CN106478978A - Nano-particle compounds the preparation method of ADC foaming agent - Google Patents

Nano-particle compounds the preparation method of ADC foaming agent Download PDF

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Publication number
CN106478978A
CN106478978A CN201510831984.2A CN201510831984A CN106478978A CN 106478978 A CN106478978 A CN 106478978A CN 201510831984 A CN201510831984 A CN 201510831984A CN 106478978 A CN106478978 A CN 106478978A
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nano
adc
preparation
foaming agent
particle
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罗小平
张群志
陈新文
贺军
朱志宏
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Hengyang Jinhong Chemical Co Ltd
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Hengyang Jinhong Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound

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  • 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)
  • Silicon Compounds (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses nano-particle compounds the preparation method of ADC foaming agent, comprise the steps：（1）The synthesis of biruea；（2）The synthesis of ADC；（3）Nano-ZnO-SiO2The preparation of powder；（4）Nano-ZnO-SiO2 powder is mixed in proportion with Foam agent ADC, is fully ground.The nano-particle that the present invention is provided compounds ADC foaming agent, and activation effect is very good, greatly improves the quality of product.

Description

Nano-particle is compounded ADC The preparation method of foaming agent
Technical field
The present invention relates to foaming agent technical field, the preparation method of the compounding ADC foaming agent of specially a kind of nano-particle.
Background technology
Foam agent ADC（Chemical name：Azodicarbonamide）It is a kind of nontoxic, tasteless, pollution-free, orange-yellow azo foaming agent, its maximum feature is that heat can release a large amount of N2, and gas forming amount, up to 200 ~ 250 mL/g, is a kind of broad-spectrum CBA containing-N=N- structure in molecule.The decomposition temperature of pure Foam agent ADC be 195 ~ 220 DEG C, far beyond the plasticization temperature of polyvinyl chloride resin（About 165 ~ 170 ℃）, it is therefore desirable to add activator in Foam agent ADC, reduce the decomposition temperature of Foam agent ADC, the processing request of polyvinyl chloride resin could be met.Zinc in zinc oxide ion has the ability for receiving lone pair electrons, can receive the nitrogen-atoms in Foam agent ADC and the lone pair electrons on carbonylic oxygen atom, reduces the decomposition temperature of Foam agent ADC, is a kind of excellent activator of comparison.
At present, the synthesis technique of Foam agent ADC mainly synthesizes biruea by hydrazine hydrate through acid system or weak base method, oxidized dose of oxidative synthesis Foam agent ADC of biruea.It is in reaction system, add substantial amounts of acid to carry out regulation system pH value that acid system and weak base method prepare biruea, serious to equipment corrosion, and waste water is difficult to process.
Therefore, a kind of nano-particle of necessary design compounds the preparation method of ADC foaming agent.
Content of the invention
Technical problem solved by the invention is to provide the preparation method that nano-particle compounds ADC foaming agent, so as to solve the problems, such as in above-mentioned background technology.
Technical problem solved by the invention is employed the following technical solutions to realize：
Nano-particle compounds the preparation method of ADC foaming agent, comprises the steps：
（1）The synthesis of biruea
Hydrazine hydrate and urea are added in four-hole bottle, be back at 100-102 DEG C after there is white precipitate and continue reaction 9-10 h；Room temperature is cooled to, suction filtration, 55-65 DEG C of dry cake 25-26 h obtain white solid, using urea content in spectrophotometry filtrate；
（2）The synthesis of ADC
Biruea obtained in said process, major catalyst sodium bromide, co-catalyst V is sequentially added in four-hole bottle2O5, urea, EDTA, deionized water, be heated to 65 DEG C, with the H of 10wt%2SO4 The pH value for adjusting reaction system is 2-3, drips hydrogen peroxide with the speed of 0.24-0.27mL/min, 1.5-2 h drop finishes, insulation reaction 7-8 h, cooling, suction filtration, 52-54 DEG C dry cake 25-27h, obtains orange/yellow solid；
（3）Nano-ZnO-SiO2 The preparation of powder
