CN107163493A - A kind of high durable exempts to spray imitative metal ABS composite material - Google Patents
A kind of high durable exempts to spray imitative metal ABS composite material Download PDFInfo
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- CN107163493A CN107163493A CN201710469638.3A CN201710469638A CN107163493A CN 107163493 A CN107163493 A CN 107163493A CN 201710469638 A CN201710469638 A CN 201710469638A CN 107163493 A CN107163493 A CN 107163493A
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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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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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
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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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Abstract
The present invention provides a kind of high durable and exempts to spray imitative metal ABS composite material, calculates by weight, including following raw material：80 95 parts of ABS, 5 20 parts of modified ABSs exempt from for 1 10 parts to spray imitative metal master batch, 0.5 2 parts of silane couplers, 15 parts of assistant crosslinking agents, 0.5 2 parts of dispersants, 15 parts of toughener；Wherein, the modified ABS is ABS and 4 [2 (3,5 dihydroxy phenyl) vinyl] 1,2 benzenediols, two methacrylaldehyde contracting pentaerythrite copolymers；It is described to exempt to spray imitative metal master batch and coat pearly-lustre metallic pigments for the modified ABS.
Description
Technical field
The present invention relates to polymeric material field, in particular it relates to which a kind of high durable is exempted to spray imitative metal ABS and answered
Condensation material.
Background technology
ABS resin is acrylonitrile-butadiene-styrene copolymer, and due to its combination property preferably, impact strength is higher,
Chemical stability, electrical property is good.ABS resin has two complicated phase structures.Rubber is dispersed phase, and SAN is used as matrix resin
It is continuous phase, rubber is dispersed in matrix resin with graininess.Due to the presence of rubber grain, there is ABS resin more excellent
Performance, especially shock resistance.ABS resin has impact resistance, high rigidity, oil resistivity, lower temperature resistance, chemical-resistant resistance
Property, mechanical strength and excellent electrical properties；Easy to process, processing dimension stability and lustrous surface are good, easy application,
Color, can also carry out the secondary operation such as metalling, plating, welding, hot pressing and bonding, be a kind of a very wide range of thermoplasticity of purposes
Engineering plastics, are widely used in machinery industry, auto industry, electronic apparatus industry, instrument and meter industry, textile industry and building
Industry etc..But ABS easily turns to be yellow in itself, mainly caused by butadiene, because there is unreacted double bond, weatherability is by very
Big influence, becomes fragile over time, and the mechanical performance of product is also influenceed while the outward appearance for influenceing product.
Therefore, the present invention provides a kind of ABS xanthochromias, raising product gloss, high durable of impact property of being obviously improved and exempted from
The imitative metal ABS composite material of spraying.
The content of the invention
Exempt to spray imitative metal ABS composite material in view of the above-mentioned problems, the first aspect of the invention provides a kind of high durable,
Calculate by weight, including following raw material：
Wherein, the modified ABS is ABS and 4- [2- (3,5- dihydroxy phenyl) vinyl] -1,2- benzenediols, two propylene
Aldehyde contracting pentaerythrite copolymer；It is described to exempt to spray imitative metal master batch and coat pearly-lustre metallic pigments for the modified ABS.
In one embodiment, calculate by weight, including following raw material：
In one embodiment, calculate by weight, including following raw material：
In one embodiment, ABS described in the modified ABS and the 4- [2- (3,5- dihydroxy phenyl) ethene
Base] -1,2- benzenediols, the two methacrylaldehyde contracting pentaerythrite weight ratio be 1：(0.2-1)：(0.1-0.3)；Preferably, institute
State ABS and the 4- [2- (3,5- dihydroxy phenyls) vinyl] -1,2- benzenediols, the weight of the two methacrylaldehyde contracting pentaerythrite
Amount is than being 1：0.8：0.16.
In one embodiment, the silane coupler be it is a kind of in KH560, KH570, vinyl silanes A-171 or
It is a variety of.
