CN103585947B - Densification and polycondensation reaction equipment and method for preparing nanometer polyamide composite material - Google Patents
Densification and polycondensation reaction equipment and method for preparing nanometer polyamide composite material Download PDFInfo
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Abstract
The invention provides a densification and polycondensation reactor and a preparation method, which are used for preparing a nanometer polyamide composite material. The densification and polycondensation reactor comprises a polymerizer, a fixed station and a screw system, wherein the polymerizer is fixed on the fixed station, and the screw system comprises a screw motor, a screw shaft and screw stirring blades. The densification and polycondensation reactor and preparation method, provided by the invention, can improve various physical and chemical properties of polymers, save process time so as to enable the process pace to be compact, achieve intelligent control through a thermal system, do not waste energy sources, and reduce cost, thereby producing the novel material namely nanometer polyamide composite material, which meets the above seven control requirements of users.
Description
technical field:
The invention belongs to Nano-composite materials field, particularly a kind of density polycondensation reactor and preparation method, for the preparation of Nano polyamide composite.
background technology:
Polyamide-engineering plastics (PA6, PA66 and PA series) are widely used, market potential is very large, along with every scientific and technological progress, it is as follows that user proposes some requirements at the higher level to Polyamide Engineering Plastic: Polyamide Engineering Plastic cost control, the control of Polyamide Engineering Plastic water absorption rate, the control of Polyamide Engineering Plastic dimensional stability, the control of Polyamide Engineering Plastic physicochemical property, the control of Polyamide Engineering Plastic shrinkage factor, Polyamide Engineering Plastic density domination, Flameproof polyamide engineering plastics reusability control etc.
Seven kinds of control overflow in above requirement how are reached in industrialization is produced, solve its batch production process of polyamide-engineering plastics and occur that the difficulties of technology is: imvite dispersion is general, phenomenon is separated out in imvite, imvite secondary agglomeration, the factors such as imvite polymerization is not fully, cost is excessive, therefore must carry out technological innovation to polyamide-engineering plastics: adopt new technology, new proportioning, new design and new equipment.
Along with petro chemical industry and other industrial expansions, the development for polyamide provides abundant, inexpensive raw material and wide market.Polyamide is because itself distinctive physical property, the fields such as machinery, automobile, electrical equipment, textile equipment, chemical industry equipment, aviation, metallurgy can be widely used in, and become indispensable structural material in all trades and professions, Nano polyamide composite has higher specific aim simultaneously, Simultaneous Stabilization is higher, and nanometer polyamide mother slurry is as the important composition of preparation Nano polyamide composite, the preparation of its nanometer polyamide mother slurry also becomes now industrial and gives priority to project.
For above-mentioned all kinds of difficulties, the present invention, in mass production technological innovation, innovation and research, comprises " waterless nano preparation ", " preparation of nanometer polyamide mother slurry ", " density reaction polycondensation preparation ".In order to production control energy consumption, the present invention selects new technology, new method: comprise one-step method polymerization (polycondensation), three-dimensional effect etc. make Nano polyamide composite, makes nano imvite play its performance in polyamide organic intercalation comprehensively.That is: " waterless nano imvite is affine, and polycondensation (copolymerization/polymerization) is reacted in the density of monomer of polyamide female slurry processes intercalation " makes polyamide nano-composite.The method is through " nanometer polyamide mother slurry " polymerization: prepare nano imvite through three-dimensional dry by waterless nano imvite preparing device, dehumidifying, rear input waterless nano polyamide mother slurry preparing device input density reaction polycondensation preparing device after nano imvite and the monomer of polyamide three dimension high efficiency evenly affine synthesis that organises comprehensively " female slurry " carries out the novel technique of intercalation polycondensation, nano imvite polyamide organic matter body tool organised is accelerated in density, through omnidistance new technology of the present invention, new technology, new proportioning, brand-new is standby reaches nano imvite good dispersion, nano imvite is not separated out, nano imvite is without secondary agglomeration, nano imvite is thoroughly polymerized with monomer of polyamide comprehensively, thus improve the performances such as every physics and chemistry of polymer, reach user's requirement, not only saved the process time but technique beat compact, and reduce production cost by heat energy system Based Intelligent Control.
summary of the invention:
The object of the invention is to, overcome the defect of above-mentioned prior art, and a kind of density polycondensation reactor and preparation method are provided, for the preparation of Nano polyamide composite.
