CN103756249B - Modified phenolic resin and synthesis method thereof - Google Patents
Modified phenolic resin and synthesis method thereof Download PDFInfo
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- CN103756249B CN103756249B CN201410010590.6A CN201410010590A CN103756249B CN 103756249 B CN103756249 B CN 103756249B CN 201410010590 A CN201410010590 A CN 201410010590A CN 103756249 B CN103756249 B CN 103756249B
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Abstract
The invention relates to a modified phenolic resin and a synthesis method thereof, and particularly relates to a nano copper particle-butadiene-acrylonitrile rubber combined modified phenolic resin and a preparation method thereof. The modified phenolic resin is a thermosetting resin, and contains 2-4 percent of nano copper particles and 6-10 percent of butadiene-acrylonitrile rubber. The preparation method of the modified phenolic resin comprises the following steps: (1), preparing a copper crystal seed; (2), preparing a phenolic resin prepolymer; and (3) preparing the modified phenolic resin. According to the modified phenolic resin and the preparation method provided by the invention, compared with pure phenolic resin, the nano copper particle and butadiene-acrylonitrile rubber combined modified phenolic resin has the advantages that the flexibility, the thermal property and the friction wear property are more excellent, wherein the thermal property and the mechanical property are remarkably improved, the thermal decomposition temperature can be increased by above 60 DEG C, and the impact strength can be improved by above 80 percent; the modified phenolic resin is widely applicable to manufacturing of a dry type or wet type organic friction material product with high performance.
Description
Technical field
The invention belongs to polymer modification technology, it is related to a kind of phenol-formaldehyde resin modified and preparation method thereof, particularly to one
Plant combined modified phenolic resin of nanometer copper particle nitrile rubber and preparation method thereof.
Background technology
Phenols and aldehyde condensation polymer product are commonly referred to as phenolic resin.Phenolic resin is to realize industrialized production in the world earliest
Synthetic resin, exceeded so far a century history.Be easy to get due to its raw material, cheap, production technology and equipment simple, and
Product has excellent mechanicalness, thermostability, tolerance to cold, dimensional stability, molding processibility, anti-flammability and low smoke, because
This it become the indispensable material of industrial department, be widely used in molded composite material, emery wheel, binding agent and coating etc..Fat
The trielement composite material that organic-type friction material is made up of binding agent, reinforcing fiber and filler, wherein binding agent are the quickest to heat
The constituent element of sense, is also the major components determining friction material toughness quality.Used in organic-type friction material, binding agent is main
It is phenolic resin.
Weak link on phenolic resin structure is phenolic hydroxyl group and methylene easily aoxidizes, and begins to heat at 250 DEG C about
Decompose；In addition, the elongation percentage of phenolic resin is low, fragility is big, and therefore, pure phenolic resin can not keep abreast of the times.It is full
The needs of the new and high technologies such as sufficient automobile, electronics, Aero-Space and national defense industry, are modified to phenolic resin, improve its toughness
It is the developing direction of phenolic resin with hot property.At present, the approach both at home and abroad phenolic resin being modified studying mainly has two
Individual：One be additional flexible polymer or in phenol structure introduce flexible structure unit, to improve the toughness of phenol-formaldehyde resin modified；Two
It is to improve heteroaromatic content or the construction unit introducing other polymer or simple substance in phenolic resin structure, to improve phenolic resin
Hot property.Obviously, both modifications approach is difficult to make the hot property of phenolic resin and toughness be improved simultaneously.
