CN109535701A - A kind of 6 direct injection of nylon molding efficient enhanced flame retarding function master batch and preparation method thereof - Google Patents
A kind of 6 direct injection of nylon molding efficient enhanced flame retarding function master batch and preparation method thereof Download PDFInfo
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- C08K7/14—Glass
Abstract
The invention belongs to modifying plastics and processing technique field more particularly to a kind of efficient enhanced flame retarding function master batches and preparation method thereof that may be directly applied to the injection moulding processing of 6 product of nylon；The functional agglomerate is composed of two kinds of master batches of A and B, and the mass percentage composition of A master batch is as follows: 50.0~70.0 wt.%, Gao Liudong nylon 6 resin of glass fibre, 15.0~35.0 wt.%, maleic anhydride are grafted from 3.0~10.0wt.% of aggressiveness, 3.0~6.0 wt.% of star nylon 6 resin, 0.1~0.3 wt.% of antioxidant；Functional agglomerate prepared by the present invention is compared with conventional plastic functional agglomerate, it avoids in enhanced halogen-free flame-retardant nylon 6 modified system process, modified performance mutually damages caused by mutually shearing abrasion with fire retardant because of glass fibre, it solves above-mentioned two unmatched problem of modified system processing temperature simultaneously, significantly improves the modified performance of the two；The master batch has easily dispersion easy processing feature, and rear injection molding can directly be simply mixed according to the ratio with nylon 6 resin.
Description
Technical field
The invention belongs to modifying plastics and processing technique field more particularly to one kind may be directly applied to 6 product of nylon note
Penetrate the efficient enhanced flame retarding function master batch and preparation method thereof of processing and forming.
Background technique
Implementing melt blending using double screw extruder is the conventional method for implementing modifying plastics, is squeezed using parallel dual-screw
Thermoplastic can be carried out serialization melt blending extrusion with all kinds of modified additives and made by the efficiently excellent mixing efficiency of machine out
Grain, prepared modified special material will be re-used for injecting or extrusion machine-shaping goes out various products.This technology path is not only
Effectively improve the physical mechanical properties such as intensity, toughness, rigidity, creep resistance, the warp resistance of plastic products, but also can
Assign the special physical chemistry effects such as fire-retardant plastic products, conductive, thermally conductive, magnetic conduction, antistatic, antibacterial.Although the technology road
Position of mainstream is occupied in current modifying plastics manufacture field, however in the technology implementation process, all substrates resin with change
Property additive all have to pass through twin-screw extrusion and injection moulding melt-processed thermal history twice, polymer molecular chain and its correlation
Modified additive will appear different degrees of degradation, and the Long Service Life for causing plastic products final shortens.This technology road
Line also increases process-cycle and the energy consumption of modified plastics, runs counter to the basic concept of the current sustainable industrial development of green.This
Outside, for the modified additive of different shape and different materials matter there may be the greatest differences of process unit and processing technology,
Such as high temperature high shear effect can be played using twin-screw extrusion machining, the modified performances such as activeness and quietness are performed into maximum limit
Degree；And utilize the low temperature of mixer and mediate effect for a long time, can will not heatproof auxiliary agent, low melting point auxiliary agent, low bulk density it is difficult
The various additives such as feeding powder, hygroscopic auxiliary agent, liquid and colloid auxiliary agent, whisker are sufficiently mixed and are uniformly dispersed, however adopt
It then cannot achieve such processing effect with double screw extruder melting extrusion blending.
It is in the development process of current plastics modification technology field that modified plastics is prepared by the way of plastic functional master batch
An important measures.Passed through using the functional agglomerate well prepared in advance containing high concentration modified additive and plastic raw materials double
Screw extruder or mixer implement melt blending and extruding pelletization, can not only more effectively improve point of additive in the base
It dissipates property and obtains superior modified effect, additionally it is possible to which the dust pollution for reducing processing workshop is to realize that modified plastics green adds
One of important channel of work.With the rapid development of the functionalized design and technology of preparing of plastic master batch, the function of plastic master batch
It is stronger and stronger, kind is more and more abundant, application field is also constantly expanded, and the master batch applications of modifying plastics will become not
Carry out an indispensable Key Common Technologies in modified plastics cleanly production field.
Currently, the requirement to its performance carrys out higher and higher, many application fields with the continuous expansion in plastic applications field
Plastic products are needed to have multi-functionals such as high intensity, high tenacity, high temperature resistant, fire-retardant, thermally conductive, conductive and excellent comprehensive
Can, the modified additive and auxiliary agent that add various material and form are required to the preparation processing of each modified materials, this
Great challenge is proposed to conventional plastic modification technology.Although the development of plastic functional master-batch techniques provides for this challenge
Technical support, but many technical problems are still had in the actual operation process.Wherein main technical problem includes following three
Point: 1. the modified additive and auxiliary agent of unlike material and form only could to the maximum extent using different process units and technique
Play its respective modified effect；2. the modified additive and auxiliary agent and matrix resin of unlike material and form are filled in same processing
Modified performance caused by wearing can be mutually sheared because of it for implementation melt blending on (double screw extruder or mixer) mutually to damage；3. no
The processing temperature otherness of same material modified additive and auxiliary agent and matrix resin melt blending is big, if simultaneously in identical processing
Implement to be blended in equipment that serious temperature mismatch problem can be generated, modified effect is caused to be deteriorated.Such as enhancing flame retardant type
Modifying plastics system, when enhancing glass fibre, organic fire-retardant and inorganic fire-retarded synergist simultaneously and matrix resin in double spiral shells
It, can be because of fiber major diameter caused by wearing each other between fiber and inorganic particulate when carrying out melt blending in bar extruder or mixer
Than declining to a great extent, fiber-reinforcing effect is caused to be deteriorated；Fiber and organic fire-retardant can also lead to fire retardant point because of internal frictional heat generation
Solution, seriously affects flame retardant effect.In addition, the processing temperature of fiberglass reinforced plastics modified system and flame-retardant modified plastics system
There are apparent differences, and the processing temperature for usually enhancing modified system is 40~70 DEG C higher than the processing temperature of flame-retardant system, such as
These two types of modified systems are implemented melt blending under same process unit same process conditions by fruit, will damage one of body
Modification effect of system.Modified performance mutually damages problem between above-mentioned different additive system, at present in the high performance of plastics and more
Functional modification technology implementation process is especially prominent.