Nano composite material refers to that in composite, decentralized photo yardstick has the composite of any dimension size in 1-100nm.Except the powder that spherical particle diameter is little, the stratiform reinforced structure of high length-diameter ratio (Aspect ratio) is more subject to whole world Polymeric Industry and attractes attention, and stratified material can fill the architectural characteristic that part plays molecule level after peeling off dispersion.Imvite (Montmorillonite) is the mineral belonging to imvite race, imvite race mineral find 11 altogether, they be sliding between bentonite, shellfish obtain native, lithium soap is native, imvite, the de-soil of sodium, bentonite, zinc soap soil, this bentonite, lithium montmorillonite and copper imvite etc., but imvite subtribe (dioctahedron) and bentonite subtribe (trioctahedron) can be divided into from internal structure.Imvite is one of typical layer silicate mineral, that space is large especially between layers with other layer silicate mineral dissimilarities, contain hydrone and the exchangeable cation of not determined number so between the layers, adopt the three-dimensional drying equipment of the waterless nano imvite newly designed and developed in the present invention, by the three-dimensional drying process of new waterless nano imvite, nano imvite hydrone etc. between layers thoroughly can be got rid of.
Nano polyamide composite and production method as follows, wherein production method comprises the following steps:
One, the preparation of anhydrous imvite:
The preparation of anhydrous imvite is made by three-dimensional drier, drying appliance is for high-speed ultrasonic ripple nibbling shear cut agitating function (rotating speed: 2000-10000 rev/min), baking temperature reaches between 60-200 DEG C, three-dimensional drier specification RISE-NM-01 volume 600L heat transfer rapidly, do not hinder nano imvite heat transfer, and stable performance, control sensitive, compact conformation, environmentally-friendly sanitary.Dried waterless nano imvite powder is input in waterless nano polyamide mother slurry preparing device for when preparing waterless nano polyamide mother slurry in good time by automatic gauge pump.
Waterless nano imvite preparation technology flow process:
11) nano imvite powder is checked: wherein the related request of nano imvite powder is: apparent solid volume density: 370 ± 10 g/l, free moisture (110 ° of C, 2 hours): < 3%, calcination loss (1000 ° of C, 2 hours): <6%, pH (10% suspension): 3.0-4.0, dry powder sieve analysis (> 63 um): < 25%, surface area: 240 ± 10 m
2/ g, micro pore volume: 0-80 nm:0.36 ml/g, 0-24 nm:0.30 ml/g, 0-14 nm:0.26 ml/g and cation exchange total amount through organic-treating is the nano imvite of 70-130mmol/100g;
12) nano imvite powder metering: by follow-up making waterless nano polyamide mother's slurry constituent content (weight portion) metering, according to monomer of polyamide be 100, nano imvite is that the ratio of 10-82 is to measure the amount of nano imvite.
13) start shooting after checkout facility, carry out temperature control, and carry out the shearing stirring of three-dimensional high-speed: be warming up to 110-150 DEG C; Start to stir with the speed of 2500-3000r/min while intensification, mixing time is 1-1.5 hour;
14) removal moisture drying: stop stirring, opens and vacuumizes and the steam in piece-rate system removing drier and air; Three Dimensional Thermal nitrogen pressurization is dry, wherein closes vacuum pumping valve when the Pressure gauge display pressure on drier be-0.1MPa, to start in drier slowly nitrogen injection and is pressurized to 1.2-2MPa, the temperature 110-150 DEG C kept dry in device, maintenance 1-1.5 hour;
15) on-line checkingi: open vacuumize with piece-rate system removing drier in steam and nitrogen after detect particle gaping, whether reach stratiform clearly demarcated;
16) input organosilicon carry out the shearing stirring of three-dimensional high-speed: after detecting by follow-up making waterless nano polyamide mother slurry constituent content (weight portion) monomer of polyamide be 100 parts, nano imvite is the ratio input organosilicon of 10-82 part, organosilicon 0.1-10 part, and with the speed of 2500-3000r/min stirring three-dimensional high-speed shearing stirring 0.5-1 hour;
17) insulation balance after decrease temperature and pressure: be cooled to 60-85 DEG C, unloads after being depressed into 0.5MPa and carries out insulation balance 0.5-1 hour;
18) with measuring pump input nanometer mother slurry device: open delivery pump, dried waterless nano imvite is delivered in waterless nano polyamide mother slurry preparing device.
Two,
the preparation of waterless nano polyamide mother slurry
The preparation of waterless nano polyamide mother slurry is by the preparation of nanometer mother slurry device: the anhydrous polyamide mother slurry of preparation is input in density reaction polycondensation polymerizer in good time.
Female slurry device comprises cavity and platform, cavity is fixed on platform, cavity top right side is provided with inflated with nitrogen mouth, device cavity top left side is provided with dog-house, two heating mouths of pipe are provided with on the right side of cavity, connect gas-liquid separation device and air exhauster successively on the left of cavity, cavity bottom is provided with metering outlet, and stirring system is installed at cavity top center place;
Described stirring system comprises motor, drive link and paddle, drive link top access motor, and paddle is fixed on drive link; Paddle side is coniform, and drive link also can move up and down within the specific limits, and stirring system can realize three-dimensional free to tumble;
Inside cavity installs radiating tube, and radiating tube is communicated with the heating mouth of pipe, and described radiating tube solid is arranged in device cavity; Described radiating tube comprises ring wall radiating tube and vertical radiating tube, and ring wall heat radiation pipe ring is put at device inside cavity chamber wall, and described vertical radiating tube vertically accesses ring wall radiating tube, and is in two paddle interlayers;
Its medium speed 0-3000 rev/min, nitrogen pressure 0-2.5 MPa; Between cavity temperature 60-300 DEG C.
21) monomer of polyamide is checked: the technical grade caprolactam that selecting liquidity is good and one-level nylon salt;
22) monomer of polyamide is measured: caprolactam and the weight portion of nylon salt are that 8-9 part is than 2-1 part;
23) add solution after checkout facility start and stir with medium-shear formula: the solution wherein added is chemical pure absolute ethyl alcohol, and stirs 0.5-1.0 hour with the speed of 25-50r/min;
24) heat up stir after vacuumize: intensification degree stirs 1.5-2.0 hour with the speed of 25-50r/min simultaneously to about 70-75 DEG C and opens and vacuumizes and steam in piece-rate system removing drier and air, the closedown vacuum pumping valve when the Pressure gauge display pressure on waterless nano polyamide mother slurry preparing device is-0.1MPa;
25) waterless nano imvite powder high-speed stirred is received: receive the three-dimensional dry waterless nano imvite powder of input and also carry out three-dimensional high-speed shearing stirring 1-1.5 hour with the speed of 300-1000r/min;
26) disperse with hot nitrogen pressurized three dimension: in waterless nano polyamide mother slurry preparing device, slowly nitrogen injection is put, heat up after being pressurized to 1.2-1.5MPa, and keep the pressure in waterless nano polyamide mother slurry preparing device to be 2.0-2.5Mpa, until temperature reaches 220-240 DEG C;
27) comprehensively affine: to keep temperature in waterless nano polyamide mother slurry preparing device to be 220-240 DEG C, nitrogen pressure 2.0-2.5MPa, retention time 2-2.5 hour;
28) carry out step-down after on-line checkingi and be incubated balance: unloading after being depressed into 0.5MPa and be also incubated balance 0.5-1 hour;
29) by step 28) in waterless nano polyamide mother slurry input density reaction condensation kettle: open delivery pump, the waterless nano polyamide prepared mother slurry be delivered in density reaction polycondensation polymerizer.
three, density polycondensation reaction finally makes Nano polyamide composite:
Density polycondensation reaction is reacted in the reactor, reactor comprises polymerizer, fixed station and spiral system, described polymerizer is fixed on fixed station, top and the bottom, described polymerizer both sides are installed into deep fat mouth respectively, smelting furnace pump is installed bottom polymerizer, polymerizer top left side is provided with charging aperture, and top right side is provided with pressure nitrogen mouth; Described smelting furnace pump is provided with meter and online viscosimeter.
