CN1570009A - Organic voelknerite heat-resistant filling suitable for epoxy-resin adhesive - Google Patents
Organic voelknerite heat-resistant filling suitable for epoxy-resin adhesive Download PDFInfo
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- CN1570009A CN1570009A CN 03146671 CN03146671A CN1570009A CN 1570009 A CN1570009 A CN 1570009A CN 03146671 CN03146671 CN 03146671 CN 03146671 A CN03146671 A CN 03146671A CN 1570009 A CN1570009 A CN 1570009A
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- China
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- hydrotalcite
- heat
- epoxy
- resistant filler
- organic
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- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides an active heat-resistant gasket material suitable for epoxy-resin adhesive characterized in that, (1) the filling material is an organic hydrotalcite adapted for epoxide-resin adhesive, (2) the organic hydrotalcite is synthesized through the reaction between magnesium, aluminium nitrate anion hydrotalcite and alkyl aminoacetic acid.
Description
Technical field
Tackiness agent, coating and pluronic polymer.
Technical background
The epoxyn bonding strength is big, and cure shrinkage is little, and chemical stability is good, and most of base materials are all had excellent adhesiveproperties, occupies critical role in synthetic adhesive, is widely used in fields such as electronics, automobile, Aeronautics and Astronautics.But the epoxy resin cured product poor toughness of non-modified, the thermotolerance deficiency, this has just limited its application in many aspects.Many in recent years investigators have done a large amount of work aspect epoxy resin modification, in the hope of obtain toughness good, high temperature resistant, significantly do not reduce the modified epoxy of its adhesiveproperties again.From existing patent, epoxy resin modification can be divided into chemical modification and physically modified.Chemical modification is to introduce high temperature resistant and soft segment by selection appropriate resin and Resins, epoxy copolymerization, thereby reaches the purpose of modification.For example Chinese patent 87100265 uses carboxylic acrylonitrile butadiene rubber modified Resins, epoxy, by the epoxy-butadiene-acrylonitrile rubber adhesive composition of certain formulation; The adhesive compound that Chinese patent 90103787.7 uses the snappiness microgel of unsaturated polyesters and vinyl monomer copolymerization to add to prepare in the Resins, epoxy etc.Physically modified is to add mineral filler in tackiness agent, makes it homodisperse by mechanical mill.Facts have proved that the inoganic solids filler plays an important role to the thermotolerance of resin.The advantage of physically modified is that technology is simple, is easy to industrial production, but the affiliation that adds of mineral filler descends toughness and adhesiveproperties significantly, so the research of physically modified report is few.In recent years along with the development of nano materials research, many toughening effects that studies have shown that the small scale rigid particles.Therefore, contain inorganic-organic compounded mix of functional groups, carry out physically modified, be expected to reach nano level and disperse, both improved resistance toheat, again the purpose that does not cause toughness and adhesiveproperties to descend significantly by adding.The present invention has synthesized a kind of novel organic hydrotalcite that contains amino, and its application in Resins, epoxy is studied.Studies show that organic hydrotalcite of the present invention can well be scattered in the Resins, epoxy, significantly improve the thermotolerance and the mechanical property of Resins, epoxy, and do not cause the epoxy cement degradation.
The present invention is directed to Resins, epoxy, synthesize a kind of amino novel organic hydrotalcite heat-resistant filler that contains, this heat-resistant filler can be wetting preferably by Resins, epoxy, is easy to be dispersed in the Resins, epoxy.Add in the Resins, epoxy, can obviously improve the resistance toheat and the intensity of tackiness agent, realize heat-resisting simultaneously and enhancing.
Summary of the invention
The purpose of this invention is to provide a kind of heat-resistant filler that is suitable for epoxyn, it can be used under comparatively high temps.
Main advantage of the present invention is: organic hydrotalcite of the present invention contains amino, belongs to active filler, participates in curing reaction in the adhesive solidification process, makes tackiness agent have mechanical property preferably.
