CN109486154A - A kind of PC-ABS alloy direct injection molding enhanced flame retarding function master batch of efficient halogen-free and preparation method thereof - Google Patents
A kind of PC-ABS alloy direct injection molding enhanced flame retarding function master batch of efficient halogen-free and preparation method thereof Download PDFInfo
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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- C08K5/3492—Triazines
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- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
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- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
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- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Abstract
The invention belongs to modifying plastics and processing technique field more particularly to a kind of efficient enhanced halogen-free flameproof functional agglomerates and preparation method thereof that may be directly applied to the injection moulding processing of PC/ABS alloy product；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: 50.0~60.0wt.% of glass fibre, 20.0~25.0wt.% of Gao Liudong PC resin, 10.0~15.0wt.% of ABS resin, 5.0~10.0wt.% of thermoplastic styrene elastomer, styrene -2.0~3.0wt.% of maleic anhydride random copolymer, 1.0~2.0wt.% of hyper-branched polyester, 0.1~0.3wt.% of antioxidant；Functional agglomerate of the invention avoids in process compared with conventional plastic functional agglomerate, and modified performance mutually damages caused by mutually shearing abrasion with fire retardant because of glass fibre, and more traditional enhancing halogen-free flame-retardant system is compared, and significantly improves the modified performance of the two；The master batch has easily dispersion easy processing feature, rear injection molding directly can be simply mixed according to the ratio with PC/ABS alloy resin.
Description
Technical field
The invention belongs to modifying plastics and processing technique field more particularly to one kind may be directly applied to PC/ABS alloy system
The efficient enhanced halogen-free flameproof functional agglomerate and preparation method thereof of product injection moulding processing.
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 could need to be sent out to the maximum extent using different process units and technique
Wave its respective modified effect；2. the modified additive and auxiliary agent and matrix resin of unlike material and form are in same process unit
On (double screw extruder or mixer) implement melt blending can because its mutually shear wear caused by modified performance mutually damage；3. different
The processing temperature otherness of material modified additive and auxiliary agent and matrix resin melt blending is big, if filled simultaneously in identical processing
Standby middle implementation blending can generate serious temperature mismatch problem, and modified effect is caused to be deteriorated.Such as the fire-retardant shape of enhancing
Expect modified system, when enhancing glass fibre, organic fire-retardant and inorganic fire-retarded synergist simultaneously and matrix resin in twin-screw
It, can be because of Fiber Aspect Ratio caused by wearing each other between fiber and inorganic particulate when carrying out melt blending in extruder or mixer
It declines to a great extent, fiber-reinforcing effect is caused to be deteriorated；Fiber also can cause fire retardant to decompose with organic fire-retardant because of internal frictional heat generation,
Seriously affect flame retardant effect.In addition, fiberglass reinforced plastics modified system and the processing temperature of flame-retardant modified plastics system are deposited
In apparent difference, the processing temperature for usually enhancing modified system is 40~70 DEG C higher than the processing temperature of flame-retardant system, if
These two types of modified systems are implemented into melt blending under same process unit same process conditions, one of system will be damaged
Modification effect.Modified performance mutually damages problem between above-mentioned different additive system, at present in the high performance of plastics and more function
It is especially prominent that modification technology implementation process can be changed.
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.
Polycarbonate (PC)/styrene-polybutadiene-styrol copolymer (ABS) alloy be Present Global usage amount most
Big engineering plastics can greatly expand its application field by carrying out high performance and functional modification to PC/ABS alloy.Make
For a kind of important PC/ABS alloy modification material, enhance flame retardant type PC/ABS alloy complex machinery, automobile, track efficiency,
The fields such as electronic apparatus are widely applied.With the continuous improvement of people's environmental consciousness, halogen containing flame-retardant is in PC/ABS alloy
Application in modification is restricted, and the application of enhanced halogen-free flame retardant PC/ABS alloy material is promoted.But enhanced
In halogen-free flame retardant PC/ABS alloy modified special material processing preparation process, inorganic reinforcing fiber and fire retardant are added to simultaneously
Melt blending extrusion is carried out in PC/ABS alloy resin, just be will appear typical additive agent modified efficiency and is mutually damaged phenomenon.