Described spiral system comprises screw motor, helical axis and auger leaf, and described polymerizer inside is provided with three-dimensional heat dissipation oil pipe, and described three-dimensional heat dissipation oil pipe accesses into deep fat mouth; Screw motor is arranged on the top center place of described polymerizer, and helical axis is arranged on the inside of described polymerizer and is connected on screw motor, and auger leaf is fixed on helical axis, and described auger leaf central part is provided with rotational viscometer; Auger leaf side is coniform, and rotating shaft also can move up and down within the specific limits, and spiral system can realize three-dimensional free to tumble;
Described three-dimensional heat dissipation oil pipe comprises vertically heat radiation oil pipe and level heat radiation oil pipe, the adherent ring of described vertical heat radiation oil pipe is put at polymerizer inner chamber wall, described level heat radiation oil pipe accesses the oil pipe that vertically dispels the heat, and described level heat radiation oil pipe is in two auger leaf interlayers;
The rotating speed 0-3500 rev/min of described polymerizer, between heating-up temperature 200-350 DEG C, nitrogen pressure 0.5-2.5 MPa.
The technological process of density polycondensation reaction:
31) polymer raw monomer of polyamide is checked:
This monomer of polyamide can be caprolactam+nylon salt, also can be caprolactam+nylon 1010, or caprolactam+nylon salt+nylon 1010
32) monomer of polyamide is measured:
The ratio of the constituent content between the constituent content wherein between caprolactam+nylon salt, caprolactam+nylon 1010 be 8-9 than 2-1, the ratio of caprolactam+nylon salt+nylon 1010 constituent content is that 7-6 compares 1-2 than 2-3
32) the shearing stirring of three-dimensional high-speed is adopted after checkout facility start:
1.5-2 hour is stirred with the speed of 2500-3000r/min while heating up; When being warming up to about 60-80 DEG C input waterless nano polyamide mother slurry, and stir 1.5-2 hour with the speed of 500-1000r/min;
33) add solution and adopt the shearing stirring of three-dimensional high-speed:
Wherein solution adopts water (H20) as ring opening agent, and the one in acetic acid, sulfuric acid, hydrochloric acid, phosphoric acid or phosphorous acid is as molecular weight stabilizer; Adopt the shearing stirring of three-dimensional high-speed, keep the temperature of 60-80 DEG C to stir 0.1-0.5 hour with the speed of 500-1000r/min in the process simultaneously;
34) pressurized heat nitrogen three-dimensional density mixing dispersion:
In polymerizer, slowly nitrogen injection displacement waterless nano polyamide mother starches the air in preparing device, heats up, and keep the pressure in polymerizer to be 1-1.2Mpa, until temperature reaches 150-180 DEG C after being pressurized to 0.5-0.8MPa;
35) density supercharging issue should:
Keep pressure 1-1.2Mpa in polymerizer, temperature is 150-180 DEG C, and the time is 1-1.5 hour;
36) nitrogen pick-up supercharging:
Slowly nitrogen injection in polymerizer, is pressurized to 2.0-2.5MPa, until temperature reaches 240-300 DEG C;
37) rapid depressurization be incubated balance after on-line checkingi:
Unload and be depressed into 0.5MPa and be incubated balance, open smelting furnace and pump material, and cut into slices after unloading pressure balanced 2-3 hour, wherein section adopts water cutting process or dry cutting process to cut into slices;
38) packaging warehouse-in:
Carry out extracting after feed bin enters, dewater, drying, solid phase, vibrations screening step after discharging bin, and carry out vacuum packaging and warehouse-in.
This step is as adopted batchwise polymerization, and its process will meet the condition of first inflating pressure, rear intensification polymerization; As adopted continuous polymerization, its process needs while material enters polymerization pipe, uses high-pressure pump supercharging.
Effect prepared by density polycondensation reaction: solve the difficult problem that technology appears in nanometer polyamide engineering plastics in its batch production process: the factors such as the dispersion of nano imvite is uneven, the precipitation phenomenon of nano imvite, the polymerization of nano imvite remains, the secondary agglomeration of nano imvite, nanometer polyamide cost are excessive.
Density polycondensation reaction object: be, for solution market demand user, following requirement is proposed to Polyamide Engineering Plastic: Polyamide Engineering Plastic cost control, Polyamide Engineering Plastic water absorption rate control, Polyamide Engineering Plastic dimensional stability controls, Polyamide Engineering Plastic physicochemical property controls, Polyamide Engineering Plastic shrinkage factor controls, Flameproof polyamide engineering plastics are reused, Polyamide Engineering Plastic density domination etc.
Reach nano imvite disperse excellent through omnidistance new technology of the present invention, new technology, new proportioning, new equipment, do not separate out, without secondary agglomeration, comprehensively thoroughly polymerization.Both improved every physicochemical property of polymer, save the process time technique beat is linked closely, by the control of heat energy system intelligence can be realized, accomplish not waste energy, cost-saving.Thus produce the new material-Nano polyamide composite of the above seven kinds of control overflow reaching user.
Accompanying drawing explanation
Fig. 1 is structural representation of the present invention.
detailed description of the invention:
For further setting forth the present invention for the technological means reaching predetermined goal of the invention and adopt and effect, below in conjunction with drawings and the specific embodiments, to density polycondensation reactor of the present invention and structure, feature and effect thereof, describe in detail.
As shown in Figure 1, reactor of the present invention mainly comprises polymerizer 1, fixed station 2 and spiral system, and described spiral system is made up of screw motor 3, helical axis 7 and auger leaf 8; Described polymerizer 1 is fixed on fixed station 2, and screw motor 3 is arranged on the top center place of polymerizer 1, and it is inner that helical axis 7 is arranged on polymerizer 1, and be connected to screw motor 3 by chamber wall, auger leaf 8 is fixed on helical axis 7
,auger leaf 8 length is successively successively decreased from top to bottom, and in turbination, described polymerizer 1 top left side is provided with charging aperture 4, and top right side is provided with pressure nitrogen mouth 5, and top and the bottom, described polymerizer 1 both sides are installed into deep fat mouth 6 respectively, install smelting furnace pump 11 bottom polymerizer 1.
Described smelting furnace pump 11 is provided with meter and online viscosimeter, and meter is used for measuring and controlling discharging, material viscosity when online viscosimeter is for measuring static.
Described polymerizer 1 inner tip installs control box 12, and control box 12 comprises Pressure gauge and thermometer.
Be provided with rotational viscometer in the middle part of described auger leaf 8, rotational viscometer is for measuring material viscosity during stirring.
Institute's polymerizer 1 inside is provided with three-dimensional heat dissipation oil pipe, three-dimensional heat dissipation oil pipe accesses into deep fat mouth 6, three-dimensional heat dissipation oil pipe is made up of vertically dispel the heat oil pipe 9 and the level oil pipe 10 that dispels the heat, the adherent ring of vertical heat radiation oil pipe 9 is put at polymerizer 1 inner chamber wall, level heat radiation oil pipe 10 accesses vertically heat radiation oil pipe 9, and the locus of level heat radiation oil pipe 10 is in two auger leaf 8 interlayers, heat radiation oil pipe realizes solid and is arranged in polymerizer 1, each some homogeneous heating in polymerizer 1 can be made, the heat of each site absorption is identical, the product local heating in polymerizer 1 can be prevented, heat trnasfer uneven or heat trnasfer such as to be obstructed at the phenomenon.
Operation principle: check and meter feedstock monomer of polyamide, checkout facility is started shooting, input base polyamide monomer also carries out the shearing stirring of three-dimensional high-speed of heating, screw motor 3 drives auger leaf 8 to carry out auger by helical axis 7, drive helical axis 7 and auger leaf 8 to do up and down displacement by a small margin simultaneously, auger leaf 8 displacement can not touch level heat radiation oil pipe 10, rotating speed is 2500-3000r/min, after being warmed to 60-80 DEG C, stir 1.5-2 hour, then waterless nano polyamide mother slurry is inputted, adjustment rotating speed is to 500-1000r/min, stir 1.5-2 hour, add solution, solution is acetum, sulfuric acid solution, hydrochloric acid solution, (water is ring opening agent to the one of phosphoric acid solution or phosphorous acid solution, acetic acid, sulfuric acid, hydrochloric acid, one in phosphoric acid or phosphorous acid is as molecular weight stabilizer), keep the temperature of 60-80 DEG C and the rotating speed 0.1-0.5 hour of 500-1000r/min, then in polymerizer 1, nitrogen pressurization is filled with by pressure nitrogen mouth 5, start after being pressurized to 0.5-0.8MPa to heat up simultaneously, be pressurized to 1-1.2MPa, be warming up to 150-180 DEG C, keep 1-1.5 hour, react under comprehensive density supercharging, then continue to be pressurized to 2.0-2.5MPa, heat to 240-300 DEG C and be maintained, detected by meter online, until testing result qualified after be depressurized to 0.5MPa, insulation balance, unload pressure balanced duration 2-3 hour, open smelting furnace pump 11 and measure discharging.
