a continuous phase (KP) and one or more discontinuous - -phases (DP) in a dispersed state. The literature [2]_ subdivides coalescence and sedimentation of the discontinuous phase into several stages:
2 0 - coalescence of single drops to form larger drops ascending or descending of larger drops controlled by density unification of larger drops with already formed phase.
In all these processes, in particular the rising or settling velocities, respectively, of single drops are important. A comparatively simple mathematical modellation is obtained when the drops are considered as rigid spheres in the KP.
The modellation of the motion of sperically shaped solid particles in a continuous phase is made according to Clift R. et al [3] and Brauer [2J by using the equation of motion. The 3 0 equation of motion (eq. l ) represents a term for the stationary velocity of falling spherically shaped particles.
wp= 4 Pp ~'g'dP' eq~ ~I) 3 pF ~
Therein, wP represents settling or rising velocity of particles, pp and pF
respectively, the den-sity of the discontinuous Windex P) and the continuous phase (index F), respectively, g the acceleration due to gravity, dP the particle diameter and ~ the drag coe~cient.
Equation 1 is generally valid for solid or fluid high viscous particles. The special characteris-tics of the phase boundary surface are described by the drag coefficient for which the follow-ing interrelation is valid:
I eq. (2) x-Re wherein wpda Ar eq. (3) Re= =18 1+ 9 -I
In equation 3, vF represents the kinematic viscosity of the continuous phase and Ar the Ar-2 0 chimedian number. The introduction of the dimensionless Archimedian number is useful, . since hereby the settling velocity wP of particles in equation 1 can be represented in explicit form. It is:
Ar = PP
pF yF
Equation (4) teaches that only the viscosity of the continuous phase, the particle diameter of the discontinuous phase and the density difference between continuous and discontinuous phase are important for the separation. Short residence times are advantageous to save opera-tion and investment costs and to suppress chemical reactions.
According to the teaching of the literature, the phase separation time can be improved in par-ticular by reducing the viscosity of KP. Possibilities known in the literature are increasing the temperature or changing the nature of the solvent which forms KP together with the polymer, both measures with the aim to reduce the viscosity of KP. The said measures do not lead to the goal in the separation of mixed polymer by liquid-liquid-phase separation, since the temperature does not only change the viscosity, but due to the thermodynamics in particular the purity/yield of the polymers to be separated. Therefore, an improvement of the separation time must be paid for with a deterioration of selectivity;
changing the nature of the solvent changes the thermodynamics to an extent that the separation temperatures are either shifted into ranges which are uneconomic or the phase separation does no longer exist in the range of temperatures which can be techni-cally reached.
This problem is solved by a method according to claim 1 in an elegant and novel manner.
Preferred embodiments are subject-matter of the subclaims.
As an example, the thermal separation of polyolefme mixtures as polymers of different type is 2 0 considered, with n-alkanes having five to seven carbon atoms in the molecule as solvent. The teachings of the patent are applicable to all other separation methods which include the sepa-ration of polymer mixtures by forming liquid phases.
The method described in [1] separates polyolefmes in that two liquid phases are formed in n-hexane at 180°C, wherein the upper light phase contains under certain conditions polyethyl-ene from high pressure synthesis (LDPE), and the lower one polyethylene from low pressure synthesis (HDPE). Due to the amount, the low viscous upper phase is KP, and the high vis-cous lower phase is DP in the dispersed system. The low viscosity of the upper phase, how-ever, does not lead to technically acceptable separation times, so that the above mentioned disadvantages (costs, reactions) become effective.
Experimental runs, however, have surprisingly shown that the use of branched solvents with same carbon number significantly and advantageously changes the separation times. Therein, AMENDED SHEET
In all these processes, in particular the rising or settling velocities, respectively, of single drops are important. A comparatively simple mathematical modellation is obtained when the drops are considered as rigid spheres in the KP.
The modellation of the motion of sperically shaped solid particles in a continuous phase is made according to Clift R. et al [3] and Brauer [2J by using the equation of motion. The 3 0 equation of motion (eq. l ) represents a term for the stationary velocity of falling spherically shaped particles.
wp= 4 Pp ~'g'dP' eq~ ~I) 3 pF ~
Therein, wP represents settling or rising velocity of particles, pp and pF
respectively, the den-sity of the discontinuous Windex P) and the continuous phase (index F), respectively, g the acceleration due to gravity, dP the particle diameter and ~ the drag coe~cient.