The present invention is mainly by the following technical solutions:
The preparation of 1 hydrotalcite
Press n (Mg: Al)=2: 1, take by weighing a certain amount of Mg (NO
3)
26H
2O and Al (NO
3)
39H
2O is made into mixing salt solution after with deionized water dissolving, and other takes by weighing appropriate amount of NaOH with deionized water proportionaling alkali-forming solution.At N
2Protection slowly is added drop-wise to mixing salt solution and alkaline solution in the four-hole boiling flask under vigorous stirring down.After dripping end, regulating the pH value is about 9, at 100 ℃ of following backflow 6h.After being washed till neutrality with dope filtration and with distilled water, the gained filter cake grinds and obtains sample at 70 ℃ of dry 24h down.The hydrotalcite layers distance is 0.79nm.
The preparation of 2 organic hydrotalcites
Get a certain amount of alkyl glycine and add in the deionized water, neutralizing with the NaOH of equimolar amount is made into alkyl Sodium glycocollate solution, and other takes by weighing a certain amount of Mg-Al-NO for preparing
3Abundant decentralized system becomes slurries in the type hydrotalcite adding deionized water, wherein hydrotalcite and alkyl glycine mass ratio are about 2～3, the two mixing is placed four-hole boiling flask, regulating the pH value is about 10～13, refluxed 3～5 hours 70 ℃ of following vigorous stirring, filter then, wash and, grind and obtain sample at 70 ℃ of following dry 24h.The interlamellar spacing of organic hydrotalcite is 2.4nm.
Alkyl glycine used among the present invention is a kind of amphoterics, in strongly acidic aqueous solution, almost can all exist with cationic form, in strong alkaline aqueous solution, almost all exist, and when the approaching neutrality of pH, then the form with inner salt exists with anionic form.Hydrotalcite has the interlayer anion interchangeability, can enter hydrotalcite layers so the alkyl glycine only exists just with anionic form in the aqueous solution.Therefore pH value of aqueous solution suits between 10～13 among the present invention.
Inventive embodiments
To set forth several embodiment below the present invention will be described in further detail.
Embodiment 1
Take by weighing 20.4gMg (NO respectively
3)
26H
2O and 15gAl (NO
3)
39H
2O, with being made into mixing salt solution behind the 100ml deionized water dissolving, other takes by weighing NaOH11.2g, with 100ml deionized water proportionaling alkali-forming solution.At N
2Protection slowly is added drop-wise to mixing salt solution and alkaline solution in the 500ml four-hole boiling flask under vigorous stirring down.After dripping end, regulating the pH value is about 9, at 100 ℃ of following backflow 6h.After being washed till neutrality with dope filtration and with distilled water, the gained filter cake is at 70 ℃ of dry 24h down, grinds that to obtain sample standby.
Get N-dodecyl glycine 9g and add in the 100ml deionized water, be made into N-dodecyl Sodium glycocollate solution with the 1.47gNaOH neutralization, other takes by weighing the Mg-Al-NO that has prepared
3Type hydrotalcite 25g fully is dispersed into slurries in the adding 100ml deionized water.The two mixing is placed the 500ml four-hole boiling flask, and regulating the pH value is about 11, refluxes 3 hours 70 ℃ of following vigorous stirring, filters then, washes and at 70 ℃ of following dry 24h, grind and obtain sample.
Embodiment 2
Take by weighing 20.4gMg (NO respectively
3)
26H
2O and 15gAl (NO
3)
39H
2O, with being made into mixing salt solution behind the 100ml deionized water dissolving, other takes by weighing NaOH11.2g, with 100ml deionized water proportionaling alkali-forming solution.At N
2Protection slowly is added drop-wise to mixing salt solution and alkaline solution in the 500ml four-hole boiling flask under vigorous stirring down.After dripping end, regulating the pH value is about 9, at 100 ℃ of following backflow 6h.After being washed till neutrality with dope filtration and with distilled water, the gained filter cake is at 70 ℃ of dry 24h down, grinds that to obtain sample standby.
