CN103483227B - Azodicarbonamide composition and preparation method thereof - Google Patents
Azodicarbonamide composition and preparation method thereof Download PDFInfo
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- CN103483227B CN103483227B CN201310226608.1A CN201310226608A CN103483227B CN 103483227 B CN103483227 B CN 103483227B CN 201310226608 A CN201310226608 A CN 201310226608A CN 103483227 B CN103483227 B CN 103483227B
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- azodicarbonamide
- oxide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
- C07C281/06—Compounds containing any of the groups, e.g. semicarbazides
- C07C281/08—Compounds containing any of the groups, e.g. semicarbazides the other nitrogen atom being further doubly-bound to a carbon atom, e.g. semicarbazones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/04—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- C07C2521/08—Silica
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The present invention provides a process for preparing azodicarbonyl useful as blowing agent by using oxide catalystAmine compositions and methods of making the same. The process for the preparation of the azodicarbonamide composition is characterized in that biurea (HDCA) and chlorine (Cl) are reacted in the presence of oxide particles2) To prepare azodicarbonamide (ADCA). And the azodicarbonamide composition comprises 10 to 99.9 wt% of azodicarbonamide crystal particles and 0.1 to 90 wt% of oxide particles uniformly dispersed in the azodicarbonamide crystal particles. Here, the oxide is preferably an oxide of an element selected from the group consisting of Si, Al, Zn, Ti, Na, K, Mg, Ca, and C.
Description
Technical field
The present invention relates to azodicarbonamide composition and preparation method thereof, more specifically, oxide catalyst system is utilized
The method of the standby azodicarbonamide composition advantageous as foaming agent.
Background technology
Azodicarbonamide（Azodicarbonamide：ADCA）It is widely used in as to polyethylene, polypropylene, second
Alkene-vinyl acetate co-polymer（EVA）, polyvinyl chloride, SBR styrene butadiene rubberses, the thermoplasticity such as acrylonitrile-butadiene rubber
The foaming agent of resin, rubber etc..Azodicarbonamide generally uses chlorine（Chlorine, Cl2）To aoxidize biruea
（Hydrazodicarbon amide, HDCA）And prepare.In the existing process aoxidized with chlorine of azodicarbonamide, one
The chlorine divided is used as gas phase（gas phase）Release, it is therefore desirable to using excessive chlorine, reaction is also required to up to 4 more than hour
Time.Also, the strong acid hydrochloric acid as accessory substance is together generated with azodicarbonamide, therefore with neutralization accessory substance
（Waste water）In be also required to the shortcoming of substantial amounts of alkali compounds.
The content of the invention
Technical problem
Thus, the usage amount of chlorine can be not only reduced it is an object of the invention to provide a kind of, and reaction can be shortened
The preparation method of the azodicarbonamide composition of time.
It is another object of the present invention to provide a kind of economically and environmentally desired azodicarbonamide combination
The preparation method of thing.
A further object of the present invention is that a kind of mobility middle in the resin foamed of offer is excellent, without
The azodicarbonamide composition of the extra fluidity improver of addition.
Solution to problem
In order to achieve the above object, the present invention provides a kind of preparation method of azodicarbonamide composition, and its feature exists
In, in the presence of oxide particle, reaction biruea（HDCA）And chlorine（Cl2）And prepare azodicarbonamide（ADCA）.
Also, the present invention provides a kind of azodicarbonamide composition, its comprising azodicarbonamide crystalline particle 10 to
99.9 weight %;And it is homogeneously dispersed in the weight of oxide particle 0.1 to 90 % of the azodicarbonamide crystalline particle.
The effect of invention
It is that, because reaction speed is very fast, chlorine is used according to the preparation method of the azodicarbonamide composition of the present invention
Amount is few, so that the productivity with not only azodicarbonamide is excellent, and the azodicarbonamide generated is in the tree foamed
The excellent advantage of mobility in fat.
Brief description of the drawings
Fig. 1 be in display azodicarbonamide composition of the present invention oxide equably interior bag in the formyl of azo two
The photo of the state of the inside of amine crystalline particle.
Fig. 2 is to show that oxide is evenly dispersed in the formyl of azo two in azodicarbonamide composition of the present invention
The photo of the state of the outer surface of amine crystalline particle.
Embodiment
Hereinafter, the more detailed description present invention.
The preparation method of azodicarbonamide composition of the present invention, it is characterised in that such as following institutes of reaction equation 1
Show, in the presence of oxide particle, react biruea（HDCA）And chlorine（Cl2）And prepare azodicarbonamide（ADCA）.
