WO2005063866A1 - Process for preparation of nucleated polyolefins - Google Patents
Process for preparation of nucleated polyolefins Download PDFInfo
- Publication number
- WO2005063866A1 WO2005063866A1 PCT/IN2003/000426 IN0300426W WO2005063866A1 WO 2005063866 A1 WO2005063866 A1 WO 2005063866A1 IN 0300426 W IN0300426 W IN 0300426W WO 2005063866 A1 WO2005063866 A1 WO 2005063866A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- nucleating agent
- solvent
- polyolefin
- gel
- carbon atoms
- Prior art date
Links
Classifications
-
- 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
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/2053—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the additives only being premixed with a liquid phase
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
-
- 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
Definitions
- the present invention provides an improved process for preparation of nucleated polyolefins. More particularly it relates to the said process for nucleating polyolefins using a nucleating agent in a gel form. Still more particularly it relates using gels of alkali and alkaline earth metal salts of organic carboxylic salts, such as sodium benzoate gel.
- a nucleating agent such as polypropylene
- N nucleating agent
- nucleating agents are high melting compounds which do not melt at processing temperature of the polymer and remain as discrete particles embedded in polymer melt. These insoluble particles behave as nucleator for the crystallization of polymer melt and generate innumerable crystallization sites resulting innumerous small spherulites. Some nucleating agents are soluble in polymer melt but they solidify before crystallization of polymer melt and, thus, generate sites for crystallization. Apart from the structure, the size as well as the ability to disperse homogeneously in a melt of polymer also has profound effect on nucleation efficiency of a nucleating agent. Large number of particles having small size increases the number of nucleation sites and improves efficiency.
- nucleating agent as a powder with a base polymer along with other additives such as antioxidants, acid scavengers, dispersing agent, lubricant etc, followed by extrusion produces the nucleated polymer.
- Homogenous mixing of a nucleating agent in base polymer is essential for good results.
- the nucleating agent in powder form agglomerates to form bigger particles, thus reducing number of crystallization sites and hence reduction in efficiency of a nucleating agent.
- the method of incorporation of a nucleating agent in polymer has effect on its efficiency.
- several classes of organic and inorganic compounds have been reported as efficient nucleating agents.
- US Patent 4,184,026 describes a method in which nucleating agent dissolved in low boiling solvent is sprayed in polymer powder for uniform mixing of nucleating agent in polymer before processing.
- Inorganic nucleating agents are generally considered as less efficient because of the difficulties associated with the efficient dispersal of the nucleating agent in the polymer. They tend to aggregate into large particles in polymer melt due to their intrinsic thermodynamic in compatibility causing loss of both nucleating efficiency as well as optical and mechanical properties.
- the nucleation of the polyolefins is carried out using a nucleating agent in solid form or using a solution of the nucleating agent.
- the main object of this the present invention is to provide an improved process for nucleating polyolefins
- Another object of the present invention is to prepare a gel of alkali metal and alkaline earth metal salts of organic carboxylic acid in organic solvents to enable the material to be dispersed efficiently in a polyolefin.
- Yet another object of the present invention is to obtain polyolefin with good optical and physical properties using alkali metal salts of carboxylic acids as nucleating agent.
- the present invention provides an improved process for nucleating polyolefins using the nucleating agent or mixture thereof in gel form optionally in combination with other additives such as antioxidants, antislip agents, acid scavengers, lubricants or UN absorbers, which comprises forming a gel of an nucleating agent either by dissolving the said nucleating agent in a solvent optionally heating the solution of the nucleating agent to the boiling point of the solvent used and cooling, or optionally by addition of another solvent, mixing the gel with a polypropylene powder optionally added with the other additives, removing the solvent by conventional methods, extruding the mixture at minimum temperature of melting point of the polyolefin to obtain the nucleated polyolefin.
- additives such as antioxidants, antislip agents, acid scavengers, lubricants or UN absorbers
- the nucleating agent used for the nucleation of polyolefins may be metallic salts, for example but not restricted to, of sodium, potassium, lithium, calcium, magnesium, aluminum with organic carboxylic acids such as but not restricted to, aliphatic mono and dicarboxylic acids of 2-16 carbon atoms, preferably 2-8 carbon atoms, aromatic mono and poly carboxylic acids ⁇ substituted aromatic carboxylic acids and aliphatic and aromatic sulfonic acids.
