CN104497241A - Graphene phenolic resin as well as preparation method and application thereof - Google Patents
Graphene phenolic resin as well as preparation method and application thereof Download PDFInfo
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- CN104497241A CN104497241A CN201410755779.8A CN201410755779A CN104497241A CN 104497241 A CN104497241 A CN 104497241A CN 201410755779 A CN201410755779 A CN 201410755779A CN 104497241 A CN104497241 A CN 104497241A
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Abstract
The invention relates to the technical field of phenolic resin composite materials, and especially relates to a graphene phenolic resin composite material. A preparation method comprises the following steps: adding graphene oxide, hydrazine hydrate, a surfactant and formaldehyde solution in a reactor, stirring, and heating to 80-100 DEG C and reacting; cooling the obtained reaction liquid to 60-80 DEG C, adding an acid catalyst and phenols, heating to 85-100 DEG C and reacting, and heating and dehydrating. The invention further relates to an application of the graphene phenolic resin composite material in bakelite powder. By using the proper surfactant, the problem of the dispersion of graphene in resin is solved, and the uniformly-mixed graphene-modified phenolic resin is obtained; the unreduced graphene oxide is capable of further reacting with phenolic resin to form the graphene-modified phenolic resin with an inorganic complexing structure; a bakelite powder material prepared from the resin has high impact property and low moulding shrinkage.
Description
Technical field
The present invention relates to phenolic resin composite material technical field, particularly a kind of graphene phenolic-resin, also relate to the preparation method of graphene phenolic-resin, also relate to the application of graphene phenolic-resin.
Background technology
Resol realizes industrialized synthetic resins the earliest in the world, the history of existing last 100 years so far, because its raw material is easy to get, cheap, production technique and equipment simple, the more important thing is the mechanical property of its excellence, resistance toheat, ablation resistance, electrical insulation properties, molding processibility and flame retardant properties, become the indispensable material of bakelite industry.Traditional unmodified resol fragility is large, shrinkability in poor toughness and moulding process limits the application on high-end bakelite goods.
Patent CN101974199A describes a kind of lower shrinkage phenolaldehyde moulding compound, and it adopts thermosetting and thermoplastic resol to arrange in pairs or groups, and controls shrinking percentage by adding shrinking agent in formula.
Graphene, because of its exclusive two dimensional crystal structure, has higher electron transfer rate, and is the material that known physical strength is the highest, all has broad application prospects in a lot of field.
Therefore, have in prior art and a lot Graphene is added in resol, improve the research of its performance.The feed postition of Graphene, mainly contains two kinds, and one adds in resol by Graphene, physical mixed, but Graphene is easily reunited, and simple physical mixed cannot effectively mix, and can not play the excellent properties of Graphene.Also having a kind of is add Graphene in the preparation process of phenolic aldehyde, by chemical reaction, Graphene is added resol inside.Latter event such as publication number is the Chinese invention patent application of CN103788318A, disclose a kind of preparation method of phenol formaldehyde foam of graphene-containing, according to the following steps realize: one, by mass concentration be 0.5% ~ 10% silane coupling agent ethanolic soln join in the ethanolic soln of expansible black lead, stirring reaction 1 ~ 5h at 30 ~ 70 DEG C, adopt 16000r/min centrifugation 15 ~ 60min, centrifugal gained solid is placed in vacuum drying oven dry 24 ~ 48h at 60 ~ 90 DEG C, obtains the expansible black lead of silane coupling agent process; Two, the expansible black lead of gained silane coupling agent process in 0.1 ~ 20 weight part step one is joined in 100 parts by weight of phenol, sonic oscillation 0.5 ~ 5h, then formalin and 0.5 ~ 5 parts by weight acetic acid zinc that 46 ~ 138 weight part mass concentrations are 37% is added, with the heat-up rate of 1 ~ 5 DEG C/min, temperature of reaction is risen to 60 ~ 80 DEG C again, react 30 ~ 90min at this temperature, obtain mixture A; Three, by 40 ~ 122 weight part mass concentrations be 37% formalin and 1 ~ 10 weight part volumetric concentration be 30% NaOH solution join in mixture A, reaction 1 ~ 3h is continued at 60 ~ 80 DEG C, after being cooled to room temperature, at 70 DEG C, vacuumize under 0.08MPa vacuum tightness and remove 60 ~ 100 weight parts waters, obtain the resol of graphene-containing; Four, the resol of gained graphene-containing in 100 weight part step 3,1 ~ 10 weight part tween 80,2 ~ 20 weight part Skellysolve As, 3 ~ 30 weight part tosic acid and 1 ~ 10 weight part poly(oxyethylene glycol) 400 are mixed and stir, obtain mixture B, then mixture B to be poured in container and to be placed in the constant temperature oven 30min of 50 ~ 80 DEG C, room temperature is placed 3 ~ 7 days again, obtains the phenol formaldehyde foam of graphene-containing.This kind of method is actually and adopts ultrasonic discrete form to join in phenol by expanded graphite, and Graphene itself also has neither part nor lot in the synthesis of resin.