Zinc diacetate dihydrate is dissolved in absolute ethyl alcohol, diethanol amine is added under agitation, continue stirring to Zinc diacetate dihydrate to be completely dissolved. it is heated to 73-75 DEG C, it is slowly added dropwise a certain amount of deionized water, the pH value for adjusting mixed solution with ammoniacal liquor-ethanol solution is 7-9, and after constant temperature stirring 2-5 h, standing obtains vitreosol（A）；By tetraethyl orthosilicate, after deionized water and absolute ethyl alcohol mixing, stir, the pH value for adjusting mixed solution with ammoniacal liquor-ethanol solution is 8, is heated to 51-55 DEG C, and constant temperature stirs 35-45 min, obtains leucosol（B）；By colloidal sol（A）It is slowly added into colloidal sol（B）In stir to mixing, ageing is changed into wet gel in 9-15 days, and wet gel is vacuum dried 7-9h at 125-130 DEG C, obtain xerogel. and then xerogel is put into Muffle furnace, 3-5 h is calcined at 805-810 DEG C, room temperature is naturally cooled to, obtains white nano-ZnO-SiO2Powder；
（4）The preparation of compounding foaming agent
By nano-ZnO-SiO2Powder is mixed with Foam agent ADC, is fully ground.
In the present invention, as a kind of preferred technical scheme, hydrogen peroxide is the hydrogen peroxide of 30wt%.
In the present invention, used as a kind of preferred technical scheme, the rate of addition of the hydrogen peroxide is 0.25mL/min.
In the present invention, used as a kind of preferred technical scheme, the diethanol amine is identical in quality with the Zinc diacetate dihydrate.
In the present invention, as a kind of preferred technical scheme, the tetraethyl orthosilicate, deionized water and absolute ethyl alcohol are 1: 2: 3 mixing by volume.
In the present invention, as a kind of preferred technical scheme, the nano-ZnO-SiO2Powder is 1 with the mass ratio of Foam agent ADC：（3-5）.
Due to employing above technical scheme, the invention has the advantages that：
The nano-particle that the present invention is provided compounds ADC foaming agent, and with higher decomposition temperature, activation effect is good, and gas release is big, greatly improves the quality of product.
Specific embodiment
In order that technological means, creation characteristic, reached purpose and effect that the present invention is realized are easy to understand, with reference to specific embodiment, the present invention is expanded on further.
Embodiment 1
Nano-particle compounds the preparation method of ADC foaming agent, comprises the steps：
（1）The synthesis of biruea
Hydrazine hydrate and urea are added in four-hole bottle, be back at 100 DEG C after there is white precipitate and continue 9 h of reaction；Room temperature is cooled to, suction filtration, 55 DEG C of 25 h of dry cake obtain white solid, using urea content in spectrophotometry filtrate；
（2）The synthesis of ADC
Biruea obtained in said process, major catalyst sodium bromide, co-catalyst V is sequentially added in four-hole bottle2O5, urea, EDTA, deionized water, be heated to 65 DEG C, with the H of 10wt%2SO4 The pH value for adjusting reaction system is 2, and with the hydrogen peroxide of the speed dropping 30wt% of 0.24mL/min, 1.5h drop finishes, 7 h of insulation reaction, cooling, suction filtration, and 52 DEG C of dry cake 25h obtain orange/yellow solid；
（3）Nano-ZnO-SiO2 The preparation of powder
Zinc diacetate dihydrate is dissolved in absolute ethyl alcohol, diethanol amine is added under agitation, diethanol amine is identical in quality with the Zinc diacetate dihydrate, continue stirring to Zinc diacetate dihydrate to be completely dissolved. it is heated to 73 DEG C, it is slowly added dropwise a certain amount of deionized water, the pH value for mixed solution being adjusted with ammoniacal liquor-ethanol solution is 7, and after constant temperature stirring 2-5 h, standing obtains vitreosol（A）；By the tetraethyl orthosilicate, after deionized water and absolute ethyl alcohol are by volume for 1: 2: 3 mixing, stir, the pH value for adjusting mixed solution with ammoniacal liquor-ethanol solution is 8, is heated to 51 DEG C, and constant temperature stirs 35 min, obtains leucosol（B）；By colloidal sol（A）It is slowly added into colloidal sol（B）In stir to mixing, ageing is changed into wet gel in 9-15 days, wet gel is vacuum dried 7-9h at 125 DEG C, obtains xerogel. and then xerogel is put into Muffle furnace, calcines 3 h at 805 DEG C, naturally cool to room temperature, obtain white nano-ZnO-SiO2 Powder；
（4）The preparation of compounding foaming agent
By nano-ZnO-SiO2Powder is mixed with Foam agent ADC, is fully ground, the nano-ZnO-SiO2Powder is 1 with the mass ratio of Foam agent ADC：3.
Embodiment 2
Nano-particle compounds the preparation method of ADC foaming agent, comprises the steps：
（1）The synthesis of biruea
Hydrazine hydrate and urea are added in four-hole bottle, be back at 101 DEG C after there is white precipitate and continue 10 h of reaction；Room temperature is cooled to, suction filtration, 60 DEG C of 25 h of dry cake obtain white solid, using urea content in spectrophotometry filtrate；
（2）The synthesis of ADC
