A kind of heat-and corrosion-resistant engineering plastics preparation method
Technical field
The present invention relates to engineering plastics technical field more particularly to a kind of heat-and corrosion-resistant engineering plastics preparation methods.
Background technique
Engineering plastics mechanical performance, durability, corrosion resistance, in terms of can reach higher requirement, and
Processing is more convenient and alternative metal material.Engineering plastics are widely used in electric, automobile, building, office equipment, machine
The industries such as tool, aerospace, to mould Dai Gang, have become international popular trend to mould Dai Mu.
With the continuous development of science and technology, the sophisticated industries such as aerospace, telecommunications and military affairs department is to fiber reinforcement
The requirement of composite material " lightweight ", " high temperature resistant " and " high-performance " is higher and higher.China's aerospace and other high skills at present
The advanced configuration material of art field application is mainly same with thermosetting compound material, but since same with thermosetting compound material is in the prevalence of anti-
The shortcomings such as impact and antibody Monoclonal ability are relatively low, heat resistance is poor, manufacturing cost is high are badly in need of heat resistance more thus
Height, and the advanced composite material (ACM) of its good mechanical properties at high temperature.High Performance FRTP Composites have tough
Property good, endurance damage and the advantages that shock resistance damage performance height, short molding cycle, recoverable, so by increasingly
More attention.
Radiation Chemistry of Polymer be study ionising radiation and polymer and chemical change that monomer interaction generates and its
Effect, it includes various polymerizations, crosslinking, grafting and the cracking etc. that ionising radiation causes.With nuclear reactor and accelerator art
Rapid development, for radiation provide various radiation sources, Radiation Chemistry of Polymer is gradually applied to the life of macromolecule product material
It produces and modified.Cross-linking radiation can get preferable cross-linking effect using suitable formula, have crosslinking engineering plastics both originally
Flexible, fire retardant advantage, and have the characteristics of very high-wearing feature, heat resistance, corrosion resistance.
Summary of the invention
The present invention provides a kind of heat-and corrosion-resistant engineering plastics preparation method, solve regenerated engineering it is above-mentioned not
Foot, the engineering plastics mechanical property being prepared is good, heat-and corrosion-resistant superior performance.
In order to solve the above technical problems, the present invention provides a kind of heat-and corrosion-resistant engineering plastics preparation methods, including such as
Lower step:
(1) heat-and corrosion-resistant engineering plastics masterbatch is prepared
Polycondensation reaction, which is carried out, using M-phthalic acid, ethylene glycol and phenolphthalein as base stock, under vacuum obtains heat-and corrosion-resistant
Engineering plastics masterbatch;
(2) according to following parts by weight ingredient:
88-105 parts of above-mentioned heat-and corrosion-resistant engineering plastics masterbatch
1-3 parts of cross-linked accelerating agent for irradiation
Modified 2-4 parts of aging-resistant flame-proof system
1-3 parts of weather resisting agent
0.5-1.5 parts of plasticizer;
(3) above-mentioned various raw materials are 3-5 minutes dry-mixed in super mixer, then be placed in double screw extruder through melting
Extrusion, cooling, pelletizing, packed products;Wherein, one area's temperature of double screw extruder is 150-160 DEG C, and 2nd area are 170-
180 DEG C, 3rd area are 185-205 DEG C, and 4th area are 180-200 DEG C;5th area are 200-210 DEG C, and the residence time is 6-10 minutes, pressure
For 15-20Mpa;
Plastic strip after extrusion is carried out cooling and shaping by water-cooling groove by water cooling bracing;
Air-cooled drying, the plastic strip after water cooling pass through air cooling equipment, will adhere to the drying of the moisture on plastic strip;
Pelletizing is drawn, granular by being cut into the plastic strip feeding blank after drying, the revolving speed of pelleter is 600-800r/
min;
Cross-linking radiation obtains heat-and corrosion-resistant engineering plastics.