Summary of the invention
It is mutual to solve modified performance present in existing glass fiber reinforced flame retardant PC/ABS alloy PP Pipe Compound preparation process
Problem is damaged, it is fire-retardant that the present invention provides a kind of efficiently enhancing that may be directly applied to the injection moulding processing of PC/ABS alloy plastic product
Functional agglomerate 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 being chopped
Glass fibre, Gao Liudong PC resin, ABS resin, thermoplastic styrene elastomer, styrene-maleic anhydride random copolymer and
Hyper-branched polyester composition with superelevation dispersibility, making low be prepared by double screw extruder high-temperature fusion extrusion enhances mother
Grain；B master batch is mainly by bromo- antimony compound flame retardant, thermoplastic styrene elastomer, low-molecular polyphenylene ether, styrene-maleic acid
Acid anhydride random copolymer and the ultra-dispersed property vector resin composition of hyper-branched polyester, are prepared into halogen-free flameproof by the mixing of mixer low temperature
Master batch.It can use to obtain following technical advantage with the method for processing two kinds of master batches respectively: 1. avoiding glass fibre and phosphorus/nitrogen system
Fire retardant, which is directly blended, generates internal frictional heat generation, leads to the decomposition of phosphorus/nitrogenated flame retardant；2. solving glass fiber reinforcement PC/
ABS alloy and phosphorus-two kinds of nitrogen compositional flame-retardant PC/ABS alloy unmatched problem of modified system melt blending processing temperature；3. transporting
It is carrier with the lower ultra-dispersed property resin of processing temperature and adjuvant system, not only contributes to improve fire retardant in plastic substrate
Dispersibility, also significantly reduce the processing preparation temperature of phosphorous/nitrogenated flame retardant master batch, avoid the thermal decomposition of fire retardant；
4. can not only be improved between fiber and matrix using styrene-maleic anhydride random copolymer as A and B master batch carrier component
Interface adhesion can also play compatibilization between PC/ABS alloy resin and vector resin；5. low by being introduced in B master batch
Molecular weight polyphenylene ether is not only advantageous to improve phosphorus/nitrogenated flame retardant dispersibility and the compatibility with matrix as carrier, moreover it is possible to
The effect for playing carbon forming agent, promotes phosphorus/nitrogenated flame retardant flame retardant efficiency.In addition, for two kinds of master batches of A and B all in accordance with its institute
The physical property characteristic of the modified additive of load implements the formula system design for promoting its lubrication and high efficiency dispersion.It therefore, can root
Rear injection molding directly is simply mixed with PC/ABS alloy resin according to a certain ratio in A and B master batch according to performance requirement, can also be increased
Other resins and/or master batch injection molding together: including but not limited to: PC resin, ABS resin, Masterbatch, antibacterial matrices,
Weatherable master batch, antistatic master granule.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.Therefore, this method effectively prevents glass
Glass fiber and fire retardant greatly improve pair because mutually damaging again by the modified performance caused by the processing of twin-screw blending extrusion
The flame-retardant modified effect of the enhancing of PC/ABS alloy, to practice modifying plastics formula of the 1+1 greater than 2 and processing technology optimization
Design concept.