Equation 1 is generally valid for solid or fluid high viscous particles. The special characteris-tics of the phase boundary surface are described by the drag coefficient for which the follow-ing interrelation is valid:
I eq. (2) x-Re wherein wpda Ar eq. (3) Re= =18 1+ 9 -I
In equation 3, vF represents the kinematic viscosity of the continuous phase and Ar the Ar-2 0 chimedian number. The introduction of the dimensionless Archimedian number is useful, . since hereby the settling velocity wP of particles in equation 1 can be represented in explicit form. It is:
Ar = PP
pF yF
Equation (4) teaches that only the viscosity of the continuous phase, the particle diameter of the discontinuous phase and the density difference between continuous and discontinuous phase are important for the separation. Short residence times are advantageous to save opera-tion and investment costs and to suppress chemical reactions.
According to the teaching of the literature, the phase separation time can be improved in par-ticular by reducing the viscosity of KP. Possibilities known in the literature are increasing the temperature or changing the nature of the solvent which forms KP together with the polymer, both measures with the aim to reduce the viscosity of KP. The said measures do not lead to the goal in the separation of mixed polymer by liquid-liquid-phase separation, since the temperature does not only change the viscosity, but due to the thermodynamics in particular the purity/yield of the polymers to be separated. Therefore, an improvement of the separation time must be paid for with a deterioration of selectivity;
changing the nature of the solvent changes the thermodynamics to an extent that the separation temperatures are either shifted into ranges which are uneconomic or the phase separation does no longer exist in the range of temperatures which can be techni-cally reached.
This problem is solved by a method according to claim 1 in an elegant and novel manner.
Preferred embodiments are subject-matter of the subclaims.
As an example, the thermal separation of polyolefme mixtures as polymers of different type is 2 0 considered, with n-alkanes having five to seven carbon atoms in the molecule as solvent. The teachings of the patent are applicable to all other separation methods which include the sepa-ration of polymer mixtures by forming liquid phases.
The method described in [1] separates polyolefmes in that two liquid phases are formed in n-hexane at 180°C, wherein the upper light phase contains under certain conditions polyethyl-ene from high pressure synthesis (LDPE), and the lower one polyethylene from low pressure synthesis (HDPE). Due to the amount, the low viscous upper phase is KP, and the high vis-cous lower phase is DP in the dispersed system. The low viscosity of the upper phase, how-ever, does not lead to technically acceptable separation times, so that the above mentioned disadvantages (costs, reactions) become effective.
Experimental runs, however, have surprisingly shown that the use of branched solvents with same carbon number significantly and advantageously changes the separation times. Therein, AMENDED SHEET
the viscosity of KP is about the same for the non-branched and the branched solvent, so that the effect cannot be explained at the moment.
Branched solvents are such aliphatic materials in which at least one carbon atom has more than two carbon atoms as neighbors and which may also carry functional groups along with further C and H atoms.
To illustrate the proceedings according to the patent, the branched solvent 2,3-dimethylbutane shall be compared with the unbranched solvent n-hexane.
Example 1 Two experimental runs were performed having the separation of a polyethylene-polypropylene mixture as a goal. As polyolefines, HDPE (high density polyethylene), LDPE
(low density polyethylene) and polypropylene PP were supplied in a proportion of 15/43/42, wherein the total content of polyolefine in solution was 20 weight %.
In the first experimental run V_1 n-hexane was used as a solvent, for the second experimental run V_2 2,3-dimethylbutane. The phase separation times as well as the viscosities of the so-lution were observed. They are represented in table 1. It is noticeable that periods of 300 min cannot be realized with an unbranched solvent or only in a difficult way.
The parities of the different polymers were practically identical in both phases in both runs, since the nature of the solvent had not been changed (in both cases, a hexane is concerned).
However, the considerably shorter separation times in the experimental run V 2 using the branched solvent are surprising. Even though the viscosity of KP and the density difference pP-pF did not change significantly in both runs, it has been detected surprisingly that the sys-tem with the branched solvent had been separated faster by a factor of 150 than the system with n-alkane as a solvent.
Branched solvents are such aliphatic materials in which at least one carbon atom has more than two carbon atoms as neighbors and which may also carry functional groups along with further C and H atoms.
To illustrate the proceedings according to the patent, the branched solvent 2,3-dimethylbutane shall be compared with the unbranched solvent n-hexane.