Summary of the invention
The problem that graphene dispersion is uneven, cause performance limited is there is in graphene phenolic-resin preparation in order to solve in above prior art, the invention provides a kind of Graphene to be more evenly distributed in resol, the obtained graphene phenolic-resin that resin shock strength is high, molding shrinkage is low.
Present invention also offers the preparation method of described graphene phenolic-resin.
Present invention also offers the application of described graphene phenolic-resin.
The present invention is achieved by the following measures:
A kind of graphene phenolic-resin, is obtained by following steps:
(1) graphene oxide, hydrazine hydrate, tensio-active agent, aldehyde solution are joined in reactor, stir, react at being warming up to 80 ~ 100 DEG C;
(2) reaction solution that step (1) obtains is cooled to 60 ~ 80 DEG C, reconciles pH value to 1.5-4.5, add phenol, be warming up to 85 ~ 100 DEG C of reactions, heat up dehydration, to obtain final product.
Described graphene phenolic-resin, the weight ratio of preferential oxidation Graphene, hydrazine hydrate, tensio-active agent, aldehyde and phenol is 1-15:1-15:3-20:114-163:600.
Formaldehyde solution mass percentage is 44%.
Described graphene phenolic-resin, preferred steps reacts 5-10 hour in (1) at 80-100 DEG C.
Described graphene phenolic-resin, 85-100 DEG C of reaction 2 ~ 6 hours in preferred steps (2).
Described graphene phenolic-resin, the weight ratio of preferential oxidation Graphene, hydrazine hydrate, tensio-active agent, aldehyde and phenol is 1-10:5:5-20:114-159:600.
More preferably the weight ratio of graphene oxide, hydrazine hydrate, tensio-active agent, aldehyde and phenol is 5-10:5:5:114.4:600,1-5:20:145.2:260.
Described graphene phenolic-resin, the ratio of preferential oxidation graphene carbon oxygen quantity is 1.8-3.4:1.
Described graphene phenolic-resin, is not particularly limited for the phenol in the present invention, and preferred phenol is more than one in phenol, cresols, xylenol, nonylphenol, dihydroxyphenyl propane, Bisphenol F, Resorcinol and cardanol.Being not particularly limited for the aldehyde in the present invention, can be one or more in formaldehyde, acetaldehyde, furfural.Tensio-active agent is more than one in aliphatic sulfonic salt and fatty alcohol sulfate class, is preferably more than one in Sodium dodecylbenzene sulfonate, dioctyl succinate disulfonate acid, sodium lauryl sulphate and sodium laurylsulfate.An acidic catalyst comprises organic acid and mineral acid, more than one in example hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid and tosic acid.
The application of described graphene phenolic-resin in bakelite.
Described application, after preferably graphene phenolic-resin being pulverized, mixes with wood powder, filler, solidifying agent and curing catalyst, after plasticizing, pulverizes and is prepared into bakelite.
