CA1220341A - Blowing agent combination based on azodicarbonamide, the production and use thereof for the foaming of plastics - Google Patents
Blowing agent combination based on azodicarbonamide, the production and use thereof for the foaming of plasticsInfo
- Publication number
- CA1220341A CA1220341A CA000426757A CA426757A CA1220341A CA 1220341 A CA1220341 A CA 1220341A CA 000426757 A CA000426757 A CA 000426757A CA 426757 A CA426757 A CA 426757A CA 1220341 A CA1220341 A CA 1220341A
- Authority
- CA
- Canada
- Prior art keywords
- azodicarbonamide
- blowing agent
- foaming
- titanium
- production
- 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.)
- Expired
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
- 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
- C08J9/10—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 developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Abstract of the Disclosure The invention relates to a new blowing agent combination based on azodicarbonamide, characterized in that the azodi -carbonamide is doped with one or more metal compounds of boron, molybdenum, tungsten and/or titanium in an amount of from 0.001 to 2% by weight of the azodicarbonamide used. The invention also relates to the production and use thereof for the foaming of plastics.
Description
~2;2C3 , A new blowing agent combination based on azodicarbon-.
aside, the production and use thereof for the foaming of plastics This invention relates to new blowing agent combinations based on azodicarbonamide with the addition of metal compounds, and the production and use thereof for the production of cellular and porous articles, such as foams of thermoplastic polymers.
As is known, it is possible to produce foamed lo products from organic polymeric materials by decomposing a blowing agent which is worked into the polymer or is applied onto the surface of the plastics material.
These blowing agents decompose in a controlled manner above a certain temperature with the release of a blowing gas and the formation of a residue which remains in the foam. The literature describes substances of the most varied compound classes for this purpose, for example ago compounds, horsehides, semicarbazides, in-Azores, tetrazoles, Nutrias compounds and benzoxa-zincs, inter aria (Kunststoffe 66 (1976) lo pages 698-701).
Aside derivatives of azodicarboxylic acid generally meet these conditions. Azodicarbonamide is particularly suitable owing to its outstanding stability, its high decomposition temperature, its favorable decomposition characteristics and the relatively large volume of the gases which are released per unit weight.
Moreover, the gases which are released mostly consist of nitrogen and the decomposition residues are sub Stan-tidally colorless and odorless.
Depending on the polymer to be foamed, additives may be mixed with the azodicarbonamide which, for example, lower the decomposition temperature or have a favorable effect on the pore structure and on the color of the resulting foam.
For example, different zinc salts on their own or in admixture with other heavy metal salts, for lo A 21 628 r.
~"~, , .. . .
example lead, tin and cadmium salts etc. and, in particular, chromium compounds such as chromates or chromium salts may be used very effectively as additives for the production of, for example cross-linked polyethylene foams, foam rubber or polyvinyl chloride foams (for example West German Auslegeschrift 1,936,098 published March 29, 1973 (Tray Industries, ha.), West German Auslegeschri~t
aside, the production and use thereof for the foaming of plastics This invention relates to new blowing agent combinations based on azodicarbonamide with the addition of metal compounds, and the production and use thereof for the production of cellular and porous articles, such as foams of thermoplastic polymers.
As is known, it is possible to produce foamed lo products from organic polymeric materials by decomposing a blowing agent which is worked into the polymer or is applied onto the surface of the plastics material.
These blowing agents decompose in a controlled manner above a certain temperature with the release of a blowing gas and the formation of a residue which remains in the foam. The literature describes substances of the most varied compound classes for this purpose, for example ago compounds, horsehides, semicarbazides, in-Azores, tetrazoles, Nutrias compounds and benzoxa-zincs, inter aria (Kunststoffe 66 (1976) lo pages 698-701).
Aside derivatives of azodicarboxylic acid generally meet these conditions. Azodicarbonamide is particularly suitable owing to its outstanding stability, its high decomposition temperature, its favorable decomposition characteristics and the relatively large volume of the gases which are released per unit weight.
Moreover, the gases which are released mostly consist of nitrogen and the decomposition residues are sub Stan-tidally colorless and odorless.
Depending on the polymer to be foamed, additives may be mixed with the azodicarbonamide which, for example, lower the decomposition temperature or have a favorable effect on the pore structure and on the color of the resulting foam.
For example, different zinc salts on their own or in admixture with other heavy metal salts, for lo A 21 628 r.