[reaction equation 1]
Herein, above-mentioned oxide is to be adsorbed in its surface or hole as reactant（Oxidant）Chlorine increase
The holdup time of chlorine, so as to play a part of improving the reactive catalyst of biruea and chlorine.Above-mentioned oxide is preferably selected from
The oxide of element in the group being made up of Si, Al, Zn, Ti, Na, K, Mg, Ca and C, for example, can be aerosil
（fumed silica）, gel-type（Gel type）Silica, zeolite（Zeolite）Deng silica（SiO2）And oxygen
Change aluminium, zinc oxide, titanium oxide etc..Also, above-mentioned oxide can have various form, preferably specific surface area（B.E.T.）For
50m2/ more than g, more preferably specific surface area are 50 to 2,000m2/ g, most preferably specific surface area are 50 to 1,000m2/ g's is inorganic
Thing.Herein, the specific surface area of above-mentioned oxide is too small, then may have the insufficient worry of the holdup time increase effect of chlorine,
The specific surface area of above-mentioned oxide is excessive, then under not special interests, the worry that may have easily damaged oxide.Will not
Especially limit the size of above-mentioned oxide, but usually 10nm to 100 μm, preferably 0.1 to 50 μm.Herein, above-mentioned oxide
Size it is too small, then may have the worry that surface area is reduced because of the hydrochloric acid of generation, and the size of above-mentioned oxide is excessive, then may be used
The ADCA that can have generation separates the worry to be formed with above-mentioned oxide.On the usage amount of above-mentioned oxide, can suitably it add
Addition is, in the azodicarbonamide of generation（ADCA）In composition, the content of above-mentioned azodicarbonamide crystalline particle is 10
To 99.9 weight %, preferably 40 to 99.5 weight %, more preferably 50 to 99 weight %, the content of above-mentioned oxide is 0.1 to 90 weight
Measure %, more preferably preferably 0.5 to 60 weight %, 1 to 50 weight %.General, from biruea（HDCA）To azodicarbonamide
（ADCA）Yield be 90% degree, and can consider that the oxide that uses is all dispersed in azodicarbonamide in reaction,
Therefore compared to being finally dispersed in azodicarbonamide（ADCA）Oxide content, a small amount of oxygen of about 10% degree can be put into
Compound is to biruea（HDCA）With the reaction of chlorine.Herein, the usage amount of above-mentioned oxide is very few, then when may have the delay of chlorine
Between the insufficient worry of increase effect, cross the worry that may at most have unit-gas generating capacity reduction.
Biruea（HDCA）And chlorine（Cl2）Reaction, can be carried out according to common condition.For example, although Bu Huite
Xian Zhi not be with biruea（HDCA）The chlorine of reaction（Cl2）Usage amount, but generally make to HDCA solution sustainable supply chlorine relative to 1
Mole HDCA reacts 1 mole of chlorine（Cl2）.Biruea（HDCA）And chlorine（Cl2）Reaction temperature be usually 20 to 40 DEG C, it is and anti-
It is usual less than 4 hours, such as 2 to 3.5 hours between seasonable, as needed, can comes anti-to be dispersed in the state of water equal solvent
Should, and can also be carried out in the presence of the catalysts such as NaBr.
According to the azodicarbonamide composition of the present invention, comprising azodicarbonamide crystalline particle and it is uniformly dispersed
In the oxide of above-mentioned azodicarbonamide crystalline particle.Herein, relative to whole azodicarbonamide composition, above-mentioned oxygen
The content of compound is, 0.1 to 90 weight %, preferably 0.5 to 60 weight %, more preferably 1 to 50 weight %, and the formyl of above-mentioned azo two
The content of amine crystalline particle is 10 to 99.9 weight %, more preferably preferably 40 to 99.5 weight %, 50 to 99 weight %.Herein, on
The content for stating oxide is too small, then in the resin foamed, and may have can not fully improve foaming agent（Azodicarbonamide）
Mobility worry, and the content of above-mentioned oxide is excessive, then the content of foaming agent may be reduced, so that foaminess is not filled
The worry divided.Also, the size of above-mentioned azodicarbonamide crystalline particle, but usually 5 to 50 μm are not specially limited, preferably
10 to 30 μm, and also it is not particularly limited the size of above-mentioned oxide, but usually 10nm to 100 μm, preferably 0.1 to 50 μm.
It is the conduct in the reaction of generation azodicarbonamide to be contained according to the oxide of the azodicarbonamide composition of the present invention
Catalyst is used, therefore is evenly dispersed in surface inside and out the azodicarbonamide crystalline particle of generation.Such as
Really, in the case of content of the content of above-mentioned oxide more than azodicarbonamide, it is also assumed that azodicarbonamide is uniform
Ground is scattered in above-mentioned oxide.Fig. 1 is display oxide equably interior bag（That is, embed and scattered）In azodicarbonamide crystallization
The photo of the state of the inside of particle（It is oxide around the small particles of the azodicarbonamide of cuboid in Fig. 1）, Fig. 2 is
Display oxide is uniformly dispersed（Around encirclement as cloud）In the shape of the outer surface of azodicarbonamide crystalline particle
The photo of state.Like this, the oxide of azodicarbonamide crystalline particle is evenly dispersed in, in the resin foamed, is changed
The melt fluidity of kind foaming agent, so that with preventing the premature degradation of foaming agent, and extra mobility need not be added
The effect of modifier.