In one embodiment, the assistant crosslinking agent includes sulfonation octaphenyl-POSS, eight (oxosilanes of aminophenyl three)
Middle one or more.
In one embodiment, the assistant crosslinking agent is sulfonation octaphenyl-POSS, eight (oxosilanes of aminophenyl three)；
The weight ratio of the sulfonation octaphenyl-POSS and described eight (oxosilanes of aminophenyl three) is 1：(0.5-1).
In one embodiment, the dispersant includes bisamide class dispersant, paraffin class dispersant, organic metal salt
It is one or more in class dispersant.
In one embodiment, the high durable exempts to spray imitative metal ABS composite material also including 1-5 parts of antioxidant,
3-15 parts of light stabilizers, 1-5 parts of ultraviolet absorbers.
Another aspect of the present invention provides a kind of high durable and exempts to spray the preparation method of imitative metal ABS composite material, at least wraps
Include following steps：
(1) by weight by ABS, modified ABS, exempt to spray imitative metal master batch, silane coupler, assistant crosslinking agent, dispersant,
Add in homogenizer, at 40~100 DEG C, stir 60~120min；
(2) toughener, antioxidant, light stabilizer, ultraviolet absorber is added into step (1) to continue to stir 30~90min,
Obtain mixed material；
(3) mixed material in step (2) is added into double screw extruder, it is 50~250r/min to control screw speed,
Temperature is 150~260 DEG C, melting extrusion granulation, obtains the high durable and exempts to spray imitative metal ABS composite material.
The above-mentioned of the application and other features, aspect and advantage is more readily understood with reference to described further below.
Embodiment
The participation in the election detailed description of the invention below for being preferable to carry out method and including embodiment this hair can be more easily understood
Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with art of the present invention
The identical implication that technical staff is generally understood that.When there is contradiction, the definition in this specification is defined.
As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover including for non-exclusionism.For example, the combination comprising listed elements
Thing, step, method, product or device are not necessarily limited to those key elements, but can include not expressly listed other key elements or
Such a composition, step, method, product or the intrinsic key element of device.
Conjunction " Consists of " excludes any key element do not pointed out, step or component.If be used in claim, this
Phrase will make claim be closed, it is not included the material in addition to materials of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following in the clause that phrase " Consists of " appears in claim main body after theme,
It is only limited to the key element described in the clause；Other key elements are not excluded outside as the overall claim.
Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit
During the Range Representation that choosing value is limited, this, which is appreciated that, specifically discloses by any range limit or preferred value and any scope
All scopes that any pairing of lower limit or preferred value is formed, regardless of whether whether the scope separately discloses.For example, when open
During scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When number range is described herein, unless otherwise indicated, otherwise the scope is intended to include its end
Value and all integers and fraction within the range.
Singulative includes plural number and object is discussed, unless the context clearly dictates otherwise." optional " or it is " any
It is a kind of " refer to that the item or event that describe thereafter may or may not occur, and the description include situation that event occurs and
The situation that event does not occur.
Approximate term in specification and claims is used for modifying quantity, represents that the present invention is not limited to this specific
Quantity, includes the part of the amendment of the acceptable change without cause related basic function close to the quantity.Phase
Answer, modify a numerical value with " about ", " about " etc., mean that the invention is not restricted to the exact numerical.In some examples, approximately
Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, scope is limited can be with
Combine and/or exchange, these scopes include all subranges contained therebetween if not stated otherwise.
In addition, the indefinite article " one kind " and " one " before key element of the present invention or component are to key element or the quantitative requirement of component
(i.e. occurrence number) unrestriction.Therefore " one " or " one kind " should be read as including one or at least one, and odd number
The key element or component of form also include plural form, unless the obvious purport of the quantity refers to singulative.
" polymer " means by the polymerizable compound prepared by the monomer that polymerize identical or different type.Generic term
" polymer " includes term " homopolymer ", " copolymer ", " terpolymer " and " EVA ".