Described application, preferred plasticization temperature 80-110 DEG C, time 3-15 minute.
Bakelite is joined in mould, prepares the moulded parts of bakelite under the following conditions:
Pressing conditions: temperature 140-180 DEG C, pressure 8-20MPa, time 5-20 minute shaping.
Post-treatment condition: 120 DEG C-140 DEG C, 2 hours; 140 DEG C-180 DEG C, 4 hours.
Resol in the present invention belongs to novolac resin.Under the effect of reductive agent, graphene oxide is reduced into the formaldehyde solution of Graphene in formaldehyde solution, then reacts with phenol and generates thermoplastic resol.Carboxyl in simultaneous oxidation Graphene and hydroxyl can further with the reaction of resol, the Graphene modified phenolic resins of inorganic complexing can be formed.It is high that resin in the present invention has shock strength, the feature that molding shrinkage is low.Can be used for preparing in the field of compound material such as bakelite, friction materials, grinding tool abrasive material.
The invention provides one and prepare graphene thermal plastic phenolic resin composite materials and preparation method thereof, compared with common thermoplastic resol, the resin prepared by the method not only can improve the mechanical property of resol, and the product size preparing bakelite with resol has extremely low shrinking percentage.
Beneficial effect of the present invention:
Graphene novolac resin prepared by A, the present invention, in formaldehyde solution with reductive agent by graphene oxide in-situ reducing, and use suitable tensio-active agent, solve the scattering problem of Graphene in resin, obtain the Graphene modified phenolic resins mixed;
The graphene oxide be not reduced in B, the present invention can react with resol further, forms the Graphene modified phenolic resins of inorganic chelation structure;
Graphene phenolic-resin prepared by C, the present invention, operating procedure is simple, and reduce operation easier, technology stability is reliable;
Thermoplastic resol prepared by D, the present invention adopts graphene oxide composite modified, and due to adding of Graphene, the bakelite material making resin-made standby has higher impact property and low molding shrinkage.
Embodiment
For a better understanding of the present invention, further illustrate below in conjunction with specific embodiment.
embodiment 1:
(1) by 1 gram of graphene oxide, 5 grams of hydrazine hydrates, 5 grams of Sodium dodecylbenzene sulfonatees, concentration be 44% 260 grams of formaldehyde solutions join in four-hole bottle, start stirring, at being slowly warming up to 100 DEG C react 6 hours;
(2) when reaction solution is cooled to 75 DEG C, add acid for adjusting pH to 2.3, after then adding 600g phenol, react 2 hours at 95 DEG C, after reaction, the dehydration that heated up by reaction mixture, to temperature 160 DEG C, obtains thermoplasticity graphene phenolic-resin.
embodiment 2:
Compared with embodiment 1, unlike the graphene oxide adding 5 grams, 25 grams of hydrazine hydrates, 20 grams of Sodium dodecylbenzene sulfonatees.
embodiment 3:
Compared with embodiment 2, unlike adding 15 grams of hydrazine hydrates,
embodiment 4:
Compared with embodiment 2, unlike the Sodium dodecylbenzene sulfonate adding 10 grams.
embodiment 5:
Compared with embodiment 2, unlike adding 35 grams of hydrazine hydrates.
embodiment 6:
Compared with embodiment 2, unlike the Sodium dodecylbenzene sulfonate adding 5 grams.
Embodiment 7:
Compared with embodiment 1, unlike the graphene oxide adding 5 grams.
Embodiment 8:
Compared with embodiment 1, unlike the graphene oxide adding 10 grams.