- the solvent used for dissolving the nucleating agent may be preferably solvent having low boiling points, but not restricted to, water, ketones containing 3-10 carbon atoms, preferably 3-7 carbon atoms, aliphatic alcohols containing 1- 12 carbon atoms, preferably, 1-6 carbon atoms, aliphatic esters, ethers, cyclic ethers, hydrocarbons of 5-15 carbon atoms or a mixture of hydrocarbons, aromatic hydrocarbons such as toluene, xylene etc., petrol, kerosene, chlorinated hydrocarbons, dimethylformamide, dimethyl acetamide, dimethyl sulfoxide.
- the solvent used for gelling the nucleating may be preferably solvent having low boiling points, but not restricted to, water, ketones containing 3-10 carbon atoms, preferably 3-7 carbon atoms, aliphatic alcohols containing 1- 12 carbon atoms, preferably, 1-6 carbon atoms, aliphatic esters, ethers, cyclic
- the agent may be a solvent or a nonsolvent to the solvent used for preparing solution of the nucleating agent exemplified by alcohols or ketones or aliphatic or aromatic hydrocarbons or esters such as methanol, ethanol, toluene, xylene, n-hexane, cyclohexane, acetone , MLBK, ethylacetate rtc.
- the quantity of nucleating agent in gel used in polyolefin may be 0.01 to 10 wt %, preferably 0.01 to 2 wt % and more preferably 0.1 to 0.5 wt % based on polyolefins.
- the present invention provides an improved process for nucleating polyolefins using one or more nucleating agent in gel form.
- additives such as antioxidants, antislip agents, acid scavengers, lubricants or UN absorbers may also be added to the mixture of the polyolefin and the nucleating agent gel.
- the gel of the nucleating agent is formed by dissolving the nucleating agent in a solvent and optionally heating the solution to boiling point of the solvent used and then cooling.
- another solvent is added to the solution of the nucleating agent to gel the agent.
- the second solvent may be a solvent or a non-solvent for the first solvent.
- the nucleating agent gel is then mixed with the polyolefin powder which could for example be polypropylene powder optionally with other additives.
- the solvent is then removed by conventional methods and the mixture extruded at minimum temperature of melting point of the polyolefin to obtain the nucleated polyolefin.
- the nucleating agent used for the nucleation of polyolefins are metallic salts, for example but not restricted to salts of sodium, potassium, lithium, calcium, magnesium, aluminum with organic carboxylic acids such as but not restricted to, aliphatic mono and dicarboxylic acids of 2-16 carbon atoms, preferably 2-8 carbon atoms, aromatic mono and poly carboxylic acids, substituted aromatic carboxylic acids and aliphatic and aromatic sulfonic acids.
- the solvent used for dissolving the nucleating agent is preferably solvent having low boiling points, such as but not restricted to, water, ketones containing 3-10 carbon atoms, preferably 3-7 carbon atoms, aliphatic alcohols containing 1-12 carbon atoms, preferably, 1-6 carbon atoms, aliphatic esters, ethers, cyclic ethers, hydrocarbons of 5-15 carbon atoms or a mixture of hydrocarbons, aromatic hydrocarbons such as toluene, xylene etc., petrol, kerosene, chlorinated hydrocarbons, dimethylformamide, dimethyl acetamide, dimethyl sulfoxide.
- solvent having low boiling points such as but not restricted to, water, ketones containing 3-10 carbon atoms, preferably 3-7 carbon atoms, aliphatic alcohols containing 1-12 carbon atoms, preferably, 1-6 carbon atoms, aliphatic esters, ethers, cyclic ethers, hydrocarbons of 5-15 carbon atom
- the second solvent used for gelling the nucleating agent is a solvent or a nonsolvent to the solvent used for preparing solution of the nucleating agent exemplified by alcohols or ketones or aliphatic or aromatic hydrocarbons or esters such as methanol, ethanol, toluene, xylene, n-hexane, cyclohexane, acetone, MLBK, ethylacetate rtc.