the technological process of density polycondensation reaction in the present invention:
1) polymer raw monomer of polyamide is checked:
This monomer of polyamide can be caprolactam+nylon salt, also can be caprolactam+nylon 1010, or caprolactam+nylon salt+nylon 1010;
2) monomer of polyamide is measured:
The ratio of the constituent content between the constituent content wherein between caprolactam+nylon salt, caprolactam+nylon 1010 is that 8-9:2-1(is preferably 8:2), the ratio of caprolactam+nylon salt+nylon 1010 constituent content is 7-6:2-3:1-2 (being preferably 7:2:1);
3) the shearing stirring of three-dimensional high-speed is adopted after checkout facility start:
1.5-2 hour is stirred with the speed of 2500-3000r/min while heating up; When being warming up to about 60-80 DEG C input waterless nano polyamide mother slurry, and stir 1.5-2 hour with the speed of 500-1000r/min;
4) add solution and adopt the shearing stirring of three-dimensional high-speed:
Wherein solution adopts water (H20) as ring opening agent, and the one in acetic acid, sulfuric acid, hydrochloric acid, phosphoric acid or phosphorous acid is as molecular weight stabilizer; And fire retardant and antioxidant, and adopt the shearing stirring of three-dimensional high-speed, keep the temperature of 60-80 DEG C to stir 0.1-0.5 hour with the speed of 500-1000r/min in the process simultaneously;
5) pressurized heat nitrogen three-dimensional density mixing dispersion:
In polymerizer, slowly nitrogen injection displacement waterless nano polyamide mother starches the air in preparing device, heats up, and keep the pressure in polymerizer to be 1-1.2Mpa, until temperature reaches 150-180 DEG C after being pressurized to 0.5-0.8MPa;
6) react under density supercharging:
Keep pressure 1-1.2Mpa in polymerizer, temperature is 150-180 DEG C, and the time is 1-1.5 hour;
7) nitrogen pick-up supercharging:
Slowly nitrogen injection in polymerizer, is pressurized to 2.0-2.5MPa, until temperature reaches 240-300 DEG C;
8) rapid depressurization be incubated balance after on-line checkingi:
Unload after detected temperatures and pressure and be depressed into 0.5MPa and be incubated balance, open smelting furnace and pump material, and cut into slices after unloading pressure balanced 2-3 hour, wherein section adopts water cutting process or dry cutting process to cut into slices;
9) packaging warehouse-in:
Carry out extracting after feed bin enters, dewater, drying, solid phase, vibrations screening step after discharging bin, and carry out vacuum packaging and warehouse-in.
This step is as adopted batchwise polymerization, and its process will meet the condition of first inflating pressure, rear intensification polymerization; As adopted continuous polymerization, its process needs while material enters polymerization pipe, uses high-pressure pump supercharging.
Proportioning in this step: by constituent content (weight portion): monomer of polyamide 99.5-60 part, female slurry 0.5-40 part, distilled water 8-20 part, fire retardant 0.5-12 part, antioxidant 0.5-8 part.Wherein fire retardant can select APP etc., and antioxidant can select BHT etc.The polymerization of 6-9 hour its process time is by cut into slices after Melt Pump discharging (adopting water cutting process or dry cutting process to cut into slices).
Operation control stress point: nano imvite dispersion, nano imvite precipitation, nano imvite secondary agglomeration, exhaust and water suction, thickening technology.
Effect prepared by density polycondensation reaction: solve the difficult problem that technology appears in nanometer polyamide engineering plastics in its batch production process, the factors such as the dispersion of such as nano imvite is uneven, the precipitation phenomenon of nano imvite, the polymerization of nano imvite remains, the secondary agglomeration of nano imvite, nanometer polyamide cost are excessive.