Biruea obtained in said process, major catalyst sodium bromide, co-catalyst V is sequentially added in four-hole bottle2O5, urea, EDTA, deionized water, be heated to 65 DEG C, with the H of 10wt%2SO4 The pH value for adjusting reaction system is 3, and with the hydrogen peroxide of the speed dropping 30wt% of 0.26mL/min, 1.7h drop finishes, 7.5 h of insulation reaction, cooling, suction filtration, and 53 DEG C of dry cake 25-27h obtain orange/yellow solid；
（3）Nano-ZnO-SiO2 The preparation of powder
Zinc diacetate dihydrate is dissolved in absolute ethyl alcohol, diethanol amine is added under agitation, diethanol amine is identical in quality with the Zinc diacetate dihydrate, continue stirring to Zinc diacetate dihydrate to be completely dissolved. it is heated to 74 DEG C, it is slowly added dropwise a certain amount of deionized water, the pH value for mixed solution being adjusted with ammoniacal liquor-ethanol solution is 8, and after constant temperature stirs 4 h, standing obtains vitreosol（A）；By the tetraethyl orthosilicate, after deionized water and absolute ethyl alcohol are by volume for 1: 2: 3 mixing, stir, the pH value for adjusting mixed solution with ammoniacal liquor-ethanol solution is 8, is heated to 53 DEG C, and constant temperature stirs 40 min, obtains leucosol（B）；By colloidal sol（A）It is slowly added into colloidal sol（B）In stir to mixing, ageing is changed into wet gel in 9-15 days, wet gel is vacuum dried 7-9h at 128 DEG C, obtains xerogel. and then xerogel is put into Muffle furnace, calcines 4 h at 805 DEG C, naturally cool to room temperature, obtain white nano-ZnO-SiO2 Powder；
（4）The preparation of compounding foaming agent
By nano-ZnO-SiO2Powder is mixed with Foam agent ADC, is fully ground, the nano-ZnO-SiO2Powder is 1 with the mass ratio of Foam agent ADC：4.
Embodiment 3
Nano-particle compounds the preparation method of ADC foaming agent, comprises the steps：
（1）The synthesis of biruea
Hydrazine hydrate and urea are added in four-hole bottle, be back at 102 DEG C after there is white precipitate and continue 10 h of reaction；Room temperature is cooled to, suction filtration, 65 DEG C of 26 h of dry cake obtain white solid, using urea content in spectrophotometry filtrate；
（2）The synthesis of ADC
Biruea obtained in said process, major catalyst sodium bromide, co-catalyst V is sequentially added in four-hole bottle2O5, urea, EDTA, deionized water, be heated to 65 DEG C, with the H of 10wt%2SO4 The pH value for adjusting reaction system is 3, and with the hydrogen peroxide of the speed dropping 30wt% of 0.27mL/min, 2 h drop finishes, 8 h of insulation reaction, cooling, suction filtration, and 54 DEG C of dry cake 27h obtain orange/yellow solid；
（3）Nano-ZnO-SiO2 The preparation of powder
Zinc diacetate dihydrate is dissolved in absolute ethyl alcohol, diethanol amine is added under agitation, diethanol amine is identical in quality with the Zinc diacetate dihydrate, continue stirring to Zinc diacetate dihydrate to be completely dissolved. it is heated to 75 DEG C, it is slowly added dropwise a certain amount of deionized water, the pH value for mixed solution being adjusted with ammoniacal liquor-ethanol solution is 9, and after constant temperature stirs 5 h, standing obtains vitreosol（A）；By the tetraethyl orthosilicate, after deionized water and absolute ethyl alcohol are by volume for 1: 2: 3 mixing, stir, the pH value for adjusting mixed solution with ammoniacal liquor-ethanol solution is 8, is heated to 55 DEG C, and constant temperature stirs 45 min, obtains leucosol（B）；By colloidal sol（A）It is slowly added into colloidal sol（B）In stir to mixing, ageing is changed into wet gel in 15 days, wet gel is vacuum dried 9h at 130 DEG C, obtains xerogel. and then xerogel is put into Muffle furnace, calcines 5 h at 810 DEG C, naturally cool to room temperature, obtain white nano-ZnO-SiO2 Powder；
（4）The preparation of compounding foaming agent
By nano-ZnO-SiO2Powder is mixed with Foam agent ADC, is fully ground, the nano-ZnO-SiO2Powder is 1 with the mass ratio of Foam agent ADC：5.
Contrast with commercially available sulfonyl hydrazines compound blowing agents, inventive can be as follows：
Project Embodiment 1 Embodiment 2 Embodiment 3 Commercially available prod
Decomposition temperature（℃） 265 272 267 ---
Gas forming amount（ml/g） 168 171 169 132
Those of ordinary skill in the art should be understood：The discussion of any of the above embodiment is exemplary only, it is not intended that hint the scope of the present disclosure (including claim) is limited to these examples；Under the thinking of the present invention, can also be combined between technical characteristic in above example or different embodiments, step can be realized with random order, and there are many other changes of the different aspect of the present invention as above, for their not offers in details simple and clear.Therefore, all any omissions that within the spirit and principles in the present invention, is made, modification, equivalent, improvement etc., should be included within the scope of the present invention.

