WO2005090456A1 - Blowing agents for the production of foamed halogen-containing organic plastics - Google Patents
Blowing agents for the production of foamed halogen-containing organic plastics Download PDFInfo
- Publication number
- WO2005090456A1 WO2005090456A1 PCT/EP2005/051208 EP2005051208W WO2005090456A1 WO 2005090456 A1 WO2005090456 A1 WO 2005090456A1 EP 2005051208 W EP2005051208 W EP 2005051208W WO 2005090456 A1 WO2005090456 A1 WO 2005090456A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- vinyl
- polymers
- blowing agent
- vinyl chloride
- copolymers
- Prior art date
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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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- 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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
- C08J2201/024—Preparation or use of a blowing agent concentrate, i.e. masterbatch in a foamable composition
-
- 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
- C08J2327/00—Characterised by the use 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; Derivatives of such polymers
Definitions
- the present invention refers to the area of halogen-containing organic plastics and concerns a method for the production of foamed plastics as well as a suitable blowing agent mixture therefore.
- halogen-containing organic polymers like poly(vinyl chloride) (PVC) are versatile materials for manufacturing sections, tubes and sheets. For example, they are applied preferably in form of foam core tubes, celluka or free foamed sheets and foamed sections.
- the preparation of these materials can be based on direct gassing processes or chemical or physical blowing processes, as well as combinations thereof.
- the physical methods comprise the expansion of compressed gases added to the polymers like previously compressed CO 2 or nitrogen, as well as vaporization of volatile liquids like methylene chloride, pentane or fluorochlorinated hydrocarbons, for example.
- these methods have lost importance in the last years because of their ecologically undesirable effects .
- Direct gassing processes as described in the European Patent EP 1144490 Bl in which nitrogen gas is injected during the extrusion of poly(vinyl chloride) using an injection system at the extruder, also have far less ecologically undesirable effects.
- US Patent US 5 158 986 the physical method is applied in form of a supercritical fluid as blowing agent. These processes have the drawback of a relatively complex and expensive apparatus assembly, which has to be adjusted specifically. Therefore, chemical blowing agents are used more often.
- the European Patent EP 0461745 Bl discloses, for instance, the use of amides, especially azoamides, which are highly dispersed in the product to be extruded and which release nitrogen on thermal decomposition.
- Object of the present invention is a method for producing foamed halogen-containing organic plastics, wherein a blowing agent mixture comprising chemical blowing agents, polyols and salts of perchloric acid in form of a physical mixture is added to the plastic- containing pre-mixture before the extrusion and after homogeneous dispersion the resulting mixture is manipulated accordingly.
- a blowing agent mixture comprising chemical blowing agents, polyols and salts of perchloric acid in form of a physical mixture is added to the plastic- containing pre-mixture before the extrusion and after homogeneous dispersion the resulting mixture is manipulated accordingly.
- a further object of the present invention is a blowing agent mixture comprising chemical blowing agents, 0,01 to 35 % polyols and 0,01 to 35 % salts of perchloric acid by weight based on the blowing agent mixture, as well as the use of this blowing agents combination for the production of foamed halogen-containing plastics.
- Halogen-containing organic plastics which can be foamed using the blowing agent compositions according to the present invention, are particularly chlorine-containing polymers and their regrinds.
- Examples for this kind of chlorine-containing polymers and their regrinds, which have to be stabilized are: polymers of vinyl chloride, vinyl resins comprising vinyl chloride motifs in their structure, copolymers of vinyl chloride and vinyl ester of aliphatic acids, particularly vinyl acetate, copolymers of vinyl chloride with esters of acrylic and methacrylic acid and with acrylonitrile, copolymers of vinyl chloride with diene compounds and unsaturated dicarboxylic acids or their anhydrides, like copolymers of vinyl chloride with diethyl maleate, diethyl fiimarate or maleic anhydride, post- chlorinated polymers and copolymers of vinyl chloride, copolymers of vinyl chloride and vinylidene chloride with unsaturated aldehydes, ketones and others like acrolein, cro
- PVC means also copolymers or grafted polymers of PVC with polymerisable compounds like acrylonitrile, vinyl acetate or ABS, wherein the polymers can be suspension, mass or emulsion polymers.