To achieve the above object, The technical solution adopted by the invention is as follows:
A kind of efficient enhanced halogen-free flameproof functional agglomerate of PC/ABS alloy direct injection molding, the functional agglomerate is by A and B
Two kinds of master batches are composed, and the mass percentage composition of the A master batch is as follows: 50.0~60.0wt.% of glass fibre, Gao Liudong
20.0~25.0wt.% of PC resin, 10.0~15.0wt.% of ABS resin, 5.0~10.0wt.% of thermoplastic styrene elastomer, benzene
Ethylene -2.0~3.0wt.% of maleic anhydride random copolymer, 1.0~2.0wt.% of hyper-branched polyester, antioxidant 0.1~
The mass percentage composition of 0.3wt.%, the B master batch are as follows: 40.0~60.0wt.% of phosphorus flame retardant, nitrogen combustion inhibitor 25.0~
45.0wt.%, 5.0~10.0wt.% of thermoplastic styrene elastomer, 3.0~5.0wt.% of low-molecular polyphenylene ether, styrene-horse
Come 2.0~3.0wt.% of acid anhydrides random copolymer, 1.0~2.0wt.% of hyper-branched polyester, 0.5~1.0wt.% of lubricant.
Further, the glass fibre is the fixed length chopped strand that distribution of lengths is 3.0~5.0mm.
Further, the melt index of the high flowing PC resin is greater than 15g/10min.
Further, the molecular weight of the low-molecular polyphenylene ether is 3000~10000 grams/mol.
Further, the thermoplastic styrene elastomer be styrene-butadiene-styrene block copolymer (SBS),
Styrene-isoprene-styrene block copolymer (SIS), styrene-hydrogenated butadiene-styrene block copolymer
(SEBS), one or more of styrene-hydrogenated isoprene-styrene block copolymer (SEIS), preferably SEBS.
Further, the hyper-branched polyester is using pentaerythrite as core, using poly- dihydromethyl propionic acid as the four of branched chain
Arm polyester copolymer.
Further, the antioxidant is 4- [(4,6- bis- pungent sulfenyls -1,3,5-triazines -2- base)] -2,6- di-t-butyl
Phenol (trade name antioxidant 565) and bis- (2,4-dicumylphenyl) pentaerythritol diphosphites (trade name antioxidant
It S9228 is in mass ratio) compound of 1:1 composition.
Further, the phosphorus flame retardant is triphenyl phosphate, resorcinol bis- (diphenyl phosphates), the bis- (phosphorus of bisphenol-A
Diphenyl phthalate), resorcinol bis- [two (2,6- 3,5-dimethylphenyl) phosphates], diethyl hypophosphites aluminium, Methylethyl time phosphorus
Any one or a few in hydrochlorate aluminium, calcium hypophosphite, ammonium polyphosphate and Melamine Polyphosphate.
Further, the nitrogenated flame retardant is any one in melamine cyanurate and melamine or two
Kind.
Further, the lubricant is one in E wax, OP wax, pentaerythritol stearate and ethylene bis stearamide
Kind is several.
A kind of method for preparing efficient enhanced halogen-free flameproof functional agglomerate of PC/ABS alloy direct injection molding, it is described
Method is related to the preparation method of A master batch and B master batch, the preparation method of the A master batch the following steps are included:
(1) short glass fiber, Gao Liudong PC resin, ABS resin, thermoplastic styrene elastomer, styrene-are weighed according to the ratio
Maleic anhydride random copolymer, hyper-branched polyester and antioxidant, and will be mixed in pellet therein and powder investment super mixer
It closes uniform；
(2) the weighed short glass fiber of the mixture obtained in step (1) and institute is passed through into taper feeder and side respectively
Feeder feeding double screw extruder carries out blending extrusion and is granulated, and obtains the A master batch.
Further, the screw speed of double screw extruder is 200~300 revs/min, and barrel temperature is 220~260
℃。
A kind of method for preparing efficient enhanced halogen-free flameproof functional agglomerate of PC/ABS alloy direct injection molding, it is described
Method is related to the preparation method of A master batch and B master batch, the preparation method of the B master batch the following steps are included:
(1) phosphorus flame retardant, nitrogenated flame retardant, thermoplastic styrene elastomer, low-molecular polyphenylene ether, benzene second are weighed according to the ratio
Alkene-maleic anhydride random copolymer, hyper-branched polyester and lubricant, are then put into super mixer and are turned after mixing
It moves to and carries out hot milling in mixer, 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 150~160 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 phosphorus-nitrogen compositional flame-retardant master batch (B master batch), effectively prevent PC/ABS alloy and glass
When fiber and the direct melt blending of halogen-free flame retardants squeeze out, because halogen-free flame retardants decomposition is made caused by mutually shearing with frictional heat generation
At flame-retarded efficiency it is impaired, while also solving two unmatched technical problems of modified system processing temperature, to significantly mention
High two kinds of respective modified performances of modified additive.
