CN105273359B - High silica containing Mo-phenolic resin of carbon residue and preparation method thereof - Google Patents
High silica containing Mo-phenolic resin of carbon residue and preparation method thereof Download PDFInfo
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- CN105273359B CN105273359B CN201510577652.6A CN201510577652A CN105273359B CN 105273359 B CN105273359 B CN 105273359B CN 201510577652 A CN201510577652 A CN 201510577652A CN 105273359 B CN105273359 B CN 105273359B
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- phenolic resin
- phenol
- carbon residue
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- silica containing
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 43
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 43
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 26
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000003377 acid catalyst Substances 0.000 claims description 8
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 230000032050 esterification Effects 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 2
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 claims 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 claims 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract description 8
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 238000002679 ablation Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 230000003014 reinforcing effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 229920001342 Bakelite® Polymers 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229960004011 methenamine Drugs 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of high silica containing Mo-phenolic resin of carbon residue and preparation method thereof, the molecular structure of the Mo-phenolic resin is shown in formula I：
Description
Technical field
The present invention relates to technical field of chemistry, more particularly to field of material technology.
Background technology
Phenolic resin poor heat resistance, decomposed seriously in 500 DEG C or so of temperature ranges, matter carbon easily aoxidizes under high temperature
Decarburized layer is formed, which has limited its application on refractory material.Certain metallic element is introduced in high-polymer molecular chain, makes it
It is present in the chemical bond of high bond energy in phenolic resin molecular backbone, is one of effective way for improving phenolic resin heat resistance.
It is domestic successively to have developed boron bakelite resin, W-phenolic resin and Mo-phenolic resin.Wherein Mo-phenolic resin can be used as high temperature ablation
Material, friction material, adhesive etc., application prospect is extensive.However, Mo-phenolic resin is present, fragility is big, impact strength is weak
Shortcoming needs to overcome.
The content of the invention
First aspect technical problem to be solved by this invention is to provide a kind of high carbon residue Mo-phenolic resin containing silica.
In order to solve the above-mentioned technical problem, the present invention provides a kind of high silica containing Mo-phenolic resin of carbon residue, and it is special
Sign is that the molecular structure of the Mo-phenolic resin is shown in formula I：
Wherein, the n is 2-12 natural number, and preferably n is 3,4,5,6,7, and more preferably n is 4,5.
In the preferred technical solution of the present invention, described silica is nano silicon.
In the preferred technical solution of the present invention, it is 0.5- that described silica, which accounts for Mo-phenolic resin total amount percentage,
5wt%.
The second aspect of the present invention is to provide the preparation method of the above-mentioned silica containing Mo-phenolic resin of high carbon residue, and it is wrapped
Include following steps：
(1) SiO 2 powder, phenol, formaldehyde are placed in reaction bulb, the mol ratio 1 of phenol and formaldehyde:0.6~0.9,
Heating allows phenol to be completely dissolved, and stirring three is well mixed, and adds acidic catalyst, adjusts pH value 1.5-3.0, continues to heat
To 60-85 DEG C, insulated and stirred reaction 0.5-3 hours, phenol under acidic catalyst, occurs polycondensation reaction and forms hydroxyl first with formaldehyde
Base phenol homologue,
(2) molybdic acid obtains Mo-phenolic resin with hydroxymethyl phenol generation esterification：Molybdic acid is added in system, molybdic acid adds
Amount accounts for Mo-phenolic resin percentage by weight 2-12%, temperature rising reflux 4-5 hours, neutralization reaction system, last decompression dehydration, produces
To the Mo-phenolic resin containing Nano particles of silicon dioxide.
In the preferred technical solution of the present invention, the acid catalyst that adds in the step (1) include organic acid catalyst and
Inorganic acid catalyst.Organic acid catalyst includes but is not limited to acetic acid；Inorganic acid catalyst includes but is not limited to hydrochloric acid, nitric acid,
Sulfuric acid.
In the preferred technical solution of the present invention, described SiO 2 powder is nanometer silicon dioxide material.
In the preferred technical solution of the present invention, in the step (1), reaction system regulation to pH value to 2.0 continues to add
Heat to 70 DEG C, react 1 hour by insulated and stirred.