- the polymer is a PVC homopolymer, in particular a suspension polymer or mass polymer.
- Chemical blowing agents suitable for the method according to the present invention are organic azo and hydrazo compounds, tetrazoles, oxazines, sulfohydrazines as well as soda and sodium bicarbonate and blends of these compounds with further additives like urea, waxes and zinc oxide.
- azodicarbonamide and sodium bicarbonate are especially suitable.
- Perchlorates according to the present invention are metal salts and ammonium salts of perchloric acid.
- Examples for perchlorates suitable according to the present invention are those with the formula M(ClO 4 ) n , wherein M represents particularly ammonium, Li, Na, K, Mg, Ca, Sr, Zn, Ti, Al, La or Ce.
- n represents according to the valency of the cation M 1, 2 or 3.
- Lithium, potassium and sodium perchlorate are preferred.
- the perchlorates can be employed in an amount ranging from 0,001 to 35, for instance, preferably from 0,01 to 20, and more preferably from 1 to 15 parts per weight based on 100 parts per weight blowing agent mixture.
- Polyols suitably employed for the present invention are pentaerythritol, dipentaerythritol, tripentaerythritol, bistrimethylolpropane, inositol, poly(vinyl alcohol), bistrimethylolethane, trimethylolpropane (TMP), sorbitol, maltitol, isomaltitol, lactitol, Lycasin ® , mannitol, inositol, lactose, Leucrose ® , tris-2-hydroxyethyl isocyanurate (THEIC), Palatinit ® , tetramethylol cyclohexanol, tetramethylol cyclopentanol, tetramethylol cylcopyranol, glycerol, diglycerol, polyglycerol or thiodiglycerol as well as reaction products of these polyols with ethylene
- the polyols can be employed in an amount ranging from 0,01 to 35, preferably from 0,1 to 30 and more preferably from 1 to 25 % by weight based on 100 % by weight blowing agent mixture.
- blowing agent SB 453 blowing agent, Co. Clariant
- the extrusion product prepared with the blowing agent according to present invention and according to the method of the present invention is characterized by a considerably lower density however concurrent with a constant thermal stability.
Abstract
A method for the production of foamed halogen-containing organic plastics is proposed, wherein a blowing agent mixture comprising chemical blowing agents, polyols and salts of perchloric acid in form of a physical mixture is added to the plastic-containing pre-mixture before the extrusion and after homogeneous dispersion the resulting mixture is manipulated accordingly. The method according to the present invention leads to PVC-foams with a lower density than using perchlorate and polyol in the stabilizing agent. Furthermore a blowing agent mixture is proposed comprising polyols and salts of perchloric acid.
Description
BLOWING AGENTS FOR THE PRODUCTION OF FOAMED HALOGEN- CONTAINING ORGANIC PLASTICS
Field of the invention The present invention refers to the area of halogen-containing organic plastics and concerns a method for the production of foamed plastics as well as a suitable blowing agent mixture therefore.
State of the art Foamed plastics have a wide range of applications as they show decisive advantages compared with high-density plastics because of weight and cost savings. In particular, halogen-containing organic polymers like poly(vinyl chloride) (PVC) are versatile materials for manufacturing sections, tubes and sheets. For example, they are applied preferably in form of foam core tubes, celluka or free foamed sheets and foamed sections.
The preparation of these materials can be based on direct gassing processes or chemical or physical blowing processes, as well as combinations thereof. The physical methods comprise the expansion of compressed gases added to the polymers like previously compressed CO2 or nitrogen, as well as vaporization of volatile liquids like methylene chloride, pentane or fluorochlorinated hydrocarbons, for example. However, these methods have lost importance in the last years because of their ecologically undesirable effects .
Therefore, chemical methods, in which the blowing process is induced by - the usually thermal decomposition of- added blowing agents, are used more and more often.