~"~, , .. . .
example lead, tin and cadmium salts etc. and, in particular, chromium compounds such as chromates or chromium salts may be used very effectively as additives for the production of, for example cross-linked polyethylene foams, foam rubber or polyvinyl chloride foams (for example West German Auslegeschrift 1,936,098 published March 29, 1973 (Tray Industries, ha.), West German Auslegeschri~t
2,653,748 published May 24, 1978 (Dynamite Nobel A), European Patent Application No. 0 027 688 published April 29, 1981 (Bisons Limited)).
It is also known that the foaming operation may be favorably influenced by the addition of, for example, magnesium oxide (West German Auslegeschrift 2,852,287 published April 9, 1981 (~ynamit Nobel A), West German Offenlegungsschrift 2,351,515 published April 24, 1975 (Bayer A)). The addition of, for example, zinc compounds combined with Al, Sun-, B- and Si-compounds to the blowing agent has also been described (Japan Application 49-70931 filed June 20, 1974 (Ohtsuka, Kagako, Yakuhin OK
It has now been found that it is possible to dispense with additives, for example chromates or chromium compounds come brined with known zinc salts or other heavy metal salts, by adding compounds such as boron molybdenum tungsten and/or titanium compounds, individually or mixed together, to the azodicarbonamide.
According to the present invention, metal compounds are added to the blowing agent. Compounds of boron, molybdenum, tungsten and titanium are used. They may be used individually or in mixtures.
The present invention is directed to a blowing agent which comprises azodicarbonamide (ADO), doped with one or more - pa -metal compounds selected from the group consisting of boric acid, boron trioxides sodium borate, calcium borate, perorates, molt-bdenum oxide, sodium molybdate, ammonium molybdate, tungsten oxide, tungstic acid, sodium tungstate, calcium tungstate, ammonium tungstate, titanium dioxide, sodium titan ate, calcium titan ate, titanium sulfite, titanium oxide sulfite, titanium peroxide sulfite or titanium chloride, which metal compound is present in an amount of from 0.05 to 0.6% by weight based on the weight of azodicarbonamide.
Sodium perorate can be mentioned as one example of a perorate.
I, . . .
3L~2~3~
The blowing agent combination according to the present invention consisting of azodicarbonamide (ADO) and metal compound may be used, for example, in the foaming of polymers such as thermoplastic polymers. It is preferably used in the foaming of thermoplastic polymers which are processed in a temperature range of from 140 to 350C, the processing temperature depending on the thermoplast which is used in each case.
The following are mentioned as examples of thermoplasts:
polyvinyl chloride, polyethylene, polypropylene, copolymers of VC/VAC, VC/EVAC, EVOKE, propylene/VC, EVOKE, ethylene, propylene polystyrene, polyamides, polysulphones, PET, PUT, PRO, polyp acrylates, rubbers, plastics based on cellulose esters, awry-lonitrile-butadiene-styrene polymers (AS), mixtures of polyp cellophane and styrene-acrylonitrile- or ABS-polymers, mixtures of PVC and AS polymers or acrylonitrile polymers, polymeric mixtures and mixtures of the polymers mentioned.
The blowing agent combination according to the present invention is preferably used in the production of cross-linked polyolefin foams, in which case polyethylene is particularly pro-furred.
The blowing agent combination of the present inventions added in conventional quantities to the polymer to be foamed.
The polymer to be foamed preferably contains from 0.1 to 35% by weight, more preferably from 1 to 20~ by weight, of the blowing agent combination according to the present invention which consists of azodicarbonamide DO and one or more metal coup-wounds.
- pa -The cross-linked polyethylene foams which are prefer-ably produced therewith are generally light in color and odor-less, they exhibit a very wine, regular pore form at a low volt use weight and have a I
smooth, pale surface. Another advantage of the blowing agent combination according to the present invention is seen in the fact that the foaming operation is accelerated. This advance is particularly visible in the case of high production speeds, because in such a case, the desired volume weight of the respective foam is achieved in a shorter time or at a lower temperature. The use of the blowing agent combination of the present invention improves the economy of the foam production, and a higher space-time yield is achieved thereby.
The azodicarbonamide may be doped with metal compounds in any phase of production, for example before oxidation of the hydrazodicarbonamide with a conventional oxidizing agent, such as chlorine, bromide, iodine, hydrogen peroxide or sodium chlorate etc., during oxidation or after oxidation. It is also possible to add the substances during isolation through a conventional filter unit, for example a pressure suction filter a rotary filter, a box suction filter or a filter press etc., while the solid is being washed or after washing. The metal compounds may also be charged before drying in a conventional conveying or mixing unit, during the drying procedure or after drying in a generally conventional mixing or grinding unit. The components which have been mentioned may be added separately or combined in a solution. If they are added separately, it is possible to add them to the azodicarbonamide as a solid, a paste or a liquid.
