CN104987658B - A kind of boron/anacardol/nano material modified phenolic resins material and preparation method thereof - Google Patents
A kind of boron/anacardol/nano material modified phenolic resins material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the modified field of phenolic resin, and in particular to a kind of boron/anacardol/nano material modified phenolic resins material and preparation method thereof.Boron/anacardol/nano material modified phenolic resins the material is prepared via a method which：(1) by anacardol, catalyst, boric acid and water entrainer, reflux water-dividing reacts 0.5~5h at 100~130 DEG C, is then dividedly in some parts phenol and continues to react 1~5h, then is warming up to 130~150 DEG C, distills out part water entrainer；(2) to addition paraformaldehyde, nano material and catalyst in the reactant of step (1) acquisition, reflux water-dividing reacts 1~5h at 90~130 DEG C of temperature, 140 DEG C are warming up to again and distill out remaining water entrainer, discharged, that is, obtain boron/anacardol/nano material modified phenolic resins.Boron/anacardol/the nano material modified phenolic resins have excellent thermal stability, mechanical property and frictional behaviour, can apply to friction material field.
Description
Technical field
The invention belongs to the modified field of phenolic resin, and in particular to a kind of boron/anacardol/nano-material modified phenolic aldehyde tree
Fat material and preparation method thereof.
Background technology
Used as one of three big synthesis thermosetting resins, its raw material is easy to get, synthesizes convenient, cheap phenolic resin, has
Good mechanical performance, against weather, corrosion resistance, water resistance and certain heat resistance, are widely used in communications and transportation, aviation
The industries such as industry, military equipment, electronic apparatus.But with technologies such as industrial expansion, particularly auto industry and bullet trains
High Performance Phenolic Resins are proposed new requirement by innovation.Traditional pure phenolic resin due to the phenolic hydroxyl group with easy oxidation and
Methylene and easily aoxidize, its heat resistance is affected, secondly the not good use scope that also limit it of toughness.Modern various cars
And mechanical applying working condition condition, the friction material (such as vehicle brake piece, clutch) with phenolic resin as base material need compared with
Heat decomposition temperature high, good hot restorative, enough coefficient of friction, preferable wearability and relatively low noise.Traditional phenol
Urea formaldehyde fragility is big, poor toughness, heat resistance are not enough, limits the exploitation of high-quality friction material.At present, high-quality friction material
Import is relied primarily on phenolic resin, the development of China's friction material industry is strongly limit.Therefore it is badly in need of exploitation high-performance phenol
Urea formaldehyde.
Boron modified phenolic resin is appeared in as a kind of preferably modified phenolic resin of heat resistance the fifties in last century
Then, the country such as English, day, moral, method and Soviet Union is successively studied, and domestic University Of Hebei and the factory of Beijing 251 are the sixties in the U.S.
Later stage, the seventies have developed boron modified phenolic resin for military project, be also used for other industries.Boric acid modified phenolic resin is with phenol
Class, boron compound, aldehydes react generation under certain catalytic condition.Because the bond energy of B-O keys is higher than C-O keys, so boron
The heat resistance and mechanical property of phenol-formaldehyde resin modified are better than phenolic resin, possess the superiority required for making friction material
Can, boron modified phenolic resin can be produced with three kinds of methods：(1) boric acid phenolic ester method, boric acid first generates boric acid with phenol reactant
Phenolic ester, then again with formaldehyde or polyformaldehyde reaction, generate boron modification resin；(2) saligenin method, phenol first reacts life with formaldehyde
Into saligenin, then (100~110 DEG C) and acid reaction at a higher temperature, and the moisture in reaction is steamed, obtain final product boron and change
Property phenolic resin；(3) blending method, phenolic resin and boride are blended, and both just react in product curing molding.Boron
Phenol-formaldehyde resin modified is not widely applied at home so far, and major reason is that above-mentioned three kinds of methods have the following disadvantages：Boron
The esterification of sour phenolic ester method mesoboric acid is more difficult, and reaction condition is harsher, at the same the reaction of boric acid phenolic ester and aldehyde according to
Formalin, boric acid phenolic ester facile hydrolysis, modified effect is restricted, and using paraformaldehyde, the viscosity of system is very big, and mass transfer is passed
Hot difficult, course of reaction is difficult to control to, easy implode, and reaction generation water, will also result in boric acid phenol ester hydrolysis；Saligenin method
The reaction later stage has that viscosity is big, is difficult to control to；, there is obvious microfacies in blending method boric acid and the mixing that phenolic resin is physically
Separate, two-phase Interaction Force is poor, easily forms larger " island " structure, and both are in segment level or molecular level
It is incompatible, prevent mixed reactant from comprehensive engagement and fully react, and it is hot-forming during boron it is anti-with phenolic resin
Shorter between seasonable, not thoroughly, modified effect is limited for reaction.
