CN106977893A - Flame-retardant PET and PC composites that a kind of color is modified and preparation method thereof - Google Patents
Flame-retardant PET and PC composites that a kind of color is modified and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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Abstract
Flame-retardant PET and PC composites for being modified the invention discloses a kind of color and preparation method thereof, include the raw material of following parts by weight：Makrolon：45~70 parts；Polyethylene terephthalate：30~45 parts；Hollow glass micropearl:5~15 parts；Fire retardant:0.5~1.0 part；Toughness reinforcing compatilizer:3~15 parts；Antioxidant:0.5~1 part；Lubricant:0.2~1 part；Colouring agent：0.1 0.2 parts；Colouring agent is the one or more in the organic transparent blue dyestuff of Anthraquinones and the organic transparent cudbear of Anthraquinones.It is while good flame retardant effect is possessed with good color and transparency.
Description
Technical field
The present invention relates to technical field of polymer materials, Flame-retardant PET and PC composite woods that more particularly to a kind of color is modified
Material and preparation method thereof.
Background technology
Makrolon (Polycarbonate, abbreviation PC) is the family macromolecule chemical combination containing carbonic ester in strand
The general name of thing, wherein bisphenol A polycarbonate are that yield is maximum, a kind of purposes most wide makrolon.Bisphenol A polycarbonate
Not only there is excellent impact strength, creep resistant, heat resistance, cold resistance and the good transparency, also with higher
Tensile strength, bending strength, elongation and rigidity, resistance to ag(e)ing, excellent electrical properties, water absorption rate are low, but its oil resistivity, wearability
It is not good enough with processing characteristics.
Polyethylene terephthalate (polyethyleneterephthalate) abbreviation PET, belongs to thermoplastic poly
Ester, with good heat endurance, corrosion resistance, barrier and higher transparency and hardness, there is preferable rigidity and intensity, inhales
Moist small, high to the barrier of non-polar gas, creep resistant is good.
PET and PC alloys are made in PET and PC blendings, can not only have PET and PC excellent properties concurrently can also improve
Processing fluidity, stress crack resistance performance and solvent resistance poor PC, can finally obtain the high score with high comprehensive performance
Sub- alloy material.
PC is widely used in the field such as household building materials, electric, office equipment, and the fire resistance for PC composites will
More and more higher is sought, PC decomposition temperatures itself are high, and its combustion heat is low, charring rate is high, therefore existing certain fire resistance, pure PC's
Limited oxygen index LOI is that 22%~29%, UL94 tests only belong to HB or V-2 grades, so changing for the fire-retardant of PC materials
Property is very necessary.
Be in place of the deficiencies in the prior art, it is flame-retardant modified after the colourity of polycarbonate sample turn yellow, brightness declines, and
And PC particles are presented slightly yellow in itself so that the overall color shades of product turn yellow, brightness declines, its transparency and glossiness
There is certain reduction so that its application scenario is limited.
The content of the invention
The first object of the present invention is to provide the Flame-retardant PET and PC composites that a kind of color is modified, and it is possessing good
With good color and transparency while flame retardant effect.
The present invention above-mentioned technical purpose technical scheme is that：
Flame-retardant PET and PC composites that a kind of color is modified, include the raw material of following parts by weight：Makrolon：45~70 parts；
Polyethylene terephthalate：30~45 parts；Hollow glass micropearl:5~15 parts；Fire retardant:0.5~1.0 part；Toughness reinforcing is compatible
Agent:3~15 parts；Antioxidant:0.5~1 part；Lubricant:0.2~1 part；Colouring agent：0.01-0.1 parts；Colouring agent has for Anthraquinones
One or more in machine transparent blue dyestuff and the organic transparent cudbear of Anthraquinones.
PET the and PC composites prepared have excellent fire resistance, using the organic transparency dye pair of Anthraquinones
Product colour is modified, by using the colouring agent, product it is transparent good, colourity is obviously improved, and appearance glossiness is good.Together
When, PET the and PC composites prepared have good mechanical strength and shock resistance.The organic transparency dye of Anthraquinones
There is phenolic hydroxyl group on molecule, can be reacted with the terminal hydroxy group or end carboxyl on PC and PET, therefore with well compatible
Property, so the organic transparency dye of Anthraquinones has good compatibility with PET and PC composites, it is in PET and PC composite woods
Dispersedly visibly homogeneous in material, the color to PET and PC composites is modified with excellent effect.