Example 1 Two experimental runs were performed having the separation of a polyethylene-polypropylene mixture as a goal. As polyolefines, HDPE (high density polyethylene), LDPE
(low density polyethylene) and polypropylene PP were supplied in a proportion of 15/43/42, wherein the total content of polyolefine in solution was 20 weight %.
In the first experimental run V_1 n-hexane was used as a solvent, for the second experimental run V_2 2,3-dimethylbutane. The phase separation times as well as the viscosities of the so-lution were observed. They are represented in table 1. It is noticeable that periods of 300 min cannot be realized with an unbranched solvent or only in a difficult way.
The parities of the different polymers were practically identical in both phases in both runs, since the nature of the solvent had not been changed (in both cases, a hexane is concerned).
However, the considerably shorter separation times in the experimental run V 2 using the branched solvent are surprising. Even though the viscosity of KP and the density difference pP-pF did not change significantly in both runs, it has been detected surprisingly that the sys-tem with the branched solvent had been separated faster by a factor of 150 than the system with n-alkane as a solvent.
ExperimentalSolvent wpeed.PolSystem SeparationViscosityViscosity of of ~n [weighttemperaturetime of upper lower phase phase %] phases KP DP
V_1 n-hexane 20 180 300 Low High V_2 2,3- 20 180 2 Low Low dimethylbu-tanP.
Table 1: Experimental runs to separate polyolefme with a branched (experimental run V 2 and an unbranched solvent (experimental run V_1) According to the teaching of the literature, these reduced separation times lead to smaller separation containers and therefore to a reduction of investment costs and of residence times at the necessary high temperatures.
The teaching of this patent can be applied to all separations of liquid phases which contain polymers and solvents of which branched and unbranched representatives exists.
Citation [1] DE 199 OS 029 A, published after the priority date of the present application [2] Brauer, H.: Grundlagen der Einphasen- and Mehrphasenstromungen;
Verlag Sauerlander, Aarau, 1971 [3] Clift, R.; Grace, J.R.; Weber, M.E.: Bubbles, Drops and Particles Academic Press, New York, 1978 AMENDED SHEET
V_1 n-hexane 20 180 300 Low High V_2 2,3- 20 180 2 Low Low dimethylbu-tanP.
Table 1: Experimental runs to separate polyolefme with a branched (experimental run V 2 and an unbranched solvent (experimental run V_1) According to the teaching of the literature, these reduced separation times lead to smaller separation containers and therefore to a reduction of investment costs and of residence times at the necessary high temperatures.
The teaching of this patent can be applied to all separations of liquid phases which contain polymers and solvents of which branched and unbranched representatives exists.
Citation [1] DE 199 OS 029 A, published after the priority date of the present application [2] Brauer, H.: Grundlagen der Einphasen- and Mehrphasenstromungen;
Verlag Sauerlander, Aarau, 1971 [3] Clift, R.; Grace, J.R.; Weber, M.E.: Bubbles, Drops and Particles Academic Press, New York, 1978 AMENDED SHEET
Claims (7)
1) A method for acceleration of the separation of phases containing different polymers, characterized in that a) said polymers are solved in a branched solvent or solvent mixture and b) the resulting solvent phases which include solved polymers of different type in different concentrations are separated after sedimentation.
2) The method of claim 1, characterized in that said solvent is selected such that the sedi-mentation times of the phases in the branched solvent or solvent mixture are shorter than those in a non-branched solvent or solvent mixture.
3) The method of claim 1 or 2, characterized in that said polymers of different type are mixtures of polyolefins and said solvent is a branched alkane having a carbon number between 4 and 16.
4) The method of claim 3, characterized in that said solvent is a branched alkane having a carbon number between 4 and 10.
5) The method of claim 3, characterized in that said solvent is a branched alkane having a carbon number between 6 and 8.
6) The method of any of claims 1 and 5, characterized in that said solvent is dimethylbu-tare or methylpentane.