The application at home of current boron modified phenolic resin is not also universal, in addition to preparation technology defect, matches somebody with somebody in its condensation polymer
The unsaturated easily deliquescence of digit, home products cannot be crushed mostly, and solvent need to be added to be made liquid phenolic resin, can only be applied wet
Method produces brake block, and most domestic friction material manufacturing enterprise uses dry process, and scope is used which has limited it.Together
When, the Boron contents that current boron bakelite resin is added generally will not be too high, the Boron contents of existing commercially available boron bakelite resin
Only 3% or so, Boron contents are not high, make in boron bakelite resin structure, and adjacent phenyl rings are most of to be still largely connected by methylene, its
Fragility is still very big, have impact on the combination property of its friction material.
Anacardol is the liquid of vicidity obtained by extraction from ripe cashew nut shell, and its primary structure is meta upper band one
The monoene of 15 carbon or the phenol of diolefin long-chain, thus the existing phenolic compound of anacardol feature, have aliphatic compound again
Flexibility, improving phenolic resin with it can improve the toughness of phenolic resin.But, there is waist in current Cardanol Modified PF Resin
Fruit phenol activity is low, and reaction thoroughly, the problems such as phenolic resin molecular weight is relatively low, does not cause its performance improvement to be restricted.
Nano material has unique physicochemical properties, when being added in polymer, its dimensional effect, skin effect,
Macroscopical tunnel-effect can make polymer performance be increased dramatically, and be a kind of new material with broad prospect of application.
The content of the invention
The present invention is in view of the shortcomings of the prior art, it is therefore intended that provide a kind of boron/anacardol/nano-material modified phenolic aldehyde tree
Fat material and preparation method thereof.
For achieving the above object, the technical solution adopted in the present invention is：
A kind of preparation method of boron/anacardol/nano material modified phenolic resins material, it is characterised in that including as follows
Step：
(1) esterification of anacardol/phenol-boric acid：By anacardol, catalyst, boric acid and water entrainer 100~130
Reflux water-dividing reacts 0.5~5h at a temperature of DEG C, is then dividedly in some parts phenol and continues to react 1~5h, after reaction terminates, is warming up to
130~150 DEG C, distill out part water entrainer；
(2) polymerisation：To paraformaldehyde, nano material and catalyst is added in the reactant that step (1) is obtained, in temperature
Reflux water-dividing reacts 1~5h at a temperature of 90~130 DEG C of degree, after reaction terminates, tape remaining is distilled out after being warming up to 140~150 DEG C
Aqua, is subsequently reduced to room temperature discharging, that is, obtain boron/anacardol/nano material modified phenolic resins.
By such scheme, the nano material is the SiO modified through silane coupler2。
By such scheme, the mass ratio of the phenol, boric acid, anacardol and paraformaldehyde is 100：7~40：0.01~
40：16~64, the consumption of the nano material is the 5~20% of phenol quality.
By such scheme, step (1) described catalyst be acetic acid, oxalic acid, hydrochloric acid, sulfuric acid, trifluoroacetic acid, methane-siliconic acid and
In ethyl silicic acid one or more.
By such scheme, step (2) described catalyst is inorganic salts, the inorganic salts of manganese, the inorganic salts of copper, the nothing of zinc of barium
One or more in the inorganic salts of machine salt, the inorganic salts of calcium and magnesium.
By such scheme, the consumption of step (1) described catalyst is the 1~10% of phenol quality, step (2) described catalysis
The consumption of agent is the 0.01~10% of phenol usage.
Being dividedly in some parts phenol by such scheme, described in step (1) is：Divide 5 batches of addition phenol, every batch adds phase homogenous quantities
Phenol.
By such scheme, the water entrainer is conventional esterification water entrainer, such as benzene, toluene.
By such scheme, the consumption of the water entrainer is 0.5~5 times of phenol quality.
By such scheme, the amount of the part water entrainer distilled out in step (1) is the 0.1~0.9 of water entrainer gross mass.