Claims (7)
1. the process for the preparation of the density polycondensation reaction of Nano polyamide composite, described process adopts density polycondensation reactor, comprise polymerizer (1), fixed station (2) and spiral system, described polymerizer (1) is fixed on fixed station (2), and described spiral system comprises screw motor (3), helical axis (7) and auger leaf (8); It is characterized in that, said method comprising the steps of:
1) monomer of polyamide is checked: the monomer of polyamide in this step is caprolactam, nylon salt and/or nylon 1010;
2) monomer of polyamide is measured: each constituent content of metering monomer of polyamide;
3) check density polycondensation reactor, after start, adopt the shearing stirring of three-dimensional high-speed: while intensification, stir 1.5-2 hour with the speed of 2500-3000r/min; When being warming up to 60-80 DEG C, input waterless nano polyamide mother slurry, and stir 1.5-2 hour with the speed of 500-1000r/min;
4) add solution and adopt the shearing stirring of three-dimensional high-speed:
Wherein solution adopts distilled water as ring opening agent, and the one in acetic acid, sulfuric acid, hydrochloric acid, phosphoric acid, phosphorous acid is as molecular weight stabilizer; And fire retardant and antioxidant, and adopt the shearing stirring of three-dimensional high-speed, keep the temperature of 60-80 DEG C to stir 0.1-0.5 hour with the speed of 500-1000r/min in the process simultaneously;
5) pressurized heat nitrogen three-dimensional density mixing dispersion: slowly nitrogen injection replaces the air in waterless nano polyamide mother slurry preparing device in the polymerizer in density polycondensation reactor, heat up after being pressurized to 0.5-0.8MPa, and keep the pressure in polymerizer to be 1-1.2MPa, until temperature reaches 150-180 DEG C;
6) react under density supercharging: keep pressure 1-1.2MPa in polymerizer, temperature is 150-180 DEG C, and the time is 1-1.5 hour;
7) nitrogen pick-up supercharging: slowly nitrogen injection in polymerizer, is pressurized to 2.0-2.5MPa, until temperature reaches 240-300 DEG C;
8) rapid depressurization be incubated balance after on-line checkingi: unload after detected temperatures and pressure and be depressed into 0.5MPa and be incubated balance, open smelting furnace after unloading pressure balanced 2-3 hour and pump material, and cut into slices, wherein section adopts water cutting process or dry cutting process to cut into slices;
9) packaging warehouse-in: after section through feed bin enter and carry out extracting, dewater, drying, solid phase, vibrations screen after discharging bin, carry out vacuum packaging and warehouse-in;
The preparation of described waterless nano polyamide mother slurry comprises the following steps:
21) monomer of polyamide is checked: the technical grade caprolactam that selecting liquidity is good and one-level nylon salt;
22) monomer of polyamide is measured: caprolactam and the weight portion of nylon salt are that 8-9 part is than 2-1 part;
23) checkout facility, adds solution after start and stirs with medium-shear formula: the solution wherein added is chemical pure absolute ethyl alcohol, and stirs 0.5-1.0 hour with the speed of 25-50r/min;
24) heat up stir after vacuumize: stir 1.5-2.0 hour with the speed of 25-50r/min while of being warming up to 70-75 DEG C and open and vacuumize and steam in piece-rate system removing drier and air, the closedown vacuum pumping valve when the Pressure gauge display pressure on waterless nano polyamide mother slurry preparing device be-0.1MPa;
25) waterless nano imvite powder high-speed stirred is received: receive the three-dimensional dry waterless nano imvite powder of input and also carry out three-dimensional high-speed shearing stirring 1-1.5 hour with the speed of 300-1000r/min;
26) disperse with hot nitrogen pressurized three dimension: slowly nitrogen injection in waterless nano polyamide mother slurry preparing device, heat up after being pressurized to 1.2-1.5MPa, and keep the pressure in waterless nano polyamide mother slurry preparing device to be 2.0-2.5MPa, until temperature reaches 220-240 DEG C;
27) comprehensively affine: to keep temperature in waterless nano polyamide mother slurry preparing device to be 220-240 DEG C, nitrogen pressure 2.0-2.5MPa, retention time 2-2.5 hour;
28) carry out step-down after on-line checkingi and be incubated balance: unloading after being depressed into 0.5MPa and be also incubated balance 0.5-1 hour;
29) by step 28) in waterless nano polyamide mother slurry input density reaction condensation kettle, open delivery pump, the waterless nano polyamide prepared mother slurry be delivered in density reaction polycondensation polymerizer;
Described mother's slurry preparing device comprises cavity and platform, cavity is fixed on platform, cavity top right side is provided with inflated with nitrogen mouth, device cavity top left side is provided with dog-house, two heating mouths of pipe are provided with on the right side of cavity, connect gas-liquid separation device and air exhauster successively on the left of cavity, cavity bottom is provided with metering outlet, and stirring system is installed at cavity top center place;
Described stirring system comprises motor, drive link and paddle, drive link top access motor, and paddle is fixed on drive link; Paddle side is coniform, and drive link moves up and down within the specific limits, and stirring system realizes three-dimensional free to tumble;
Inside cavity installs radiating tube, and radiating tube is communicated with the heating mouth of pipe, and described radiating tube solid is arranged in device cavity; Described radiating tube comprises ring wall radiating tube and vertical radiating tube, and ring wall heat radiation pipe ring is put at device inside cavity chamber wall, and described vertical radiating tube vertically accesses ring wall radiating tube, and is in two paddle interlayers;
Its medium speed 0-3000 rev/min, nitrogen pressure 0-2.5MPa; Between cavity temperature 60-300 DEG C.