" EVA " means by polymerizeing polymer prepared by least two different monomers.Generic term " EVA " includes
(its is general with term " terpolymer " for term " copolymer " (it is typically to refer to the polymer prepared by two kinds of different monomers)
To refer to the polymer prepared by three kinds of different monomers).It also includes the polymerization planted monomer by polymerization four or more and manufactured
Thing." blend " means two or more polymer by polymerizeing formed by physics or chemistry method jointly mixing
Thing.
In order to solve the above-mentioned technical problem, the first aspect of the invention provides a kind of high durable and exempts to spray imitative metal ABS
Composite, is calculated by weight, including following raw material：
Wherein, the modified ABS is ABS and 4- [2- (3,5- dihydroxy phenyl) vinyl] -1,2- benzenediols, two propylene
Aldehyde contracting pentaerythrite copolymer；It is described to exempt to spray imitative metal master batch and coat pearly-lustre metallic pigments for the modified ABS.
In one embodiment, calculate by weight, including following raw material：
In one embodiment, calculate by weight, including following raw material：
ABS
ABS resin is acrylonitrile, along butadiene (Butadiene), the copolymer of styrene (Styrene) three kinds of monomers.
Wherein A represents acrylonitrile there is provided chemical resistance and heat endurance, and B represents butadiene there is provided toughness and impact resilience, and S represents benzene second
Alkene, assigns rigidity and workability.Generally, acrylonitrile accounts for 15%~35% in ABS strands, and 5%~30% is accounted for along butadiene,
Styrene accounts for 40%~60%；ABS resin has two complicated phase structures.Rubber is dispersed phase, and SAN is to connect as matrix resin
Continuous phase.Rubber is dispersed in matrix resin with graininess.Due to the presence of rubber grain, make ABS resin that there is more excellent property
Energy, especially shock resistance.ABS resin has impact resistance, high rigidity, oil resistivity, lower temperature resistance, chemical proofing,
Mechanical strength and excellent electrical properties；Easy to process, processing dimension stability and lustrous surface are good, easy application, coloring, also
The secondary operation such as metalling, plating, welding, hot pressing and bonding can be carried out, are a kind of a very wide range of engineering thermoplastics of purposes
Plastics.
In one embodiment, ABS described in the modified ABS and the 4- [2- (3,5- dihydroxy phenyl) ethene
Base] -1,2- benzenediols, the two methacrylaldehyde contracting pentaerythrite weight ratio be 1：(0.2-1)：(0.1-0.3)；Preferably, institute
State ABS and the 4- [2- (3,5- dihydroxy phenyls) vinyl] -1,2- benzenediols, the weight of the two methacrylaldehyde contracting pentaerythrite
Amount is than being 1：(0.2-1)：(0.1-0.3).
The preparation method of the modified ABS is as follows：
By weight addition ABS, 4- [2- (3,5- dihydroxy phenyls) vinyl] -1,2- benzenediols, two into reactor
Methacrylaldehyde contracting pentaerythrite, is warming up to 80~90 DEG C, divides 3 batches to sequentially add initiator, reacts 6-10h, obtain the modification
ABS；The weight ratio of the ABS and the initiator is 1：0.002, the initiator is azodiisobutyronitrile.
Pass through ABS and 4- [2- (3,5- dihydroxy phenyls) vinyl] -1,2- benzenediols, two methacrylaldehyde contracting seasons in the present invention
Penta tetrol carries out copolymerization, forms phenolic hydroxyl group in modified ABS, 4- [2- (3,5- dihydroxy phenyl) vinyl] -1,2- benzenediols
Introducing and the additions of two methacrylaldehyde contracting pentaerythrites can promote to improve modified ABS and ABS while ABS weatherability
The degree of cross linking.