This may be carried out in a finely-divided form for example as a mist, as a vapor or as droplets, or as a compact mass. Suitable measures are used to distribute the material regularly over the surface of the azodicarbonamide.
The plastics to be foamed may be mixed, according to requirements and depending on the area of use, with additives such as fillers, pigments, flame-lo A 21 628 proofing agents, plasticizers, thermostabilisers, peroxides, anti-agers, and cross-linking and vulcanizing agents.
Example 1 300 g (2.54 mows) of hydrazodicarbonamide in 1,200 ml of water are introduced into a stirrer-equipped apparatus. 3 g of molybdenum trioxides are then added and the suspension is oxidized with chlorine. After 3 hours, oxidation of the hydrazodicarbonamide is complete with a chlorine consumption of 249 g. The yellow solid is filtered off on a suction filter, washed with water and dried in a vacuum drying chamber.
Yield : 284 g (96.3 % based on hydrazodicarbonamide (HDC) Amount of molybdenum in the ADC1) : 0.45 %
0 grain ADO (~) : 32 (ADO - Azodicarbonamide) Example 2 . _ Instead of molybdenum trioxides 3.0 g of boric acid are introduced, with otherwise identical conditions.
248 g of chlorine have been consumed after the same reaction time.
Yield : 280 g - 94.9 % based on HDC
Amount of boron in ADO : 0.0075 %
0 grain ADO (~) : 29 Example 3 _..
The reaction was carried out analogously with
It is also known that the foaming operation may be favorably influenced by the addition of, for example, magnesium oxide (West German Auslegeschrift 2,852,287 published April 9, 1981 (~ynamit Nobel A), West German Offenlegungsschrift 2,351,515 published April 24, 1975 (Bayer A)). The addition of, for example, zinc compounds combined with Al, Sun-, B- and Si-compounds to the blowing agent has also been described (Japan Application 49-70931 filed June 20, 1974 (Ohtsuka, Kagako, Yakuhin OK
It has now been found that it is possible to dispense with additives, for example chromates or chromium compounds come brined with known zinc salts or other heavy metal salts, by adding compounds such as boron molybdenum tungsten and/or titanium compounds, individually or mixed together, to the azodicarbonamide.
According to the present invention, metal compounds are added to the blowing agent. Compounds of boron, molybdenum, tungsten and titanium are used. They may be used individually or in mixtures.
The present invention is directed to a blowing agent which comprises azodicarbonamide (ADO), doped with one or more - pa -metal compounds selected from the group consisting of boric acid, boron trioxides sodium borate, calcium borate, perorates, molt-bdenum oxide, sodium molybdate, ammonium molybdate, tungsten oxide, tungstic acid, sodium tungstate, calcium tungstate, ammonium tungstate, titanium dioxide, sodium titan ate, calcium titan ate, titanium sulfite, titanium oxide sulfite, titanium peroxide sulfite or titanium chloride, which metal compound is present in an amount of from 0.05 to 0.6% by weight based on the weight of azodicarbonamide.
Sodium perorate can be mentioned as one example of a perorate.
I, . . .
3L~2~3~
The blowing agent combination according to the present invention consisting of azodicarbonamide (ADO) and metal compound may be used, for example, in the foaming of polymers such as thermoplastic polymers. It is preferably used in the foaming of thermoplastic polymers which are processed in a temperature range of from 140 to 350C, the processing temperature depending on the thermoplast which is used in each case.
The following are mentioned as examples of thermoplasts:
polyvinyl chloride, polyethylene, polypropylene, copolymers of VC/VAC, VC/EVAC, EVOKE, propylene/VC, EVOKE, ethylene, propylene polystyrene, polyamides, polysulphones, PET, PUT, PRO, polyp acrylates, rubbers, plastics based on cellulose esters, awry-lonitrile-butadiene-styrene polymers (AS), mixtures of polyp cellophane and styrene-acrylonitrile- or ABS-polymers, mixtures of PVC and AS polymers or acrylonitrile polymers, polymeric mixtures and mixtures of the polymers mentioned.
The blowing agent combination according to the present invention is preferably used in the production of cross-linked polyolefin foams, in which case polyethylene is particularly pro-furred.
The blowing agent combination of the present inventions added in conventional quantities to the polymer to be foamed.
The polymer to be foamed preferably contains from 0.1 to 35% by weight, more preferably from 1 to 20~ by weight, of the blowing agent combination according to the present invention which consists of azodicarbonamide DO and one or more metal coup-wounds.