More preferably：Include the raw material of following parts by weight：Makrolon：50.5 parts；Polyethylene terephthalate
Ester：35 parts；Hollow glass micropearl:10 parts；Fire retardant:0.5 part；Toughness reinforcing compatilizer:8 parts；Antioxidant:0.6 part；Lubricant:0.4
Part；Colouring agent：0.1 part；Colouring agent is the organic transparent blue dyestuff A1 of Anthraquinones, the organic transparent cudbear A2 of Anthraquinones, anthracene
One or more in the organic transparent cudbear A3 of quinones；A1, A2, A3 correspond to Germany Lang Shengmagaoliesi productions respectively
The Violet 3R of Violet B, Germany the Lang Shengmagaoliesi production of Blue RR, Germany Lang Shengmagaoliesi production.
More preferably：Colouring agent is the 1 of A1 and A3:1 compounding.
As seen from the experiment, face of the colouring agent of the compounding of both organic transparency dyes to PET and PC composites
Color, which is modified, has more preferable effect.
More preferably：Toughness reinforcing compatilizer is：Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer
With one kind in ethylene-methyl acrylate-glyceryl methacrylate copolymer.
The toughness reinforcing compatilizer of use is the ternary atactic copolymer containing glyceride type epoxide group (GMA), GMA in molecule
In epoxide group can be reacted with PET and PC terminal hydroxy group and end carboxyl so that the toughness reinforcing compatilizer has very with PET and PC
Good compatibility.Acrylate in the toughness reinforcing compatilizer has high resiliency and impact, and toughness reinforcing work is played to PET and PC
With.On the other hand, toughness reinforcing agent molecule can be connected on PET and PC molecules simultaneously, so as to improve the compatibility of the two.Hollow glass
The addition of glass microballon serves the humidification to resin matrix.Therefore PET the and PC composite woods prepared using the formula
Material not only has excellent fire resistance, moreover it is possible to improve intensity and toughness to a certain extent.
More preferably：Hollow glass micropearl is the hollow glass micropearl treated by silane coupler and colouring agent,
The colouring agent is the one or more in Anthraquinones organic transparency dye A1, A2 and A3.
Hollow glass micropearl is a kind of just spherical, hollow, contents fine vitreum, and its main component is SiO2With
Al2O3, with lightweight, nontoxic, sound insulation, low water absorption rate, the high and low heat conduction of compressive strength, free mobility is good, chemical stability is good,
The advantages of good dispersion, using the hollow glass micropearl filling PET and PC alloys of super quality and competitive price can not only be strengthened with loss of weight, moreover it is possible to
Reducing the use of resin raw material reduces cost.The mechanism of action of silane coupler, which is that silane is hydrolyzed first, becomes silanol, then silicon
With hollow glass micropearl surface dehydration occurs for alcohol radical, carries out the group hydrolysis in chemical bond connection, silane --- after hydrolysis
Hydroxyl and hollow glass micropearl react --- and the hollow glass micropearl through coupling agent treatment is filled when preparing composite, even
Organic group in connection agent will interact with organic polymer, finally set up the bridge between hollow glass micropearl and organic matter
Beam, reduces hollow glass micropearl to resin matrix surface migration.Hollow glass micropearl is entered using Anthraquinones organic transparency dye
Row surface treatment, makes to connect pigment molecule on hollow glass micropearl.In this way, hollow glass micropearl is added in resin matrix,
Hollow glass micropearl and resin matrix interface difference can be reduced, be distributed final product colour more uniform.
More preferably：Fire retardant is silicone flame retardant and Sulfonates fire retardant, sulfonamide based flame retardant
In one or more kinds of compoundings form.
Using the above method, organic silicon fibre retardant forms the inoxidizability containing Si~O by the heated PC surfaces that are diffused into
Layer of charcoal and it is fire-retardant, but individually addition organosilicon fire retardant effect it is not good enough, Sulfonates fire retardant and sulfanilic acid salt
Fire retardant makes PC catabolite be crosslinked the hard aromatic compound layer of charcoal of generation, and flame retardant effect is very prominent, but sulfonate
Based flame retardant and sulfonic amine salt based flame retardant price are higher, and its too many economic benefit of addition is not high, and therefore, both are compounded, obtained
To the flame retardant formulations for meeting V0 flame retardant ratings.
More preferably：Silane coupler is γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane.
Using such scheme, epoxide group is included in the silane coupler, epoxy radicals can be anti-with terminal hydroxy group in PC and PET
Should, be conducive to improving the adhesion of silane coupled agent molecule and organic body, so as to be conducive to improving hollow glass micropearl with having
Compatibility between machine matrix, reduces boundary defect, improves the toughness and intensity of PET and PC composites.
More preferably：Antioxidant includes primary antioxidant and auxiliary antioxidant, and primary antioxidant is β-(3,5- bis- tertiary fourths
Base -4- hydroxy phenyls) the positive octadecanol ester of propionic acid, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters
In one kind, auxiliary antioxidant be phosphorous acid three (2,4- di-tert-butyl-phenyl) ester.
The second object of the present invention is to provide a kind of Flame-retardant PET of color modification and the preparation method of PC composites.
The above-mentioned technical purpose of the present invention is achieved through the following technical solutions.
Flame-retardant PET and the preparation method of PC composites that a kind of color is modified, comprise the following steps：
S1：Weigh the makrolon of formula ratio, polyethylene terephthalate, hollow glass micropearl, fire retardant, toughness reinforcing compatible
Agent, antioxidant and lubricant, the makrolon weighed and polyethylene terephthalate are dried at a temperature of 115-125 DEG C
At least 4 hours, other components were dried at least 2 hours at a temperature of 50-80 DEG C；
S2：By the makrolon after drying process, polyethylene terephthalate, hollow glass micropearl, fire retardant, toughness reinforcing phase
Hold agent, antioxidant and lubricant to be sufficiently mixed at 20-30 DEG C；
S3：It will be extruded through the mixed materials of step S2 in double screw extruder through melt blending, and tie rod, cooling, air-dry, cut
Grain, be dried to obtain described PET and PC composites, the process conditions that the double screw extruder is used for：One area：180-
220℃；2nd area：220-230℃；3rd area：230-250℃；4th area：250-280℃；5th area：265-280℃；6th area：255-
270℃；7th area：250-260℃；8th area：240-250℃；Head temperature：240-270℃；Screw speed is controlled in 300-
400r/min, vacuum -0.3~-0.5kPa.
More preferably：In step S1, hollow glass micropearl is using the step of preceding surface treated, surface treatment such as
Under：The silane coupler absolute ethyl alcohol that the 1-2% of hollow glass micropearl gross mass will be accounted for enters water-filling in 35-45 DEG C of water-bath
The mass ratio of solution dilution, absolute ethyl alcohol and the silane coupler is 5:1-10:1, at 15-35 DEG C, in agitation and dilution liquid
Load weighted hollow glass micropearl in proportion is added, continues to stir after hollow glass micropearl is all added, in mixed dispersion liquid
The middle colouring agent for adding the 5-10% for accounting for hollow glass micropearl gross mass, stirs 1-2h, then dries, finally by dried powder
Body is placed on standby in closed container.
In summary, the invention has the advantages that：
1st, the matrix material in the present invention is PC and PET compounding uses, product is possessed the characteristic of the two respectively, possesses good
Intensity and rigidity, resistance to chemical reagents, and the toughness reinforcing compatilizer containing glyceride type epoxide group class used causes PET's and PC
Compatibility improvement, the toughness of alloy material is improved；
2nd, the fire retardant that the present invention is used is in silicone flame retardant and Sulfonates fire retardant, sulfonamide based flame retardant
One or more compounding is formed, and with synergistic fire retardation, makes the flame-retarding characteristic of product good；
3rd, in the Anthraquinones tri- kinds of toners of organic transparency dye A1, A2, A3 of the present invention using Germany Lang Shengmagaoliesi productions
One or more flame-retardant modified PET and PC composites are mixed colours, material modified appearance color can be improved, its
Solve to a certain extent existing Flame-retardant PET and PC composites add flame retardant after colourity turn yellow, brightness decline, it is transparent
The problem of degree and glossiness decline, with the color of Flame-retardant PET and PC composites is improved, reduces yellow colour index, improves its bright
Degree, improves the advantage of transparency and appearance glossiness；
4th, the hollow glass micropearl filling PET and PC alloy materials that the present invention is used, can drop the enhancing of this loss of weight, hollow glass is micro-
Pearl is surface-treated using silane coupler, is conducive to improving the compatibility of hollow glass micropearl and PET and PC composites,
Reduce the boundary defect of hollow glass micropearl and PET and PC composites, thus improve the toughness of PET and PC composites with it is strong
Degree；
5th, hollow glass micropearl of the invention is using one kind in the organic tri- kinds of toners of transparency dye A1, A2, A3 of Anthraquinones
Or it is several hollow glass micropearl is surface-treated, reduce the interface difference between hollow glass micropearl and resin matrix, carry
The color homogeneity of high product.
Embodiment
The present invention is described in further detail below.
This specific embodiment is only explanation of the invention, and it is not limitation of the present invention, people in the art
Member can make the modification without creative contribution to the present embodiment as needed after this specification is read, but as long as at this
All protected in the protection domain of invention by Patent Law.
Embodiment 1-5：Flame-retardant PET and PC composites that a kind of color is modified, are prepared from, its group using following steps
Divide and content is referring to table 1：
S0：The processing of hollow glass micropearl：1.5% silane coupler absolute ethyl alcohol of hollow glass micropearl gross mass will be accounted for
It is hydrolyzed dilution in 35-45 DEG C of water-bath, the mass ratio of absolute ethyl alcohol and silane coupler is 8:1, at 15-35 DEG C,
Load weighted hollow glass micropearl in proportion is added in agitation and dilution liquid, continues to stir after hollow glass micropearl is all added
5-10min, adds 5% colouring agent for accounting for hollow glass micropearl gross mass, stirs 2h, and more than 4h is then dried at 80 DEG C,
Finally dried powder is placed on standby in closed container；Silane coupler is γ-(2,3- the third oxygen of epoxy) propyl group front three
TMOS；
S1：Each component is weighed according to the proportioning of table 1, wherein hollow glass micropearl is the hollow glass micropearl treated through step S0,
And dry the PC weighed and PET at least 4 hours at a temperature of 120 DEG C, other components are dried 2 hours at a temperature of 50-80 DEG C；
S2：By the PC after drying process, PET, fire retardant, toughness reinforcing compatilizer, surface treated hollow glass micropearl, antioxygen
Agent, lubricant are put into high-speed mixer and are sufficiently mixed 5-10min at 20-30 DEG C；
S3：To be added to through the mixed materials of step S2 in the hopper of double screw extruder, extruded through melt blending, tie rod,
Cooling, air-dry, pelletizing, be dried to obtain PET and PC modified composite materials.
Wherein, the process conditions of double screw extruder are：One 200 DEG C of area's temperature, two 230 DEG C of area's temperature, three area's temperature 240
DEG C, 260 DEG C of four area's temperature, 270 DEG C of five area's temperature, 260 DEG C of six area's temperature, seven 255 DEG C of area's temperature, eight 245 DEG C of area's temperature, head
260 DEG C of temperature, engine speed is 300r/min, vacuum -0.4kPa.
The embodiment 1-8 of table 1 component and content table
Wherein, PC is bisphenol A polycarbonate, and weight average molecular weight is 20,000-3 ten thousand；Colouring agent is the organic transparent dye of Anthraquinones
It is 1 according to mass ratio to expect A1 and A3:1 compounding, fire retardant is silicone flame retardant octaphenylcyclotetrasiloxane, Sulfonates
The lauseto neu potassium sulfonate of fire retardant two and sulfonamide based flame retardant trimethyl fluoride sulfonyl amine potassium compounding are formed, and the mass ratio of three is
5:3:2；Toughness reinforcing compatilizer is Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer；Antioxidant is β-(3,5-
Di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid and phosphorous acid three (2,4- di-tert-butyl-phenyl) ester be by weight 2：1
Compounding is formed；Lubricant is magnesium stearate.
Embodiment 9：Flame-retardant PET and PC composites that a kind of color is modified, the difference with embodiment 1 is, colouring agent
For 0.1 part of A1.
Embodiment 10：Flame-retardant PET and PC composites that a kind of color is modified, the difference with embodiment 1 is, colouring agent
For 0.1 part of A2.
Embodiment 11：Flame-retardant PET and PC composites that a kind of color is modified, the difference with embodiment 1 is, colouring agent
For 0.1 part of A3.
Embodiment 12：Flame-retardant PET and PC composites that a kind of color is modified, the difference with embodiment 1 is, colouring agent
For the 1 of A1 and A2:1 compounding, A1 and A2 total amount are 0.1 part.
Embodiment 13：Flame-retardant PET and PC composites that a kind of color is modified, the difference with embodiment 1 is, colouring agent
For the 1 of A2 and A3:1 compounding, A2 and A3 total amount are 0.1 part.
Embodiment 14：Flame-retardant PET and PC composites that a kind of color is modified, the difference with embodiment 1 is, colouring agent
For the 3 of A1, A2 and A3:3:4 compoundings, A1, A2 and A3 total amount are 0.1 part.
Embodiment 15：Flame-retardant PET and PC composites that a kind of color is modified, the difference with embodiment 1 is, toughness reinforcing phase
Appearance agent is ethylene-methyl acrylate-glyceryl methacrylate copolymer.
Embodiment 16：Flame-retardant PET and PC composites that a kind of color is modified, the difference with embodiment 1 is, hollow glass
Glass microballon is before using without step S0 processing.
Embodiment 17：Flame-retardant PET and PC composites that a kind of color is modified, the difference with embodiment 1 is, fire retardant
For 0.5 part of octaphenylcyclotetrasiloxane.
Embodiment 18：Flame-retardant PET and PC composites that a kind of color is modified, the difference with embodiment 1 is, fire retardant
It is octaphenylcyclotetrasiloxane and two lauseto neu potassium sulfonates with mass ratio 1:1 compounding, fire retardant total amount is 0.5 part.
Embodiment 19：Flame-retardant PET and PC composites that a kind of color is modified, the difference with embodiment 1 is, fire retardant
It is octaphenylcyclotetrasiloxane and trimethyl fluoride sulfonyl amine potassium with mass ratio 1:1 compounding, fire retardant total amount is 0.5 part.
Embodiment 20：Flame-retardant PET and PC composites that a kind of color is modified, the difference with embodiment 1 are that silane is even
Connection agent is aminopropyl triethoxysilane.
Embodiment 21：Flame-retardant PET and PC composites that a kind of color is modified, the difference with embodiment 1 is, lubricant
For calcium stearate.
Embodiment 22：Flame-retardant PET and PC composites that a kind of color is modified, the difference with embodiment 1 is, step S0
For the processing of hollow glass micropearl：2% silane coupler absolute ethyl alcohol of hollow glass micropearl gross mass will be accounted in 35-45
DEG C water-bath in be hydrolyzed dilution, the mass ratio of absolute ethyl alcohol and silane coupler is 10:1, at 15-35 DEG C, side stirring
Dilution side adds load weighted hollow glass micropearl in proportion, continues to stir 5- after hollow glass micropearl is all added
10min, adds 5% colouring agent for accounting for hollow glass micropearl gross mass, stirs 2h, more than 4h is then dried at 80 DEG C, most
Dried powder is placed on afterwards standby in closed container；Silane coupler is γ-(2,3- the third oxygen of epoxy) propyl group trimethoxy
Base silane.
Embodiment 23：Flame-retardant PET and PC composites that a kind of color is modified, the difference with embodiment 1 is, step S0
For the processing of hollow glass micropearl：1% silane coupler absolute ethyl alcohol of hollow glass micropearl gross mass will be accounted in 35-45
DEG C water-bath in be hydrolyzed dilution, the mass ratio of absolute ethyl alcohol and silane coupler is 5:1, at 15-35 DEG C, side stirring is dilute
Release liquid side and add load weighted hollow glass micropearl in proportion, continue to stir 5-10min after hollow glass micropearl is all added,
5% colouring agent for accounting for hollow glass micropearl gross mass is added, 2h is stirred, more than 4h is then dried at 80 DEG C, finally will be dry
Powder after dry is placed on standby in closed container；Silane coupler is γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicon
Alkane.
Embodiment 24：Flame-retardant PET and PC composites that a kind of color is modified, the difference with embodiment 1 is, step S0
For the processing of hollow glass micropearl：1% silane coupler absolute ethyl alcohol of hollow glass micropearl gross mass will be accounted in 35-45
DEG C water-bath in be hydrolyzed dilution, the mass ratio of absolute ethyl alcohol and silane coupler is 5:1, at 15-35 DEG C, side stirring is dilute
Release liquid side and add load weighted hollow glass micropearl in proportion, continue to stir 5-10min after hollow glass micropearl is all added,
10% colouring agent for accounting for hollow glass micropearl gross mass is added, 1h is stirred, more than 4h is then dried at 80 DEG C, finally will be dry
Powder after dry is placed on standby in closed container；Silane coupler is γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicon
Alkane.
Embodiment 25：Flame-retardant PET and PC composites that a kind of color is modified, the difference with embodiment 1 is, twin-screw
The process conditions of extruder are：One 200 DEG C of area's temperature, two 220 DEG C of area's temperature, 250 DEG C of three area's temperature, 270 DEG C of four area's temperature, five
275 DEG C of area's temperature, 265 DEG C of six area's temperature, seven 250 DEG C of area's temperature, eight 240 DEG C of area's temperature, 240 DEG C of head temperature, engine speed
For 300r/min, vacuum -0.4kPa.
Embodiment 26：Flame-retardant PET and PC composites that a kind of color is modified, the difference with embodiment 1 is, twin-screw
The process conditions of extruder are：One 180 DEG C of area's temperature, two 200 DEG C of area's temperature, 240 DEG C of three area's temperature, 250 DEG C of four area's temperature, five
275 DEG C of area's temperature, 265 DEG C of six area's temperature, seven 260 DEG C of area's temperature, eight 250 DEG C of area's temperature, 270 DEG C of head temperature, engine speed
For 300r/min, vacuum -0.4kPa.
Embodiment 27：Flame-retardant PET and PC composites that a kind of color is modified, the difference with embodiment 1 is, twin-screw
The process conditions of extruder are：One 200 DEG C of area's temperature, two 230 DEG C of area's temperature, 240 DEG C of three area's temperature, 260 DEG C of four area's temperature, five
270 DEG C of area's temperature, 260 DEG C of six area's temperature, seven 255 DEG C of area's temperature, eight 245 DEG C of area's temperature, 260 DEG C of head temperature, engine speed
For 400r/min, vacuum -0.6kPa.
Embodiment 28：Flame-retardant PET and PC composites that a kind of color is modified, the difference with embodiment 1 is, twin-screw
The process conditions of extruder are：One 200 DEG C of area's temperature, two 230 DEG C of area's temperature, 240 DEG C of three area's temperature, 260 DEG C of four area's temperature, five
270 DEG C of area's temperature, 260 DEG C of six area's temperature, seven 255 DEG C of area's temperature, eight 245 DEG C of area's temperature, 260 DEG C of head temperature, engine speed
For 400r/min, vacuum -0.5kPa.
Embodiment 29：Flame-retardant PET and PC composites that a kind of color is modified, the difference with embodiment 1 is, with purchased from
The acid anthraquinone blue 2AL of moral color painting Chemical Co., Ltd. of Shenzhen substitutes A1, purchased from the acid of Shanghai Mai Kun Chemical Co., Ltd.s
Property anthraquinone purple replaces A3.
Performance test and evaluation：
In order to preferably evaluate the performance of the present patent application, comparative example 1-4, comparative example 1-4 preparation method and implementation are prepared for
Example 1 is identical, and comparative example 1-4 component and content is as shown in table 2.
The comparative example 1-4 of table 2 component and content table
Wherein, PC is bisphenol A polycarbonate, and weight average molecular weight is 20,000-3 ten thousand；Colouring agent is the organic transparent dye of Anthraquinones
It is 1 according to mass ratio to expect A1 and A3:1 compounding, fire retardant is silicone flame retardant octaphenylcyclotetrasiloxane, Sulfonates
The lauseto neu potassium sulfonate of fire retardant two and sulfonamide based flame retardant trimethyl fluoride sulfonyl amine potassium compounding are formed, and the mass ratio of three is
5:3:2；Toughness reinforcing compatilizer is Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer；Antioxidant is β-(3,5-
Di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid and phosphorous acid three (2,4- di-tert-butyl-phenyl) ester be by weight 2：1
Compounding is formed；Lubricant is magnesium stearate.
Test object：PET and PC composites prepared by embodiment 1-5, embodiment 9-14, embodiment 29, comparative example 1-4
Finished product；The performance of test includes：Mechanical property, fire resistance, heat distortion temperature, colourity test and xenon lamp aging test, test
Condition and relevant criterion are referring to table 3；Test result is referring to table 4.
The testing standard of table 3 and test condition
The performance test results one of table 4
The performance test results two of table 5
As shown in table 4, in the present invention, used from PC and PET blend alloys as matrix material, above-mentioned base of the invention
Only a small amount of composite flame-retardant agent need to be added in material, you can realize the lifting of oxygen index (OI) and flame retardant rating.That is added in the present invention is hollow
Glass microballoon improves the intensity of composite, and apparent density slightly has reduction, and the use of toughness reinforcing compatilizer makes composite
Impact strength is greatly improved.The colouring agent of compounding is with the addition of in the present invention to improve the appearance colour of product, compound colorant
After addition, although the lightness L values of sample have to a certain degree decline but sample initial stage yellow colour index YI and colourity b values it is all obvious
Decline.
As shown in table 5, after addition colouring agent, although the lightness L values of sample have the initial stage of decline but sample to a certain degree yellow
Colour index YI and colourity b values are all decreased obviously.Compared with a kind of colouring agent being used alone in A1, A2 and A3, in A1, A2 and A3
Both any compoundings can improve its color modified effect to PET and PC composites, the yellow colour index YI at initial stage of sample
All it is decreased obviously with colourity b values.A1, A2 and A3 three, which compound, can further reduce yellow colour index YI and colourity b values, but lightness
Also certain resin is have dropped therewith, it is therefore preferable that scheme is both compoundings in A1, A2 and A3.
The test data of comparative example 1 and embodiment 29 is understood, using the Anthraquinones of German Lang Shengmagaoliesi productions
Organic transparency dye has more preferable effect to the color modified effect of PC products.
Visually observe the product of embodiment 1 and embodiment 16, find hollow glass micropearl and resin matrix in embodiment 1
More preferably, distribution of color is more uniform, and obtained PET and PC composites have good transparency and glossiness for compatibility.
Claims (10)
1. Flame-retardant PET and PC composites that a kind of color is modified, it is characterized in that, include the raw material of following parts by weight：
Makrolon：45~70 parts；
Polyethylene terephthalate：30~45 parts；
Hollow glass micropearl：5~15 parts；
Fire retardant：0.5~1.0 part；
Toughness reinforcing compatilizer：3~15 parts；
Antioxidant：0.5~1 part；
Lubricant：0.2~1 part；
Colouring agent：0.1-0.2 parts；
The colouring agent is the one or more in the organic transparent blue dyestuff of Anthraquinones and the organic transparent cudbear of Anthraquinones.
2. Flame-retardant PET and PC composites that a kind of color according to claim 1 is modified, it is characterized in that, including it is as follows
The raw material of parts by weight：
Makrolon：50.5 parts；
Polyethylene terephthalate：35 parts；
Hollow glass micropearl：10 parts；
Fire retardant：0.5 part；
Toughness reinforcing compatilizer：8 parts；
Antioxidant：0.6 part；
Lubricant：0.4 part；
Colouring agent：0.01 part；
The colouring agent is that the organic transparent blue dyestuff A1 of Anthraquinones, the organic transparent cudbear A2 of Anthraquinones, Anthraquinones are organic
One or more in transparent cudbear A3；A1, A2, A3 correspond to Blue RR, the moral of Germany Lang Shengmagaoliesi productions respectively
The Violet 3R of Violet B, Germany the Lang Shengmagaoliesi production of state Lang Shengmagaoliesi productions.
3. Flame-retardant PET and PC composites that a kind of color according to claim 2 is modified, it is characterized in that：The coloring
Agent is the 1 of A1 and A3:1 compounding.
4. Flame-retardant PET and PC composites that a kind of color according to claim 2 is modified, it is characterized in that：The toughness reinforcing
Compatilizer is：Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer and ethylene-methyl acrylate-metering system
One kind in acid glycidyl ester copolymer.
5. Flame-retardant PET and PC composites that a kind of color according to claim 2 is modified, it is characterized in that：It is described hollow
Glass microballoon is that, by silane coupler and the treated hollow glass micropearl of the colouring agent, the colouring agent is that Anthraquinones are organic
One or more in transparency dye A1, A2 and A3.
6. Flame-retardant PET and PC composites that a kind of color according to claim 1 is modified, it is characterized in that：It is described fire-retardant
Agent is that silicone flame retardant is formed with one or more kinds of compoundings in Sulfonates fire retardant, sulfonamide based flame retardant.
7. Flame-retardant PET and PC composites that a kind of color according to claim 6 is modified, it is characterized in that：The silane
Coupling agent is γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane.
8. Flame-retardant PET and PC composites that a kind of color according to claim 1 is modified, it is characterized in that：The antioxygen
Agent includes primary antioxidant and auxiliary antioxidant, and the primary antioxidant is β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid is just
One kind in octadecanol ester, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, the auxiliary antioxygen
Agent is phosphorous acid three (2,4- di-tert-butyl-phenyl) ester.
9. Flame-retardant PET and the preparation side of PC composites that a kind of color as described in any one in claim 1-8 is modified
Method, it is characterized in that, comprise the following steps：S1：Weigh the makrolon, polyethylene terephthalate, hollow glass of formula ratio
Glass microballon, fire retardant, toughness reinforcing compatilizer, antioxidant and lubricant, by the makrolon weighed and polyethylene terephthalate
Ester is dried at least 4 hours at a temperature of 115-125 DEG C, and other components are dried at least 2 hours at a temperature of 50-80 DEG C；S2：Will be dry
Makrolon, polyethylene terephthalate, hollow glass micropearl, fire retardant, toughness reinforcing compatilizer, antioxidant after dry processing
It is sufficiently mixed with lubricant at 20-30 DEG C；S3：It will be total to through the mixed materials of step S2 in double screw extruder through melting
Mixed extrusion, tie rod, cooling, air-dry, pelletizing, be dried to obtain described PET/PC composites, the double screw extruder use
Process conditions be：One area：180-220℃；2nd area：220-230℃；3rd area：230-250℃；4th area：250-280℃；Five
Area：265-280℃；6th area：255-270℃；7th area：250-260℃；8th area：240-250℃；Head temperature：240-270℃；
Screw speed is controlled in 300-400r/min, vacuum -0.3~-0.5kPa.
10. Flame-retardant PET and the preparation method of PC composites that a kind of color according to claim 9 is modified, its feature
It is：In the step S1, the hollow glass micropearl is using the step of preceding surface treated, surface treatment as follows：By duty
Dilution, institute are hydrolyzed with absolute ethyl alcohol in 35-45 DEG C of water-bath for the 1-2% of heart glass microballoon gross mass silane coupler
The mass ratio for stating absolute ethyl alcohol and the silane coupler is 5:1-10:1, at 15-35 DEG C, add and press in agitation and dilution liquid
The load weighted hollow glass micropearl of ratio, continues to stir after hollow glass micropearl is all added, is added in mixed dispersion liquid
The 5-10% of hollow glass micropearl gross mass colouring agent is accounted for, 1-2h is stirred, then dries, finally place dried powder
It is standby in closed container.
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| CN109608832A (en) * | 2018-11-29 | 2019-04-12 | 常熟市沈氏塑业有限公司 | A kind of illusion-colour bloom plastic bottle and its processing technology |
| CN109666278A (en) * | 2018-12-19 | 2019-04-23 | 东莞市旺品实业有限公司 | A kind of PC material of stress crack resistant and preparation method thereof |
| CN114456427A (en) * | 2022-01-24 | 2022-05-10 | 江苏新光镭射包装材料股份有限公司 | Impact-resistant and cold-resistant PC multicolor film and preparation method thereof |
| CN114716802A (en) * | 2022-03-30 | 2022-07-08 | 郑州圣莱特空心微珠新材料有限公司 | Low-dielectric mobile phone middle frame base material and preparation method thereof |
| CN116444960A (en) * | 2023-03-23 | 2023-07-18 | 东莞市万塑成塑料有限公司 | Composite PETG material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114716802A (en) * | 2022-03-30 | 2022-07-08 | 郑州圣莱特空心微珠新材料有限公司 | Low-dielectric mobile phone middle frame base material and preparation method thereof |
| CN116444960A (en) * | 2023-03-23 | 2023-07-18 | 东莞市万塑成塑料有限公司 | Composite PETG material |
| CN116444960B (en) * | 2023-03-23 | 2023-11-24 | 东莞市万塑成塑料有限公司 | Composite PETG material |
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Application publication date: 20170725 |