The preparation method for exempting to spray imitative metal master batch is as follows：
Silver powder (being less than 600 mesh), pearl essence HK111, orange pigment, diffusant, silane coupler are mixed with masterbatch
Even, dual-screw-stem machine extruding pelletization obtains silver color and imitates metal master batch；The diffusant is stearic amide and EBS, by weight 3：
1 mixture is made；Masterbatch is modified ABS, and the modified ABS is ABS and 4- [2- (3,5- dihydroxy phenyl) vinyl] -1,2- benzene
Diphenol, two methacrylaldehyde contracting pentaerythrite copolymers；Institute's silane coupler be KH560 and vinyl silanes A-171 by weight
3:1 mixed at high speed is made；The silane coupler accounts for the 0.10%~1.5% of silver powder weight.
In one embodiment, the silane coupler be it is a kind of in KH560, KH570, vinyl silanes A-171 or
It is a variety of；Preferably, the silane coupler is KH570.
In one embodiment, the assistant crosslinking agent includes sulfonation octaphenyl-POSS, eight (oxosilanes of aminophenyl three)
Middle one or more.
In one embodiment, the assistant crosslinking agent is sulfonation octaphenyl-POSS, eight (oxosilanes of aminophenyl three)；
The weight ratio of the sulfonation octaphenyl-POSS and described eight (oxosilanes of aminophenyl three) is 1：(0.5-1)；Preferably, it is described
Sulfonation octaphenyl-POSS (silsesquioxane of octaphenyl eight, No. CAS：5256-79-1) with described eight (oxosilanes of aminophenyl three)
(No. CAS：Weight ratio 518359-82-5) is 1：0.6.
By adding sulfonation octaphenyl-POSS and eight (oxosilanes of aminophenyl three), sulfonation octaphenyl-POSS in the present invention
In it is sulfonic be introduced into and eight (oxosilanes of aminophenyl three) in the introducing of amino add the benzene of sulfonation eight with rigid structure
The dispersiveness and compatibility of base-POSS and eight (oxosilanes of aminophenyl three) in the composite, in addition amino, sulfonic deposit
In the presence of assistant crosslinking agent, sulfonation octaphenyl-POSS and eight (oxosilanes of aminophenyl three), modified ABS, ABS are formed
Three-dimensional crosslinking structure, while improving the toughness of ABS composite material, also improves the mechanical property of composite and weather-proof
Property.
The preparation method of the sulfonation octaphenyl-POSS is as follows：
By the dissolving of the silsesquioxane of octaphenyl eight in concentrated sulfuric acid, it is warming up to after 90 DEG C -120 DEG C, insulation reaction 5-10h,
Room temperature is down to, is poured into deionized water, fully after washing to neutrality, filters and dries 12h at 120 DEG C in vacuum drying oven, obtain
To the silsesquioxane of sulfonation octaphenyl eight；The weight ratio of the silsesquioxane of octaphenyl eight and the concentrated sulfuric acid is 1：(16-
20)。
In one embodiment, the dispersant includes bisamide class dispersant, paraffin class dispersant, organic metal salt
It is one or more in class dispersant.
In one embodiment, the dispersant is vinyl bis-stearamides.
In one embodiment, the high durable exempts to spray imitative metal ABS composite material also including 1-5 parts of antioxidant,
3-15 parts of light stabilizers, 1-5 parts of ultraviolet absorbers.
In one embodiment, the antioxidant includes copper compound, organic or inorganic halogen-based compounds, hindered phenol
The phosphorus species of class, hindered amines, hydrazine, sulphur class compound, sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, magnesium hypophosphite etc.
Middle one or more.
In one embodiment, the antioxidant is antioxidant 1010, antioxidant 1035；Described in the antioxidant
The weight ratio of antioxidant 1010 and the antioxidant 1035 is 1：(1-3)；Preferably, antioxidant 1010 described in the antioxidant
Weight ratio with the antioxidant 1035 is 1：1.2.
In one embodiment, the light stabilizer is light stabilizer 770, light stabilizer 944；In the light stabilizer
The weight ratio of the light stabilizer 770 and the light stabilizer 944 is 1：0.2.