Boron/anacardol that the preparation method of above-mentioned boron/anacardol/nano material modified phenolic resins material is prepared/
Nano material modified phenolic resins material.
In preparation method of the present invention, in the esterification stage of anacardol/phenol-boric acid, anacardol and boric acid are allowed first
Reaction, then phenol is dividedly in some parts, not only contribute to increase the conversion ratio of anacardol, the generation of pf resin of low molecular weight is reduced,
Free phenol content is also set to be reduced to 0.1~2% by common 4~6% simultaneously, this is conducive to strengthening the heat-resisting of phenol-formaldehyde resin modified
Property and character of heat-fading；In polymerization stage, inorganic metal salt catalyst is added, can effectively control polymerization rate, it is to avoid
Because reaction system viscosity is excessive, system mass transfer and heat transfer are influenceed, effectively increase the conversion ratio of boric acid, make gained boron, anacardol
Phenol-formaldehyde resin modified has Boron contents higher, increases its heat resistance；Meanwhile, in polymerization stage, the present invention stays remaining part point
Water entrainer, to reduce reaction system viscosity, can effectively prevent reaction system mass transfer and heat transfer difficult from causing system implode, while
Reflux water-dividing, removes the water that condensation reaction is produced, and increases anacardol, the conversion ratio of boric acid.
Beneficial effects of the present invention are as follows：
(1) present invention is using boric acid, anacardol and Nano-meter SiO_22Phenol-formaldehyde resin modified, comprehensive boron modification, modified by cardanol
With the advantage of nano material modified phenolic resins, while improving the heat resistance and toughness of phenolic resin；
(2) boron/anacardol/Nano-meter SiO_2 that the present invention is prepared2The ligancy of boron element is most in phenol-formaldehyde resin modified
Saturation can be reached, can effectively suppress the deliquescence of phenol-formaldehyde resin modified, effectively improve the stability of phenol-formaldehyde resin modified storage, can be with
Dry process friction material technique is applied to, the use scope of phenolic resin is expanded；
(3) preparation method production equipment of the present invention is simple, and course of reaction has controllability and quantification, and industrialization is held
Easily；Boron/anacardol/nano material modified phenolic resins the material for preparing has excellent thermal stability, mechanical property
And frictional behaviour, friction material field is can apply to, such as various automobiles, the brake block of rail locomotive and clutch disc.
Brief description of the drawings
Fig. 1 is phenol-formaldehyde resin modified TG figures in the embodiment of the present invention 1.
Fig. 2 is phenol-formaldehyde resin modified TG figures in the embodiment of the present invention 2.
Fig. 3 is phenol-formaldehyde resin modified TG figures in the embodiment of the present invention 3.
Fig. 4 is phenol-formaldehyde resin modified TG figures in the embodiment of the present invention 4.
Specific embodiment
For a better understanding of the present invention, it is with reference to the embodiment content that the present invention is furture elucidated but of the invention
Content is not limited solely to the following examples.
Embodiment 1
A kind of boron/anacardol/nano material modified phenolic resins material, is prepared via a method which to obtain：
(1) esterification of anacardol/phenol-boric acid：By 0.01 part of anacardol, 7 parts of boric acid, 1 part of acetic acid and 50
Part water entrainer reflux water-dividing reaction 3h at a temperature of 100 DEG C, then divides 5 batches of every batch of additions 20 parts of phenol, continues to react 3h, then rise
Temperature distills out 5 parts of water entrainers to 130 DEG C, is then cooled to less than 60 DEG C；
(2) polymerisation：To added in the reactant that step (1) is obtained 16 parts of paraformaldehydes, 5 parts repaiied through silane coupler
The Nano-meter SiO_2 of decorations2, 0.01 part of calcium chloride, the reflux water-dividing reaction 5h at a temperature of 90 DEG C, after reaction terminates, after being warming up to 140 DEG C
Remaining water entrainer is distilled out, room temperature discharging is subsequently reduced to, that is, obtains boron/anacardol/nano material modified phenolic resins.