Get the N-tetradecyl Sodium glycocollate 12g that has prepared and add in the 100ml deionized water, be made into N-tetradecyl Sodium glycocollate solution with the 1.8gNaOH neutralization, other takes by weighing the Mg-Al-NO that has prepared
3Type hydrotalcite 25g, abundant decentralized system becomes slurries in the adding 100ml deionized water.The two mixing is placed the 500ml four-hole boiling flask, and regulating the pH value is about 12, refluxes 4 hours 70 ℃ of following vigorous stirring, filters then, washes and at 70 ℃ of following dry 24h, grind and obtain sample.
Embodiment 3
Take by weighing 20.4gMg (NO respectively
3)
26H
2O and 15gAl (NO
3)
39H
2O, with being made into mixing salt solution behind the 100ml deionized water dissolving, other takes by weighing NaOH11.2g, with 100ml deionized water proportionaling alkali-forming solution.At N
2Protection slowly is added drop-wise to mixing salt solution and alkaline solution in the 500ml four-hole boiling flask under vigorous stirring down.After dripping end, regulating the pH value is about 9, at 100 ℃ of following backflow 6h.After being washed till neutrality with dope filtration and with distilled water, the gained filter cake is at 70 ℃ of dry 24h down, grinds that to obtain sample standby.
Get the N-hexadecyl Sodium glycocollate 14g that has prepared and add in the 100ml deionized water, be made into N-hexadecyl Sodium glycocollate solution with the 1.7gNaOH neutralization, other takes by weighing the Mg-Al-NO that has prepared
3Type hydrotalcite 30g, abundant decentralized system becomes slurries in the adding 100ml deionized water.The two mixing is placed the 500ml four-hole boiling flask, and regulating the pH value is about 13, refluxes 4 hours 70 ℃ of following vigorous stirring, filters then, washes and at 70 ℃ of following dry 24h, grind and obtain sample.
Embodiment 4
Take by weighing 20.4gMg (NO respectively
3)
26H
2O and 15gAl (NO
3)
39H
2O, with being made into mixing salt solution behind the 100ml deionized water dissolving, other takes by weighing NaOH11.2g, with 100ml deionized water proportionaling alkali-forming solution.At N
2Protection slowly is added drop-wise to mixing salt solution and alkaline solution in the 500ml four-hole boiling flask under vigorous stirring down.After dripping end, regulating the pH value is about 9, at 100 ℃ of following backflow 6h.After being washed till neutrality with dope filtration and with distilled water, the gained filter cake is at 70 ℃ of dry 24h down, grinds that to obtain sample standby.
Get the N-octadecyl Sodium glycocollate 16g that has prepared and add in the 100ml deionized water, be made into N-octadecyl Sodium glycocollate solution with the 1.8gNaOH neutralization, other takes by weighing the Mg-Al-NO that has prepared
3Type hydrotalcite 33g, abundant decentralized system becomes slurries in the adding 100ml deionized water.The two mixing is placed the 500ml four-hole boiling flask, and regulating the pH value is about 12, refluxes 5 hours 70 ℃ of following vigorous stirring, filters then, washes and at 70 ℃ of following dry 24h, grind and obtain sample.
Four embodiment of the present invention have synthesized 12,14,16 respectively, organic hydrotalcite of octadecyl glycine, and they all have in the epoxyn of different ingredients preferably uses.With the organic hydrotalcite of tetradecyl glycine is example, at 100 ℃ of E-44 and T31 system tackiness agent that add this organic hydrotalcite down, when organic hydrotalcite addition is 5%, the tensile strength of epoxyn can reach 12.28Mpa, improved 53.7% than the tensile strength that does not add organic hydrotalcite epoxyn, detailed data see attached list (GB GB7124-86).
The different organic hydrotalcite additions of subordinate list to E-44 Resins, epoxy at 100 ℃ of following stretching intensity effects
Organic hydrotalcite addition (%) 0135
Tensile strength (Mpa) 7.99 10.4 11.3 12.28
Claims (5)
1. the heat-resistant filler that is applicable to epoxy adhesive is generated by hydrotalcite and alkyl glycine reactant.