In one embodiment, the ultra-violet absorber includes 2- (2- hydroxy-5-methyl bases phenyl) BTA, 2-
(2- hydroxyl -5- butyl phenyls) BTA, 2- (2- hydroxyl -5- octyl phenyls) BTA, 2- (the 3- tert-butyl group -2- hydroxyls -
5- aminomethyl phenyls) -5- chlorobenzotriazoles, 2- (tertiary pentyl -2- hydroxy phenyls of 3,5- bis-) BTA, 2- hydroxyl -4- methoxyl groups
Benzophenone, 2- hydroxyl -4- n-octyl epoxides benzophenone, 2- [double (2,4- the 3,5-dimethylphenyls) -1,3,5- triazines -2- of 4,6-
Base] -5- (octyl group epoxide) phenol, 2- (4,6- diphenyl -1,3,5- triazine -2- bases) -5- (hexyl epoxide) phenol, salicylic acid pair
It is one or more in tert-butyl group phenyl ester, phenyl salicylate；Preferably, the ultra-violet absorber is 2- (2- hydroxyl -5- butyl benzenes
Base) BTA and 2- (2- hydroxyl -5- octyl phenyls) BTA.
In one embodiment, 2- (2- hydroxyl -5- butyl phenyls) BTAs and the 2- (2- hydroxyls -5-
Octyl phenyl) BTA weight ratio be 1：(1-2)；Preferably, 2- (2- hydroxyl -5- butyl phenyls) BTAs with
The weight ratio of 2- (2- hydroxyl -5- octyl phenyls) BTA is 1：1.3.
In one embodiment, the weight ratio of the antioxidant and the light stabilizer, the ultraviolet absorber is 1：
3.5：1.
In one embodiment, the toughener be sulfonated graphene and barium sulfate, the sulfonated graphene with it is described
The weight ratio of barium sulfate is 1：(0.2-0.5)；Preferably, the weight ratio of the sulfonated graphene and the barium sulfate is 1：
0.32。
Sulfonated graphene
Graphene is a kind of two-dimentional carbon nanomaterial of monoatomic thickness, with excellent light, electricity, heat and mechanical property,
And huge specific surface area.Can be (hydrogen bond, π-π effects, quiet by covalently or non-covalently acting between graphene and macromolecule
Electro ultrafiltration etc.) it is combined.These interactions had both added dissolubility or dispersiveness of the graphene in macromolecule, can also
Improve the performance of composite or expand its function.
Sulfonating reaction is directed to organic molecule and introduces sulfonic group (SO3H), sulphonate-base (such as SO3) or sulphonyl halogen Na
(SO2X chemical reaction), wherein halogen sulfonating reaction can be defined as by introducing the reaction of sulphonyl halogen again.According to sulfonating reaction institute
The substituent of introducing, the product of sulfonating reaction can be sulfonic acid (RSO3H), sulfonate (RSO3M, M are ammonium or metal ion) or sulphur
Carboxylic acid halides (RSO2X).It is different according to sulphur atom in sulfonic group and the atom that is connected in organic molecule, obtained product can be with
Connected sulfoacid compound (the RSO of carbon atom3H)；Sulfuric ester (the ROSO being connected with oxygen atom3H)；The sulfanilamide (SN) being connected with nitrogen-atoms
Compound (RNHSO3H)。
The preparation method of the sulfonated graphene is as follows：
(1) graphene oxide：The concentrated sulfuric acid and sodium nitrate of mass concentration 98%, ice-water bath are added in dry reactor
Lower cooling, under the conditions of 0-5 DEG C, stirring adds crystalline flake graphite, it is well mixed after be slowly added to potassium permanganate, controlling reaction temperature is
10-15 DEG C, continuation stirring reaction 2h under the conditions of 2h, 35 DEG C is reacted, deionized water is added, reacting liquid temperature is controlled at 98 DEG C, after
Continuous stirring 0.5h, adds the hydrogen peroxide that mass concentration is 30%, filters while hot, and product is carried out with watery hydrochloric acid (1mol/L)
Washing is dried under reduced pressure 24h, that is, the graphene oxide arrived to neutrality under the conditions of 60 DEG C；The crystalline flake graphite and the sodium nitrate, institute
The weight ratio for stating potassium permanganate is 1：0.6：2.1；The crystalline flake graphite and the concentrated sulfuric acid of the mass concentration 98%, the quality
Hydrogen peroxide that concentration is 30%, the mass volume ratio of the deionized water are 1：25：2.8：25；