2. process according to claim 1, it is characterized in that: screw motor (3) is arranged on the top center place of described polymerizer (1), helical axis (7) is arranged on the inside of described polymerizer (1) and is connected on screw motor (3), auger leaf (8) is fixed on helical axis (7), and described auger leaf (8) middle part is provided with rotational viscometer.
3. process according to claim 1, is characterized in that: described polymerizer (1) inside is provided with three-dimensional heat dissipation oil pipe, and described three-dimensional heat dissipation oil pipe accesses into deep fat mouth (6); Described polymerizer (1) top and the bottom, both sides are installed into deep fat mouth (6) respectively.
4. process according to claim 3, it is characterized in that: described three-dimensional heat dissipation oil pipe comprises the oil pipe that vertically dispels the heat (9) and level heat radiation oil pipe (10), the adherent ring of described vertical heat radiation oil pipe (9) is put at polymerizer (1) inner chamber wall, described level heat radiation oil pipe (10) access is vertically dispelled the heat oil pipe (9), and described level heat radiation oil pipe (10) is in two auger leaf (8) interlayers.
5. process according to claim 1, is characterized in that: described polymerizer (1) top left side is provided with charging aperture (4), and top right side is provided with pressure nitrogen mouth (5).
6. the Nano polyamide composite adopting the described process of one of claim 1-5 to prepare, it is characterized in that, described composite is generated by the following weight component reaction in reactor: monomer of polyamide 99.5-60 part, waterless nano polyamide mother slurry 0.5-40 part, distilled water 8-20 part, fire retardant 0.5-12 part, antioxidant 0.5-8 part.
7. Nano polyamide composite according to claim 6, is characterized in that, described monomer of polyamide is caprolactam, nylon salt and/or nylon 1010.
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| CN1982373A (en) * | 2005-12-12 | 2007-06-20 | 上海杰事杰新材料股份有限公司 | Production of peel montmorillonite/casting nylon nano-composite material |
| CN101596440A (en) * | 2009-06-30 | 2009-12-09 | 四川晨光科新塑胶有限责任公司 | A kind of macromolecular material polymerization reaction kettle |
| CN201394451Y (en) * | 2009-05-21 | 2010-02-03 | 无锡科伦达化工热力装备有限公司 | Novel polymeric kettle |
| CN103122064A (en) * | 2012-12-21 | 2013-05-29 | 中仑塑业（福建）有限公司 | Fire-retarding nylon nanometer composite material and preparation method thereof |
| CN203610138U (en) * | 2013-11-21 | 2014-05-28 | 倪任林 | Densification and poly-condensation reactor |
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| CN1982373A (en) * | 2005-12-12 | 2007-06-20 | 上海杰事杰新材料股份有限公司 | Production of peel montmorillonite/casting nylon nano-composite material |
| CN201394451Y (en) * | 2009-05-21 | 2010-02-03 | 无锡科伦达化工热力装备有限公司 | Novel polymeric kettle |
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Effective date of registration: 20170122 Address after: Guo village in Yueqing city of Zhejiang province in 325608 Shifan town in Wenzhou City Patentee after: Chen Hanmeng Address before: 325608 Wenzhou City, Yueqing Province, Hongqiao Town, West Industrial Zone, West Creek Road 119-127 Patentee before: Ni Renlin Patentee before: Ni Chunyang |