7) The method of any of claims 1 to 6, characterized in that the supplied polyolefins origi-nate from waste to be recycled.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19922944A DE19922944A1 (en) | 1999-05-14 | 1999-05-14 | Acceleration of phase separation of liquid polymer-containing phases used for polyolefins involves using branched solvents to increase speed |
| DE19922944.9 | 1999-05-14 | ||
| PCT/DE2000/001475 WO2000069952A1 (en) | 1999-05-14 | 2000-05-12 | Acceleration of the phase separation of liquid phases which contain polymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2372121A1 true CA2372121A1 (en) | 2000-11-23 |
Family
ID=7908497
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2372121 Abandoned CA2372121A1 (en) | 1999-05-14 | 2000-05-12 | Acceleration of the phase separation of liquid phases which contain polymers |
Country Status (28)
| Country | Link |
|---|---|
| EP (1) | EP1181328B1 (en) |
| JP (1) | JP2002544355A (en) |
| KR (1) | KR20020005672A (en) |
| CN (1) | CN1350564A (en) |
| AT (1) | ATE230774T1 (en) |
| AU (1) | AU769019B2 (en) |
| BG (1) | BG106036A (en) |
| BR (1) | BR0010535A (en) |
| CA (1) | CA2372121A1 (en) |
| CZ (1) | CZ20014084A3 (en) |
| DE (2) | DE19922944A1 (en) |
| DK (1) | DK1181328T3 (en) |
| EA (1) | EA200101023A1 (en) |
| EE (1) | EE200100590A (en) |
| ES (1) | ES2188548T3 (en) |
| HK (1) | HK1046008B (en) |
| HR (1) | HRP20010658A2 (en) |
| HU (1) | HUP0201501A3 (en) |
| IL (1) | IL144807A0 (en) |
| MX (1) | MXPA01011554A (en) |
| NO (1) | NO20015535L (en) |
| NZ (1) | NZ515191A (en) |
| PL (1) | PL352023A1 (en) |
| PT (1) | PT1181328E (en) |
| SK (1) | SK12742001A3 (en) |
| TR (1) | TR200103287T2 (en) |
| WO (1) | WO2000069952A1 (en) |
| YU (1) | YU80701A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011008955A1 (en) | 2009-07-16 | 2011-01-20 | Dow Global Technologies Inc. | Polymerization process for olefin-based polymers |
| WO2012088235A2 (en) | 2010-12-21 | 2012-06-28 | Dow Global Technologies Llc | Olefin-based polymers and dispersion polymerizations |
| US11041030B2 (en) | 2018-09-19 | 2021-06-22 | Exxonmobil Chemical Patents Inc. | Devolatilization processes |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10032918C2 (en) * | 2000-07-06 | 2002-06-20 | Siemens Axiva Gmbh & Co Kg | Method for determining the proportion of HDPE and LDPE in polyolefin mixtures |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2399558A (en) * | 1942-12-31 | 1946-04-30 | Standard Oil Dev Co | Organic cementing solutions |
| US2801234A (en) * | 1955-03-11 | 1957-07-30 | Phillips Petroleum Co | Method of removing olefin polymer from process equipment |
| FR2259923B1 (en) * | 1974-01-31 | 1978-10-27 | Raffinage Cie Francaise |
-
1999
- 1999-05-14 DE DE19922944A patent/DE19922944A1/en not_active Withdrawn
-
2000
- 2000-05-12 DK DK00936671T patent/DK1181328T3/en active
- 2000-05-12 HU HU0201501A patent/HUP0201501A3/en unknown
- 2000-05-12 BR BR0010535A patent/BR0010535A/en not_active IP Right Cessation
- 2000-05-12 DE DE50001053T patent/DE50001053D1/en not_active Expired - Fee Related
- 2000-05-12 PL PL35202300A patent/PL352023A1/en not_active Application Discontinuation
- 2000-05-12 CN CN00807514A patent/CN1350564A/en active Pending
- 2000-05-12 JP JP2000618367A patent/JP2002544355A/en not_active Ceased
- 2000-05-12 CA CA 2372121 patent/CA2372121A1/en not_active Abandoned
- 2000-05-12 EE EEP200100590A patent/EE200100590A/en unknown
- 2000-05-12 TR TR200103287T patent/TR200103287T2/en unknown
- 2000-05-12 AU AU52083/00A patent/AU769019B2/en not_active Ceased
- 2000-05-12 CZ CZ20014084A patent/CZ20014084A3/en unknown