- the quantity of nucleating agent in gel used in polyolefin is 0.01 to 10 wt %, preferably 0.01 to 2 wt % and more preferably 0.1 to 0.5 wt % based on polyolefins.
- the polyolefins may be homopolymers, copolymers of olefin with one or more ethylenically unsaturated comonomers.
- the comonomer if present, is provided in minor quantities about 10% or even lower percent based on the weight of olefin. Such comonomers are provided to modify the properties of polymers.
- Examples of the polymers ⁇ whose transparency can be improved by incorporation of nucleating agent include polymer and copolymers of aliphatic mono olefins containing two to about six carbon atoms having molecular weight of about 30,000 to about 5,00,000, preferably from 30,000 to about 3,00,000 such as polyethylene, polypropylene, ethylene- propylene copolymers.
- the solvent gel of nucleating agent is mixed with polymer little at a time by blending mechanically or by any suitable method of blending followed by removal of solvent by suitable methods such as exposing to air/ heating in oven or air circulated oven at ⁇ 50°C. This blend is further compounded with other additives and extruded.
- the solvent in gel can be removed by heating at low temperature in an oven, preferably, air circulated oven or exposing to atmosphere.
- an oven preferably, air circulated oven or exposing to atmosphere.
- MMBK methyl isobutyl ketone
- EXAMPLE-1 This example illustrated the use of sodium benzoate gel in methyl isobutyl ketone (MLBK) - for nucleating. 0.2 g of gel was mixed with 100 g of polypropylene resin (MFI 12) in small lot of 10 gm each at a time followed by stirring to ensure efficient mixing. After complete mixing, the resin was dried in an air circulated oven over night at room temperature to remove any residual solvent.
- MFI 12 polypropylene resin
- This resin was further compounded with additives namely, IrganoxlOlO, 500 ppm; Ultranox-626, 800 ppm; Hydrotalcite DHT 4A, 200 ppm; Calcium stearate, 500 ppm; GMS-Finast 9500, 400 ppm on a Brabander single screw extruder.
- the extrusion temperature profile was 170 - 180 - 200 - 210 °C.
- the screw RPM was 60.
- the residence time was 30 seconds.
- the extruded material was pelletized to obtained the product.
- Sodium benzoate (0.2 g) was dissolved in methanol (7 mL) in a 100 mL beaker to which methyl isobutylketone (45 mL) was added drop wise with magnetic stirring. A gel with bluish tinge was formed.
- 0.2 g of salt, prepared by methods described in above examples, were mixed with 100 g of polypropylene resin ( MFI 12 ) in small lot of 5-10 gm each at a time followed by stirring to ensure efficient mixing. After complete mixing, the resin was dried in an air circulated oven over night at room temperature to remove any residual solvent.
- This resin was further compounded with additives namely, IrganoxlOlO, 500 ppm; Ultranox- 626, 800 ppm; Hydrotalcite DHT 4A, 200 ppm; Calcium stearate, 500 ppm; GMS-Finast 9500, 400 ppm on a Brabander single screw extruder.
- the extrusion temperature profile was 170 - 180 - 200 - 210 °C.
- the screw RPM was 60.
- the residence time was 30 seconds.
- the extruded material was pelletized.
- EXAMPLE-2 Preparation of acetone-sodium benzoate gel: Sodium benzoate (0.2 g.) was dissolved in methanol (7.0 mL) in a 100 mL beaker to which acetone (40 mL) was added drop by drop with magnetic stirring. A gel was formed. .2 g of salt, prepared by methods described in above examples, were mixed with 100 g of polypropylene resin (MFI 12) in small lot of 5-10 gm each at a time followed by stirring to ensure efficient mixing. After complete mixing, the resin was dried in an air circulated oven over night at room temperature to remove any residual solvent.
- MFI 12 polypropylene resin
- This resin was further compounded with additives namely, IrganoxlOlO, 500 ppm; Ultranox-626, 800 ppm; Hydrotalcite DHT 4A, 200 ppm; Calcium stearate, 500 ppm; GMS-Finast 9500, 400 ppm on a Brabander single screw extruder.