Rubber toughened phenolic resin is modal toughened system, early studies have reported that both at home and abroad, selects solid-state more（Block
Or it is granular）The rubber such as Macromolecule acrylonitrile, butylbenzene are toughness reinforcing to phenolic resin, and in terms of technological angle, rubber toughened phenolic resin belongs to thing
Reason mixes modification, but its grafting of various degrees or block copolymerization reaction in the curing process；Rubber toughened phenolic aldehyde tree
Fat effect is significant, but to reach obvious toughening effect, the addition of rubber is big, and this not only can affect the resistance to of phenolic resin
Hot, also can affect the compatibility between phenolic resin simultaneously, make the uneven of rubber disperse, otherwise then affect toughening effect, this
Outer production cost also can increase.Nano material is the hitech materials that nearly more than ten years new development is got up.Because its size is little（Logical
It is often 1～100nmol/L）, specific surface area big, there is skin effect, bulk effect, quantum effect and macro quanta tunnel effect
Deng, thus compared with conventional material, there are many special performances, and when being applied to traditional material modification, can be by a relatively large margin
Ground changes the macro property of original material.Phenolic resin is modified be that one kind of new development in recent years changes using nano material
Property method, this method can make the hot property of phenolic resin and toughness be improved simultaneously, thus, have before luring man-based development
Scape, becomes the study hotspot in this field.At present, domestic have the units such as Institutes Of Technology Of Nanjing that nano material modified phenolic resins are entered
Gone preliminary study, using nano material mainly have the inorganic nano-particles such as TiO, AIO, SiO and clay, the technique master of employing
If being simultaneously introduced the raw material of the nano material preparing and synthetic resin in reaction vessel, to the building-up process in resin
Middle nano material is dispersed in resin.This kind of technique is difficult to nanoparticle to be dispersed in resin, and it is mainly former
Because being that synthetic resin will be carried out under high gentle agitation, the nanoparticle of addition is easily made to reunite.Another kind of technique is to adopt physics
Mixing method, by mechanical agitation, nanoparticle is mixed in phenolic resin, and because resin viscosity is big, nanoparticle is also difficult to uniformly
It is distributed in phenolic resin.Because the reunion of nano material is so as to excellent performance can not be played, thus, to phenolic aldehyde tree
The improvement result of lipid energy is inconspicuous.Copper powder or fiber have excellent heat conductivity and friction and wear behavior, are organic rubbing
Wipe conventional metal packing in material.So, do changing of organic-type friction material binding agent phenolic resin from nanometer copper particle
Property agent, can make full use of excellent properties and the nano material characteristic of copper, improve hot property and the friction and wear behavior of phenolic resin.
Inventor once developed nanometer copper particle and nano-alumina fiber phenol-formaldehyde resin modified, and the nanometer copper particle of use is in phenolic aldehyde
Generate through reduction reaction in resins synthesis reaction system, the reproducibility of the reducing agent formaldehyde due to adopting is weaker, so, should be also
Former reaction need to be reacted under 75 DEG C～85 DEG C higher temperatures, causes the nanometer copper particle size of generation uneven, and easy group
Poly-.
Content of the invention
The technical problem to be solved in the present invention is the drawbacks described above how overcoming prior art, provides a kind of nanometer copper particle
Combined modified phenolic resin and preparation method thereof with nitrile rubber.
For solving above-mentioned technical problem, this phenol-formaldehyde resin modified is thermosetting resin, and it includes 2%～4% nanometer copper particle
The sub nitrile rubber with 6%～10%.
As optimization, described nanometer copper particle adopts crystal seed reducing process to prepare, and it is in phenolic resin building-up process situ
Generate.It is so designed that it is ensured that nanometer copper particle size is homogeneous, good dispersion, do not reunite, do not aoxidize；In addition, it is possible to decrease technique becomes
This, have commercial viability.
As optimization, described nitrile rubber is LNBR.It is so designed that, LNBR closes in phenolic resin
The one-tenth process initial stage adds reaction system, because its molecular weight is little, more easily fuses with phenolic resin phase, and can uniformly divide
It is dispersed in phenolic resin, and produce chemical action and phenolic resin macromole between.Make phenol-formaldehyde resin modified good toughness, hot property
Excellent with friction and wear behavior it is adaptable to manufacture high performance dry type or wet type organic-type friction material product.