Embodiment 9:
Compared with embodiment 1, unlike the graphene oxide adding 15 grams.
embodiment 10:
(1) by 1 gram of graphene oxide, 5 grams of hydrazine hydrates, 5 grams of Sodium dodecylbenzene sulfonatees, concentration is that the formaldehyde solution of 44%330 grams joins in four-hole bottle, starts stirring, reaction response 6 hours at being slowly warming up to 100 DEG C,
(2) when reaction solution is cooled to 75 DEG C, add acid for adjusting pH 1.7, after then adding 600 grams of phenol, react 3 hours at 95 DEG C, after reaction, the dehydration that heated up by reaction mixture, to temperature 160 DEG C, obtains thermoplasticity graphene phenolic-resin.
embodiment 11:
Compared with embodiment 10, unlike the dodecyl phenyl-hydrogen-sulfate acid sodium adding 20 grams
embodiment 12:
Compared with embodiment 10, unlike adding 5 grams of graphene oxides.
embodiment 13:
(1) by 1 gram of graphene oxide, 5 grams of hydrazine hydrates, 5 grams of Sodium dodecylbenzene sulfonatees, concentration be 44% 360 grams of formaldehyde solutions join in four-hole bottle, start stirring, at being slowly warming up to 100 DEG C react 6 hours;
(2), when reaction solution is cooled to 75 DEG C, acid adjustment PH to 2.0 is added, after then adding 600 grams of phenol, react 4 hours at 95 DEG C, after reaction, the dehydration that heated up by reaction mixture, to temperature 160 DEG C, obtains thermoplasticity graphene phenolic-resin.
comparative example 1
By 600g phenol, concentration be 44% 260 grams of formaldehyde solutions join in four-hole bottle, start stirring, add acid adjustment PH to 2.1, react 4 hours at being slowly warming up to 100 DEG C, reaction mixture is heated up dehydration to temperature 160 DEG C, add after 5 grams of graphene oxides stir and namely obtain thermoplasticity graphene phenolic-resin.
comparative example 2
By 600g phenol, concentration be 44% 260 grams of formaldehyde solutions join in four-hole bottle, start stirring, add acid adjustment PH to 2.1, react 4 hours at being slowly warming up to 100 DEG C, reaction mixture is heated up dehydration to temperature 160 DEG C, add 5 grams of graphene oxides, after 20 grams of Sodium dodecylbenzene sulfonatees stir, namely obtain thermoplasticity graphene phenolic-resin.
comparative example 3
By 600g phenol, concentration is 260 grams of formaldehyde of 44%, 5 grams of graphene oxides, 20 grams of Sodium dodecylbenzene sulfonate solution join in four-hole bottle, start stirring, add acid adjustment PH to 2.1, react 4 hours at being slowly warming up to 100 DEG C, reaction mixture is heated up dehydration to temperature 160 DEG C, obtain thermoplasticity graphene phenolic-resin.
comparative example 4
By 600g phenol, concentration is 260 grams of formaldehyde of 44%, 5 grams of graphene oxides, join in four-hole bottle, start stirring, add acid adjustment PH to 2.1, react 4 hours at being slowly warming up to 100 DEG C, reaction mixture is heated up dehydration to temperature 160 DEG C, add after 20 grams of Sodium dodecylbenzene sulfonatees stir and namely obtain thermoplasticity graphene phenolic-resin.
Resin in above embodiment, prepares the bakelite goods of corresponding embodiment according to the forming method described in summary of the invention.Test in the present invention comprises: molding shrinkage, shock strength, density, water-absorbent, volume coefficient.Its test data is as follows:
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not by the restriction of embodiment; other is any do not deviate from spirit of the present invention and principle under make change, modification, combination, substitute, simplify and all should be equivalent substitute mode, be included within protection scope of the present invention.
Claims (9)
1. a graphene phenolic-resin, it is characterized in that being obtained by following steps:
(1) graphene oxide, hydrazine hydrate, tensio-active agent, aldehyde solution are joined in reactor, stir, react at being warming up to 80 ~ 100 DEG C;
(2) reaction solution that step (1) obtains is cooled to 60 ~ 80 DEG C, regulates pH to 1.5-4.5, add phenol, be warming up to 85 ~ 100 DEG C of reactions, heat up dehydration, to obtain final product;
The weight ratio of graphene oxide, hydrazine hydrate, tensio-active agent, aldehyde and phenol is 1-10:1-10:1-20:100-160:600.