- pa -The cross-linked polyethylene foams which are prefer-ably produced therewith are generally light in color and odor-less, they exhibit a very wine, regular pore form at a low volt use weight and have a I
smooth, pale surface. Another advantage of the blowing agent combination according to the present invention is seen in the fact that the foaming operation is accelerated. This advance is particularly visible in the case of high production speeds, because in such a case, the desired volume weight of the respective foam is achieved in a shorter time or at a lower temperature. The use of the blowing agent combination of the present invention improves the economy of the foam production, and a higher space-time yield is achieved thereby.
The azodicarbonamide may be doped with metal compounds in any phase of production, for example before oxidation of the hydrazodicarbonamide with a conventional oxidizing agent, such as chlorine, bromide, iodine, hydrogen peroxide or sodium chlorate etc., during oxidation or after oxidation. It is also possible to add the substances during isolation through a conventional filter unit, for example a pressure suction filter a rotary filter, a box suction filter or a filter press etc., while the solid is being washed or after washing. The metal compounds may also be charged before drying in a conventional conveying or mixing unit, during the drying procedure or after drying in a generally conventional mixing or grinding unit. The components which have been mentioned may be added separately or combined in a solution. If they are added separately, it is possible to add them to the azodicarbonamide as a solid, a paste or a liquid.
This may be carried out in a finely-divided form for example as a mist, as a vapor or as droplets, or as a compact mass. Suitable measures are used to distribute the material regularly over the surface of the azodicarbonamide.
The plastics to be foamed may be mixed, according to requirements and depending on the area of use, with additives such as fillers, pigments, flame-lo A 21 628 proofing agents, plasticizers, thermostabilisers, peroxides, anti-agers, and cross-linking and vulcanizing agents.
Example 1 300 g (2.54 mows) of hydrazodicarbonamide in 1,200 ml of water are introduced into a stirrer-equipped apparatus. 3 g of molybdenum trioxides are then added and the suspension is oxidized with chlorine. After 3 hours, oxidation of the hydrazodicarbonamide is complete with a chlorine consumption of 249 g. The yellow solid is filtered off on a suction filter, washed with water and dried in a vacuum drying chamber.
Yield : 284 g (96.3 % based on hydrazodicarbonamide (HDC) Amount of molybdenum in the ADC1) : 0.45 %
0 grain ADO (~) : 32 (ADO - Azodicarbonamide) Example 2 . _ Instead of molybdenum trioxides 3.0 g of boric acid are introduced, with otherwise identical conditions.
248 g of chlorine have been consumed after the same reaction time.
Yield : 280 g - 94.9 % based on HDC
Amount of boron in ADO : 0.0075 %
0 grain ADO (~) : 29 Example 3 _..
The reaction was carried out analogously with
3 g of titanium dioxide instead of molybdenum trioxides Chlorine consumption 241 g, time 4 hours.
lo A 21 623 2~4~
Yield : 290 g -I 98.3 based on HO
Amount of titanium in ADO : 0.7 %
0 grain (~) : 25 Example 4 _ 3 g of tungsten trioxides were used as the metal compound in an analogous reaction. Reaction time 4 hours, chlorine consumption 253 g.
Yield : 283 g - 95.9 % based on HDC
lo Amount of tungsten : 1.6 %
0 grain ADO (~) : 33 Example 5 I_ . .
The following were introduced into a stirrer-equipped apparatus:
1,200 ml of water, 300 g of hydrazodicarbonamide, and 3 g of titanium dioxide.
The mixture is oxidized using chlorine, with a chlorine consumption of 241 g.
Yield : 280 g - 94.9 % based on HDC
Amount of titanium in ADO : 0.7 %
0 grain (~) : 12 Example 6 .
A solution of 0.2 g of boric acid in 200 ml of water is added to 222 g of moist ADO and stirred regularly.
The suspension is freed from water. Yield about 200 g of dry product.
0 grain ADO (~) : 15.5.
Example 7 As in Example 6, with an ADO product of an average grain size of 27 and with 0.2 g of boric acid in 200 ml of water.
lo A 21 628 Lo Example 8 As in Example 6, but the ADO is treated with a suspension of 1 g of tungstic acid in 200 ml of water, a regular distribution being achieved by evaporation.
0 grain ADO I 15.5.
:
I:
lo A 21 628 :: `
.
lo A 21 623 2~4~
Yield : 290 g -I 98.3 based on HO
Amount of titanium in ADO : 0.7 %
0 grain (~) : 25 Example 4 _ 3 g of tungsten trioxides were used as the metal compound in an analogous reaction. Reaction time 4 hours, chlorine consumption 253 g.