The preparation method of this phenol-formaldehyde resin modified comprises the following steps,
Step（1）The preparation of copper crystal seed：Prepare solution of potassium borohydride and the copper sulfate containing disodiumedetate
Solution；Then, under room temperature and stirring condition, solution of potassium borohydride is added drop-wise in copper-bath, to the color of mixed liquor
Till being changed into yellow green, obtain final product copper crystal seed liquid；
Step（2）Prepared by phenolic resin performed polymer：By phenol, formaldehyde, sodium hydroxide and LNBR in proportion
Add in reactive modified phenolic resin container, reacted under conditions of 95 DEG C ± 3 DEG C and stirring, react and reach to the conversion ratio of phenol
To 45～65%, then rapidly reactor temperature is down to 50 DEG C ± 5 DEG C, vacuum dehydration, obtain final product phenolic resin performed polymer；
Step（3）Prepared by phenol-formaldehyde resin modified：Under conditions of stirring, by step（1）The copper crystal seed liquid of preparation adds
To in reactive modified phenolic resin container, adjust the pH value of reactant liquor to 8～10 using sodium hydroxide solution；Then, at 50 DEG C ± 5 DEG C
Under conditions of stirring, the copper-bath comprising chelating agent and deflocculant is added dropwise in reaction vessel, reacts 60min
～90min, vacuum dehydration, add ethanol in reactant liquor, stir, obtain final product the acrylonitrile butadiene rubber modified phenolic aldehyde of nanometer copper particle
Resin.
As optimization, step（1）Described solution of potassium borohydride concentration is 0.04～0.08mol/L, copper-bath concentration
For 0.02～0.04mol/L, the addition of disodiumedetate is based on 2 times of copper sulfate mole.
As optimization, step（2）Described phenol is 1 with the mol ratio of formaldehyde:1.5～2；Sodium hydroxide is used to adjust molten
The pH value size of liquid, its solution concentration is 20%, and addition is so that solution ph reaches 8～10 is defined；The adding of LNBR
Dosage is 6%～10%；Vacuum is 75～95kpa.
As optimization, step（3）The concentration of described copper-bath is 0.10～0.25mol/L, and its addition presses phenol
Mole 2%～4% is counted；Chelating agent adopts disodiumedetate, and its addition is based on 2 times of copper sulfate mole；Colloid
Stabilizer adopts Polyvinylpyrrolidone, and its addition is 0.8%～1.2%；The addition of copper crystal seed liquid presses copper-bath body
10～30% long-pending meters, the concentration of sodium hydroxide is 20%；Vacuum is 75～95kpa；The addition of ethanol presses reactant liquor volume
10～15% meter.
In this preparation method：1）Described Nanometer Copper is anti-with the reduction of copper sulfate using novolak resin raw material formaldehyde
Should be obtained, this reaction be in low temperature, have crystal seed under conditions of carry out, the nanometer copper particle size of generation is easily controlled and homogeneous.
Nanometer copper particle is to generate in phenolic resin building-up process situ, and phenolic resin, nitrile rubber and Polyvinylpyrrolidone are big
Molecule all has certain protection to it so as to being difficult to reunite and aoxidizing, and is evenly distributed in phenolic resin.2）Described butyronitrile rubber
Glue adopts the less LNBR of number-average molecular weight, starts to add reaction system what phenolic resin synthesized.Due to height
Gentle agitation acts on, and nitrile rubber may be homogenously dispersed in phenolic resin macromole, and its itrile group and double bond can be with phenolic resin
There is chemical action in methylol, improve the compatibility of itself and phenolic resin, advantageously form strong interfacial interaction.3）Institute
Stating nanometer copper particle is in phenolic resin synthetic system, carries out reduction reaction using inexpensive formaldehyde and copper sulfate and makes, separately
Outward, nanometer copper particle without separate with mother solution and be dried etc., thus, nanometer copper particle low production cost.
The having the beneficial effect that of this phenol-formaldehyde resin modified and preparation method thereof：
1st, because nanometer copper particle has superior heat conductivity in itself and is uniformly dispersed in resin, thus can substantially improve
The heat conductivity of resin, this point is even more important to organic-type friction material.Friction surface meeting during organic-type friction material uses
Produce substantial amounts of heat, if these heats can distribute so that it may make the temperature of friction surface reduce in time from friction surface,
The thermograde of organic-type friction material reduces, thus being equivalent to the use temperature that indirectly improve organic-type friction material.
2nd, when rubbing with antithesis, nanometer copper particle will form layer of surface film in surface of friction pair to organic-type friction material,
This film can make organic-type friction material and the wearability of antithesis be greatly improved.
3rd, the more purely a modified phenolic resin of the hot property of phenol-formaldehyde resin modified improves a lot, and heat conductivity dramatically increases, heat point
Solution temperature can improve 50 DEG C～60 DEG C.