For plastics high performance and multifunction modified synchronous implementation process the problem of, invention
The thinking of double master batches is combined using function to implement the enhancing and multi-functional modified developing thought of plastics.Change for plastics
Property additive material the characteristics of, will be blended processing in there may be the additives that modified performance mutually damages to be prepared into A and two kinds of B respectively
Master batch, and the structure of the modified additive according to contained by both master batches, material and physical property feature, separately design out respective height
Dispersed system.Then two kinds of functional agglomerate synchronous applications are injection moulded in plastic products and are processed, can avoid modeling in this way
In material enhancing and functional modification process the modified additive efficiency that generates mutually damage, processing temperature mismatch problem, simultaneously
The maximum modification efficiency of unlike material modified additive and auxiliary agent is played, also can avoid traditional function master batch and matrix resin again
Extruding pelletization processing to effectively improve the effect of modifying plastics, reduce the production of production and processing period, and has saved production energy
Source consumption.This thinking will provide important approach to realize that energy-efficient green plastic is processed.
Nylon 6 is the maximum engineering plastics of current global dosage, by changing to the progress high performance of nylon 6 and functionalization
Property, it can greatly expand its application field.As a kind of important modified nylon 6 PP Pipe Compound, enhance flame retardant type nylon 6 composite in machine
The fields such as tool, automobile, track efficiency, electronic apparatus equipment are widely applied.But it is dedicated in the modification of enhanced fire-retardant Nylon 6
In the processing preparation process of material, inorganic reinforcing fiber and fire retardant are added to progress melt blending in nylon 6 resin simultaneously and squeezed
Out, it just will appear typical additive agent modified efficiency and mutually damage phenomenon.
Summary of the invention
Difficulty is mutually damaged to solve modified performance present in existing 6 PP Pipe Compound preparation process of glass fiber reinforced flame retardant nylon
Topic, the present invention provide a kind of efficient enhancing flame retarding function master batch that may be directly applied to the injection moulding processing of nylon 6 plastic product
And preparation method thereof.The functional agglomerate is composed of two kinds of functional agglomerates of A and B.Wherein A master batch is mainly by glass fibre, height
Nylon 6 and low sticky star nylon 6 resin composition are flowed, it is female to be prepared into long fiber reinforcement toughening by melting pultrusion method processing
Grain；B master batch is mainly by bromo- antimony compound flame retardant and with maleic anhydride grafted elastomeric from the ultra-dispersed property vector resin based on aggressiveness
Composition, is prepared as flame retardant type functional agglomerate by mixer.It can use to obtain following skill with the method for processing two kinds of master batches respectively
Art advantage: it 1. avoids glass fibre and generation internal frictional heat generation is directly blended with bromide fire retardant, lead to point of halogenated flame retardant
Solution；2. avoiding between inorganic fire-retarded synergist (such as antimony oxide or zinc borate) and glass fibre because mutually shearing abrasion is made
At Fiber Aspect Ratio decline to a great extent；3. solving glass fiber reinforced nylon 6 and bromo- 6 two kinds of modifications of antimony compositional flame-retardant nylon
The unmatched problem of system melt blending processing temperature；4. melting pultrusion technique is utilized to prepare than traditional chopped strand glass fiber
Enhance the enhancing master batch of the bigger Fiber Aspect Ratio of master batch；5. using maleic anhydride grafted elastomeric from aggressiveness respectively as A and B master batch
Carrier component, reactive terminal group can have maximum contact with the end group of nylon 6 resin in the environment of non-antiflaming powder interferes
Chance plays its toughening effect to greatest extent, moreover it is possible to the interface adhesion in formula between organic-inorganic each component is improved, while
It has been improved composite melt mobility, has improved product surface finish and non-deformability.In addition, being directed to two kinds of mothers of A and B
The physical property characteristic for the modified additive that grain is loaded all in accordance with it implements and the formula system of its lubrication and high efficiency dispersion is promoted to set
Meter.Therefore, rear injection molding directly can be simply mixed in A and B master batch with nylon 6 resin according to a certain ratio according to performance requirement,
Also can increase the injection molding together of other resins and/or master batch: including but not limited to: nylon66 fiber, copolymer nylon, Masterbatch,
Filler parent granule, plasticizing mother particle, nucleation master batch, chain extension master batch, lubrication master batch, antistatic master granule, anti-aging master batch, conductive agglomerate,
Heat conduction master batch, laser carving master batch, silicone master batch and antibacterial matrices.Due to it is used in injection molding machine be that single screw rod melt promotes mode,
It is very faint to the shear action of glass fibre and fire retardant, substantially will not modification effect to the two damage.Therefore, this
One method not only effectively prevents glass fibre and fire retardant because again by the modification caused by the processing of twin-screw blending extrusion
Efficiency is mutually damaged, and is greatly improved to the flame-retardant modified effect of the enhancing of nylon 6, at the same also make invention master batch have greatly
Design is flexible, can be required to carry out more resins, the joint injection molding of more master batches according to client's difference, and quickly, easily achieve the goal requirement,
To practice modifying plastics formula and processing technology optimized design theory of the 1+1 greater than 2.
