CN101899166A - Preparation method of intercalated nanocomposite foaming agent - Google Patents
Preparation method of intercalated nanocomposite foaming agent Download PDFInfo
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- CN101899166A CN101899166A CN200910084826XA CN200910084826A CN101899166A CN 101899166 A CN101899166 A CN 101899166A CN 200910084826X A CN200910084826X A CN 200910084826XA CN 200910084826 A CN200910084826 A CN 200910084826A CN 101899166 A CN101899166 A CN 101899166A
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Abstract
The invention relates the field of chemical foaming agents for foaming micro-bubble plastic and mainly discloses a method for preparing an intercalated nanocomposite foaming agent and a use of using a prepared intercalated composite as the plastic foaming agent. The invention provides the preparation method of the intercalated nanocomposite with simple operation, low production cost and high production efficiency for overcoming the shortcomings in the prior art. Compared with the prior art, the method has the advantage that the method can prepare the intercalated nanocomposite foaming agent by exploring and improving experimental conditions and adopting the appropriate washing process. The intercalated nanocomposite foaming agent is different from the simple adsorption composite foaming agent, has the advantages of an organic-inorganic nanocomposite material and can be well mixed with a plastic raw material, effectively control the dosage of the foaming agent, avoid the local overheating during the foaming process, have high foaming efficiency, lead formed foams to be uniform and lead the hole diameter to be small.
Description
Technical field:
The present invention relates to intercalated compound preparation method field.Mainly be that a kind of solution intercalation legal system is equipped with intercalated nanocomposite foaming agent and the prepared intercalation nano composite foamable agent purposes as plastics blowing agent.
Background technology:
One of industrial use of whipping agent is to be used for PVC, rubber, polyolefine, for example polyethylene or polypropylene, or the foaming of other polymkeric substance.Cellmic C 121 (AC) and 4,4 OBSH (OBSH) are two kinds of most widely used whipping agents.At present because the remarkable superiority of microvesicle plastics, the research difficult point of expanded plastic how effectively to concentrate on control foaming dosage, increase nucleation site and how simple economy to prepare the aperture little, density is big, on the direction of the uniform microvesicle plastics of abscess.Present whipping agent majority is directly to mix with plastic raw materials, or whipping agent, frothing aid foam with its mixing, and because the easy reunion of whipping agent self, in plastic raw materials, be difficult for homodisperse, form local superheating in the production process easily, the aperture that causes foaming is inhomogeneous, and nucleation site is low, wayward foaming pore size greatly reduces foaming efficient and quality.In publication (200710098714.0) with the composite foamable agent of mentioning (200710064945.X), a kind of is that the intercalation molecule has decomposed in reaction process, another kind is the whipping agent that is combined into by the polynite adsorption, organic blowing agent is outside the layer of polynite, show mainly on the nuclear magnetic spectrogram that the resonance absorbing peak of organic blowing agent does not change before and after the intercalation.These all do not reach initial purpose is exactly that intercalations such as the most frequently used blowing agent AC or OBSH are entered between the nanometer laminate of stratified materials such as polynite, finally makes organic-inorganic nanocomposite.Mainly be owing to following reason, at first organic blowing agent such as AC is easy to decompose under different acid-base conditions; The second, the water-content in the reaction system has very large influence to the intercalation process; The 3rd, the intercalation process is academicly still clearly explained at present to the more complicated that influences of the decomposition mechanism of organic blowing agents such as AC.
Summary of the invention:
The objective of the invention is to overcome deficiency of the prior art, a kind of simple to operate, low production cost is provided, the preparation method of the novel nano intercalated compound that production efficiency is high.The inventive method is by groping and control acid-basicity in the intercalation process, water content in the composite dispersing agent, concrete experiment parameter such as temperature of reaction and time and wash conditions, finally must successfully chemical foaming agent entered between nano level cheating engaging layer by solution intercalation method intercalation under the experiment condition, overcome AC in the nearest disclosed patent (200710098714.0) and behind intercalation, be decomposed into organic blowing agent in the situation of hydrazo-dicarbonamide and the publication (200710064945.X) and be adsorbed on situation outside the cheating engaging layer.AC among the present invention or OBSH are successful respectively, and intercalation has entered between the nano level cheating engaging layer, has prepared the nano intercalated mixture of target.
The present invention is a kind of method for preparing intercalated nanocomposite foaming agent, it is characterized in that inorganic lamellar material is scattered in a certain amount of water.Organic raw material is dissolved in the certain amount of solvent, mixes with layered inorganic material suspension liquid.Stir at a certain temperature, repeatedly wash to remove the organic blowing agent of the outer absorption of layer with suitable solvent, centrifugal, drying obtains intercalated nanocomposite foaming agent.