- the extrusion temperature profile was 170 - 180 - 200 - 210 °C.
- the screw RPM was 60.
- the residence time was 30 seconds.
- the extruded material was pelletized.
- EXAMPLE-3 Preparation of acetone-toluene-sodium benzoate gel: In a beaker (50 mL), NaOH (0.108 gm) moistened with 4 drops of water was dissolved in alcohol (1.5 mL). To this solution benzoic acid (0.33 g) dissolved in acetone (13 mL) was added drop wise with stirring. A gel is formed. To this gel, toluene (15 + 10 mL) was added in two installments. A transparent solution was formed. 0.2 g of salt, prepared by methods described in above examples, were mixed with 100 g of polypropylene resin ( MFI 12 ) in small lot of 5-10 gm each at a time followed by stirring to ensure efficient mixing.
- MFI 12 polypropylene resin
- the resin was dried in an air circulated oven over night at room temperature to remove any residual solvent.
- This resin was further compounded with additives namely, IrganoxlOlO, 500 ppm; Ultranox-626, 800 ppm; Hydrotalcite DHT 4A, 200 ppm; Calcium stearate, 500 ppm; GMS-Finast 9500, 400 ppm on a Brabander single screw extruder.
- the extrusion temperature profile was 170 - 180 - 200 - 210°C.
- the screw RPM was 60.
- the residence time was 30 seconds.
- the extruded material was pelletized.
- EXAMPLE-4 Preparation of methyl isobutyl ketone-sodium benzoate-toluene gel: Sodium benzoate (0.2gm) was dissolved in methanol (7.0 mL) to which MIBK (25 mL) was added drop by drop with magnetic stirring. A gel with slight bluish tinge was formed. This was diluted with toluene (25 mL) to form an almost transparent liquid. The particles dispersed in the liquid had an average size of ⁇ 40 nano meters.
- 0.2 g of salt, prepared by methods described in above examples, were mixed with 100 g of polypropylene resin ( MFI 12 ) in small lot of 5-10 gm each at a time followed by stirring to ensure efficient mixing.
- the resin was dried in an air circulated oven over night at room temperature to remove any residual solvent.
- This resin was further compounded with additives namely, IrganoxlOlO, 500 ppm; Ultranox-626, 800 ppm; Hydrotalcite DHT 4A, 200 ppm; Calcium stearate, 500 ppm; GMS-Finast 9500, 400 ppm on a Brabander single screw extruder.
- the extrusion temperature profile was 170 - 180 - 200 - 210 °C.
- the screw RPM was 60.
- the residence time was 30 seconds.
- the extruded material was pelletized.
- EXAMPLE-5 Preparation of acetone-sodium benzoate-toluene gel: Sodium benzoate (0.2 g) was dissolved in methanol (7.0 mL) to which acetone (25 mL) was added drop by drop with magnetic stirring. A gel with slight bluish tinge was formed. This was diluted with toluene (25 mL). It forms almost transparent liquid. This liquid was mixed with polypropylene resin. .2 g of salt, prepared by methods described in above examples, were mixed with 100 g of polypropylene resin ( MFI 12 ) in small lot of 5-10 gm each at a time followed by stirring to ensure efficient mixing.
- MFI 12 polypropylene resin
- the resin was dried in an air circulated oven over night at room temperature to remove any residual solvent.
- This resin was further compounded with additives namely, IrganoxlOlO, 500 ppm; Ultranox-626, 800 ppm; Hydrotalcite DHT 4A, 200 ppm; Calcium stearate, 500 ppm; GMS-Finast 9500, 400 ppm on a Brabander single screw extruder.
- the extrusion temperature profile was 170 - 180 - 200 - 210°C.
- the screw RPM was 60.
- the residence time was 30 seconds.
- the extruded material was pelletized.