Embodiment 2
A kind of boron/anacardol/nano material modified phenolic resins material, is prepared via a method which to obtain：
(1) esterification of anacardol/phenol-boric acid：By 6 parts of anacardols, 15 parts of boric acid, 2 parts of oxalic acid, 1 part of hydrochloric acid, 1
Part sulfuric acid, 100 parts of water entrainer the reflux water-dividing reaction 0.5h at a temperature of 115 DEG C, then divide 5 batches of every batch of additions 20 parts of phenol,
Continue to react 5h, be warming up to 140 DEG C, distill out 90 parts of water entrainers, be then cooled to less than 60 DEG C；
(2) polymerisation：To added in the reactant that step (1) is obtained 25 parts of paraformaldehydes, 8 parts repaiied through silane coupler
The Nano-meter SiO_2 of decorations2, 1.5 parts of barium chloride, 1.3 parts of manganese sulfate, the reflux water-dividing reaction 1h at a temperature of 105 DEG C, reaction terminates
Afterwards, remaining water entrainer is distilled out after being warming up to 140 DEG C, room temperature discharging is subsequently reduced to, that is, is obtained boron/anacardol/nano material and is changed
Property phenolic resin.
Embodiment 3
A kind of boron/anacardol/nano material modified phenolic resins material, is prepared via a method which to obtain：
(1) esterification of anacardol/phenol-boric acid：By 40 parts of anacardols, 22 parts of boric acid, 2 parts of oxalic acid, 3.2 parts of trifluoros
Acetic acid, 2.6 parts of methane-siliconic acid, 500 parts of water entrainer reflux water-dividing reaction 5h at a temperature of 130 DEG C, then divide 5 batches of every batch of additions
20 parts of phenol, continue to be warming up to 140 DEG C after reacting 1h, distill out 25 parts of water entrainers, are then cooled to less than 60 DEG C；
(2) polymerisation：To adding 54 parts of paraformaldehydes in the reactant that step (1) is obtained, 16 parts through silane coupler
The Nano-meter SiO_2 of modification2, 1 part of copper chloride, 6.2 parts of magnesium chloride, the reflux water-dividing reaction 2.5h at a temperature of 130 DEG C, reaction knot
Shu Hou, distills out remaining water entrainer after being warming up to 140 DEG C, be subsequently reduced to room temperature discharging, that is, obtain boron/anacardol/nano material
Phenol-formaldehyde resin modified.
Embodiment 4
A kind of boron/anacardol/nano material modified phenolic resins material, is prepared via a method which to obtain：
(1) esterification of anacardol/phenol-boric acid：By 23 parts of anacardols, 40 parts of boric acid, 5 parts of sulfuric acid, 3 parts of oxalic acid, 2
Part ethyl silicic acid, 340 parts of water entrainer reflux water-dividings reaction 4h at a temperature of 125 DEG C, then divide 5 batches of every batch of additions 20 parts of phenol,
Continue to be warming up to 150 DEG C after reacting 1h, distill out 200 parts of water entrainers, be then cooled to less than 60 DEG C；
(2) polymerisation：To adding 64 parts of paraformaldehydes in the reactant that step (1) is obtained, 20 parts through silane coupler
The Nano-meter SiO_2 of modification2, 2 parts of magnesium chloride, 3 parts of barium chloride, 5 parts of copper chloride, the reflux water-dividing reaction at a temperature of 120 DEG C
3.5h, after reaction terminates, distills out remaining water entrainer after being warming up to 150 DEG C, be subsequently reduced to room temperature discharging, that is, obtain boron/cashew nut
Phenol/nano material modified phenolic resins.
1 boron of table/anacardol/Nano-meter SiO_22The performance of phenol-formaldehyde resin modified
| Performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Boron contents/% | 5.9 | 9.8 | 9.6 | 16.2 |
| Free phenol/% | 0.8 | 1.5 | 2.3 | 2.1 |
| Polymerization time/s | 66.4 | 75.3 | 49.2 | 88.8 |
| Fluidity/mm | 33.20 | 67.24 | 88.46 | 28.10 |
| Softening point/DEG C | 85.2 | 92.6 | 100.4 | 97.5 |
| Ash content/% | 0.23 | 0.12 | 0.28 | 0.43 |
Using conventional formulation, boron/anacardol/nano material modified phenolic resins are prepared as base material and rubbed with embodiment 1~4
Material is wiped, according to the performance of the method testing friction materials of GB 5763-1998, its performance is as shown in the table：
The Properties of Friction Materials of 2 embodiment of table 1~4
The result of table 2 is illustrated：Boron/anacardol that the present invention is prepared/nano material modified phenolic resins material tool
There are excellent thermal stability, mechanical property and frictional behaviour, can apply to friction material field, such as various automobiles, track
The brake block and clutch disc of locomotive.