In the preferred technical solution of the present invention, the mol ratio of phenol and formaldehyde is preferably 1:0.75~0.82.
The advantages of the present invention are：
Mo-phenolic resin of silica of the present invention and preparation method thereof can make nano material introducing phenolic resin
The composite of standby excellent performance.Nano silicon because specific surface area is big, activity is high, can exist with phenolic resin as matrix resin compared with
Strong active force, toughness reinforcing enhancing effect is obvious, while also significantly improves the heat resistance of resin.
High carbon residue Mo-phenolic resin containing silica high temperature resistant that the present invention is prepared, resistance to ablation, carbon forming rate are high, its machine
Tool intensity is high, process industrial art performance is good；Have broad application prospects：It is more to can be applied not only to casting, building materials, other resins
Functional modifier, apply also for making rocket, the contour scientific and technological thermally protective materials of guided missile.
Embodiment
To further understand the present invention, preferred scheme of the present invention is described with reference to specific embodiment, but should
Work as understanding, these descriptions are simply further explanation the features and advantages of the present invention, rather than the limit to the claims in the present invention
System.
Embodiment 1：
The 40-50 nano silicons, 282 parts by weight of phenol, 68 parts by weight of 1.56 parts by weight are contained to 37% formalin
Solution is placed in the three-necked flask with condensing unit.Heating allows phenol to be completely dissolved, and stirring three is well mixed, and is adjusted with hydrochloric acid
PH value 1.8 is saved, continues to be heated to 70 DEG C, insulated and stirred 1 hour.
Second step molybdic acid occurs esterification with hydroxymethyl phenol and obtains Mo-phenolic resin：9.72 parts by weight molybdic acids are added, are risen
Temperature backflow 4-5 hours, with sodium hydrate aqueous solution neutralization reaction system, last decompression dehydration, obtain containing silica dioxide nano particle
The Mo-phenolic resin of son 0.5%.
Embodiment 2：
3.12 parts by weight 40-50 nano silicons, 282 parts by weight of phenol, 68 parts by weight are water-soluble containing 37% formaldehyde
Liquid is placed in the three-necked flask with condensing unit.Heating allows phenol to be completely dissolved, and stirring three is well mixed, and is adjusted with hydrochloric acid
PH value 2, continue to be heated to 70 DEG C, insulated and stirred 1 hour.
Second step molybdic acid occurs esterification with hydroxymethyl phenol and obtains Mo-phenolic resin：6.48 parts by weight molybdic acids are added, are risen
Temperature backflow 4-5 hours, with sodium hydrate aqueous solution neutralization reaction system, last decompression dehydration, obtain containing silica dioxide nano particle
The Mo-phenolic resin of son 1%.
Sample carbon forming rate prepared by testing example 1,2, to being consolidated with containing 10% hexamethylene tetramine Mo-phenolic resin
Change and carry out heat analysis, and contrasted with phenolic resin, it is as a result as shown in the table；
From the results, it was seen that high carbon residue Mo-phenolic resin containing Nano particles of silicon dioxide thermal decomposition temperature prepared by the present invention
Degree, Residual carbon are obviously improved.It can be dissolved in the organic solvents such as acetone, alcohol, high temperature resistant, resistance to ablation, carbon forming rate after solidification
Height, its high mechanical strength, casting, building materials, other resin multifunctional modification agent are can be applied not only to, can also be applied to make fire
The contour scientific and technological thermally protective materials of arrow, guided missile.
The technology contents and technical characteristic of the present invention have revealed that as above, but those skilled in the art still may base
Make a variety of replacements and modification without departing substantially from spirit of the present invention, therefore, the scope of the present invention in teachings of the present invention and announcement
The content disclosed in embodiment should be not limited to, and various replacements and modification without departing substantially from the present invention should be included, and is this patent Shen
Please claim covered.