Yield : 283 g - 95.9 % based on HDC
lo Amount of tungsten : 1.6 %
0 grain ADO (~) : 33 Example 5 I_ . .
The following were introduced into a stirrer-equipped apparatus:
1,200 ml of water, 300 g of hydrazodicarbonamide, and 3 g of titanium dioxide.
The mixture is oxidized using chlorine, with a chlorine consumption of 241 g.
Yield : 280 g - 94.9 % based on HDC
Amount of titanium in ADO : 0.7 %
0 grain (~) : 12 Example 6 .
A solution of 0.2 g of boric acid in 200 ml of water is added to 222 g of moist ADO and stirred regularly.
The suspension is freed from water. Yield about 200 g of dry product.
0 grain ADO (~) : 15.5.
Example 7 As in Example 6, with an ADO product of an average grain size of 27 and with 0.2 g of boric acid in 200 ml of water.
lo A 21 628 Lo Example 8 As in Example 6, but the ADO is treated with a suspension of 1 g of tungstic acid in 200 ml of water, a regular distribution being achieved by evaporation.
0 grain ADO I 15.5.
:
I:
lo A 21 628 :: `
.
Claims (5)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A blowing agent which comprises azodicarbonamide (ADC), doped with one or more metal compounds selected from the group consisting of boric acid, boron trioxide, sodium borate, calcium borate, perborates, molybdenum oxide, sodium molybdate, ammonium molybdate, tungsten oxide, tungstic acid, sodium tungstate, calcium tungstate, ammonium tungstate, titanium dioxide, sodium titanate, calcium titanate, titanium sulphate, titanium oxide sulphate, titanium peroxide sulphate and titanium chloride, which metal compound is present in an amount of from 0.05 to 0.6% by weight based on the weight of azodicarbonamide.
2. A process for the production of a blowing agent as claimed in claim 1 which process comprises adding the metal compound in an amount of from 0.05 to 0.6% by weight to the azodicarbonamide or to reactants used in the production of the azodicarbonamide.
3. A process for foaming a polymer which comprises foaming a thermoplastic polymer with a blowing agent as claimed in claim 1.
4. A process for foaming a cross-linked polyolefin which comprises foaming the cross-linked polyolefin with a blowing agent as claim in claim 1.
5. A process for foaming a cross-linked polyethylene which comprises foaming the cross-linked polyethylene with a blowing agent as claimed in claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19823215837 DE3215837A1 (en) | 1982-04-28 | 1982-04-28 | COMBINATION OF BLOWING AGENTS BASED ON AZODICARBONAMIDE, THE PRODUCTION AND USE THEREOF FOR FOAMING PLASTICS |
| DEP3215837.8 | 1982-04-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1220341A true CA1220341A (en) | 1987-04-14 |
Family
ID=6162168
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000426757A Expired CA1220341A (en) | 1982-04-28 | 1983-04-26 | Blowing agent combination based on azodicarbonamide, the production and use thereof for the foaming of plastics |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0092739A3 (en) |
| JP (1) | JPS58196241A (en) |
| CA (1) | CA1220341A (en) |
| DE (1) | DE3215837A1 (en) |
| ES (1) | ES8402604A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6140379A (en) * | 1998-12-07 | 2000-10-31 | Armstrong World Industries, Inc. | Chemically embossed metallocene polyethylene foam |
| KR101966951B1 (en) * | 2012-06-07 | 2019-04-08 | 주식회사 동진쎄미켐 | Azodicarbonamide composition and method for preparing the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5239428B2 (en) * | 1972-11-08 | 1977-10-05 | ||
| US4021380A (en) * | 1976-02-27 | 1977-05-03 | Mattel, Inc. | Expandable resin composition |
-
1982
- 1982-04-28 DE DE19823215837 patent/DE3215837A1/en not_active Withdrawn
-
1983
- 1983-04-14 EP EP83103588A patent/EP0092739A3/en not_active Withdrawn
- 1983-04-25 JP JP7154883A patent/JPS58196241A/en active Pending
- 1983-04-26 CA CA000426757A patent/CA1220341A/en not_active Expired
- 1983-04-27 ES ES521886A patent/ES8402604A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| ES521886A0 (en) | 1984-02-01 |
| JPS58196241A (en) | 1983-11-15 |
| ES8402604A1 (en) | 1984-02-01 |
| EP0092739A3 (en) | 1984-06-13 |
| DE3215837A1 (en) | 1983-11-03 |
| EP0092739A2 (en) | 1983-11-02 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |