A kind of phenolic resin black functional master batch and preparation method thereof
Technical field
The present invention relates to a kind of phenolic resin black functional master batch and preparation method thereof, and in particular to one kind is with nano material
Modified colour carbon black is phenolic resin black functional master batch of coloring agent and preparation method thereof.
Background technology
It using phenol and formaldehyde is raw material in acidic catalyst that phenolic resin, which is,(Or base catalyst)Under the conditions of, it is polymerized
High polymer material.Its stable processing technique is simple to operate, and the prices of raw materials are cheap, and has good heat resistance, and electricity is absolutely
Many advantages, such as edge, corrosion resistance, low smokiness, product size stability.Therefore, using phenolic resin as main raw material(s)
Phenolaldehyde moulding compound(It is commonly called as phenolic moulding powder)Have extensively in many fields such as household electrical appliance, domestic cookers, Aero-Space, auto industry
Application.In numerous phenolic molding compound material products, black product is occupied an leading position, and constitutes about more than the 95% of product population.Mesh
Preceding phenolaldehyde moulding compound is mainly dyed with oil black nigrosine and carbon black.
Oil black nigrosine is earliest organic synthetic dye.It has strong coloring force, and good fluidity, photo absorption performance is strong, face
The advantages that color stability is good.It is easily scattered in phenolaldehyde moulding compound, dyeing capacity is strong, and the product of production is black and bright.But oil is molten
For nigrosine in production, environmental pollution is than more serious;Because containing chromium to also having certain influence in Human Physiology health.With
China《Law on Environmental Protection》Strict implementation, the production cost more and more higher of oil black nigrosine, the growth of selling price also at double.
In black phenolaldehyde moulding compound, color matching cost has accounted for selling price 7%~9%.The economic effect of enterprise is had a strong impact on
Benefit.Carbon black is also one of ancient black dye and relatively inexpensive.But carbon black should not disperse, influence to dye.Present work
The carbon black particle almost spherical of industry production, particle diameter is between micron and nanometer.Many particles are often agglomerated into three-dimensional key branch
Chain or aggregating state.The dyeing capacity of carbon black has necessary correlative connection with self structure, in general the high carbon black of structure
It is easier to disperse, but dyeing capacity is relatively low, the low carbon black dyeing power of structure is higher, but needs bigger cut when scattered
Shear force.Colour carbon black is that scattered one kind is most difficult in all pigment.In order to reduce production cost, the performance of enterprises, phenolic aldehyde mould are improved
Plastics-production enterprise largely substitutes oil black nigrosine using carbon black.
At present, the main technique of phenolaldehyde moulding compound application carbon black dyeing is carbon black(Or add a small amount of glossy black)With phenolic aldehyde tree
After the blending of the other materials such as fat, wood powder, methenamine, inorganic filler, plastified in two-roll mill and dyeing is handled, so
Cooling crush is granulated afterwards.This traditional handicraft has certain effect to the dyeing cost for reducing phenolaldehyde moulding compound;But to carbon black
Disperse and utilize have certain limitation.Major defect is as follows:(1)Dosage is bigger;(2)It is scattered uneven;(3)Products appearance
Unsightly;(4)Product is more crisp;(5)Influence the curing rate of phenolic resin;(6)Easily pollution production link.
Through market survey, currently also the molten aniline of oil is substituted using colour carbon black without a kind of in phenolaldehyde moulding compound production
Black, carbon black and the product for obtaining more satisfactory effect.Therefore, in order to reduce the dyeing cost of phenolaldehyde moulding compound, phenolic aldehyde is improved
The combination property of resin, it is necessary to research and develop a kind of Color is good, production cost is low, stable performance, good fluidity, using simplicity
Multi-functional resins masterbatch.
The content of the invention
For overcome the deficiencies in the prior art, the invention provides a kind of phenolic resin black functional master batch and its preparation side
Method, the masterbatch have that dyeability is good, good fluidity, can any amount addition, increasing tougheness and heat distortion temperature can be improved again so that
Combination property is obviously improved.
The technical scheme adopted by the invention to solve the technical problem is that:A kind of phenolic resin black functional master batch, its group
Include phenol, formaldehyde, catalyst and coloring agent into raw material, it is characterised in that the phenolic resin black functional master batch is by following
The raw material of parts by weight is prepared:200 parts of phenol, 148~152 parts of formaldehyde, 2~10 parts of catalyst, 4~10 parts of coloring agent.
Above-mentioned coloring agent is complex function black dye, and the complex function black dye is by following parts by weight
Raw material is prepared:0.1~0.7 part of inorganic nano material, 6~8 parts of colour carbon black, 0.1 part of dispersant, lubricant 0.1~
0.15 part, 0.01 part of defoamer, 0.1~0.2 part of emulsifying agent, 0.2 part of coupling agent.
Above-mentioned inorganic nano material is one or more groups in nano-calcium carbonate, nano imvite and nano silicon
Close.
Above-mentioned complex function black dye is prepared by the raw material of following parts by weight:Nano-calcium carbonate 0~0.1
Part, 0.1~0.3 part of nano imvite, 0~0.4 part of nano silicon, 6~8 parts of colour carbon black, 0.1 part of dispersant, lubrication
0.1~0.15 part of agent, 0.01 part of defoamer, 0.1~0.2 part of emulsifying agent, 0.2 part of coupling agent.
Above-mentioned coupling agent is silane coupler.
Complex function black dye in the present invention is to prepare complex function dye using nanometer particle-modified colour carbon black
Toner.Its preparation method is:Inorganic nano material mixes in proportion after silane coupler is surface-treated with colour carbon black,
Add dispersant, lubricant, defoamer, emulsifying agent;Disperse by pre-dispersed, ball milling or ultrasonic wave disperses and emulsification treatment system
It is standby to form.Specifically carry out according to the following steps:
Step 1:It is pre-dispersed
Inorganic nano material is placed in homogenizer;Bonus point powder, lubricant, through high-speed stirred, 1~3 point of time
Clock;Coupling agent is added, continues stirring 1~2 minute;Then colour carbon black is added, continues stirring 5~8 minutes, maintains the temperature at
25℃~45℃;
Step 2:Ball milling is scattered or ultrasonic wave disperses
Step 1 resulting material is put into ball mill or ultrasonic wave dispersing apparatus, further disperseed, temperature is 25 DEG C ~ 45
℃;
Step 3:Emulsification treatment
Material prepared by step 2 is launched into emulsifier, is added emulsifying agent, defoamer and is suitably added some techniques
Water carries out stirring at low speed, treats material stirring uniformly and in untill thick shape.
Above-mentioned catalyst is inorganic acid or organic acid, i.e. hydrochloric acid, sulfuric acid or oxalic acid.
The present invention phenolic resin black functional master batch preparation method be using phenolic resin as carrier, it is black with complex function
Color coloring agent is modifying agent, using phenolic resin in-situ synthetic method, prepares phenolic resin black functional master batch.
Above-mentioned preparation method concretely comprises the following steps:In three mouthfuls of beakers equipped with agitator, condenser and thermometer, first
Add melting 200 parts of phenol, by phenol with formaldehyde mol ratio be 1:0.74~1:0.76 condition adds formaldehyde 148~152
Part, stirring, heating are started, temperature of reaction system control is reacted at 100 DEG C~104 DEG C, when observation liquid has backflow, according to
1%~5% condition of phenol weight adds 2~10 parts of catalyst, and catalyst is inorganic acid or organic acid, i.e. hydrochloric acid, sulfuric acid
Or oxalic acid.Continue to react 1h~2h, when observation liquid occurs muddy, add 4~10 parts of complex function black by weight ratio
Agent emulsion is dyed, back flow reaction 1.5h~2h starts decompression dehydration, treats that resin reaches certain viscosity(10~15Pas)When,
Polycondensation synthetic reaction terminates, quick blowing, then through cooling, disintegrating process processing, phenolic resin black functional master batch is made.
In summary, the present invention proposes one or more using inorganic nano-particle and carbon black, colour carbon black as science group
Close, and equipped with dispersant, defoamer, emulsifying agent, and using phenolic resin as carrier, using phenolic resin fabricated in situ technique side
Method, nano-particle and colour carbon black are uniformly distributed in vector resin, are made with dyeability, can improve again increasing tougheness and
The new function masterbatch of heat distortion temperature.Due to carrier and phenolic resin, so intermiscibility is good, good fluidity, operating procedure
It is easy;Can any amount addition so that combination property is obviously improved.
Compared with used phenolaldehyde moulding compound staining technique, phenolic resin black functional master batch of the invention has following special
Point:
First, good dispersion dyeability is strong:By the way of in-situ polymerization, complex function black dye in phenolic resin
Added in building-up process, dispersiveness of the colour carbon black in resin can be significantly improved, the agglomeration of carbon black is overcome, improve
The colouring power of carbon black.
2nd, application amount, which is reduced, reduces cost:It is black using phenolic resin in the case where phenolaldehyde moulding compound blackness is basically identical
Color functional master batch ratio is significantly reduced with the molten black dyeing cost of material of oil;Compared with rear addition carbon black, the dosage of carbon black is also significantly
Decline, so reducing the production cost of phenolaldehyde moulding compound.
3rd, the good impact strength of soft and moist property is higher:Nano-particle not only serves isolation and the effect of carrier to carbon black particle;
Toughening modifying effect is also played to phenolic resin simultaneously, improves soft and moist property, impact strength and the compactness of resin;Thermal deformation
Temperature also improves.
4th, using simplicity:It is good that phenolic resin black functional master batch easily mixes intermiscibility with phenolic resin, using simplicity.
The phenolaldehyde moulding compound product that the material such as curing agent, wood powder, inorganic filler produces the various trades mark can be added after mixing.
5th, product is highly polished:The plastic product surface finish that the phenolaldehyde moulding compound prepared using the masterbatch produces
It is high.
Embodiment
In order that the above-mentioned technology contents of the present invention more easily can be understood by persons skilled in the art, tie below
Specific embodiment is closed to the application further instruction.
First prepare model F081-A and model F082-A complex function black dye.Complex function black dye
Formula is shown in Table 1, and the dosage in table 1 is ratio of weight and number.
Embodiment 1
Prepare model F081-A phenolic resin black functional master batch.It is prepared by the raw material of following parts by weight:
0.1 part of nano-calcium carbonate, 0.3 part of nano imvite, 6 parts of colour carbon black, 0.1 part of dispersant, 0.1 part of lubricant, defoamer
0.01 part, 0.2 part of emulsifying agent, 0.2 part of coupling agent.
The preparation method of model F081-A phenolic resin black functional master batch, is carried out according to the following steps:
Step 1:It is pre-dispersed
Nano-calcium carbonate and nano imvite are placed in homogenizer;Bonus point powder, lubricant, through high-speed stirred,
1~3 minute time;Coupling agent is added, continues stirring 1~2 minute;Then colour carbon black is added, continues stirring 5~8 minutes,
Maintain the temperature at 25 DEG C ~ 45 DEG C.
Step 2:Ball milling is scattered or ultrasonic wave disperses
Step 1 resulting material is put into ball mill or ultrasonic wave dispersing apparatus, further disperseed, temperature is 25 DEG C ~ 45
℃。
Step 3:Emulsification treatment
Material prepared by step 2 is launched into emulsifier, is added emulsifying agent, defoamer and is suitably added some techniques
Water carries out stirring at low speed, treats material stirring uniformly and in untill thick shape.
Embodiment 2
Prepare model F082-A phenolic resin black functional master batch.It is prepared by the raw material of following parts by weight:
0.1 part of nano imvite, 0.4 part of nano silicon, 8 parts of colour carbon black, 0.1 part of dispersant, 0.15 part of lubricant, defoamer
0.01 part, 0.1 part of emulsifying agent, 0.2 part of coupling agent.
The preparation method of model F082-A phenolic resin black functional master batch, is carried out according to the following steps:
Step 1:It is pre-dispersed
Nano imvite and nano silicon are placed in homogenizer;Bonus point powder, lubricant, through high-speed stirring
Mix, 1~3 minute time;Coupling agent is added, continues stirring 1~2 minute;Then colour carbon black is added, continues 5~8 points of stirring
Clock, maintain the temperature at 25 DEG C ~ 45 DEG C.
Step 2:Ball milling is scattered or ultrasonic wave disperses
Step 1 resulting material is put into ball mill or ultrasonic wave dispersing apparatus, further disperseed, temperature is 25 DEG C ~ 45
℃。
Step 3:Emulsification treatment
Material prepared by step 2 is launched into emulsifier, is added emulsifying agent, defoamer and is suitably added some techniques
Water carries out stirring at low speed, treats material stirring uniformly and in untill thick shape.
Complex function black dye F081-A, F082-A are prepared respectively through above-mentioned technique.
Embodiment 1-1 F081 model phenolic resin black functional master batch
Preparation comprises the following steps that:Equipped with agitator, condenser, in the 500mL three-necked flasks of thermometer, first plus
Enter to melt phenol 200g, by phenol with formaldehyde mol ratio be 1:0.74 condition adds formaldehyde 148g, starts stirring, adds
Heat, temperature of reaction system control is set to be reacted at 100 DEG C -104 DEG C, when observation liquid has backflow, according to phenol quality
1%-5% condition adds 2g-10g catalyst.Catalyst is inorganic acid or organic acid, i.e. hydrochloric acid, sulfuric acid or oxalic acid, after
Continuous reaction 1h-2h, when observation liquid occurs muddy, 4g-10g complex function black dye F081- is added by proportioning
A emulsions, back flow reaction 1.5h- 2h, start decompression dehydration, treat that resin reaches certain viscosity(10~15Pas)When, contracting
Aggregate into reaction to terminate, quick blowing.Prepared again through cooling, disintegrating process processing, F081 phenolic resin black functional master batch
Form.
Embodiment 2-1 F082 model phenolic resin black functional master batch
Preparation comprises the following steps that:Equipped with agitator, condenser, in the 500mL three-necked flasks of thermometer, first plus
Enter to melt phenol 200g, by phenol with formaldehyde mol ratio be 1:0.76 condition adds formaldehyde 152g, starts stirring, adds
Heat, temperature of reaction system control is set to be reacted at 100 DEG C -104 DEG C, when observation liquid has backflow, according to phenol quality
1%-5% condition adds 2g-10g catalyst.Catalyst is inorganic acid or organic acid, i.e. hydrochloric acid, sulfuric acid or oxalic acid, after
1 h-2h of continuous reaction, when observation liquid occurs muddy, 4g-10g complex function coloring agent F082-A is added by proportioning
Emulsion, the h-2h of back flow reaction 1.5, start decompression dehydration, treat that resin reaches certain viscosity(10~15Pas)When, polycondensation
Synthetic reaction terminates, quick blowing.Again through cooling, disintegrating process processing, F082 phenolic resin black functional master batch prepare and
Into.
Using F081, F082 phenolic resin black functional master batch and phenolic resin, curing agent, wood powder, inorganic filler etc.
The techniques such as material is blended, is kneaded plasticizing dyeing, cools down, crushing is granulated, the ton of phenolaldehyde moulding compound more than 100 of the various trades mark of production
It has been launched that, applied through the injection of Duo Jia manufacturing enterprises, molding, processing characteristics is good, and outward appearance, the quality of plastic products are good.
Embodiments of the invention are the foregoing is only, are not intended to limit the scope of the invention, it is every to utilize this hair
The equivalent structure or equivalent flow conversion that bright description is made, or directly or indirectly it is used in other related technology necks
Domain, it is included in the scope of patent protection of the present invention.