Claims (7)
1. a kind of preparation method of the silica containing Mo-phenolic resin of high carbon residue, it is characterised in that it comprises the following steps：
(1) SiO 2 powder, phenol, formaldehyde are placed in reaction bulb, the mol ratio 1 of phenol and formaldehyde:0.6~0.9, heating
Phenol is allowed to be completely dissolved, stirring three is well mixed, and adds acidic catalyst, adjusts pH value 1.5-3.0, continues to be heated to
60-85 DEG C, insulated and stirred reaction 0.5-3 hours, phenol under acidic catalyst, occurs polycondensation reaction and forms methylol with formaldehyde
Phenol homologue,
(2) molybdic acid obtains Mo-phenolic resin with hydroxymethyl phenol generation esterification：Molybdic acid is added in system, molybdic acid addition accounts for
Mo-phenolic resin percentage by weight 2-12%, temperature rising reflux 4-5 hours, neutralization reaction system, last decompression dehydration, that is, obtain height
The silica containing Mo-phenolic resin of carbon residue.
2. preparation method according to claim 1, it is characterised in that state the acid catalyst added in step (1) and include
Machine acid catalyst and inorganic acid catalyst.
3. preparation method according to claim 1, it is characterised in that in the step (1), pH is arrived into reaction system regulation
It is worth 2.0, continues to be heated to 70 DEG C, insulated and stirred is reacted 1 hour.
4. preparation method according to claim 1, it is characterised in that in the step (1), the mol ratio of phenol and formaldehyde
For 1:0.75~0.82.
5. the silica containing Mo-phenolic resin of high carbon residue that a kind of the method as described in claim 1 is prepared, its feature
It is, the molecular structure of the Mo-phenolic resin is shown in formula I：
Wherein, the n is 2-12 natural number；It is 0.5-5wt% that described silica, which accounts for Mo-phenolic resin total amount percentage,.
6. the silica containing Mo-phenolic resin of high carbon residue according to claim 5, it is characterised in that the n is 3,4,
5,6,7.
7. the silica containing Mo-phenolic resin of high carbon residue according to claim 5, it is characterised in that described titanium dioxide
Silicon is nano silicon.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510577652.6A CN105273359B (en) | 2015-09-11 | 2015-09-11 | High silica containing Mo-phenolic resin of carbon residue and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510577652.6A CN105273359B (en) | 2015-09-11 | 2015-09-11 | High silica containing Mo-phenolic resin of carbon residue and preparation method thereof |
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| Publication Number | Publication Date |
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| CN105273359A CN105273359A (en) | 2016-01-27 |
| CN105273359B true CN105273359B (en) | 2018-01-23 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632937B (en) * | 2016-09-27 | 2018-11-27 | 中国林业科学研究院林产化学工业研究所 | Organic phenolic substances-nano silica system and its preparation method and application |
| CN109651758B (en) * | 2018-11-06 | 2021-11-30 | 中国神华能源股份有限公司 | Modified phenolic resin, preparation method thereof and modified phenolic resin plate |
| CN110170614B (en) * | 2019-06-19 | 2020-11-03 | 浙江瓯赛汽车部件铸造有限公司 | Precoated sand shell mold casting process |
| CN110951212B (en) * | 2019-12-21 | 2023-03-10 | 北华大学 | Preparation method of nano silicon dioxide modified melamine formaldehyde resin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181025A (en) * | 2011-03-28 | 2011-09-14 | 浙江嘉民塑胶有限公司 | Method for preparing phenolic resin cooperatively modified by nano silicon oxide and rubber |
| CN103467911A (en) * | 2013-09-27 | 2013-12-25 | 厦门大学 | Method for preparing nano-silica-boron modified phenolic resin |
| CN104419365A (en) * | 2013-09-04 | 2015-03-18 | 黑龙江工程学院 | Inorganic-organic hybrid high-temperature resistant adhesive for SiC splicing and application method thereof |
-
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- 2015-09-11 CN CN201510577652.6A patent/CN105273359B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181025A (en) * | 2011-03-28 | 2011-09-14 | 浙江嘉民塑胶有限公司 | Method for preparing phenolic resin cooperatively modified by nano silicon oxide and rubber |
| CN104419365A (en) * | 2013-09-04 | 2015-03-18 | 黑龙江工程学院 | Inorganic-organic hybrid high-temperature resistant adhesive for SiC splicing and application method thereof |
| CN103467911A (en) * | 2013-09-27 | 2013-12-25 | 厦门大学 | Method for preparing nano-silica-boron modified phenolic resin |
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