To achieve the above object, The technical solution adopted by the invention is as follows:
A kind of efficient enhanced flame retarding function master batch of 6 direct injection of nylon molding, the functional agglomerate is by two kinds of master batches of A and B
It is composed, the mass percentage composition of the A master batch is as follows: 50.0~70.0 wt.%, Gao Liudong nylon of glass fibre, 6 tree
15.0~35.0 wt.% of rouge, maleic anhydride be grafted from 3.0~10.0wt.% of aggressiveness, 3.0~6.0 wt.% of star nylon 6 resin,
0.1~0.3 wt.% of antioxidant, the mass percentage composition of the B master batch are as follows: 45.0~70.0 wt.% of bromide fire retardant,
Inorganic fire-retarded 15.0~40.0 wt.% of synergist, maleic anhydride grafted elastomeric are from 5.0~10.0 wt.% of aggressiveness, star nylon
6 resin, 3.0~8.0 wt.%, 1.0~3.0 wt.% of dispersing agent, 0.5~1.0 wt.% of lubricant.
Further, the glass fibre is continuous long glass fiber.
Further, the inherent viscosity of the high flowing nylon 6 is 1.8~2.0.
Further, the star nylon 6 resin is three arms, four arms, six arms or eight arm star nylon 6.
Further, the maleic anhydride grafted elastomeric is the horse being crosslinked by sodium, calcium, magnesium, barium or zinc ion from aggressiveness
Maleic anhydride grafted ethylene-octene-acrylic acid copolymer elasticity is from aggressiveness.
Further, the antioxidant is 1,3,5- trimethyls -2,4,6- (3,5- di-t-butyl -4- hydroxyphenylmethyl) benzene
(trade name antioxidant 1330) and bis- (2,4-dicumylphenyl) pentaerythritol diphosphites (trade name antioxidant
It S9228 is in mass ratio) compound of 1:1 composition.
Further, the bromide fire retardant is decabromodiphenylethane, brominated epoxy resin, brominated Polystyrene and poly- bromine
Change any one or a few in styrene, preferably brominated Polystyrene.
Further, the inorganic fire-retarded synergist is any one in antimony oxide and zinc borate or two kinds.
Further, the dispersing agent is one of zinc stearate, aluminum foil stearate, magnesium stearate and lithium stearate or several
Kind.
Further, the lubricant be ethylene-vinyl acetate co-polymer wax, ethylene-acrylic copolymer wax, E wax,
One or more of OP wax and dimethyl silicone polymer.
A kind of method for preparing efficient enhanced flame retarding function master batch of 6 direct injection of nylon molding, the method are related to A
The preparation method of master batch and B master batch, the preparation method of the A master batch the following steps are included:
(1) weigh according to the ratio glass fibre, Gao Liudong nylon 6 resin, star nylon 6 resin, maleic anhydride grafted elastomeric from
Powder therein and pellet are pre-mixed uniformly with super mixer respectively, and pass through major ingredient and auxiliary material material by aggressiveness and antioxidant
Bucket is added progress melt blending extrusion in double screw extruder and is prepared into composite melt；
(2) composite melt obtained in step (1) is directly squeezed by the mouth mold being connected with double screw extruder head
In the die cavity of impregnation mold, at the same time, continuous long glass fiber enters die cavity by another mouth mold of the impregnation mold,
It is impregnated in melt by the draw of die cavity inner guide wire roller, the glass fiber strand after melt impregnation is involved out of die cavity
And after cooling, the elongate in shape pellet that length is 8~12 mm is cut by pelleter, to obtain the A master batch.
Further, the barrel of double screw extruder to head temperature of each section is controlled at 230~280 DEG C, and screw speed is
150~200 revs/min；The mould-cavity temperature control of impregnation mold at 275~285 DEG C, dragger speed control 50~70 meters/
Minute.
A kind of method for preparing efficient enhanced flame retarding function master batch of 6 direct injection of nylon molding, the method are related to A
The preparation method of master batch and B master batch, the preparation method of the B master batch the following steps are included:
(1) weigh according to the ratio bromide fire retardant, inorganic fire-retarded synergist, star nylon 6 resin, maleic anhydride grafted elastomeric from
Aggressiveness, dispersing agent and lubricant, and put into be transferred to after mixing in mixer in super mixer and carry out hot milling,
Obtain bulk blend；
(2) the bulk blend obtained in step (1) is fed into single screw extrusion machine by taper feeder, is squeezed out simultaneously through melting
It is granulated, obtains the B master batch.
Further, the melting temperature of mixer is 110~130 DEG C, and mixing time is 15~20 minutes；Single screw rod squeezes out
The screw speed of machine is 150~200 revs/min, and barrel temperature is 160~165 DEG C.
It is using the beneficial effect of technical solution of the present invention:
It (1) is, using the method for A master batch and B master batch separate machined, to be prepared for growing respectively for the physical property feature of modified additive
Glass fiber reinforcement master batch (A master batch) and bromine system compositional flame-retardant master batch (B master batch), effectively prevent nylon 6 and glass fibre and
When the direct melt blending of bromide fire retardant squeezes out, because the modified performance that mutually shearing and abrasion generate mutually damages, while also solving
Two unmatched technical problems of modified system processing temperature, to significantly improve the respective modified effect of two kinds of modified additives
Energy.
(2) the long master batch of glass fiber reinforcement (A master batch) is prepared by using continuous fiber pultrusion technique, ratio can be obtained
The bigger Fiber Aspect Ratio of traditional chopped strand glass fiber reinforcement master batch, to greatly improve the enhancing efficiency of glass fibre.
(3) nylon 6, low sticky star nylon 6 and maleic anhydride grafted elastomeric are flowed from aggressiveness as glass fibers using high
The joint vector of dimension enhancing master batch, can not only effectively increase the interface adhesion of glass fibre Yu nylon 6, moreover it is possible to utilize these
The high flow behavior of carrier makes the A master batch of preparation when for product injection machine-shaping, and glass fibre is in nylon 6 resin base
Superior dispersion effect is obtained in body.
(4) equally make using the excellent maleic anhydride grafted elastomeric of mobile performance from aggressiveness and low sticky star nylon 6
For the joint vector for preparing B master batch, from making A master batch and B master batch be provided commonly for nylon 6 plastic product direct injection processing and forming
When, variety classes modified additive can obtain evenly dispersed effect in resin matrix.And maleic anhydride is used to be grafted
Elasticity is used as the carrier component of A master batch and B master batch from aggressiveness simultaneously, is not only able to mention using its high fluidity for modified additive
For excellent dispersibility, moreover it is possible to play to the good toughening effect of nylon 6.
(5) functional agglomerate prepared by the present invention is ingenious to have used two kinds of different function compared with conventional plastic functional agglomerate
The combination of energy master batch is processed respectively, not only solves the modified effect of different additive in modified plastics preparation process
The problem that can mutually damage, produces the modified effect that 1+1 is much larger than 2, also has easily dispersion easy processing feature, can be moulded according to nylon 6
The performance requirement of material products directly applies to plastics after A master batch and B master batch are simply mixed with nylon 6 resin according to a certain ratio
The injection moulding of product is processed.Due to it is used in injection molding machine be that single screw rod melt promotes mode, to glass fibre and fire retardant
Shear action it is very faint, substantially will not modification effect to the two damage, be modified so as to avoid common plastics
Matrix resin and modified master batch in journey be secondary or the multiple melting mixing by processing equipment caused by antioxidant loss, increase
Strong Fiber Aspect Ratio loss and matrix resin thermal cracking problem, significantly improve the mechanical performance and long-time service of 6 product of nylon.
(6) present invention enhances flame-retardant modified efficiency simultaneously effectively improving nylon 6, simplify modifying plastics procedure of processing,
Reduce the process-cycle, reduce energy consumption, improve production efficiency, is truly realized green chemical industry idea of development.Of the invention
Combination type functional master batch can flexibly deploy A master batch and B is female according to customer requirement in nylon 6 plastic product process of injection molding
The combination of grain and its its performance and cost are adjusted with the proportion of resin raw material.Methods and techniques of the invention can answer extensively
Injection moulding and high performance and functional modification integration processing for all kinds of nylon 6 plastic products.
Specific embodiment
The following examples can make those skilled in the art that the present invention be more fully understood, but these embodiments are not
Limiting the scope of the invention." one embodiment " or " embodiment " referred to herein, which refers to, may be included in the present invention at least
A particular feature, structure, or characteristic in one implementation.In the present specification different places occur " in one embodiment
In " the same embodiment not is referred both to, nor the individual or selective embodiment mutually exclusive with other embodiments.
Embodiment 1
A kind of efficient enhanced flame retarding function master batch of 6 direct injection of nylon molding, is composed of, A two kinds of master batches of A and B
The raw material mass mixture ratio of master batch is as follows:
| Glass fibre | 70.0 kg |
| Height flowing nylon 6 | 20.0 kg |
| Four arm star nylon 6 | 5.7 kg |
| Maleic anhydride is grafted sodium ion cross-linked ethylene-octene-acrylic acid copolymer elasticity from aggressiveness | 4.0 kg |
| Antioxidant | 300.0 g |
Antioxidant is 1,3,5- trimethyl -2,4,6- (3,5- di-t-butyl -4- hydroxyphenylmethyl) benzene (trade name antioxidant
1330) and bis- (2,4-dicumylphenyl) pentaerythritol diphosphites (trade name antioxidant S9228) are 1 in mass ratio:
The compound of 1 composition.
The raw material mass mixture ratio of its B master batch is as follows:
| Brominated Polystyrene | 70.0 kg |
| Antimony oxide | 15.0 kg |
| Maleic anhydride is grafted sodium ion cross-linked ethylene-octene-acrylic acid copolymer elasticity from aggressiveness | 8.0 kg |
| Four arm star nylon 6 | 5.0 kg |
| Zinc stearate | 1.4 kg |
| Ethylene-vinyl acetate copolymer wax | 600.0 g |
A master batch the preparation method is as follows: weigh all raw materials by above-mentioned quality proportioning requirement, then by height flowing nylon 6 and horse
Two kinds from aggressiveness pellets of maleic anhydride grafted sodium ion cross-linked ethylene-octene-acrylic acid copolymer elasticity and four arm star nylon 6 with it is anti-
Two kinds of powders of oxygen agent put into different high-speed mixers respectively and are uniformly mixed, then the granule mixture mixed and powder are mixed
Conjunction object passes through major ingredient respectively and auxiliary material hopper is added progress melt blending extrusion in double screw extruder and is prepared into composite melt,
The barrel of double screw extruder to head temperature of each section is controlled at 230~280 DEG C, and screw speed is 190 revs/min, then should
Composite melt is directly squeezed into the die cavity of impregnation mold by the mouth mold being connected with double screw extruder head, same with this
When, continuous long glass fiber (direct yarn) is entered into die cavity by another mouth mold of the impregnation mold, by leading in die cavity
The draw of roll dies impregnates in melt, and the mould-cavity temperature of impregnation mold is controlled at 285 DEG C, and dragger speed control is 70
M/min, the glass fiber strand after melt impregnation involves and after cooling out of die cavity, and being cut into length by pelleter is
The elongate in shape pellet of 10 mm, to obtain the A master batch.
B master batch the preparation method is as follows: weigh all raw materials by above-mentioned quality proportioning requirement, and put into mixed at high speed
It is transferred to after mixing in device in mixer and carries out hot milling, the melting temperature of mixer is 125 DEG C, and mixing time is 20 points
Clock feeds single screw extrusion machine by taper feeder, squeezes out and be granulated through melting, obtain then by acquired bulk blend
Obtain the B master batch；The screw speed of single screw extrusion machine is 175 revs/min, and barrel temperature Discrete control is at 160~165 DEG C.
Embodiment 2
A kind of efficient enhanced flame retarding function master batch of 6 direct injection of nylon molding, is composed of, A two kinds of master batches of A and B
The raw material mass mixture ratio of master batch is as follows:
| Glass fibre | 50.0 kg |
| Height flowing nylon 6 | 35.0 kg |
| Three-arm star-shaped nylon 6 | 4.7 kg |
| Maleic anhydride is grafted zinc ion cross-linked ethylene-octene-acrylic acid copolymer elasticity from aggressiveness | 10.0 kg |
| Antioxidant | 300.0 g |
Antioxidant is 1,3,5- trimethyl -2,4,6- (3,5- di-t-butyl -4- hydroxyphenylmethyl) benzene (trade name antioxidant
1330) and bis- (2,4-dicumylphenyl) pentaerythritol diphosphites (trade name antioxidant S9228) are 1 in mass ratio:
The compound of 1 composition.