4th, nanometer copper particle has very high catalysis activity to the synthetic reaction of phenol-formaldehyde resin modified.Identical in other conditions
In the case of, the resins synthesis time can be made to shorten about 30% or reduce by 20 DEG C～30 DEG C of synthesis temperature.
5th, the nitrile rubber in the present invention adopts LNBR, may be homogenously dispersed in phenolic resin, and and phenolic aldehyde
Produce strong interface interaction between resin macromole, so that the toughness of phenol-formaldehyde resin modified is greatly improved, its impact strength can carry
High 80-110%.
A kind of phenol-formaldehyde resin modified of the present invention and preparation method thereof adopts nanometer copper particle and the combined modified phenol of nitrile rubber
Urea formaldehyde, compared with pure phenolic resin, toughness, hot property and friction and wear behavior are more excellent, wherein hot property and mechanical property
All it is significantly increased, heat decomposition temperature can improve more than 60 DEG C, impact strength can improve more than 80%, be widely used in manufacturing height
The dry type of performance or wet type organic-type friction material product.
Specific embodiment
This phenol-formaldehyde resin modified includes 2～4% nanometer copper particle and 6～10% nitrile rubber.
The synthesis route of this phenol-formaldehyde resin modified is：
The preparation of the preparation → phenol-formaldehyde resin modified of the preparation of copper crystal seed → phenolic resin performed polymer；Specifically include following step
Suddenly：
Step（1）The preparation of copper crystal seed：Weigh 7.5g copper sulphate pentahydrate and 22.3g disodiumedetate, put into
In beaker, plus distilled water stirring and dissolving makes the solution A of 1000mL；Weigh 2.7g potassium borohydride, put in beaker, plus distilled water
Stirring and dissolving makes the B solution of 1000mL；Solution A is placed on stirring on magnetic stirring apparatuss, then solution B is dropwise instilled solution A
In, stop when solution becomes blackish green, prepared copper crystal seed liquid.
Step（2）The preparation of phenolic resin performed polymer：1. by the phenol of fusing：49g, 36% formaldehyde：166.9g, liquid
Nitrile rubber -26：17g adds in reaction vessel, is warming up to 50 DEG C, starts stirring 10min；2. add 20% in reaction vessel
Sodium hydroxide solution, surveys pH value, when reaching 9, stops adding；3. controlling reaction temperature, at 95 DEG C ± 3 DEG C, carries out backflow anti-
Should, 30min；4. rapidly reaction temperature is down to 50 DEG C ± 5 DEG C, holding vacuum is 75～95kpa, carries out decompression dehydration
20min, that is, be obtained phenolic resin performed polymer.
Step（2）The preparation of phenol-formaldehyde resin modified：1. weigh 3.7g copper sulphate pentahydrate, disodiumedetate 11g,
Polyvinylpyrrolidone 0.75g, puts in beaker, plus distilled water stirring and dissolving makes the C solution of 75mL；2. in the condition of stirring
Under, 50mL copper crystal seed liquid is added in reactive modified phenolic resin container, adjusts the pH value of reactant liquor to 8 using sodium hydroxide solution
～10；3. add 20% sodium hydroxide solution in reaction vessel, survey pH value, when reaching 9, stop adding；4. at 50 DEG C ± 5
DEG C and stirring under conditions of, C solution is added dropwise in reaction vessel, react 80min；5. stop stirring, at 50 DEG C ± 5 DEG C with very
Under the conditions of reciprocal of duty cycle is 86.66～94.89kpa, carry out decompression dehydration 20min, add ethanol 10mL in reactant liquor, stirring is all
Even, obtain final product this nanometer copper particle nitrile rubber modified phenolic resin.
It can be professional and technical personnel in the field's realization or use that above-mentioned embodiment is intended to illustrate the present invention, to above-mentioned
Embodiment is modified and be will be apparent from for those skilled in the art, therefore the present invention includes but is not limited to
Above-mentioned embodiment, any meet the claims or description description, meet with principles disclosed herein and novelty,
The method of inventive features, technique, product, each fall within protection scope of the present invention.
Claims (1)
1. a kind of phenol-formaldehyde resin modified, described phenol-formaldehyde resin modified is thermosetting resin, it is characterized in that：Phenol-formaldehyde resin modified includes
2%～4% nanometer copper particle and 6%～10% nitrile rubber；
The preparation method of described phenol-formaldehyde resin modified comprises the following steps,
The preparation of step (1) copper crystal seed：Prepare solution of potassium borohydride and the copper-bath containing disodiumedetate；
Then, under room temperature and stirring condition, solution of potassium borohydride is added drop-wise in copper-bath, the color to mixed liquor is changed into yellow
Till green, obtain final product copper crystal seed liquid；Described solution of potassium borohydride concentration is 0.04～0.08mol/L, and copper-bath concentration is
0.02～0.04mol/L, the addition of disodiumedetate is based on 2 times of copper sulfate mole；
Prepared by step (2) phenolic resin performed polymer：Phenol, formaldehyde, sodium hydroxide and LNBR are proportionally added into
In reactive modified phenolic resin container, reacted under conditions of 95 DEG C ± 3 DEG C and stirring, react and reach 45 to the conversion ratio of phenol
～65%, then rapidly reactor temperature is down to 50 DEG C ± 5 DEG C, vacuum dehydration, obtain final product phenolic resin performed polymer；Described benzene
Phenol is 1 with the mol ratio of formaldehyde:1.5～2；Sodium hydroxide is used to adjust the pH value size of solution, and its solution concentration is 20%,
Addition is so that solution ph reaches 8～10 is defined；The addition of LNBR is 6%～10%；Vacuum be 75～
95kPa；
Prepared by step (3) phenol-formaldehyde resin modified：Under conditions of stirring, copper crystal seed liquid prepared by step (1) is added to phenol
In urea formaldehyde reaction vessel, adjust the pH value of reactant liquor to 8～10 using sodium hydroxide solution；Then, at 50 DEG C ± 5 DEG C and stir
Under conditions of mixing, the copper-bath comprising chelating agent and deflocculant is added dropwise in reaction vessel, reaction 60min～
90min, vacuum dehydration, add ethanol in reactant liquor, stir, obtain final product nanometer copper particle acrylonitrile butadiene rubber modified phenolic aldehyde tree
Fat；The concentration of described copper-bath is 0.10～0.25mol/L, and its addition is based on phenol mole 2%～4%；Complexation
Agent adopts disodiumedetate, and its addition is based on 2 times of copper sulfate mole；Deflocculant adopts polyvinyl pyrrole
Alkanone, its addition is 0.8%～1.2%；The addition of copper crystal seed liquid based on the 10～30% of copper-bath volume, hydrogen-oxygen
The concentration changing sodium is 20%；Vacuum is 75～95kPa；The addition of ethanol is based on the 10～15% of reactant liquor volume.
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| CN107523177A (en) * | 2017-08-22 | 2017-12-29 | 智慧超洋建设工程股份有限公司 | A kind of anticorrosive paint for building curtain wall |
Citations (2)
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|---|---|---|---|---|
| CN1482173A (en) * | 2003-07-17 | 2004-03-17 | 西安交通大学 | Modified phenolic resin and process for preparing the same |
| CN101113227A (en) * | 2007-09-06 | 2008-01-30 | 贵州大学 | Inorganic nano particle modified alkyd resin and modifying method and application thereof |
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2014
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1482173A (en) * | 2003-07-17 | 2004-03-17 | 西安交通大学 | Modified phenolic resin and process for preparing the same |
| CN101113227A (en) * | 2007-09-06 | 2008-01-30 | 贵州大学 | Inorganic nano particle modified alkyd resin and modifying method and application thereof |
Non-Patent Citations (5)
| Title |
|---|
| 丁腈橡胶共聚改性酚醛树脂;李新明等;《热固性树脂》;20020530;第17卷(第3期);11-14 * |
| 化学还原法制备纳米铜;林荣会等;《化学学报》;20041215;第62卷(第23期);2365-2368 * |
| 原位同生法制备纳米铜改性酚醛树脂;林荣会等;《高分子材料科学与工程》;20041130;第20卷(第6期);210-213 * |
| 液体NBR增韧酚醛研究;宋镕光等;《塑料工业》;20110228;第39卷(第2期);25-28 * |
| 纳米铜改性酚醛树脂对摩擦材料摩擦磨损性能的影响;林荣会等;《非金属矿》;20070731;第30卷(第4期);68-70 * |
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