2. according to the heat-resistant filler of claim 1, wherein said hydrotalcite is a magnalium nitrate radical hydrotalcite, and its molecular formula is Mg
4Al
2(OH)
12(NO
3)
24H
2O.
3. according to the heat-resistant filler of claim 1, wherein said alkyl glycine structural formula is:
4. according to the heat-resistant filler of claim 3, the R general formula is C in the wherein said alkyl glycine general formula
nH
2n+1N=8～18 wherein.
5. according to the heat-resistant filler of claim 1, wherein said reactions steps is as follows:
(a) under the normal temperature a certain amount of alkyl glycine is dissolved in the 50ml water, adds an amount of NaOH neutralization.
(b) in 150ml80 ℃ water, add a certain amount of hydrotalcite (Mg
4Al
2(OH)
12(NO
3)
24H
2O), wherein the consumption of hydrotalcite is 2～3 times of alkyl glycine consumption, fully stirs and makes it to be mixed into uniform slurries.
(c) make hydrotalcite slurries and alkyl Sodium glycocollate solution thorough mixing, regulate pH to 10～13.
(d) fully stirring reaction (at least 3 hours) filters afterwards, is washed to neutrality, grinds to be powder after 70 ℃ of vacuum-drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03146671 CN1570009A (en) | 2003-07-11 | 2003-07-11 | Organic voelknerite heat-resistant filling suitable for epoxy-resin adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03146671 CN1570009A (en) | 2003-07-11 | 2003-07-11 | Organic voelknerite heat-resistant filling suitable for epoxy-resin adhesive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1570009A true CN1570009A (en) | 2005-01-26 |
Family
ID=34471822
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03146671 Pending CN1570009A (en) | 2003-07-11 | 2003-07-11 | Organic voelknerite heat-resistant filling suitable for epoxy-resin adhesive |
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|---|---|
| CN (1) | CN1570009A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153781A (en) * | 2011-01-13 | 2011-08-17 | 杭州鸿雁电器有限公司 | Organic hydrotalcite and preparation method thereof |
| CN106674607A (en) * | 2016-12-05 | 2017-05-17 | 安徽索亚装饰材料有限公司 | Padding for improving overall characteristics of wood plastic foaming material |
| CN107236506A (en) * | 2017-06-28 | 2017-10-10 | 常州水精灵环保设备有限公司 | A kind of double-component epoxy resin embedding adhesive |
| CN107903827A (en) * | 2017-11-10 | 2018-04-13 | 雷笑天 | A kind of preparation method of high-adhesion high temperature resistant anchoring adhesive |
| CN111117452A (en) * | 2019-12-27 | 2020-05-08 | 深圳市唯特偶新材料股份有限公司 | Nano environment-friendly low-odor heat-conducting three-proofing paint |
-
2003
- 2003-07-11 CN CN 03146671 patent/CN1570009A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153781A (en) * | 2011-01-13 | 2011-08-17 | 杭州鸿雁电器有限公司 | Organic hydrotalcite and preparation method thereof |
| CN102153781B (en) * | 2011-01-13 | 2013-05-15 | 杭州鸿雁管道系统科技有限公司 | Organic hydrotalcite and preparation method thereof |
| CN106674607A (en) * | 2016-12-05 | 2017-05-17 | 安徽索亚装饰材料有限公司 | Padding for improving overall characteristics of wood plastic foaming material |
| CN106674607B (en) * | 2016-12-05 | 2019-04-23 | 安徽索亚装饰材料有限公司 | A kind of filler improving Wood-plastic foam material overall characteristic |
| CN107236506A (en) * | 2017-06-28 | 2017-10-10 | 常州水精灵环保设备有限公司 | A kind of double-component epoxy resin embedding adhesive |
| CN107903827A (en) * | 2017-11-10 | 2018-04-13 | 雷笑天 | A kind of preparation method of high-adhesion high temperature resistant anchoring adhesive |
| CN111117452A (en) * | 2019-12-27 | 2020-05-08 | 深圳市唯特偶新材料股份有限公司 | Nano environment-friendly low-odor heat-conducting three-proofing paint |
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