Hereinafter, the present invention is described in more detail by embodiment and comparative example.Following embodiments are to illustrate this hair
Bright, the scope of the present invention is not limited by these embodiments.In following embodiments and comparative example, the performance evaluation of foaming agent
Method and used sample are as follows.
（1）Reaction time：Chlorine is injected with certain speed, will be from injection starting point to azodicarbonamide（ADCA）'s
The time of the end point of oxidation reaction is used as the reaction time.
（2）Chlorine usage amount：Measure from biruea（HDCA）To the total of the oxidation reaction end point to azodicarbonamide
Chlorine aequum.
（3）Yield：Calculated according to following formula.
Yield=（The catalyst oxide of reactant-attachment of generation）/ ADCA theoretical production quantity * 100
（4）It is attached to ADCA oxide content：700 DEG C burn till kiln roasting 3 hours after, according to following formula, survey
Measure ash content.
Oxide（Catalyst）Content=（Burn till rear weight/burn till preceding weight）*100
（5）Flow behavior evaluation in resin：Originally reached using Bradley（Brabender）The plasticorderr of company
（Plasticorder）PL2100W50E is evaluated.The resin being taken as uses LDPE（Low density polyethylene (LDPE)）, in resin 100
The parts by weight of ADCA compositions 10 of generation are mixed in parts by weight.Test temperature is 120 DEG C, and test period is 10 minutes, and revolution is
37 revs/min, put into 60cc volume after 30g resin-ADCA mixtures, measure moment of torsion（Torque）Value.
NaBr：Sodium bromide
Cl2：Liquid chlorine
Zeolite（Zeolite）：Stomata（pore）In contain Na+The silica of ion（silica）
Ai Luoxier（Aerosil）：Specific surface area is 150m2/ g aluminium（Aluminum）Silica
Aerosil（Fumed silica）：Specific surface area is 250m2/ g silica
Gel-type（Gel type）Silica：Specific surface area is 800m2/ g cohesion（aggregated）Silica
[embodiment 1] ADCA synthesis
By HDCA100g, NaBr2g and zeolite（Zeolite）1g is dispersed in 200g water, is injected with 17.5g/hr speed
Liquid chlorine synthesizes ADCA.Temperature is 20 DEG C when reaction starts, and makes temperature in reaction not using cooling device maintenance reaction temperature
More than 38 DEG C.
[embodiment 2] ADCA synthesis
Except using zeolite（Zeolite）Outside 5g, ADCA is synthesized according to method same as Example 1.
[embodiment 3] ADCA synthesis
Except using zeolite（Zeolite）Outside 10g, ADCA is synthesized according to method same as Example 1.
[embodiment 4] ADCA synthesis
Use Ai Luoxier（Aerosil）5g replaces zeolite（Zeolite）1g, in addition, according to the phase of embodiment 1
Same method synthesis ADCA.
[embodiment 5] ADCA synthesis
Use Ai Luoxier（Aerosil）10g, in addition, ADCA is synthesized according to method same as Example 4.
[embodiment 6] ADCA synthesis
Use Ai Luoxier（Aerosil）20g, in addition, ADCA is synthesized according to method same as Example 4.
[embodiment 7] ADCA synthesis
Use aerosil（Fumed silica）10g replaces zeolite（Zeolite）1g, in addition, according to
Method synthesis ADCA same as Example 1.
[embodiment 8] ADCA synthesis
Use aerosil（Fumed silica）20g, in addition, is closed according to method same as Example 7
Into ADCA.
[embodiment 9] ADCA synthesis
Use aerosil（Fumed silica）30g, in addition, is closed according to method same as Example 7
Into ADCA.
[embodiment 10] ADCA synthesis
Use gel-type（Gel type）Silica 5g replaces zeolite（Zeolite）1g, in addition, according to reality
Apply the identical method of example 1 synthesis ADCA.
[embodiment 11] ADCA synthesis
Using gel-type silica 10g, in addition, ADCA is synthesized according to method same as in Example 10.
[embodiment 12] ADCA synthesis
Using gel-type silica 20g, in addition, ADCA is synthesized according to method same as in Example 10.
[comparative example 1] ADCA synthesis
Without using zeolite（Zeolite）, in addition, ADCA is synthesized according to method same as Example 1.
[comparative example 2] ADCA and silica mixing
The parts by weight of aerosil 10 are mixed in the ADCA100 parts by weight synthesized according to comparative example 1 and prepare foaming
Agent composition.