Obviously, above-described embodiment is only intended to clearly illustrate made example, and not to the limitation of implementation method.It is right
For those of ordinary skill in the art, can also make on the basis of the above description other multi-forms change or
Change.There is no need and unable to be exhaustive to all of implementation method.And the obvious change or change therefore amplified
Move within still in the protection domain of the invention.
Claims (6)
1. a kind of preparation method of boron/anacardol/nano material modified phenolic resins material, it is characterised in that including following step
Suddenly：
（1）The esterification of anacardol/phenol-boric acid：By anacardol, catalyst, boric acid and water entrainer in 100 ~ 130 DEG C of temperature
Lower reflux water-dividing reacts 0.5 ~ 5h, is then dividedly in some parts phenol and continues to react 1 ~ 5h, after reaction terminates, is warming up to 130 ~ 150 DEG C,
Distill out part water entrainer；The phenol that is dividedly in some parts is：Divide 5 batches of addition phenol, every batch of phenol of addition phase homogenous quantities；
（2）Polymerisation：To step（1）Paraformaldehyde, nano material and catalyst are added in the reactant of acquisition, in temperature 90
Reflux water-dividing reacts 1 ~ 5h at a temperature of ~ 130 DEG C, after reaction terminates, is warming up to 140 DEG C and distills out remaining water entrainer, is subsequently reduced to
Room temperature discharges, that is, obtain boron/anacardol/nano material modified phenolic resins；
The nano material is the SiO modified through silane coupler2；
The mass ratio of the phenol, boric acid, anacardol and paraformaldehyde is 100：7~40：0.01 ~40：16 ~ 64, the nanometer
The quality of material is the 5 ~ 20% of phenol quality.
2. preparation method according to claim 1, it is characterised in that step（1）The catalyst is acetic acid, oxalic acid, three
In fluoroacetic acid, methane-siliconic acid and ethyl silicic acid one or more.
3. preparation method according to claim 1, it is characterised in that step（2）The catalyst is inorganic salts, the manganese of barium
Inorganic salts, the inorganic salts of copper, the inorganic salts of zinc, the inorganic salts of the inorganic salts of calcium and magnesium in one or more.
4. preparation method according to claim 1, it is characterised in that step（1）Described in catalyst consumption be phenol
The 1 ~ 10% of quality, step（2）Described in catalyst consumption for phenol usage 0.01 ~ 10%.
5. preparation method according to claim 1, it is characterised in that the consumption of the water entrainer for phenol quality 0.5 ~
5 times.
6. preparation method according to claim 1, it is characterised in that step（1）The quality of the part water entrainer for distilling out
It is the 0.1 ~ 0.9 of water entrainer gross mass.
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| CN105837769B (en) * | 2016-05-16 | 2018-06-29 | 华南理工大学 | High water-soluble multiple thermostable phenolic resin of low burst size of methanal and preparation method thereof |
| CN106565923B (en) * | 2016-11-02 | 2018-10-30 | 中国林业科学研究院林产化学工业研究所 | Siliceous epoxy cashew nut phenolic group phenolic resin and its preparation method and application |
| CN107099009B (en) * | 2017-05-15 | 2019-01-25 | 北京林业大学 | Boric acid/pyrolysis oil is total to the preparation method of modified artificial plate thermosetting phenolic resin |
| CN109161050A (en) * | 2018-07-19 | 2019-01-08 | 中国林业科学研究院林产化学工业研究所 | Silanization organic phenol-nano silica system and its preparation method and application |
| CN110330613A (en) * | 2019-07-18 | 2019-10-15 | 河北泽田化工有限公司 | A kind of phenol-formaldehyde resin modified and preparation method thereof |
| CN112409750B (en) * | 2020-11-16 | 2022-06-14 | 杭州汉乐科新材料科技有限公司 | Engineering crane motor brake disc material and preparation method thereof |
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| CN103320092B (en) * | 2013-06-14 | 2015-04-22 | 陕西科技大学 | Method for preparing wet friction material of nano silicon carbide modified carbon cloth |
| CN103726399B (en) * | 2013-12-19 | 2015-09-30 | 陕西科技大学 | A kind of blended fiber strengthens paper friction material and preparation method thereof |
| CN104693677B (en) * | 2015-03-20 | 2016-09-07 | 福州大学 | A kind of CNT/resin-matrix friction material and preparation method thereof |
| CN104762062A (en) * | 2015-04-15 | 2015-07-08 | 桂林理工大学 | Method for preparing natural plant resource composite modified phenolic resin-based friction material |
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