The advantage of the inventive method and existing method has been to obtain the experiment condition of preparation intercalated nanocomposite foaming agent, and prepared intercalated nanocomposite foaming agent improved the reunion situation of pure organic blowing agent self, also be better than simple blended inorganic-organic composite foamable agent.
Above-mentioned preparation method has only an intercalation process, does not have decomposition course.
The preferred organic blowing agent that uses is Cellmic C 121 (AC) and 4 among the above-mentioned preparation method, 4 '-bis oxide benzene sulphur hydrazine (OBSH).
Inorganic lamellar material polynite described in the above-mentioned preparation method must be sodium-based montmorillonite or the polynite of sodium in advance.Its average primary particle size is 0.01-1000 μ m, preferred 0.01-100 μ m.
The organic solvent used among the above-mentioned preparation method is according to different organic blowing agent kinds and difference.
It is admixed together to work as two kinds of raw materials among the above-mentioned preparation method, H
2Can O and DMSO have just formed composite dispersing agent, and wherein the content of water is extremely important for this, directly have influence on AC and successfully insert between cheating engaging layer and whether can be decomposed into hydrazo-dicarbonamide.
OBSH intercalation polynite among the above-mentioned preparation method because the OBSH molecule is bigger, needs the method with pre-intercalation.With the pre-montmorillonite of cetyl trimethylammonium bromide (CTAB), OBSH is inserted easily.
Coupling agent of the present invention will be selected at employed carrier and whipping agent.
One of intercal type nano mixture purposes of preparation of the present invention is to can be used as the inorganic-organic nanocomposite composite foamable agent to be used for the microvesicle plastic working, its performance also is better than conventional organic blowing agent, and the mechanical property of the foam material made from it also improves greatly.Because organic blowing agent has successfully inserted between the nanometer layer of layered inorganic material, thereby the whipping agent particle diameter is fallen sharply, and has obviously improved agglomeration, has effectively controlled the amount of whipping agent, has avoided the local superheating in the foaming process.The laminate of inorganic clay provides a large amount of nucleation sites for the organic blowing agent of interlayer in addition, and organic blowing agent is dispersed in the plastic substrate these nucleation sites better, and the bubble that sends is more even, and efficient is higher, and the foaming aperture has reached microvesicle level level.
Description of drawings:
Fig. 1 is that the XRD spectra of the embodiment of the invention one products therefrom Cellmic C 121/montmorillonite Composite whipping agent and the XRD spectra of polynite (MMT) compare, the interlamellar spacing of the polynite behind the intercalation (1.90nm) is than the obvious increase of original soil (1.25nm), illustrate Cellmic C 121 intercalation enter interlayer.
Fig. 2 embodiment of the invention one products therefrom Cellmic C 121/montmorillonite Composite whipping agent
13CCP/MAS NMR spectrogram and Cellmic C 121 and hydrazo-dicarbonamide/polynite
13C CP/MAS NMR spectrogram relatively.Illustrating that the AC molecule has inserted between cheating engaging layer, and be not decomposed into hydrazo-dicarbonamide (LDA), be different from LDA-MMT, is the AC-MMT of intercal type, and the outer unnecessary AC of layer washed off fully.
The XRD spectra of the product OBSH-OMMT matrix material that Fig. 3 embodiment of the invention is two and the XRD spectra of OMMT are relatively.
Embodiment:
Embodiment one:
Sodium-based montmorillonite is scattered in a certain amount of deionized water, stirred 1 hour.Cellmic C 121 is dissolved in a certain amount of dimethyl sulfoxide (DMSO), in the montmorillonite slurry before joining.At a certain temperature, an amount of DMSO and CCl are used in centrifugation behind the vigorous stirring 24h successively
4The thorough washing product repeatedly, to remove the AC on MMT surface fully.At 60 ℃ of following vacuum-drying 24h, obtain intercalation composite foamable agent AC-MMT.
The preparation process parameter of table 1 Cellmic C 121/montmorillonite intercalation composite foamable agent
Embodiment two:
(1) preparation of organic montmorillonoid
Take by weighing 10g sodium-based montmorillonite suspended dispersed in the 300mL deionized water, in water-bath, stir and be heated to 80 ℃; Be dispersed in 3g cetyl trimethylammonium bromide (CTAB) in the 20mL deionized water and be added drop-wise in the above-mentioned MMT suspension. be heated to 90 ℃ in water-bath, constant temperature stirred 4 hours, and suction filtration washes with water repeatedly, to there not being bromide anion, dry under 90 ℃, be ground to 300 orders, obtain O-MMT.
(2) 4, the preparation of 4 OBSH-organic montmorillonoid intercalation composite foamable agent
Organic montmorillonoid O-MMT (1g) is scattered in 30mL H
2O; 1g 4,4 OBSH (OBSH) are dissolved among the 20mL DMSO, with the two mixing, be respectively under room temperature and 25 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ temperature at water-bath and stir 24h, centrifugal, 60 ℃ of following dry 24h obtain intercalation composite foamable agent OBSH-OMMT.