The raw material mass mixture ratio of its B master batch is as follows:
| Brominated Polystyrene | 30.0 kg |
| Decabromodiphenylethane | 25.0 kg |
| Antimony oxide | 20.0 kg |
| Zinc borate | 10.0 kg |
| Maleic anhydride is grafted zinc ion cross-linked ethylene-octene-acrylic acid copolymer elasticity from aggressiveness | 8.0 kg |
| Three-arm star-shaped nylon 6 | 5.0 kg |
| Magnesium stearate | 1.0 kg |
| E is cured | 1.0 kg |
A master batch the preparation method is as follows: weigh all raw materials by above-mentioned quality proportioning requirement, then by height flowing nylon 6 and horse
Two kinds from aggressiveness pellets of maleic anhydride grafted zinc ion cross-linked ethylene-octene-acrylic acid copolymer elasticity and three-arm star-shaped nylon 6 and anti-
Two kinds of powders of oxygen agent put into different high-speed mixers respectively and are uniformly mixed, then the granule mixture mixed and powder are mixed
Conjunction object passes through major ingredient respectively and auxiliary material hopper is added progress melt blending extrusion in double screw extruder and is prepared into composite melt,
The barrel of double screw extruder to head temperature of each section is controlled at 230~280 DEG C, and screw speed is 200 revs/min, then should
Composite melt is directly squeezed into the die cavity of impregnation mold by the mouth mold being connected with double screw extruder head, same with this
When, continuous long glass fiber (direct yarn) is entered into die cavity by another mouth mold of the impregnation mold, by leading in die cavity
The draw of roll dies impregnates in melt, and the mould-cavity temperature of impregnation mold is controlled at 280 DEG C, and dragger speed control is 70
M/min, the glass fiber strand after melt impregnation involves and after cooling out of die cavity, and being cut into length by pelleter is
The elongate in shape pellet of 12 mm, to obtain the A master batch.
B master batch the preparation method is as follows: weigh all raw materials by above-mentioned quality proportioning requirement, and put into mixed at high speed
It is transferred to after mixing in device in mixer and carries out hot milling, the melting temperature of mixer is 130 DEG C, and mixing time is 20 points
Clock feeds single screw extrusion machine by taper feeder, squeezes out and be granulated through melting, obtain then by acquired bulk blend
Obtain the B master batch；The screw speed of single screw extrusion machine is 165 revs/min, and barrel temperature Discrete control is at 160~165 DEG C.
Embodiment 3
A kind of efficient enhanced flame retarding function master batch of 6 direct injection of nylon molding, is composed of, A two kinds of master batches of A and B
The raw material mass mixture ratio of master batch is as follows:
| Glass fibre | 60.0 kg |
| Height flowing nylon 6 | 25.0 kg |
| Three-arm star-shaped nylon 6 | 4.7 kg |
| Maleic anhydride is grafted barium ions cross-linked ethylene-octene-acrylic acid copolymer elasticity from aggressiveness | 10.0 kg |
| Antioxidant | 300.0 g |
Antioxidant is 1,3,5- trimethyl -2,4,6- (3,5- di-t-butyl -4- hydroxyphenylmethyl) benzene (trade name antioxidant
1330) and bis- (2,4-dicumylphenyl) pentaerythritol diphosphites (trade name antioxidant S9228) are 1 in mass ratio:
The compound of 1 composition.
The raw material mass mixture ratio of its B master batch is as follows:
| Brominated Polystyrene | 30.0 kg |
| Brominated epoxy resin | 30.0 kg |
| Antimony oxide | 25.0 kg |
| Maleic anhydride is grafted barium ions cross-linked ethylene-octene-acrylic acid copolymer elasticity from aggressiveness | 9.0 kg |
| Three-arm star-shaped nylon 6 | 4.0 kg |
| Aluminum foil stearate | 1.5 kg |
| Dimethyl silicone polymer | 500.0 g |
A master batch the preparation method is as follows: weigh all raw materials by above-mentioned quality proportioning requirement, then by height flowing nylon 6 and horse
Two kinds from aggressiveness pellets of maleic anhydride grafted barium ions cross-linked ethylene-octene-acrylic acid copolymer elasticity and three-arm star-shaped nylon 6 and anti-
Two kinds of powders of oxygen agent put into different high-speed mixers respectively and are uniformly mixed, then the granule mixture mixed and powder are mixed
Conjunction object passes through major ingredient respectively and auxiliary material hopper is added progress melt blending extrusion in double screw extruder and is prepared into composite melt,
The barrel of double screw extruder to head temperature of each section is controlled at 230~280 DEG C, and screw speed is 200 revs/min, then should
Composite melt is directly squeezed into the die cavity of impregnation mold by the mouth mold being connected with double screw extruder head, same with this
When, continuous long glass fiber (direct yarn) is entered into die cavity by another mouth mold of the impregnation mold, by leading in die cavity
The draw of roll dies impregnates in melt, and the mould-cavity temperature of impregnation mold is controlled at 280 DEG C, and dragger speed control is 70
M/min, the glass fiber strand after melt impregnation involves and after cooling out of die cavity, and being cut into length by pelleter is
The elongate in shape pellet of 12 mm, to obtain the A master batch.
B master batch the preparation method is as follows: weigh all raw materials by above-mentioned quality proportioning requirement, and put into mixed at high speed
It is transferred to after mixing in device in mixer and carries out hot milling, the melting temperature of mixer is 120 DEG C, and mixing time is 20 points
Clock feeds single screw extrusion machine by taper feeder, squeezes out and be granulated through melting, obtain then by acquired bulk blend
Obtain the B master batch；The screw speed of single screw extrusion machine is 150 revs/min, and barrel temperature Discrete control is at 160~165 DEG C.
Embodiment 4
A kind of efficient enhanced flame retarding function master batch of 6 direct injection of nylon molding, is composed of, A two kinds of master batches of A and B
The raw material mass mixture ratio of master batch is as follows:
| Glass fibre | 65.0 kg |
| Height flowing nylon 6 | 21.0 kg |
| Six arm star nylon 6 | 5.0 kg |
| Maleic anhydride is grafted calcium ion crosslinking ethylene-octene-acrylic acid copolymer elasticity from aggressiveness | 8.8 kg |
| Antioxidant | 200.0 g |
Antioxidant is 1,3,5- trimethyl -2,4,6- (3,5- di-t-butyl -4- hydroxyphenylmethyl) benzene (trade name antioxidant
1330) and bis- (2,4-dicumylphenyl) pentaerythritol diphosphites (trade name antioxidant S9228) are 1 in mass ratio:
The compound of 1 composition.
The raw material mass mixture ratio of its B master batch is as follows:
| Brominated epoxy resin | 65.0 kg |
| Antimony oxide | 20.0 kg |
| Maleic anhydride is grafted calcium ion crosslinking ethylene-octene-acrylic acid copolymer elasticity from aggressiveness | 5.0 kg |
| Six arm star nylon 6 | 8.0 kg |
| Lithium stearate | 1.0 kg |
| Ethylene-acrylic acid copolymer wax | 1.0 kg |
A master batch the preparation method is as follows: weigh all raw materials by above-mentioned quality proportioning requirement, then by height flowing nylon 6 and horse
Two kinds from aggressiveness pellets of maleic anhydride grafted calcium ion crosslinking ethylene-octene-acrylic acid copolymer elasticity and six arm star nylon 6 with it is anti-
Two kinds of powders of oxygen agent put into different high-speed mixers respectively and are uniformly mixed, then the granule mixture mixed and powder are mixed
Conjunction object passes through major ingredient respectively and auxiliary material hopper is added progress melt blending extrusion in double screw extruder and is prepared into composite melt,
The barrel of double screw extruder to head temperature of each section is controlled at 230~280 DEG C, and screw speed is 150 revs/min, then should
Composite melt is directly squeezed into the die cavity of impregnation mold by the mouth mold being connected with double screw extruder head, same with this
When, continuous long glass fiber (direct yarn) is entered into die cavity by another mouth mold of the impregnation mold, by leading in die cavity
The draw of roll dies impregnates in melt, and the mould-cavity temperature of impregnation mold is controlled at 275 DEG C, and dragger speed control is 70
M/min, the glass fiber strand after melt impregnation involves and after cooling out of die cavity, and being cut into length by pelleter is
The elongate in shape pellet of 8 mm, to obtain the A master batch.
B master batch the preparation method is as follows: weigh all raw materials by above-mentioned quality proportioning requirement, and put into mixed at high speed
It is transferred to after mixing in device in mixer and carries out hot milling, the melting temperature of mixer is 115 DEG C, and mixing time is 20 points
Clock feeds single screw extrusion machine by taper feeder, squeezes out and be granulated through melting, obtain then by acquired bulk blend
Obtain the B master batch；The screw speed of single screw extrusion machine is 160 revs/min, and barrel temperature Discrete control is at 160~165 DEG C.
Embodiment 5
A kind of efficient enhanced flame retarding function master batch of 6 direct injection of nylon molding, is composed of, A two kinds of master batches of A and B
The raw material mass mixture ratio of master batch is as follows:
| Glass fibre | 70.0 kg |
| Height flowing nylon 6 | 20.7 kg |
| Four arm star nylon 6 | 6.0 kg |
| Maleic anhydride is grafted magnesium ion cross-linked ethylene-octene-acrylic acid copolymer elasticity from aggressiveness | 3.0 kg |
| Antioxidant | 300.0 g |
Antioxidant is 1,3,5- trimethyl -2,4,6- (3,5- di-t-butyl -4- hydroxyphenylmethyl) benzene (trade name antioxidant
1330) and bis- (2,4-dicumylphenyl) pentaerythritol diphosphites (trade name antioxidant S9228) are 1 in mass ratio:
The compound of 1 composition.
The raw material mass mixture ratio of its B master batch is as follows:
| Decabromodiphenylethane | 35.0 kg |
| Brominated polystyrene | 30.0 kg |
| Antimony oxide | 20.0 kg |
| Maleic anhydride is grafted magnesium ion cross-linked ethylene-octene-acrylic acid copolymer elasticity from aggressiveness | 5.0 kg |
| Four arm star nylon 6 | 7.0 kg |
| Aluminum foil stearate | 2.0 kg |
| OP wax | 1.0 kg |
A master batch the preparation method is as follows: weigh all raw materials by above-mentioned quality proportioning requirement, then by height flowing nylon 6 and horse
Two kinds from aggressiveness pellets of maleic anhydride grafted magnesium ion cross-linked ethylene-octene-acrylic acid copolymer elasticity and four arm star nylon 6 with it is anti-
Two kinds of powders of oxygen agent put into different high-speed mixers respectively and are uniformly mixed, then the granule mixture mixed and powder are mixed
Conjunction object passes through major ingredient respectively and auxiliary material hopper is added progress melt blending extrusion in double screw extruder and is prepared into composite melt,
The barrel of double screw extruder to head temperature of each section is controlled at 230~280 DEG C, and screw speed is 150 revs/min, then should
Composite melt is directly squeezed into the die cavity of impregnation mold by the mouth mold being connected with double screw extruder head, same with this
When, continuous long glass fiber (direct yarn) is entered into die cavity by another mouth mold of the impregnation mold, by leading in die cavity
The draw of roll dies impregnates in melt, and the mould-cavity temperature of impregnation mold is controlled at 285 DEG C, and dragger speed control is 70
M/min, the glass fiber strand after melt impregnation involves and after cooling out of die cavity, and being cut into length by pelleter is
The elongate in shape pellet of 11 mm, to obtain the A master batch.