- 2000-05-12 SK SK1274-2001A patent/SK12742001A3/en unknown
- 2000-05-12 IL IL14480700A patent/IL144807A0/en unknown
- 2000-05-12 MX MXPA01011554A patent/MXPA01011554A/en not_active Application Discontinuation
- 2000-05-12 YU YUP80701 patent/YU80701A/en unknown
- 2000-05-12 KR KR1020017012975A patent/KR20020005672A/en not_active Application Discontinuation
- 2000-05-12 AT AT00936671T patent/ATE230774T1/en not_active IP Right Cessation
- 2000-05-12 EA EA200101023A patent/EA200101023A1/en unknown
- 2000-05-12 EP EP20000936671 patent/EP1181328B1/en not_active Expired - Lifetime
- 2000-05-12 WO PCT/DE2000/001475 patent/WO2000069952A1/en not_active Application Discontinuation
- 2000-05-12 ES ES00936671T patent/ES2188548T3/en not_active Expired - Lifetime
- 2000-05-12 PT PT00936671T patent/PT1181328E/en unknown
- 2000-05-12 NZ NZ51519100A patent/NZ515191A/en unknown
-
2001
- 2001-09-07 HR HR20010658A patent/HRP20010658A2/en not_active Application Discontinuation
- 2001-10-22 BG BG106036A patent/BG106036A/en unknown
- 2001-11-13 NO NO20015535A patent/NO20015535L/en not_active Application Discontinuation
-
2002
- 2002-08-23 HK HK02106228.9A patent/HK1046008B/en not_active IP Right Cessation
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011008955A1 (en) | 2009-07-16 | 2011-01-20 | Dow Global Technologies Inc. | Polymerization process for olefin-based polymers |
| EP2738182A1 (en) | 2009-07-16 | 2014-06-04 | Dow Global Technologies LLC | Polymerization process for olefin-based polymers |
| US9018328B2 (en) | 2009-07-16 | 2015-04-28 | Dow Global Technologies Llc | Polymerization process for olefin-based polymers |
| WO2012088235A2 (en) | 2010-12-21 | 2012-06-28 | Dow Global Technologies Llc | Olefin-based polymers and dispersion polymerizations |
| US9388254B2 (en) | 2010-12-21 | 2016-07-12 | Dow Global Technologies Llc | Olefin-based polymers and dispersion polymerizations |
| EP3091038A1 (en) | 2010-12-21 | 2016-11-09 | Dow Global Technologies LLC | Olefin-based polymers and dispersion polymerizations |
| US11041030B2 (en) | 2018-09-19 | 2021-06-22 | Exxonmobil Chemical Patents Inc. | Devolatilization processes |
| US12030976B2 (en) | 2018-09-19 | 2024-07-09 | ExxonMobil Engineering & Technology Company | Devolatilization processes |
Also Published As
| Publication number | Publication date |
|---|---|
| EE200100590A (en) | 2003-04-15 |
| AU769019B2 (en) | 2004-01-15 |
| BG106036A (en) | 2002-06-28 |
| HK1046008B (en) | 2003-10-03 |
| HUP0201501A3 (en) | 2005-01-28 |
| ES2188548T3 (en) | 2003-07-01 |
| DE50001053D1 (en) | 2003-02-13 |
| HUP0201501A2 (en) | 2002-08-28 |
| HRP20010658A2 (en) | 2002-10-31 |
| EA200101023A1 (en) | 2002-04-25 |
| KR20020005672A (en) | 2002-01-17 |
| YU80701A (en) | 2003-10-31 |
| AU5208300A (en) | 2000-12-05 |
| CZ20014084A3 (en) | 2002-03-13 |
| HK1046008A1 (en) | 2002-12-20 |
| DK1181328T3 (en) | 2003-04-14 |
| JP2002544355A (en) | 2002-12-24 |
| SK12742001A3 (en) | 2002-05-09 |
| NO20015535D0 (en) | 2001-11-13 |
| ATE230774T1 (en) | 2003-01-15 |
| PT1181328E (en) | 2003-04-30 |
| DE19922944A1 (en) | 2000-11-16 |
| TR200103287T2 (en) | 2002-04-22 |
| WO2000069952A1 (en) | 2000-11-23 |
| EP1181328B1 (en) | 2003-01-08 |
| NZ515191A (en) | 2003-01-31 |
| BR0010535A (en) | 2002-02-19 |
| NO20015535L (en) | 2001-11-13 |
| CN1350564A (en) | 2002-05-22 |
| MXPA01011554A (en) | 2003-08-20 |
| PL352023A1 (en) | 2003-07-14 |
| EP1181328A1 (en) | 2002-02-27 |
| IL144807A0 (en) | 2002-06-30 |
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| Date | Code | Title | Description |
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| FZDE | Discontinued |