(2) it dexterously using low-molecular polyphenylene ether as carrier in B master batch, is not only advantageous to improve phosphorus/nitrogen system resistance
Fire the dispersibility of agent and the compatibility with matrix, moreover it is possible to which the effect for playing carbon forming agent promotes the fire-retardant function of phosphorus/nitrogenated flame retardant
Effect, at the same avoid because after outer addition carbon forming agent small molecule migrate caused by PC/ABS alloy product surface frost.
(3) it is all made of in A master batch and B master batch with polymolecularity and high-compatibility resin joint vector, can not only be had
Effect improves the interface adhesion of glass fibre Yu PC/ABS alloy substrate, moreover it is possible to which it is being directly used in PC/ABS alloy plastic system
When product injection moulding processing, glass fibre and fire retardant obtain better dispersion effect in PC/ABS alloy resin matrix, from
And obtain superior enhancing and flame retardant effect.
(4) 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 closed according to PC/ABS
The performance requirement of golden plastic products, after A master batch and B master batch are simply mixed with PC/ABS alloy resin according to a certain ratio, directly
Injection moulding applied to plastic products is processed.Due to it is used in injection molding machine be that single screw rod melt promotes mode, to glass fibers
The shear action of peacekeeping fire retardant is very faint, substantially will not modification effect to the two damage, so as to avoid routine
Matrix resin and modified master batch during modifying plastics be secondary or the multiple melting mixing by processing equipment caused by resist
Oxygen agent loss, the loss of reinforcing fiber draw ratio and matrix resin thermal cracking problem, significantly improve the machine of PC/ABS alloy product
Tool performance and long-time service.
(5) present invention is effectively improving the flame-retardant modified efficiency of PC/ABS alloy enhancing simultaneously, simplifies modifying plastics processing
Step reduces the process-cycle, reduces energy consumption, improves production efficiency, is truly realized green chemical industry idea of development.This hair
Bright combination type functional master batch can flexibly deploy A according to customer requirement in PC/ABS alloy plastic product process of injection molding
The combination of master batch and B master batch and its its performance and cost are adjusted with the proportion of resin raw material.Method and skill of the invention
Art can be widely applied to the injection moulding of all kinds of PC/ABS alloy plastic products and high performance and functional modification integration add
Work.
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 halogen-free flameproof functional agglomerate of PC/ABS alloy direct injection molding, is combined by two kinds of master batches of A and B
It forms, the raw material mass mixture ratio of A master batch is as follows:
Antioxidant is 4- [(the pungent sulfenyl -1,3,5- triazine -2- base of 4,6- bis-)] -2,6 di t butyl phenol (trade name antioxygen
Agent 565) and bis- (2,4-dicumylphenyl) pentaerythritol diphosphites (trade name antioxidant S9228) be in mass ratio
The compound of 1:1 composition.
The raw material mass mixture ratio of its B master batch is as follows:
A master batch the preparation method is as follows: weigh all raw materials by above-mentioned quality proportioning requirement, height is flowed into PC resin, ABS tree
It is uniformly mixed in rouge, SEBS, SMA, hyper-branched polyester and antioxidant investment super mixer, then by obtained mixture and institute
Weighed short glass fiber passes through taper feeder respectively and feeder feeding double screw extruder in side carries out blending extrusion simultaneously
It is granulated, obtains the A master batch, barrel to the head temperature of each section of double screw extruder is controlled at 220~260 DEG C, screw speed
It is 250 revs/min.
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 185 revs/min, and barrel temperature Discrete control is at 150~160 DEG C.
Embodiment 2
A kind of efficient enhanced halogen-free flameproof functional agglomerate of PC/ABS alloy direct injection molding, is combined by two kinds of master batches of A and B
It forms, the raw material mass mixture ratio of A master batch is as follows:
Antioxidant is 4- [(the pungent sulfenyl -1,3,5- triazine -2- base of 4,6- bis-)] -2,6 di t butyl phenol (trade name antioxygen
Agent 565) and bis- (2,4-dicumylphenyl) pentaerythritol diphosphites (trade name antioxidant S9228) be in mass ratio
The compound of 1:1 composition.
The raw material mass mixture ratio of its B master batch is as follows:
A master batch the preparation method is as follows: weigh all raw materials by above-mentioned quality proportioning requirement, height is flowed into PC resin, ABS tree
It is uniformly mixed in rouge, SEIS, SMA, hyper-branched polyester and antioxidant investment super mixer, then by obtained mixture and institute
Weighed short glass fiber passes through taper feeder respectively and feeder feeding double screw extruder in side carries out blending extrusion simultaneously
It is granulated, obtains the A master batch, barrel to the head temperature of each section of double screw extruder is controlled at 220~260 DEG C, screw speed
It is 230 revs/min.
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 175 revs/min, and barrel temperature Discrete control is at 150~160 DEG C.
Embodiment 3
A kind of efficient enhanced halogen-free flameproof functional agglomerate of PC/ABS alloy direct injection molding, is combined by two kinds of master batches of A and B
It forms, the raw material mass mixture ratio of A master batch is as follows:
Antioxidant is 4- [(the pungent sulfenyl -1,3,5- triazine -2- base of 4,6- bis-)] -2,6 di t butyl phenol (trade name antioxygen
Agent 565) and bis- (2,4-dicumylphenyl) pentaerythritol diphosphites (trade name antioxidant S9228) be in mass ratio
The compound of 1:1 composition.
The raw material mass mixture ratio of its B master batch is as follows:
A master batch the preparation method is as follows: weigh all raw materials by above-mentioned quality proportioning requirement, height is flowed into PC resin, ABS tree
It is uniformly mixed in rouge, SBS, SMA, hyper-branched polyester and antioxidant investment super mixer, then by obtained mixture and institute
Weighed short glass fiber passes through taper feeder respectively and feeder feeding double screw extruder in side carries out blending extrusion simultaneously
It is granulated, obtains the A master batch, barrel to the head temperature of each section of double screw extruder is controlled at 220~260 DEG C, screw speed
It is 200 revs/min.
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 200 revs/min, and barrel temperature Discrete control is at 150~160 DEG C.
Embodiment 4
A kind of efficient enhanced halogen-free flameproof functional agglomerate of PC/ABS alloy direct injection molding, is combined by two kinds of master batches of A and B
It forms, the raw material mass mixture ratio of A master batch is as follows:
Antioxidant is 4- [(the pungent sulfenyl -1,3,5- triazine -2- base of 4,6- bis-)] -2,6 di t butyl phenol (trade name antioxygen
Agent 565) and bis- (2,4-dicumylphenyl) pentaerythritol diphosphites (trade name antioxidant S9228) be in mass ratio
The compound of 1:1 composition.
The raw material mass mixture ratio of its B master batch is as follows:
A master batch the preparation method is as follows: weigh all raw materials by above-mentioned quality proportioning requirement, height is flowed into PC resin, ABS tree
It is uniformly mixed in rouge, SIS, SMA, hyper-branched polyester and antioxidant investment super mixer, then by obtained mixture and institute
Weighed short glass fiber passes through taper feeder respectively and feeder feeding double screw extruder in side carries out blending extrusion simultaneously
It is granulated, obtains the A master batch, barrel to the head temperature of each section of double screw extruder is controlled at 220~260 DEG C, screw speed
It is 220 revs/min.
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 128 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 185 revs/min, and barrel temperature Discrete control is at 150~160 DEG C.
Embodiment 5
A kind of efficient enhanced halogen-free flameproof functional agglomerate of PC/ABS alloy direct injection molding, is combined by two kinds of master batches of A and B
It forms, the raw material mass mixture ratio of A master batch is as follows:
Antioxidant is 4- [(the pungent sulfenyl -1,3,5- triazine -2- base of 4,6- bis-)] -2,6 di t butyl phenol (trade name antioxygen
Agent 565) and bis- (2,4-dicumylphenyl) pentaerythritol diphosphites (trade name antioxidant S9228) be in mass ratio
The compound of 1:1 composition.
The raw material mass mixture ratio of its B master batch is as follows:
A master batch the preparation method is as follows: weigh all raw materials by above-mentioned quality proportioning requirement, height is flowed into PC resin, ABS tree
It is uniformly mixed in rouge, SEBS, SMA, hyper-branched polyester and antioxidant investment super mixer, then by obtained mixture and institute
Weighed short glass fiber passes through taper feeder respectively and feeder feeding double screw extruder in side carries out blending extrusion simultaneously
It is granulated, obtains the A master batch, barrel to the head temperature of each section of double screw extruder is controlled at 220~260 DEG C, screw speed
It is 220 revs/min.
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 150~160 DEG C.
Embodiment 6
A kind of efficient enhanced halogen-free flameproof functional agglomerate of PC/ABS alloy direct injection molding, is combined by two kinds of master batches of A and B
It forms, the raw material mass mixture ratio of A master batch is as follows:
Antioxidant is 4- [(the pungent sulfenyl -1,3,5- triazine -2- base of 4,6- bis-)] -2,6 di t butyl phenol (trade name antioxygen
Agent 565) and bis- (2,4-dicumylphenyl) pentaerythritol diphosphites (trade name antioxidant S9228) be in mass ratio
The compound of 1:1 composition.
The raw material mass mixture ratio of its B master batch is as follows:
A master batch the preparation method is as follows: weigh all raw materials by above-mentioned quality proportioning requirement, height is flowed into PC resin, ABS tree
It is uniformly mixed in rouge, SEIS, SMA, hyper-branched polyester and antioxidant investment super mixer, then by obtained mixture and institute
Weighed short glass fiber passes through taper feeder respectively and feeder feeding double screw extruder in side carries out blending extrusion simultaneously
It is granulated, obtains the A master batch, barrel to the head temperature of each section of double screw extruder is controlled at 220~260 DEG C, screw speed
It is 200 revs/min.
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 155 revs/min, and barrel temperature Discrete control is at 150~160 DEG C.
Hyper-branched polyester in embodiment 1-6 is using pentaerythrite as core, using poly- dihydromethyl propionic acid as the four of branched chain
Arm polyester copolymer.
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.
To verify the efficient enhanced halogen-free flameproof functional agglomerate of PC/ABS alloy direct injection molding prepared by the present invention
Modified effect, A master batch prepared by embodiment 1-6 and B master batch are closed by the mass percent and PC/ABS of respective 25wt.%
Gold mixes simultaneously, and direct injection forms test bars, then carries out properties detection；At the same time, according to embodiment 1-6
It is middle to obtain the identical component of injection test bars and proportion, and injection molding test again is blended after processing by double screw extruder
Then batten detects its performance as reference examples.All properties test result (wherein reference examples 1-6 as shown in table 1
Injection molding test bars again are formed after but use twin-screw extrusion identical with proportion machines respectively and in embodiment 1-6
Performance).
Show directly to infuse PC/ABS alloy prepared by above embodiments of the present invention by the reference to data in table 1
Penetrate the efficient enhanced halogen-free flameproof functional agglomerate of molding, after being applied to the molding of PC/ABS alloy direct injection, in component and
It matches in identical situation, tensile strength, notch impact strength and the flame retardant property of plastic products, hence it is evident that better than using double
The performance of injection moulded products again after Screw Extrusion machining.Using functional agglomerate of the invention, will not only greatly simplifie
PC/ABS alloy modification procedure of processing improves processing efficiency, reduces energy consumption, also significantly enhances modified effect, realizes
The sustainable development theory of plastics preparation green processing.
The molding of functional agglomerate direct injection prepared by 1 embodiment 1-6 of table PC/ABS alloy test bars are matched with same materials
The performance that side is injection moulded PC/ABS alloy test bars through twin-screw extrusion machining again compares
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 halogen-free flameproof functional agglomerate of PC/ABS alloy direct injection molding, it is characterised in that: described
Functional agglomerate is composed of two kinds of master batches of A and B, and the mass percentage composition of the A master batch is as follows: glass fibre 50.0~
20.0~25.0wt.% of 60.0wt.%, Gao Liudong PC resin, 10.0~15.0wt.% of ABS resin, thermoplastic styrene elastomer
5.0~10.0wt.%, styrene -2.0~3.0wt.% of maleic anhydride random copolymer, 1.0~2.0wt.% of hyper-branched polyester, resist
0.1~0.3wt.% of oxygen agent, the glass fibre are the fixed length chopped strand that distribution of lengths is 3.0~5.0mm, the high flowing
The melt index of PC resin is greater than 15g/10min,
The mass percentage composition of the B master batch is as follows: 40.0~60.0wt.% of phosphorus flame retardant, nitrogen combustion inhibitor 25.0~
45.0wt.%, 5.0~10.0wt.% of thermoplastic styrene elastomer, 3.0~5.0wt.% of low-molecular polyphenylene ether, styrene-horse
Come 2.0~3.0wt.% of acid anhydrides random copolymer, 1.0~2.0wt.% of hyper-branched polyester, lubricant 0.5~1.0wt.%, it is described low
The molecular weight of molecular weight polyphenylene ether is 3000~10000 grams/mol.
2. a kind of PC/ABS alloy direct injection molding is female with efficiently enhanced halogen-free flameproof function according to claim 1
Grain, it is characterised in that: the thermoplastic styrene elastomer is styrene-butadiene-styrene block copolymer (SBS), benzene
Ethylene-isoprene-styrene block copolymer (SIS), styrene-hydrogenated butadiene-styrene block copolymer (SEBS),
One or more of styrene-hydrogenated isoprene-styrene block copolymer (SEIS), preferably SEBS.
3. a kind of PC/ABS alloy direct injection molding is female with efficiently enhanced halogen-free flameproof function according to claim 1
Grain, it is characterised in that: the hyper-branched polyester is to be gathered using pentaerythrite as core, by four arms of branched chain of poly- dihydromethyl propionic acid
Ester copolymer.
4. a kind of PC/ABS alloy direct injection molding is female with efficiently enhanced halogen-free flameproof function according to claim 1
Grain, it is characterised in that: the antioxidant is 4- [(4,6- bis- pungent sulfenyls -1,3,5-triazines -2- base)] -2,6- DI-tert-butylphenol compounds
It is in mass ratio the compound of 1:1 composition with bis- (2,4-dicumylphenyl) pentaerythritol diphosphites.
5. a kind of PC/ABS alloy direct injection molding is female with efficiently enhanced halogen-free flameproof function according to claim 1
Grain, it is characterised in that: the phosphorus flame retardant is triphenyl phosphate, resorcinol bis- (diphenyl phosphates), the bis- (phosphoric acid of bisphenol-A
Diphenyl ester), resorcinol bis- [two (2,6- 3,5-dimethylphenyl) phosphates], diethyl hypophosphites aluminium, Methylethyl hypophosphorous acid
Any one or a few in salt aluminium, calcium hypophosphite, ammonium polyphosphate and Melamine Polyphosphate；The nitrogenated flame retardant
For any one or two kinds in melamine cyanurate and melamine.
6. a kind of PC/ABS alloy direct injection molding is female with efficiently enhanced halogen-free flameproof function according to claim 1
Grain, it is characterised in that: the lubricant be one of E wax, OP wax, pentaerythritol stearate and ethylene bis stearamide or
It is several.
7. a kind of preparation efficient enhanced Halogen of PC/ABS alloy direct injection molding as described in any one of claim 1-6
The method of flame retarding function master batch, it is characterised in that: the preparation method of the A master batch the following steps are included:
(1) short glass fiber, Gao Liudong PC resin, ABS resin, thermoplastic styrene elastomer, styrene-are weighed according to the ratio
Maleic anhydride random copolymer, hyper-branched polyester and antioxidant, and will be mixed in pellet therein and powder investment super mixer
It closes uniform；
(2) the weighed short glass fiber of the mixture obtained in step (1) and institute is passed through into taper feeder and side respectively
Feeder feeding double screw extruder carries out blending extrusion and is granulated, and obtains the A master batch.
8. the efficient enhanced halogen-free flameproof functional agglomerate of a kind of PC/ABS alloy direct injection molding according to claim 7
Preparation method, it is characterised in that: the processing technology of the A master batch are as follows: the screw speed of double screw extruder be 200~300
Rev/min, barrel temperature is 220~260 DEG C.
9. a kind of preparation efficient enhanced Halogen of PC/ABS alloy direct injection molding as described in any one of claim 1-6
The method of flame retarding function master batch, it is characterised in that: the preparation method of the B master batch the following steps are included:
(1) phosphorus flame retardant, nitrogenated flame retardant, thermoplastic styrene elastomer, low-molecular polyphenylene ether, benzene second are weighed according to the ratio
Alkene-maleic anhydride random copolymer, hyper-branched polyester and lubricant, are then put into super mixer and are turned after mixing
It moves to and carries out hot milling in mixer, 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 PC/ABS alloy direct injection molding is female with efficiently enhanced halogen-free flameproof function according to claim 9
The preparation method of grain, 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, is mixed
Refining the time is 15~20 minutes, and the screw speed of single screw extrusion machine is 150~200 revs/min, and barrel temperature is 150~160
℃。
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112662154A (en) * | 2019-10-16 | 2021-04-16 | 惠州比亚迪电子有限公司 | Spot-decorated halogen-free flame-retardant PC/ABS plastic alloy and preparation method thereof |
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|---|---|---|---|---|
| US4740554A (en) * | 1985-11-23 | 1988-04-26 | Bayer Aktiengesellschaft | Thermoplastic moulding compositions based on polyphenylene oxide/polycarbonate block condensates |
| CN1723247A (en) * | 2002-12-10 | 2006-01-18 | 约翰逊聚合物有限责任公司 | High flow engineering theremoplastic compositions and products made therefrom |
| CN1810862A (en) * | 2006-02-23 | 2006-08-02 | 广州金发科技股份有限公司 | Continuous long fiber reinforced fire-retardant thermoplastic resin and its prepn |
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2018
- 2018-11-27 CN CN201811429212.6A patent/CN109486154B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4740554A (en) * | 1985-11-23 | 1988-04-26 | Bayer Aktiengesellschaft | Thermoplastic moulding compositions based on polyphenylene oxide/polycarbonate block condensates |
| CN1723247A (en) * | 2002-12-10 | 2006-01-18 | 约翰逊聚合物有限责任公司 | High flow engineering theremoplastic compositions and products made therefrom |
| CN1810862A (en) * | 2006-02-23 | 2006-08-02 | 广州金发科技股份有限公司 | Continuous long fiber reinforced fire-retardant thermoplastic resin and its prepn |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112662154A (en) * | 2019-10-16 | 2021-04-16 | 惠州比亚迪电子有限公司 | Spot-decorated halogen-free flame-retardant PC/ABS plastic alloy and preparation method thereof |
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