B master batch the preparation method is as follows: weigh all raw materials by above-mentioned quality proportioning requirement, and put into mixed at high speed
It is transferred to after mixing in device in mixer and carries out hot milling, the melting temperature of mixer is 125 DEG C, and mixing time is 18 points
Clock feeds single screw extrusion machine by taper feeder, squeezes out and be granulated through melting, obtain then by acquired bulk blend
Obtain the B master batch；The screw speed of single screw extrusion machine is 160 revs/min, and barrel temperature Discrete control is at 160~165 DEG C.
Embodiment 6
A kind of efficient enhanced flame retarding function master batch of 6 direct injection of nylon molding, is composed of, A two kinds of master batches of A and B
The raw material mass mixture ratio of master batch is as follows:
| Glass fibre | 67.0 kg |
| Height flowing nylon 6 | 22.7 kg |
| Four arm star nylon 6 | 5.0 kg |
| Maleic anhydride is grafted sodium ion cross-linked ethylene-octene-acrylic acid copolymer elasticity from aggressiveness | 5.0 kg |
| Antioxidant | 300.0 g |
Antioxidant is 1,3,5- trimethyl -2,4,6- (3,5- di-t-butyl -4- hydroxyphenylmethyl) benzene (trade name antioxidant
1330) and bis- (2,4-dicumylphenyl) pentaerythritol diphosphites (trade name antioxidant S9228) are 1 in mass ratio:
The compound of 1 composition.
The raw material mass mixture ratio of its B master batch is as follows:
| Brominated polystyrene | 35.0 kg |
| Decabromodiphenylethane | 27.0 kg |
| Antimony oxide | 23.0 kg |
| Maleic anhydride is grafted sodium ion cross-linked ethylene-octene-acrylic acid copolymer elasticity from aggressiveness | 10.0 kg |
| Four arm star nylon 6 | 6.0 kg |
| Aluminum foil stearate | 1.0 kg |
| OP is cured | 1.0 kg |
A master batch the preparation method is as follows: weigh all raw materials by above-mentioned quality proportioning requirement, then by height flowing nylon 6 and horse
Two kinds from aggressiveness pellets of maleic anhydride grafted sodium ion cross-linked ethylene-octene-acrylic acid copolymer elasticity and four arm star nylon 6 with it is anti-
Two kinds of powders of oxygen agent put into different high-speed mixers respectively and are uniformly mixed, then the granule mixture mixed and powder are mixed
Conjunction object passes through major ingredient respectively and auxiliary material hopper is added progress melt blending extrusion in double screw extruder and is prepared into composite melt,
The barrel of double screw extruder to head temperature of each section is controlled at 230~280 DEG C, and screw speed is 195 revs/min, then should
Composite melt is directly squeezed into the die cavity of impregnation mold by the mouth mold being connected with double screw extruder head, same with this
When, continuous long glass fiber (direct yarn) is entered into die cavity by another mouth mold of the impregnation mold, by leading in die cavity
The draw of roll dies impregnates in melt, and the mould-cavity temperature of impregnation mold is controlled at 282 DEG C, and dragger speed control is 70
M/min, the glass fiber strand after melt impregnation involves and after cooling out of die cavity, and being cut into length by pelleter is
The elongate in shape pellet of 9 mm, to obtain the A master batch.
B master batch the preparation method is as follows: weigh all raw materials by above-mentioned quality proportioning requirement, and put into mixed at high speed
It is transferred to after mixing in device in mixer and carries out hot milling, the melting temperature of mixer is 125 DEG C, and mixing time is 20 points
Clock feeds single screw extrusion machine by taper feeder, squeezes out and be granulated through melting, obtain then by acquired bulk blend
Obtain the B master batch；The screw speed of single screw extrusion machine is 160 revs/min, and barrel temperature Discrete control is at 160~165 DEG C.
Glass fibre in embodiment 1-6 is continuous long glass fiber, the inherent viscosity of Gao Liudong nylon 6 is 1.8~
2.0。
A master batch and B master batch are mixed according to any mass ratio in the present invention, unknown between the component in remaining place in the present invention
The expression for really writing proportionate relationship exactly is able to achieve according to arbitrary proportion.
For the modified effect for verifying the efficient enhanced flame retarding function master batch of 6 direct injection of nylon molding prepared by the present invention
Fruit is mixed A master batch prepared by embodiment 1-6 and B master batch by the mass percent of respective 25 wt.% simultaneously with nylon 6 resin
It closes, direct injection forms test bars, then carries out properties detection；At the same time, according to obtaining note in embodiment 1-6
The identical component of test bars and proportion are penetrated, and by injection molding test bars conduct again after double screw extruder blending processing
Then reference examples detect its performance.All properties test result as shown in table 1 (wherein reference examples 1-6 be respectively with
The performance of injection molding test bars again after but use twin-screw extrusion identical with proportion machines is formed in embodiment 1-6).
Show to form 6 direct injection of nylon prepared by above embodiments of the present invention by the reference to data in table 1
In component and identical situation is matched after being applied to the molding of 6 direct injection of nylon with efficient enhanced flame retarding function master batch
Under, tensile strength, notch impact strength and the flame retardant property of plastic products, hence it is evident that after using twin-screw extrusion machining
The performance of injection moulded products again.Using functional agglomerate of the invention, the modified processing of nylon 6 resin will be not only greatly simplified
Step improves processing efficiency, reduces energy consumption, also significantly enhances modified effect, realizes plastics preparation green processing
Sustainable development theory.
Functional agglomerate direct injection prepared by 1 embodiment 1-6 of table forms 6 test bars of nylon and same materials formula passes through
Twin-screw extrusion machining is injection moulded the performance control of 6 test bars of nylon again.