- EXAMPLE-6 Solution of sodium benzoate in water Sodium benzoate (0.2 g) was dissolved in water (100 mL). This solution was spray mixed with polypropylene resin (100 g). .2 g of salt, prepared by methods described in above examples, were mixed with 100 g of polypropylene resin ( MFI 12 ) in small lot of 5-10 gm each at a time followed by stirring to ensure efficient mixing. After complete mixing, the resin was dried in an air circulated oven over night at room temperature to remove any residual solvent.
- This resin was further compounded with additives namely, IrganoxlOlO, 500 ppm; Ultranox-626, 800 ppm; Hydrotalcite DHT 4A, 200 ppm; Calcium stearate, 500 ppm; GMS-Finast 9500, 400 ppm on a Brabander single screw extruder.
- the extrusion temperature profile was 170 - 180 - 200 - 210 °C.
- the screw RPM was 60.
- the residence time was 30 seconds.
- the extruded material was palletized.
- the main advantage of present invention is significant improvement in crystallization temperature (Tc) and reduction in spherulitic size of crystals of polyolefins thus, improving optical properties of polyolefins using alkali/alkaline metal salts of carboxylic acids.
- Tc crystallization temperature
- Table 1 Tc of PP nucleated with sodium benzoate:
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/IN2003/000426 WO2005063866A1 (en) | 2003-12-31 | 2003-12-31 | Process for preparation of nucleated polyolefins |
AU2003300699A AU2003300699A1 (en) | 2003-12-31 | 2003-12-31 | Process for preparation of nucleated polyolefins |
EP03819188A EP1699857A1 (en) | 2003-12-31 | 2003-12-31 | Process for preparation of nucleated polyolefins |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/IN2003/000426 WO2005063866A1 (en) | 2003-12-31 | 2003-12-31 | Process for preparation of nucleated polyolefins |
Publications (1)
Publication Number | Publication Date |
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WO2005063866A1 true WO2005063866A1 (en) | 2005-07-14 |
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PCT/IN2003/000426 WO2005063866A1 (en) | 2003-12-31 | 2003-12-31 | Process for preparation of nucleated polyolefins |
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EP (1) | EP1699857A1 (en) |
AU (1) | AU2003300699A1 (en) |
WO (1) | WO2005063866A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012045288A1 (en) * | 2010-10-05 | 2012-04-12 | Polymer Institute Brno, Spol. S R.O. | : method of preparation of nucleated semi-crystalline polymer |
CN104558826A (en) * | 2014-05-26 | 2015-04-29 | 江苏汉光实业股份有限公司 | Formula and preparation method of special compound additive for polypropylene film material |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1202835A (en) * | 1968-03-13 | 1970-08-19 | Dari Ind Inc | Improvements in or relating to methods and compositions for nucleating alpha-olefin polymers |
EP0278470A2 (en) * | 1987-02-11 | 1988-08-17 | Hoechst Aktiengesellschaft | Polypropylene moulding composition |
-
2003
- 2003-12-31 AU AU2003300699A patent/AU2003300699A1/en not_active Abandoned
- 2003-12-31 WO PCT/IN2003/000426 patent/WO2005063866A1/en not_active Application Discontinuation
- 2003-12-31 EP EP03819188A patent/EP1699857A1/en not_active Withdrawn
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1202835A (en) * | 1968-03-13 | 1970-08-19 | Dari Ind Inc | Improvements in or relating to methods and compositions for nucleating alpha-olefin polymers |
EP0278470A2 (en) * | 1987-02-11 | 1988-08-17 | Hoechst Aktiengesellschaft | Polypropylene moulding composition |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012045288A1 (en) * | 2010-10-05 | 2012-04-12 | Polymer Institute Brno, Spol. S R.O. | : method of preparation of nucleated semi-crystalline polymer |
US9062184B2 (en) | 2010-10-05 | 2015-06-23 | Polymer Institute Brno, Spol. S.R.O. | Method of preparation of nucleated semi-crystalline polymer |
CN104558826A (en) * | 2014-05-26 | 2015-04-29 | 江苏汉光实业股份有限公司 | Formula and preparation method of special compound additive for polypropylene film material |
Also Published As
Publication number | Publication date |
---|---|
AU2003300699A1 (en) | 2005-07-21 |
EP1699857A1 (en) | 2006-09-13 |
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