It is organized in each composition used in above-described embodiment and comparative example and content and is shown in table 1, during evaluation response
Between, chlorine usage amount, yield, the oxide for being attached to ADCA（Catalyst）Flow behavior in content and resin is simultaneously shown in table
In 2.
[table 1]
[table 2]
As shown in Table 2 above, if it is known that regarding the wide oxide of specific surface area as catalysis in ADCA synthetic reactions
When agent is to add, ADCA generated times and chlorine usage amount can be reduced with its amount, but not have on yield big difference.And
And, if it is known that using the melt fluidity of the foaming agent in oxide, resin in the synthetic reaction of ADCA foaming agents
It can improve, so that compared to the situation for adding same amount of fluidity improver, mobility is improved.The melting of foaming agent like this
Mobility is improved, then the moment of torsion of the resin melted（torque）Value reduction, even if without extra fluidity improver,
It is also possible to prevent, due to premature degradation of resin caused by latent energy etc., smoothly extrusion characteristics can be obtained.
More than, the present invention is illustrated with reference to particular implementation form, but should be interpreted that the invention is not restricted to this, and according to attached
Plus claims record, including all thoughts for being contained in the present invention and all conversion of technical scope, coordinate or
Person's substitute.
Claims (3)
1. a kind of preparation method of azodicarbonamide composition, it is characterised in that in the presence of oxide particle, such as following
Shown in reaction equation 1, reaction biruea (HDCA) and chlorine (Cl2) and prepare azodicarbonamide (ADCA), wherein, the oxide
For the oxide of the element in the group being made up of Si, Al, Zn, Ti, Na, K, Mg, Ca and C,
[reaction equation 1]
2. the preparation method of azodicarbonamide composition according to claim 1, wherein, the size of the oxide is
10nm to 100 μm.
3. a kind of azodicarbonamide composition, it is included：
The weight % of azodicarbonamide crystalline particle 10 to 99.9；And
The weight % of oxide particle 0.1 to 90 of the azodicarbonamide crystalline particle is homogeneously dispersed in,
The oxide is selected from by aerosil, gel-type silica, zeolite, aluminum oxide, zinc oxide and titanium oxide group
Into group,
The size of the azodicarbonamide crystalline particle is 5 to 50 μm, and the size of the oxide particle is 10nm to 100 μ
M,
The specific surface area of the oxide is 50 to 2,000m2/ g,
The oxide is as the catalyst to use, and to be evenly dispersed in generation in the reaction of generation azodicarbonamide
Azodicarbonamide crystalline particle inside and out surface.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020120061055A KR101966951B1 (en) | 2012-06-07 | 2012-06-07 | Azodicarbonamide composition and method for preparing the same |
| KR10-2012-0061055 | 2012-06-07 |
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| CN103483227A CN103483227A (en) | 2014-01-01 |
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| KR102374731B1 (en) * | 2014-11-17 | 2022-03-15 | 주식회사 동진쎄미켐 | A azo-based foaming agent, method for preparing the same and method for foaming resin using the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1914267A1 (en) * | 2006-10-17 | 2008-04-23 | J & J Chemical Co. | Modified blowing agent surface-treated with metallic siloxylated compound and polymer resin composition including the same |
| CN102010516A (en) * | 2009-09-04 | 2011-04-13 | 福建师范大学福清分校 | Foaming agent ADC (azodicarbonamide) with low temperature property and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3215837A1 (en) * | 1982-04-28 | 1983-11-03 | Bayer Ag, 5090 Leverkusen | COMBINATION OF BLOWING AGENTS BASED ON AZODICARBONAMIDE, THE PRODUCTION AND USE THEREOF FOR FOAMING PLASTICS |
| CN101274999A (en) * | 2007-03-30 | 2008-10-01 | 北京化工大学 | Novel composite vesicant |
-
2012
- 2012-06-07 KR KR1020120061055A patent/KR101966951B1/en active IP Right Grant
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1914267A1 (en) * | 2006-10-17 | 2008-04-23 | J & J Chemical Co. | Modified blowing agent surface-treated with metallic siloxylated compound and polymer resin composition including the same |
| CN102010516A (en) * | 2009-09-04 | 2011-04-13 | 福建师范大学福清分校 | Foaming agent ADC (azodicarbonamide) with low temperature property and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| ADC的合成及奈米离子复配ADC发泡剂的制备;赵美杰等;《河北工业大学学报》;20111231;第40卷(第6期);49-53页 * |
| 双氧水法制备发泡剂偶氮二甲酰胺及其改性研究;赵晓燕;《中国优秀硕士学位论文》;20120315(第2期);第5-3-1节 * |
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| Publication number | Publication date |
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| KR20130137437A (en) | 2013-12-17 |
| KR101966951B1 (en) | 2019-04-08 |
| CN103483227A (en) | 2014-01-01 |
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