Table 1
Taking the above-mentioned ideal embodiment according to the present invention as inspiration, through the above description, relevant staff completely may be used
Without departing from the scope of the technological thought of the present invention', to carry out various changes and amendments.It is all in spirit of the invention and
Within principle, any modification, equivalent substitution, improvement and etc. done be should all be included in the protection scope of the present invention.This item hair
Bright technical scope is not limited to the contents of the specification, it is necessary to its technical model is determined according to scope of the claims
It encloses.
Claims (10)
1. a kind of efficient enhanced flame retarding function master batch of 6 direct injection of nylon molding, it is characterised in that: the functional agglomerate by
Two kinds of master batches of A and B are composed, and the mass percentage composition of the A master batch is as follows: 50.0~70.0 wt.% of glass fibre, height
Flowing 15.0~35.0 wt.% of nylon 6 resin, maleic anhydride are grafted from 3.0~10.0wt.% of aggressiveness, star nylon 6 resin 3.0
~6.0 wt.%, 0.1~0.3 wt.% of antioxidant, the mass percentage composition of the B master batch are as follows: bromide fire retardant 45.0~
70.0 wt.%, 15.0~40.0 wt.% of inorganic fire-retarded synergist, maleic anhydride grafted elastomeric are from aggressiveness 5.0~10.0
Wt.%, 3.0~8.0 wt.% of star nylon 6 resin, 1.0~3.0 wt.% of dispersing agent, 0.5~1.0 wt.% of lubricant.
2. a kind of molding of 6 direct injection of nylon efficient enhanced flame retarding function master batch, feature according to claim 1
Be: the glass fibre is continuous long glass fiber, and the inherent viscosity of the high flowing nylon 6 is 1.8~2.0, the star
Shape nylon 6 resin is one or more of three arms, four arms, six arms and eight arm star nylon 6.
3. a kind of molding of 6 direct injection of nylon efficient enhanced flame retarding function master batch, feature according to claim 1
Be: the maleic anhydride grafted elastomeric is that the maleic anhydride being crosslinked by sodium, calcium, magnesium, barium or zinc ion is grafted second from aggressiveness
Alkene-octene-acrylic acid copolymer elasticity is from aggressiveness.
4. a kind of molding of 6 direct injection of nylon efficient enhanced flame retarding function master batch, feature according to claim 1
Be: the antioxidant is 1,3,5- trimethyls-2,4,6- (3,5- di-t-butyl-4- hydroxyphenylmethyl) benzene and bis- (2,4-two
Cumyl phenyl) pentaerythritol diphosphites be in mass ratio 1:1 composition compound.
5. a kind of molding of 6 direct injection of nylon efficient enhanced flame retarding function master batch, feature according to claim 1
Be: the bromide fire retardant be the bromide fire retardant be decabromodiphenylethane, brominated epoxy resin, brominated Polystyrene,
Any one or a few in brominated polystyrene and tetrabromobisphenol A, preferably brominated Polystyrene；The inorganic fire-retarded synergistic
Agent is any one or two kinds in antimony oxide and zinc borate.
6. a kind of molding of 6 direct injection of nylon efficient enhanced flame retarding function master batch, feature according to claim 1
Be: the dispersing agent is one or more of zinc stearate, aluminum foil stearate, magnesium stearate and lithium stearate；The lubrication
Agent is in ethylene-vinyl acetate co-polymer wax, ethylene-acrylic copolymer wax, E wax, OP wax and dimethyl silicone polymer
It is one or more of.
7. preparing the efficient enhanced fire-retardant function of 6 direct injection of a kind of nylon molding as described in any one of claim 1-6
Can master batch method, it is characterised in that: the preparation method of the A master batch the following steps are included:
(1) weigh according to the ratio glass fibre, Gao Liudong nylon 6 resin, star nylon 6 resin, maleic anhydride grafted elastomeric from
Powder therein and pellet are pre-mixed uniformly with super mixer respectively, and pass through major ingredient and auxiliary material material by aggressiveness and antioxidant
Bucket is added progress melt blending extrusion in double screw extruder and is prepared into composite melt；
(2) composite melt obtained in step (1) is directly squeezed by the mouth mold being connected with double screw extruder head
In the die cavity of impregnation mold, at the same time, continuous long glass fiber enters die cavity by another mouth mold of the impregnation mold,
It is impregnated in melt by the draw of die cavity inner guide wire roller, the glass fiber strand after melt impregnation is involved out of die cavity
And after cooling, the elongate in shape pellet that length is 8~12 mm is cut by pelleter, to obtain the A master batch.
8. a kind of preparation of the efficient enhanced flame retarding function master batch of 6 direct injection of nylon molding according to claim 7
Method, it is characterised in that: the processing technology of the A master batch are as follows: the barrel of double screw extruder to head temperature of each section controls
230~280 DEG C, screw speed is 150~200 revs/min；The mould-cavity temperature of impregnation mold controls the traction at 275~285 DEG C
Machine speed control is at 50~70 ms/min.
9. preparing the efficient enhanced fire-retardant function of 6 direct injection of a kind of nylon molding as described in any one of claim 1-6
Can master batch method, it is characterised in that: the preparation method of the B master batch the following steps are included:
(1) weigh according to the ratio bromide fire retardant, inorganic fire-retarded synergist, star nylon 6 resin, maleic anhydride grafted elastomeric from
Aggressiveness, dispersing agent and lubricant, and put into be transferred to after mixing in mixer in super mixer and carry out hot milling,
Obtain bulk blend；
(2) the bulk blend obtained in step (1) is fed into single screw extrusion machine by taper feeder, is squeezed out simultaneously through melting
It is granulated, obtains the B master batch.
10. a kind of preparation of the efficient enhanced flame retarding function master batch of 6 direct injection of nylon molding according to claim 9
Method, it is characterised in that: the processing technology of the B master batch are as follows: the melting temperature of mixer is 110~130 DEG C, and mixing time is
15~20 minutes；The screw speed of single screw extrusion machine is 150~200 revs/min, and barrel temperature is 160~165 DEG C.
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| CN112080143A (en) * | 2020-09-22 | 2020-12-15 | 上海盈固化工有限公司 | Nylon reinforced material and preparation method thereof |
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