Direct gassing processes as described in the European Patent EP 1144490 Bl, in which nitrogen gas is injected during the extrusion of poly(vinyl chloride) using an injection system at the extruder, also have far less ecologically undesirable effects. In US Patent US 5 158 986 the physical method is applied in form of a supercritical fluid as blowing agent. These processes have the drawback of a relatively complex and expensive apparatus assembly, which has to be adjusted specifically.
Therefore, chemical blowing agents are used more often. The European Patent EP 0461745 Bl discloses, for instance, the use of amides, especially azoamides, which are highly dispersed in the product to be extruded and which release nitrogen on thermal decomposition.
The combination of chemical and mechanical methods, which are realised in the European Patent Application EP 0151652 Al by thorough stirring and mixing of a PVC composition during generation of the gas on heating, leads to a good and even dispersion of the gas and thus to a homogeneous density distribution of the plastic.
However, just those proven chemical blowing methods lead with halogen-containing organic plastics, particularly with PVC, to products showing an unsatisfying low density because of the chemical structure of the polymers. The proportion of crystalline areas in these polymers melting only at very high temperatures results from a higher density of the extrusion product. However, the thermal stability of these plastics doesn't allow an appropriate increase of the processing temperature. In the patent EP 0461745 Bl blowing agents are therefore applied in combination with organic tin compounds as thermal stabilizing agents. Another solution is proposed in the patent application EP 0107064 Al, in which the blowing agent is combined with a so called "nucleating agent" which increases the ratio of closed cells in the foam. However, if the proposed azodicarbonamide is chosen as nucleating agent, the dynamic thermal stability of the foam is reduced so that higher amounts of stabilizing agents are necessary to ensure a sufficient thermal stability of the product.
Therefore it is the task of the present invention to provide a method leading to extruded products of foamed halogen-containing organic plastics characterized by a low density concurrent with high thermal stability.
Description of the invention Object of the present invention is a method for producing foamed halogen-containing organic plastics, wherein a blowing agent mixture comprising chemical blowing agents, polyols and salts of perchloric acid in form of a physical mixture is added to the plastic-
containing pre-mixture before the extrusion and after homogeneous dispersion the resulting mixture is manipulated accordingly.
A further object of the present invention is a blowing agent mixture comprising chemical blowing agents, 0,01 to 35 % polyols and 0,01 to 35 % salts of perchloric acid by weight based on the blowing agent mixture, as well as the use of this blowing agents combination for the production of foamed halogen-containing plastics.
Surprisingly it was found, that a combination of chemical blowing agents, polyols and salts of perchloric acid added to the plastic-containing pre-mixture in form of a physical mixture, provides foams with lower density than the usual use of perchlorate and polyol in the stabilizing agent.
Halogen-containing organic plastics
Halogen-containing organic plastics, which can be foamed using the blowing agent compositions according to the present invention, are particularly chlorine-containing polymers and their regrinds. Examples for this kind of chlorine-containing polymers and their regrinds, which have to be stabilized, are: polymers of vinyl chloride, vinyl resins comprising vinyl chloride motifs in their structure, copolymers of vinyl chloride and vinyl ester of aliphatic acids, particularly vinyl acetate, copolymers of vinyl chloride with esters of acrylic and methacrylic acid and with acrylonitrile, copolymers of vinyl chloride with diene compounds and unsaturated dicarboxylic acids or their anhydrides, like copolymers of vinyl chloride with diethyl maleate, diethyl fiimarate or maleic anhydride, post- chlorinated polymers and copolymers of vinyl chloride, copolymers of vinyl chloride and vinylidene chloride with unsaturated aldehydes, ketones and others like acrolein, crotonaldehyde, vinyl methyl ketone, vinyl methyl ether, vinyl isobutyl ether and the like; polymers of vinylidene chloride and their copolymers with vinyl chloride and other polymerisable compounds; polymers of vinyl chloroacetate and dichlorodivinyl ether; chlorinated polymers of vinyl acetate, chlorinated polymeric esters of acrylic acid and alpha-substituted acrylic acid; polymers of chlorinated styrenes, for example dichlorostyrene; chlorinated polymers of ethylene; polymers and post-chlorinated polymers
of chlorobutadiene and their copolymers with vinyl chloride; as well as mixtures of said polymers among themselves or with other polymerisable compounds.
Within the scope of the present invention PVC means also copolymers or grafted polymers of PVC with polymerisable compounds like acrylonitrile, vinyl acetate or ABS, wherein the polymers can be suspension, mass or emulsion polymers. Preferably the polymer is a PVC homopolymer, in particular a suspension polymer or mass polymer.
Chemical blowing agent
Chemical blowing agents suitable for the method according to the present invention are organic azo and hydrazo compounds, tetrazoles, oxazines, sulfohydrazines as well as soda and sodium bicarbonate and blends of these compounds with further additives like urea, waxes and zinc oxide. Especially suitable are azodicarbonamide and sodium bicarbonate.
Salts of perchloric acid
Perchlorates according to the present invention are metal salts and ammonium salts of perchloric acid. Examples for perchlorates suitable according to the present invention are those with the formula M(ClO4)n, wherein M represents particularly ammonium, Li, Na, K, Mg, Ca, Sr, Zn, Ti, Al, La or Ce. n represents according to the valency of the cation M 1, 2 or 3. Lithium, potassium and sodium perchlorate are preferred.
The perchlorates can be employed in an amount ranging from 0,001 to 35, for instance, preferably from 0,01 to 20, and more preferably from 1 to 15 parts per weight based on 100 parts per weight blowing agent mixture.
Polyols
Polyols suitably employed for the present invention are pentaerythritol, dipentaerythritol, tripentaerythritol, bistrimethylolpropane, inositol, poly(vinyl alcohol), bistrimethylolethane, trimethylolpropane (TMP), sorbitol, maltitol, isomaltitol, lactitol,
Lycasin®, mannitol, inositol, lactose, Leucrose®, tris-2-hydroxyethyl isocyanurate (THEIC), Palatinit®, tetramethylol cyclohexanol, tetramethylol cyclopentanol, tetramethylol cylcopyranol, glycerol, diglycerol, polyglycerol or thiodiglycerol as well as reaction products of these polyols with ethylene oxide and/or propylene oxide. Especially suitable are pentaerythritol, dipentaerythritol, TMP and THEIC.
The polyols can be employed in an amount ranging from 0,01 to 35, preferably from 0,1 to 30 and more preferably from 1 to 25 % by weight based on 100 % by weight blowing agent mixture.
Examples
1. Preparation of the blowing agent composition according to the present invention In a mixer of the Henschel Company were introduced 1000 g SB 453 (blowing agent, Co. Clariant) and 200 g trimethylolpropane (TMP). This mixture was homogenized for 30 seconds at 25 °C with 800 rotations per minute. Hereafter 200 g of a 50 % solution of sodium perchlorate in water were added and the mixture was homogenized for 4-V2 minute with 800 rotations per minute. 2. Preparation of the dry blend A dry blend was prepared by mixing PVC powder and various additives in a mixer of the Henschel Company (amount of compounds = 3 kg, heating temperature = 120 °C, afterwards cooling down); the composition is given in table 1. Table 1: composition of PVC -dry blends
To the example Bl (comparative example) 0,5 % by weight blowing agent SB 453 (blowing agent, Co. Clariant) were added under stirring at 60 °C based on the whole amount of the dry blend.
To the example B2 (according to the present invention) 0,7 % by weight of the blowing agent composition according to the present invention were added under stirring at 60 °C based on the whole amount of the dry blend, so that this batch also contained a total of 0,5 % by weight blowing agent .
3. Preparation of flat sheets The dry blends were extruded on a twin-screw extruder of the company Weber in form of a flat sheet. (Parameters of extrusion: speed = 15 rpm; machine load = 67 %, temperature = 180 °C). The thermal stability of the extruded flat sheets was determined using the congo red method at 200 °C and the density was determined according to ASTM D 792.
Table 2: Results
The extrusion product prepared with the blowing agent according to present invention and according to the method of the present invention is characterized by a considerably lower density however concurrent with a constant thermal stability.
Claims
Claims 1. Method for the production of foamed halogen-containing organic plastics, wherein a blowing agent mixture comprising chemical blowing agents, polyols and salts of perchloric acid in form of a physical mixture is added to the plastic-containing pre-mixture before the extrusion and after homogeneous dispersion the resulting mixture is manipulated accordingly.