The preparation process parameter of table 24,4 OBSH/montmorillonite intercalation composite foamable agent
Embodiment three:
With the experiment of foaming of different ingredients among the embodiment one.Raw material: earlier intercalation composite foamable agent and silane coupling agent were stirred in ethylene glycol solution 3 hours, drying, the product that obtains mixes with ethylene vinyl acetate copolymer resins (EVA) and stearic acid again.With 100 parts of EVA of above-mentioned raw materials, 1.5 parts of composite foamable agents, 1 part of stearic acid composition mixture.In high speed agitator, stirred 3 minutes, mixing in extruser then, screw diameter is Φ 32, screw rod is extruded rotating speed 50r/min, five sections temperature of extruder barrel are set to 120 ℃, 150 ℃, 170 ℃, 180 ℃, 195 ℃ respectively, select Φ 4 filament die extrusion foamings for use, obtain composite foam material.Use therein intercalation composite foamable agent carries out proportioning by the prescription among the embodiment one and haggles over.
The foaming effect of different proportioning whipping agents is different, by the observation to the back material that foams, mainly be the bubble degree of uniformity that they are sent out, and the size of bubble compares.
#: the material after the expression foaming, bubble distributes relatively not too even, and bubble ratio is bigger simultaneously;
*: the material after the expression foaming, bubble distributes generally even, and bubble is more common simultaneously;
√: the material after the expression foaming, bubble distributes relatively even, and bubble ratio is less simultaneously;
ο: the material after the expression foaming, bubble distributes relatively very even, and bubble is also very little simultaneously.
The foaming effect of table 3 embodiment one intercalation composite foamable agent/EVA
| Intercalation composite foamable agent proportioning sequence number | 1 | 2 | 3 | 4 |
| Foaming effect | # | * | √ | ο |
Embodiment four:
With the experiment of foaming of 5 to 8 prescription among the embodiment two.Raw material: earlier intercalation composite foamable agent and silane coupling agent were stirred in ethylene glycol solution 3 hours, drying, the product that obtains mixes with polyethylene (PE) and stearic acid again.With 100 parts of PE of above-mentioned raw materials, 1.5 parts of intercalation composite foamable agents, 1 part of stearic acid composition mixture.Experimental technique is with embodiment three.Use therein intercalation composite foamable agent carries out proportioning by the prescription among the embodiment two and haggles over.
The foaming effect of table 4 embodiment two intercalation composite foamable agent/EVA
| Intercalation composite foamable agent proportioning sequence number | 5 | 6 | 7 | 8 |
| Foaming effect | ο | √ | * | # |
Claims (8)
1. the method for an intercalated nanocomposite foaming agent, its feature comprises following step:
(a) will be scattered in a certain amount of water after the modification of inorganic lamellar material polynite sodium.
(b) organic raw material is dissolved in the certain amount of solvent, mixes with layered inorganic material suspension liquid.
(c) stir at a certain temperature.
(d) repeatedly wash to remove the organic blowing agent of the outer absorption of layer with suitable solvent, centrifugal, drying obtains intercalated nanocomposite foaming agent.
2. preparation method according to claim 1 has only an intercalation process, does not have decomposition course.
3. intercalation nano composite foamable agent according to claim 1 is characterized in that the organic blowing agent of this intercal type in composite foamed all in layer, the organic blowing agent appropriate solvent thorough washing of the outer absorption of layer, centrifugal after, all remove.
4. according to the H of the described preparation intercalation nano of claim 1 to 3 composite foamable agent AC-MMT
2O/DMSO composite dispersing agent water content volume fraction is 40%.
5. according to 25 ℃ of the bath temperatures of the described preparation intercalation nano of claim 1 to 3 composite foamable agent OBSH-MMT.
6. according to the H of the described preparation intercalation nano of claim 1 to 3 composite foamable agent OBSH-MMT
2O/DMSO composite dispersing agent water content volume fraction is 60%.
7. according to the pH=6 of the described preparation intercalation nano of claim 1 to 3 composite foamable agent OBSH-MMT.