Preferably, the heat-and corrosion-resistant engineering plastics masterbatch is made using following technique:
Using M-phthalic acid, ethylene glycol and phenolphthalein as base stock, M-phthalic acid, ethylene glycol and phenolphthalein are base stock
It is in parts by weight respectively 60-70 parts, 30-45 parts and 12-15 parts;
M-phthalic acid, ethylene glycol and phenolphthalein, catalyst and antioxidant are uniformly mixed, is added in reaction kettle and stirs,
Then heating carries out esterification, and the temperature of esterification is 240-250 DEG C, after esterification reaches 95% or more, esterification knot
Beam;After esterification, stabilizer is added into obtained product, carries out polycondensation reaction under vacuum, polycondensation reaction is opposite
It is carried out under vacuum pressure >=-150kPa, reaction temperature is 280-290 DEG C, reaction time 200-300min;
It discharges after polycondensation reaction, cooling, pelletizing, obtains heat-and corrosion-resistant engineering plastics masterbatch.
Wherein the catalyst is one of antimony system, titanium system, germanium series catalysts;The stabilizer is phosphoric acid ester, Asia
One or more of phosphoric acid ester;The antioxidant be phenols, amine, phosphorous acid esters, one of containing sulfur type antioxidant
Or it is several.
Preferably, the cross-linked accelerating agent for irradiation is made with the following method:
After mixing by N- ethyl-methyl allylamine and phthalate anhydride, dimethylbenzene is added, premixed solution is obtained, is added
The molar ratio of the N- ethyl-methyl allylamine and phthalate anhydride that enter is 1:(1.5-3), it is described in the premixed solution
The concentration of N- ethyl-methyl allylamine is 0.5-1mol/L;
SO is added into premixed solution4 2-/ZrO2- HMS solid acid catalyst is simultaneously dispersed with stirring, the matter of solid acid be added
Amount and the volume ratio of the premixed solution are 0.5-1.5g/L;
- 5 DEG C of stirring 3-5h of low temperature, product are filtered, washed, dry the acquisition cross-linked accelerating agent for irradiation.
Preferably, the modified aging-resistant flame-proof system is prepared by the following method:
1-3 parts of nano kaolines are taken by mass fraction, the potassium bicarbonate aqueous solution that 2-4 parts of mass fractions are 25-35%,
1.2-1.5 parts of characterization parameter diameters are 50-100nm, the halloysite nanotubes that length is 5-10 μm, 1.5-1.8 parts of graphenes,
0.5-0.8 parts of titanium dioxides, 0.5-0.7 parts of lauryl amine polyoxyethylene ether, the wollastonite that 1-1.2 parts of draw ratios are 10-13:1 are needle-shaped
Fiber is uniformly mixed, stirs in 170-190 DEG C of superheated steam reaction kettle, and decatize reacts 35-50min, true at 450-480 DEG C
Then empty microwave radiation 3-5h is dipped in the sulfamic acid solution vacuum moisture absorption that 90-110 parts of mass fractions are 35% and handles, inhales saturating
After be heated to 75-85 DEG C of ultrasonic wave dispersion 1-2.5h, be stirred for dispersion 3-5h, take suspended matter;
By mass fraction by 3-5 part suspended matter microwave plasma etching processing 25-30min of above-mentioned acquisition, with 50-80 parts
The deionized water of the potassium tripolyphosphate dispersion liquid of 3-5% containing mass fraction ultrasonication 15-30min at 65-75 DEG C, takes upper layer
Suspended matter is filtered through 100-150 mesh, distilled water washes clean, vacuum drying, obtains modified aging-resistant flame-proof system.
Preferably, the weather resisting agent includes light stabilizer and ultraviolet absorbing agent, the light stabilizer and ultraviolet radiation absorption
The mass ratio of agent is 1:(1-3).
Preferably, the ultraviolet absorbing agent is UVP-327 or ASK-215, and the light stabilizer is carbon black.
Preferably, the cross-linking radiation is irradiated using cobalt source, irradiation dose 15-20MGy.
One or more technical solution provided by the invention, has at least the following technical effects or advantages: the system of (1) masterbatch
Phenolphthalein Third monomer is introduced during standby, and the flexible diethyl alcohol part in polyester macromolecule chain is replaced with rigid phenolphthalein group,
To form the segment that rigid diacid monomer is connected with rigid phenolphthalein monomer, enhances the rigidity and crystal property of entire molecule, mention
High glass-transition temperature and fusing point;(2) irradiation crosslinking processes are used, the heat resistance and corrosion resistance of engineering plastics are promoted
Can, the cross-linking radiation agent used its using containing benzoic anhydride as synthesis material, introduce benzene ring structure, not only increase crosslinking accelerator
Fusing point, further improve the anti-radiation stability of crosslinking accelerator, the engineering plastics prepared are promoted with cross-linking radiation
Since molecular weight increases and have benzene ring structure, high-temperature volatile is low, has good compatibility with engineering plastics for agent;(3) change
The fire proofings and wollastonite raphioid fiber etc. such as graphene, titanium dioxide, halloysite nanotubes are anti-ageing in property aging-resistant flame-proof system
Change material, forms compound synergistic effect, the flame retardant property and anti-aging property of significant increase engineering plastics.
Specific embodiment
Embodiment one
Polycondensation reaction, which is carried out, using M-phthalic acid, ethylene glycol and phenolphthalein as base stock, under vacuum obtains heat-and corrosion-resistant
Engineering plastics masterbatch;The heat-and corrosion-resistant engineering plastics masterbatch is made using following technique:
Using M-phthalic acid, ethylene glycol and phenolphthalein as base stock, M-phthalic acid, ethylene glycol and phenolphthalein are base stock
It is in parts by weight respectively 60 parts, 30 parts and 12 parts;
M-phthalic acid, ethylene glycol and phenolphthalein, catalyst and antioxidant are uniformly mixed, is added in reaction kettle and stirs,
Then heating carries out esterification, and the temperature of esterification is 240 DEG C, and after esterification reaches 95% or more, esterification terminates;
After esterification, stabilizer is added into obtained product, carries out polycondensation reaction under vacuum, polycondensation reaction is in relative vacuum
It is carried out under pressure >=-150kPa, reaction temperature is 280 DEG C, reaction time 200min;It discharges after polycondensation reaction, is cold
But, pelletizing obtains heat-and corrosion-resistant engineering plastics masterbatch.Wherein the catalyst is antimony-based catalyst;The stabilizer is phosphorus
Esters of gallic acid;The antioxidant is phenolic antioxidant.
According to following parts by weight ingredient:
Above-mentioned 88 parts of heat-and corrosion-resistant engineering plastics masterbatch
1 part of cross-linked accelerating agent for irradiation
Modified 2 parts of aging-resistant flame-proof system
1 part of weather resisting agent
0.5 part of plasticizer;
The weather resisting agent includes light stabilizer and ultraviolet absorbing agent, the quality of the light stabilizer and ultraviolet absorbing agent
Than for 1:1.The ultraviolet absorbing agent is UVP-327, and the light stabilizer is carbon black.
By above-mentioned various raw materials dry-mixed 3 minutes in super mixer, then be placed in double screw extruder through melting extrusion,
Cooling, pelletizing, packed products;Wherein, one area's temperature of double screw extruder is 150 DEG C, and 2nd area are 170 DEG C, and 3rd area are 185
DEG C, 4th area are 180 DEG C;5th area are 200 DEG C, and the residence time is 6 minutes, pressure 15Mpa.
Plastic strip after extrusion is carried out cooling and shaping by water-cooling groove by water cooling bracing;
Air-cooled drying, the plastic strip after water cooling pass through air cooling equipment, will adhere to the drying of the moisture on plastic strip;
Pelletizing is drawn, granular by being cut into the plastic strip feeding blank after drying, the revolving speed of pelleter is 600r/min;
Cross-linking radiation, the cross-linking radiation are irradiated using cobalt source, and irradiation dose 15MGy obtains heat-and corrosion-resistant engineering plastic
Material.
The cross-linked accelerating agent for irradiation is made with the following method:
After mixing by N- ethyl-methyl allylamine and phthalate anhydride, dimethylbenzene is added, premixed solution is obtained, is added
The molar ratio of the N- ethyl-methyl allylamine and phthalate anhydride that enter is 1:1.5, in the premixed solution, the N- second
The concentration of ylmethyl allylamine is 0.5mol/L;
SO is added into premixed solution4 2-/ZrO2- HMS solid acid catalyst is simultaneously dispersed with stirring, the matter of solid acid be added
Amount and the volume ratio of the premixed solution are 0.5g/L;
- 5 DEG C of stirring 3h of low temperature, product are filtered, washed, dry the acquisition cross-linked accelerating agent for irradiation.
The modified aging-resistant flame-proof system is prepared by the following method:
1 part of nano kaoline, the potassium bicarbonate aqueous solution that 2 parts of mass fractions are 25%, 1.2 parts of characterizations are taken by mass fraction
The halloysite nanotubes that parameter diameter is 50-100nm, length is 5-10 μm, 1.5 parts of graphenes, 0.5 part of titanium dioxide, 0.5 part month
Osmanthus amine polyoxyethylene ether, the wollastonite raphioid fiber that 1 part of draw ratio is 10-13:1 are uniformly mixed, anti-in 170 DEG C of superheated steams
Stirring in kettle is answered, decatize reacts 35min, radiates 3h in 450 DEG C of vacuum microwaves, is then dipped in the ammonia that 90 parts of mass fractions are 35%
Base sulfonic acid solutions vacuum moisture absorption processing is heated to 75 DEG C of ultrasonic wave dispersion 1h, is stirred for dispersion 3h, takes suspended matter after inhaling thoroughly;
By mass fraction by 3 parts of suspended matter microwave plasma etching processing 25min of above-mentioned acquisition, with 50 parts containing quality point
The deionized water of several 3% potassium tripolyphosphate dispersion liquids ultrasonication 15min at 65 DEG C, takes upper layer suspended matter through 100 mesh mistakes
Filter, distilled water washes clean, vacuum drying obtain modified aging-resistant flame-proof system.
Embodiment two
Polycondensation reaction, which is carried out, using M-phthalic acid, ethylene glycol and phenolphthalein as base stock, under vacuum obtains heat-and corrosion-resistant
Engineering plastics masterbatch;The heat-and corrosion-resistant engineering plastics masterbatch is made using following technique:
Using M-phthalic acid, ethylene glycol and phenolphthalein as base stock, M-phthalic acid, ethylene glycol and phenolphthalein are base stock
It is in parts by weight respectively 65 parts, 35 parts and 14 parts;
M-phthalic acid, ethylene glycol and phenolphthalein, catalyst and antioxidant are uniformly mixed, is added in reaction kettle and stirs,
Then heating carries out esterification, and the temperature of esterification is 245 DEG C, and after esterification reaches 95% or more, esterification terminates;
After esterification, stabilizer is added into obtained product, carries out polycondensation reaction under vacuum, polycondensation reaction is in relative vacuum
It is carried out under pressure >=-150kPa, reaction temperature is 285 DEG C, reaction time 250min;It discharges after polycondensation reaction, is cold
But, pelletizing obtains heat-and corrosion-resistant engineering plastics masterbatch.Wherein the catalyst is one of Titanium series catalyst;It is described steady
Determining agent is phosphoric acid ester;The antioxidant is amine antioxidants.
According to following parts by weight ingredient:
Above-mentioned 83 parts of heat-and corrosion-resistant engineering plastics masterbatch
2 parts of cross-linked accelerating agent for irradiation
Modified 3 parts of aging-resistant flame-proof system
2 parts of weather resisting agent
1 part of plasticizer;
The weather resisting agent includes light stabilizer and ultraviolet absorbing agent, the quality of the light stabilizer and ultraviolet absorbing agent
Than for 1:2.The ultraviolet absorbing agent is UVP-327, and the light stabilizer is carbon black.
By above-mentioned various raw materials dry-mixed 4 minutes in super mixer, then be placed in double screw extruder through melting extrusion,
Cooling, pelletizing, packed products;Wherein, one area's temperature of double screw extruder is 155 DEG C, and 2nd area are 175 DEG C, and 3rd area are 195
DEG C, 4th area are 190 DEG C;5th area are 205 DEG C, and the residence time is 8 minutes, pressure 18Mpa.
Plastic strip after extrusion is carried out cooling and shaping by water-cooling groove by water cooling bracing;
Air-cooled drying, the plastic strip after water cooling pass through air cooling equipment, will adhere to the drying of the moisture on plastic strip;
Pelletizing is drawn, granular by being cut into the plastic strip feeding blank after drying, the revolving speed of pelleter is 700r/min;
Cross-linking radiation, the cross-linking radiation are irradiated using cobalt source, and irradiation dose 18MGy obtains heat-and corrosion-resistant engineering plastic
Material.
The cross-linked accelerating agent for irradiation is made with the following method:
After mixing by N- ethyl-methyl allylamine and phthalate anhydride, dimethylbenzene is added, premixed solution is obtained, is added
The molar ratio of the N- ethyl-methyl allylamine and phthalate anhydride that enter is 1:2, in the premixed solution, the N- ethyl
The concentration of methyl-prop enamine is 0.8mol/L;
SO is added into premixed solution4 2-/ZrO2- HMS solid acid catalyst is simultaneously dispersed with stirring, the matter of solid acid be added
Amount and the volume ratio of the premixed solution are 1g/L;
- 5 DEG C of stirring 4h of low temperature, product are filtered, washed, dry the acquisition cross-linked accelerating agent for irradiation.
The modified aging-resistant flame-proof system is prepared by the following method:
2 parts of nano kaolines, the potassium bicarbonate aqueous solution that 3 parts of mass fractions are 29%, 1.3 parts of characterizations are taken by mass fraction
The halloysite nanotubes that parameter diameter is 50-100nm, length is 5-10 μm, 1.6 parts of graphenes, 0.6 part of titanium dioxide, 0.6 part month
Osmanthus amine polyoxyethylene ether, the wollastonite raphioid fiber that 1-1.2 parts of draw ratios are 12:1 are uniformly mixed, and are steamed in 170-190 DEG C of overheat
Stirring in vapour reaction kettle, decatize react 40min, radiate 4h in 460 DEG C of vacuum microwaves, being then dipped in 98 parts of mass fractions is 35%
Sulfamic acid solution vacuum moisture absorption processing, 79 DEG C of ultrasonic waves dispersion 1.5h are heated to after inhaling thoroughly, dispersion 4h is stirred for, takes suspension
Object;
By mass fraction by 4 parts of suspended matter microwave plasma etching processing 27min of above-mentioned acquisition, with 70 parts containing quality point
The deionized water of several 4% potassium tripolyphosphate dispersion liquids ultrasonication 18min at 70 DEG C, takes upper layer suspended matter through 100 mesh mistakes
Filter, distilled water washes clean, vacuum drying obtain modified aging-resistant flame-proof system.
Embodiment three
Polycondensation reaction, which is carried out, using M-phthalic acid, ethylene glycol and phenolphthalein as base stock, under vacuum obtains heat-and corrosion-resistant
Engineering plastics masterbatch;The heat-and corrosion-resistant engineering plastics masterbatch is made using following technique:
Using M-phthalic acid, ethylene glycol and phenolphthalein as base stock, M-phthalic acid, ethylene glycol and phenolphthalein are base stock
It is in parts by weight respectively 70 parts, 45 parts and 15 parts;
M-phthalic acid, ethylene glycol and phenolphthalein, catalyst and antioxidant are uniformly mixed, is added in reaction kettle and stirs,
Then heating carries out esterification, and the temperature of esterification is 250 DEG C, and after esterification reaches 95% or more, esterification terminates;
After esterification, stabilizer is added into obtained product, carries out polycondensation reaction under vacuum, polycondensation reaction is in relative vacuum
It is carried out under pressure >=-150kPa, reaction temperature is 290 DEG C, reaction time 300min;It discharges after polycondensation reaction, is cold
But, pelletizing obtains heat-and corrosion-resistant engineering plastics masterbatch.Wherein the catalyst is antimony system, titanium system, one in germanium series catalysts
Kind;The stabilizer is one or more of phosphoric acid ester, phosphorous acid esters;The antioxidant is phenols, amine, phosphorous acid
Esters, one or more of containing sulfur type antioxidant.
Above-mentioned 105 parts of heat-and corrosion-resistant engineering plastics masterbatch
3 parts of cross-linked accelerating agent for irradiation
Modified 4 parts of aging-resistant flame-proof system
3 parts of weather resisting agent
1.5 parts of plasticizer;
The weather resisting agent includes light stabilizer and ultraviolet absorbing agent, the quality of the light stabilizer and ultraviolet absorbing agent
Than for 1:3.The ultraviolet absorbing agent is ASK-215, and the light stabilizer is carbon black.
By above-mentioned various raw materials dry-mixed 5 minutes in super mixer, then be placed in double screw extruder through melting extrusion,
Cooling, pelletizing, packed products;Wherein, one area's temperature of double screw extruder is 160 DEG C, and 2nd area are 180 DEG C, and 3rd area are 205
DEG C, 4th area are 200 DEG C;5th area are 210 DEG C, and the residence time is 10 minutes, pressure 20Mpa.
Plastic strip after extrusion is carried out cooling and shaping by water-cooling groove by water cooling bracing;
Air-cooled drying, the plastic strip after water cooling pass through air cooling equipment, will adhere to the drying of the moisture on plastic strip;
Pelletizing is drawn, granular by being cut into the plastic strip feeding blank after drying, the revolving speed of pelleter is 800r/min;
Cross-linking radiation, the cross-linking radiation are irradiated using cobalt source, and irradiation dose 20MGy obtains heat-and corrosion-resistant engineering plastic
Material.
The cross-linked accelerating agent for irradiation is made with the following method:
After mixing by N- ethyl-methyl allylamine and phthalate anhydride, dimethylbenzene is added, premixed solution is obtained, is added
The molar ratio of the N- ethyl-methyl allylamine and phthalate anhydride that enter is 1:3, in the premixed solution, the N- ethyl
The concentration of methyl-prop enamine is 1mol/L;
SO is added into premixed solution4 2-/ZrO2- HMS solid acid catalyst is simultaneously dispersed with stirring, the matter of solid acid be added
Amount and the volume ratio of the premixed solution are 1.5g/L;
- 5 DEG C of stirring 5h of low temperature, product are filtered, washed, dry the acquisition cross-linked accelerating agent for irradiation.
The modified aging-resistant flame-proof system is prepared by the following method:
3 parts of nano kaolines, the potassium bicarbonate aqueous solution that 4 parts of mass fractions are 35%, 1.5 parts of characterizations are taken by mass fraction
The halloysite nanotubes that parameter diameter is 50-100nm, length is 10 μm, 1.8 parts of graphenes, 0.8 part of titanium dioxide, 0.7 portion of laurel
Amine polyoxyethylene ether, the wollastonite raphioid fiber that 1.2 parts of draw ratios are 13:1 are uniformly mixed, in 190 DEG C of superheated steam reaction kettles
Interior stirring, decatize react 50min, radiate 5h in 480 DEG C of vacuum microwaves, are then dipped in the amino that 110 parts of mass fractions are 35%
Sulfonic acid solutions vacuum moisture absorption processing is heated to 85 DEG C of ultrasonic wave dispersion 2.5h, is stirred for dispersion 5h, takes suspended matter after inhaling thoroughly;
By mass fraction by 5 parts of suspended matter microwave plasma etching processing 30min of above-mentioned acquisition, with 80 parts containing quality point
The deionized water of several 5% potassium tripolyphosphate dispersion liquids ultrasonication 30min at 75 DEG C, takes upper layer suspended matter through 150 mesh mistakes
Filter, distilled water washes clean, vacuum drying obtain modified aging-resistant flame-proof system.
After tested, heat-and corrosion-resistant engineering plastics are formed through tabletting machine in each example of the present invention, and performance indicator is as follows:
Technical indicator |
Testing standard |
One test result of embodiment |
Two test result of embodiment |
Three test result of embodiment |
Bending modulus (MPa) |
ISO 178 |
91.6 |
89.2 |
93.5 |
Tensile strength (MPa) |
ISO 527 |
122.5 |
125.1 |
123.2 |
Notch impact strength (kJ/m2) |
ISO 179 |
57.4 |
53.2 |
52.7 |
Melt index (g/10min) |
ISO 1133 |
75 |
79 |
76 |
Maximum decomposition temperature (DEG C) |
GB 1035-70 |
294 |
291 |
289 |
As seen from the above table, the product mechanical strength that the present invention obtains is high, good flame resistance, and heat resistance is extremely strong.
The specific embodiment of the application above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
The limitation to the application protection scope therefore cannot be interpreted as.It should be pointed out that the present invention is not limited to embodiment here,
Those skilled in the art's announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be in this hairs
In bright protection scope.