2. Method according to claim 1 , characterized in that the applied plastics are chosen from the group consisting of polymers of vinyl chloride, vinyl resins comprising vinyl chloride motifs in their structure, copolymers of vinyl chloride and vinyl ester of aliphatic acids, particularly vinyl acetate, copolymers of vinyl chloride with esters of acrylic and methacrylic acid and with acrylonitrile, copolymers of vinyl chloride with diene compounds and unsaturated dicarboxylic acids or their anhydrides, as copolymers of vinyl chloride with diethyl maleate, diethyl fumarate or maleic anhydride, post-chlorinated polymers and copolymers of vinyl chloride, copolymers of vinyl chloride and vinylidene chloride with unsaturated aldehydes, ketones and others like acrolein, crotonaldehyde, vinyl methyl ketone, vinyl methyl ether, vinyl isobutyl ether and the like; polymers of vinylidene chloride and their copolymers with vinyl chloride and other polymerisable compounds; polymers of vinyl chloroacetate and dichlorodivinyl ether; chlorinated polymers of vinyl acetate, chlorinated polymeric esters of acrylic acid and alpha- substituted acrylic acid; polymers of chlorinated styrenes, for example dichlorostyrene; chlorinated polymers of ethylene; polymers and post-chlorinated polymers of chlorobutadiene and their copolymers with vinyl chloride; as well as mixtures of said polymers among themselves or with other polymerisable compounds.
3. Method according to claim 1 or 2, characterized in that poly(vinyl chloride) is applied as the plastic.
4. Method according to one of the claims 1 to 3, characterized in that the blowing agent mixture comprises lithium, potassium and/or sodium perchlorate.
5. Method according to on of the claims 1 to 4, characterized in that the blowing agent mixture comprises polyols chosen from the group consisting of trimethylolpropane, pentaerythritol, dipentaerythritol and tris-2-hydroxyethyl isocyanurate.
6. Blowing agent mixtures comprising chemical blowing agents, 0,01 to 35 % by weight polyols, 0,01 to 35 % salts of perchloric acid by weight based on the blowing agent mixture.
7. Blowing agent mixtures according to claim 6, characterized in that they comprise chemical blowing agents chosen from the group consisting of organic azo and hydrazo compounds, tetrazoles, oxazines, sulfohydrazines as well as soda and sodium bicarbonate and blends of these compounds with further additives like urea, waxes or zinc oxide.
8. Blowing agent mixtures according to claim 6 or 7, characterized in that they comprise polyols chosen from the group consisting of pentaerythritol, dipentaerythritol, tripentaerythritol, bistrimethylolpropane, inositol, poly(vinyl alcohol), bistrimethylolethane, trimethylolpropane (TMP), sorbitol, maltitol, isomaltitol, lactitol, Lycasin®, mannitol, inositol, lactose, Leucrose®, tris-2-hydroxyethyl isocyanurate (THEIC), Palatinit®, tetramethylol cyclohexanol, tetramethylol cyclopentanol, tetramethylol cylcopyranol, glycerol, diglycerol, polyglycerol or thiodiglycerol as well as reaction products of these polyols with ethylene oxide and/or propylene oxide.
9. Blowing agent mixtures according to at least one of the claims 6 to 8, characterized in that they comprise metal salts and/or ammonium salts of perchloric acid.