8. according to the composite foamable agent of claim 1 to 3 preparation, when being OBSH, wants organic blowing agent pre-intercalation.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898672A (en) * | 2012-10-26 | 2013-01-30 | 常州大学 | Microporous foamed-plastic foaming agent and preparation method thereof |
| CN103804709A (en) * | 2014-02-14 | 2014-05-21 | 北京化工大学 | Nano composite foaming agent and preparation method and foamed product thereof |
| CN104371137A (en) * | 2014-11-06 | 2015-02-25 | 浙江比例包装股份有限公司 | Preparation method of high-dispersity foaming agent |
| CN107033381A (en) * | 2017-03-20 | 2017-08-11 | 北京化工大学 | Nanocomposite foaming agent, foaming product and its preparation method and application |
| CN107286365A (en) * | 2017-06-06 | 2017-10-24 | 滁州市宏源喷涂有限公司 | A kind of preparation method of intercalation modifying organo montmorillonite composite foamable agent for polyvinyl chloride |
| CN107473646A (en) * | 2017-09-21 | 2017-12-15 | 成都新柯力化工科技有限公司 | A kind of building concrete that foaming is cooperateed with by modified hydrotalcite and preparation method thereof |
| CN113462061A (en) * | 2021-05-27 | 2021-10-01 | 吉泰(福建)体育用品有限公司 | Environment-friendly odorless EVA (ethylene-vinyl acetate) foaming material and preparation method thereof |
| CN115368727A (en) * | 2022-09-16 | 2022-11-22 | 上海嘉均瑞科技有限公司 | High-resilience polyurethane foam material and preparation method thereof |
| CN115521501A (en) * | 2022-09-30 | 2022-12-27 | 扬州工业职业技术学院 | Plastic product auxiliary foaming agent and foaming method thereof |
| CN117327374A (en) * | 2023-12-01 | 2024-01-02 | 饭田（佛山）橡塑有限公司 | Reinforcing film for automobile and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101294009A (en) * | 2007-04-25 | 2008-10-29 | 北京化工大学 | Intercalation-decomposition method for producing intercalation complexes |
-
2009
- 2009-05-25 CN CN200910084826XA patent/CN101899166A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101294009A (en) * | 2007-04-25 | 2008-10-29 | 北京化工大学 | Intercalation-decomposition method for producing intercalation complexes |
Non-Patent Citations (1)
| Title |
|---|
| 孙培琴: "蒙脱土改性及插层纳米复合发泡剂的研制", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898672A (en) * | 2012-10-26 | 2013-01-30 | 常州大学 | Microporous foamed-plastic foaming agent and preparation method thereof |
| CN102898672B (en) * | 2012-10-26 | 2014-05-21 | 常州大学 | Microporous foamed-plastic foaming agent and preparation method thereof |
| CN103804709A (en) * | 2014-02-14 | 2014-05-21 | 北京化工大学 | Nano composite foaming agent and preparation method and foamed product thereof |
| CN103804709B (en) * | 2014-02-14 | 2017-02-22 | 北京化工大学 | Nano composite foaming agent and preparation method and foamed product thereof |
| CN104371137A (en) * | 2014-11-06 | 2015-02-25 | 浙江比例包装股份有限公司 | Preparation method of high-dispersity foaming agent |
| CN107033381A (en) * | 2017-03-20 | 2017-08-11 | 北京化工大学 | Nanocomposite foaming agent, foaming product and its preparation method and application |
| CN107033381B (en) * | 2017-03-20 | 2020-05-12 | 北京化工大学 | Nano composite foaming agent, foamed product, preparation method and application thereof |
| CN107286365A (en) * | 2017-06-06 | 2017-10-24 | 滁州市宏源喷涂有限公司 | A kind of preparation method of intercalation modifying organo montmorillonite composite foamable agent for polyvinyl chloride |
| CN107473646B (en) * | 2017-09-21 | 2019-11-05 | 临安鼎昇建材有限公司 | A kind of building concrete and preparation method thereof by modified hydrotalcite collaboration foaming |
| CN107473646A (en) * | 2017-09-21 | 2017-12-15 | 成都新柯力化工科技有限公司 | A kind of building concrete that foaming is cooperateed with by modified hydrotalcite and preparation method thereof |
| CN113462061A (en) * | 2021-05-27 | 2021-10-01 | 吉泰(福建)体育用品有限公司 | Environment-friendly odorless EVA (ethylene-vinyl acetate) foaming material and preparation method thereof |
| CN115368727A (en) * | 2022-09-16 | 2022-11-22 | 上海嘉均瑞科技有限公司 | High-resilience polyurethane foam material and preparation method thereof |
| CN115521501A (en) * | 2022-09-30 | 2022-12-27 | 扬州工业职业技术学院 | Plastic product auxiliary foaming agent and foaming method thereof |
| CN115521501B (en) * | 2022-09-30 | 2023-09-29 | 扬州工业职业技术学院 | Auxiliary foaming agent for plastic products and foaming method thereof |
| CN117327374A (en) * | 2023-12-01 | 2024-01-02 | 饭田（佛山）橡塑有限公司 | Reinforcing film for automobile and preparation method thereof |
| CN117327374B (en) * | 2023-12-01 | 2024-02-20 | 饭田（佛山）橡塑有限公司 | Reinforcing film for automobile and preparation method thereof |
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Application publication date: 20101201 |