2. graphene phenolic-resin according to claim 1, is characterized in that at 80-100 DEG C, reacting 5-10 hour in step (1).
3. graphene phenolic-resin according to claim 1, is characterized in that in step (2) 85-100 DEG C of reaction 2 ~ 6 hours.
4. graphene phenolic-resin according to claim 1, is characterized in that the weight ratio of graphene oxide, hydrazine hydrate, tensio-active agent, aldehyde and phenol is 1-10:5:5-20:114-159:600.
5. graphene phenolic-resin according to claim 1, is characterized in that the ratio of graphite oxide olefinic carbon oxygen quantity is 1.8-3.4:1.
6. graphene phenolic-resin according to claim 1, is characterized in that phenol is more than one in phenol, cresols, xylenol, nonylphenol, dihydroxyphenyl propane, Bisphenol F, Resorcinol and cardanol; Aldehyde is more than one in formaldehyde, acetaldehyde and furfural; Tensio-active agent is more than one in aliphatic sulfonic salt and fatty alcohol sulfate class; An acidic catalyst is organic acid or mineral acid.
7. the application of graphene phenolic-resin in bakelite according to any one of a claim 1-6.
8. application according to claim 7, is characterized in that, by after the pulverizing of graphene phenolic-resin matrix material, mixing with wood powder, filler, solidifying agent and curing catalyst, after plasticizing, pulverizes and be prepared into bakelite.
9. application according to claim 8, is characterized in that plasticization temperature 80-110 DEG C, time 3-15 minute;
Bakelite is joined in mould, prepares the moulded parts of bakelite under the following conditions:
Pressing conditions: temperature 140-180 DEG C, pressure 8-20MPa, time 5-20 minute is shaping;
Post-treatment condition: 120 DEG C-140 DEG C, 2 hours; 140 DEG C-180 DEG C, 4 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106832758A (en) * | 2017-03-06 | 2017-06-13 | 东北大学秦皇岛分校 | A kind of Graphene/phenolic resin heat-conductive composite material and preparation method thereof |
| CN112778868A (en) * | 2021-01-04 | 2021-05-11 | 张茜茜 | Graphene modified phenolic resin composite coating with high thermal stability and preparation method thereof |
| CN115477532A (en) * | 2022-10-12 | 2022-12-16 | 上海烟草机械新场铸造有限责任公司 | Preparation method of water-soluble precision ceramic core for casting aluminum alloy |
-
2014
- 2014-12-11 CN CN201410755779.8A patent/CN104497241A/en active Pending
Non-Patent Citations (1)
| Title |
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| 原方圆等: "氧化石墨烯原位还原和修饰及其导电酚醛树脂纳米复合材料", 《2013年全国高分子学术论文报告会论文摘要集——主题J：高分子复合体系》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106832758A (en) * | 2017-03-06 | 2017-06-13 | 东北大学秦皇岛分校 | A kind of Graphene/phenolic resin heat-conductive composite material and preparation method thereof |
| CN106832758B (en) * | 2017-03-06 | 2019-04-12 | 东北大学秦皇岛分校 | A kind of graphene/phenolic resin heat-conductive composite material and preparation method thereof |
| CN112778868A (en) * | 2021-01-04 | 2021-05-11 | 张茜茜 | Graphene modified phenolic resin composite coating with high thermal stability and preparation method thereof |
| CN115477532A (en) * | 2022-10-12 | 2022-12-16 | 上海烟草机械新场铸造有限责任公司 | Preparation method of water-soluble precision ceramic core for casting aluminum alloy |
| CN115477532B (en) * | 2022-10-12 | 2023-04-25 | 上海烟草机械新场铸造有限责任公司 | Preparation method of water-soluble precise ceramic core for casting aluminum alloy |
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