Claims (6)

1. nano-particle compounds the preparation method of ADC foaming agent, it is characterized in that, comprises the steps：
（1）The synthesis of biruea
Hydrazine hydrate and urea are added in four-hole bottle, be back at 100-102 DEG C after there is white precipitate and continue reaction 9-10 h；Room temperature is cooled to, suction filtration, 55-65 DEG C of dry cake 25-26 h obtain white solid, using urea content in spectrophotometry filtrate；
（2）The synthesis of ADC
Biruea obtained in said process, major catalyst sodium bromide, co-catalyst V is sequentially added in four-hole bottle2O5, urea, EDTA, deionized water, be heated to 65 DEG C, with the H of 10wt%2SO4The pH value for adjusting reaction system is 2-3, drips hydrogen peroxide with the speed of 0.24-0.27mL/min, and 1.5-2 h drop finishes, insulation reaction 7-8 h, cooling, suction filtration, and 52-54 DEG C of dry cake 25-27h obtains orange/yellow solid；
（3）Nano-ZnO-SiO2The preparation of powder
Zinc diacetate dihydrate is dissolved in absolute ethyl alcohol, diethanol amine is added under agitation, continue stirring to Zinc diacetate dihydrate to be completely dissolved. it is heated to 73-75 DEG C, it is slowly added dropwise a certain amount of deionized water, the pH value for adjusting mixed solution with ammoniacal liquor-ethanol solution is 7-9, and after constant temperature stirring 2-5 h, standing obtains vitreosol（A）；By tetraethyl orthosilicate, after deionized water and absolute ethyl alcohol mixing, stir, the pH value for adjusting mixed solution with ammoniacal liquor-ethanol solution is 8, is heated to 51-55 DEG C, and constant temperature stirs 35-45 Min, obtains leucosol（B）；By colloidal sol（A）It is slowly added into colloidal sol（B）In stir to mixing, ageing is changed into wet gel in 9-15 days, and wet gel is vacuum dried 7-9h at 125-130 DEG C, obtain xerogel. and then xerogel is put into Muffle furnace, 3-5 h is calcined at 805-810 DEG C, room temperature is naturally cooled to, obtains white nano-ZnO-SiO2Powder；
（4）The preparation of compounding foaming agent
By nano-ZnO-SiO2 Powder is mixed with Foam agent ADC, is fully ground.
2. nano-particle as claimed in claim 1 compounds the preparation method of ADC foaming agent, it is characterized in that, hydrogen peroxide is the hydrogen peroxide of 30wt%.
3. nano-particle as claimed in claim 1 compounds the preparation method of ADC foaming agent, it is characterized in that, the rate of addition of the hydrogen peroxide is 0.25mL/min.
4. nano-particle as claimed in claim 1 compounds the preparation method of ADC foaming agent, it is characterized in that, the diethanol amine is identical in quality with the Zinc diacetate dihydrate.
5. nano-particle as claimed in claim 1 compounds the preparation method of ADC foaming agent, it is characterized in that, the tetraethyl orthosilicate, and deionized water and absolute ethyl alcohol are 1: 2: 3 mixing by volume.
6. nano-particle as claimed in claim 1 compounds the preparation method of ADC foaming agent, it is characterized in that, the nano-ZnO-SiO2Powder is 1 with the mass ratio of Foam agent ADC：（3-5）.
CN201510831984.2A 2015-11-25 2015-11-25 Nano-particle compounds the preparation method of ADC foaming agent Pending CN106478978A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108314801A (en) * 2018-01-04 2018-07-24 江西德弘环保科技有限公司 A kind of preparation method of modified manometer silicon dioxide
CN114479158A (en) * 2022-03-16 2022-05-13 青岛科技大学 Preparation method of high-dispersion foaming agent and composite foaming agent thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
赵美杰等: ""ADC的合成及纳米粒子复配ADC发泡剂的制备"", 《河北工业大学学报》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108314801A (en) * 2018-01-04 2018-07-24 江西德弘环保科技有限公司 A kind of preparation method of modified manometer silicon dioxide
CN108314801B (en) * 2018-01-04 2022-01-18 江西宝弘纳米科技有限公司 Preparation method of modified nano silicon dioxide
CN114479158A (en) * 2022-03-16 2022-05-13 青岛科技大学 Preparation method of high-dispersion foaming agent and composite foaming agent thereof
CN114479158B (en) * 2022-03-16 2023-10-27 青岛科技大学 High-dispersion foaming agent and preparation method of composite foaming agent thereof

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