10. Use of blowing agent mixtures according to at least one of the claims 6 to 9 for the production of foamed halogen-containing organic plastics.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE200410013237 DE102004013237A1 (en) | 2004-03-18 | 2004-03-18 | Blowing agent for the production of foamed halogen-containing organic plastics |
| DE102004013237.2 | 2004-03-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2005090456A1 true WO2005090456A1 (en) | 2005-09-29 |
Family
ID=34963408
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2005/051208 WO2005090456A1 (en) | 2004-03-18 | 2005-03-16 | Blowing agents for the production of foamed halogen-containing organic plastics |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE102004013237A1 (en) |
| WO (1) | WO2005090456A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2926545A1 (en) * | 2008-01-21 | 2009-07-24 | Snpe Materiaux Energetiques Sa | NITROGEN GENERATING COMPOSITION COMPRISING AZODICARBONAMIDE AND PROCESS FOR GENERATING NITROGEN GAS BY DECOMPOSITION OF SAID COMPOSITION |
| WO2013083492A1 (en) | 2011-12-06 | 2013-06-13 | Omya Development Ag | Fillers for foamed rigid polymer products |
| EP3750950A1 (en) | 2019-06-12 | 2020-12-16 | Omya International AG | Chemical foaming of pvc with surface-reacted calcium carbonate (mcc) and/or hydromagnesite |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6357656A (en) * | 1986-08-29 | 1988-03-12 | Akishima Kagaku Kogyo Kk | Liquid stabilizer for chlorinated resin foam |
| JPH07157587A (en) * | 1993-10-13 | 1995-06-20 | Sekisui Chem Co Ltd | Vinyl chloride-based resin composition |
| WO1997000908A1 (en) * | 1995-06-20 | 1997-01-09 | Witco Corporation | Overbased pvc stabilizer |
-
2004
- 2004-03-18 DE DE200410013237 patent/DE102004013237A1/en not_active Withdrawn
-
2005
- 2005-03-16 WO PCT/EP2005/051208 patent/WO2005090456A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6357656A (en) * | 1986-08-29 | 1988-03-12 | Akishima Kagaku Kogyo Kk | Liquid stabilizer for chlorinated resin foam |
| JPH07157587A (en) * | 1993-10-13 | 1995-06-20 | Sekisui Chem Co Ltd | Vinyl chloride-based resin composition |
| WO1997000908A1 (en) * | 1995-06-20 | 1997-01-09 | Witco Corporation | Overbased pvc stabilizer |
Non-Patent Citations (3)
| Title |
|---|
| DATABASE WPI Section Ch Week 198816, Derwent World Patents Index; Class A18, AN 1988-108876, XP002334284 * |
| DATABASE WPI Section Ch Week 199533, Derwent World Patents Index; Class A14, AN 1995-252351, XP002338715 * |
| PATENT ABSTRACTS OF JAPAN vol. 1995, no. 09 31 October 1995 (1995-10-31) * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2926545A1 (en) * | 2008-01-21 | 2009-07-24 | Snpe Materiaux Energetiques Sa | NITROGEN GENERATING COMPOSITION COMPRISING AZODICARBONAMIDE AND PROCESS FOR GENERATING NITROGEN GAS BY DECOMPOSITION OF SAID COMPOSITION |
| WO2009095578A2 (en) * | 2008-01-21 | 2009-08-06 | Snpe Materiaux Energetiques | Composition for generating nitrogenous gas and including azodicarbonamide, and method for generating nitrogen gas by decomposition of said composition |
| WO2009095578A3 (en) * | 2008-01-21 | 2009-12-10 | Snpe Materiaux Energetiques | Composition for generating nitrogenous gas and including azodicarbonamide, and method for generating nitrogen gas by decomposition of said composition |
| US8287834B2 (en) | 2008-01-21 | 2012-10-16 | Herakles | Composition for generating nitrogenous gas and including azodicarbonamide, and method for generating nitrogen gas by decomposition of said composition |
| WO2013083492A1 (en) | 2011-12-06 | 2013-06-13 | Omya Development Ag | Fillers for foamed rigid polymer products |
| EP2612881A1 (en) | 2012-01-05 | 2013-07-10 | Omya Development AG | Fillers for foamed rigid polymer products |
| EP3750950A1 (en) | 2019-06-12 | 2020-12-16 | Omya International AG | Chemical foaming of pvc with surface-reacted calcium carbonate (mcc) and/or hydromagnesite |
| WO2020249779A1 (en) | 2019-06-12 | 2020-12-17 | Omya International Ag | Chemical foaming of pvc with surface-reacted calcium carbonate (mcc) and/or hydromagnesite |
Also Published As
| Publication number | Publication date |
|---|---|
| DE102004013237A1 (en) | 2005-10-06 |
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