(2) sulfonated graphene：The graphene oxide that step (1) is obtained is added in DMF (DMF),
Ultrasonically treated 1h, is obtained after finely dispersed graphene oxide, is separately added into (the dimethylamino of BTA -1- bases epoxide three
Base) phosphorus hexafluorophosphate (No. CAS：56602-33-6) and n-hydroxysuccinimide, after stirring reaction 2h, add to amino
Benzene sulfonic acid, continuously stirs after the completion of reaction 24h, question response, is washed with water repeatedly, ultrasound peels off 1h, 60 DEG C of bars again at room temperature
24h is dried under reduced pressure under part, sulfonated graphene is obtained；The graphene oxide and the (diformazan of BTA -1- bases epoxide three
Base amino) phosphorus hexafluorophosphate, the n-hydroxysuccinimide, the p-aminobenzene sulfonic acid weight ratio be 1：7.2：4：
5；The graphene oxide and the DMF mass volume ratio are 1：1.
It can be entered between graphene and macromolecule by covalently or non-covalently acting on (hydrogen bond, π-π effects, electrostatic interaction etc.)
Row is compound.These interactions had both added dissolubility or dispersiveness of the graphene in macromolecule, can also improve composite wood
The performance of material expands its function.In the present invention, by carrying out sulfonation to graphene, polar group sulfonic group is introduced, further
Promote dissolubility or dispersiveness of the graphene in macromolecule, while it is scattered in high polymer material to also promote barium sulfate
Property；While the addition of sulfonated graphene and barium sulfate improves the performance of composite, reduce antioxidant, light stabilizer and
The mobility of ultra-violet absorber, prevents antioxidant, light stabilizer and ultra-violet absorber from there are problems that overflow.
Another aspect of the present invention provides a kind of high durable and exempts to spray the preparation method of imitative metal ABS composite material, at least wraps
Include following steps：
(1) by weight by ABS, modified ABS, exempt to spray imitative metal master batch, silane coupler, assistant crosslinking agent, dispersant,
Add in homogenizer, at 40~100 DEG C, stir 60~120min；
(2) toughener, antioxidant, light stabilizer, ultraviolet absorber is added into step (1) to continue to stir 30~90min,
Obtain mixed material；
(3) mixed material in step (2) is added into double screw extruder, it is 50~250r/min to control screw speed,
Temperature is 150~260 DEG C, melting extrusion granulation, obtains the high durable and exempts to spray imitative metal ABS composite material.
In the present invention, screw combinations are using 21 cutouts in double screw extruder described in the step (3), and extrusion is warm
The areas of Du 1 are that the 0, the 2nd area to the 6th area is 260 degree, and the-the 10 area of the 7th area is 230 degree.
The present invention is specifically described below by embodiment.It is necessarily pointed out that, following examples are only used
In the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field
Some the nonessential modifications and adaptations made according to the content of the invention described above, still fall within protection scope of the present invention.
In addition, if without other explanations, it is raw materials used be all it is commercially available, be purchased from traditional Chinese medicines chemical reagent.
Embodiment 1
The high durable exempts to spray imitative metal ABS composite material, calculates by weight, including following raw material：
Wherein, the modified ABS is ABS and 4- [2- (3,5- dihydroxy phenyl) vinyl] -1,2- benzenediols, two propylene
Aldehyde contracting pentaerythrite copolymer, it is the ABS and the 4- [2- (3,5- dihydroxy phenyl) vinyl] -1,2- benzenediols, described
The weight ratio of two methacrylaldehyde contracting pentaerythrites is 1：0.8：0.16；It is described that to exempt to spray imitative metal master batch be modified ABS cladding
Pearly-lustre metallic pigments；The silane coupler is KH570；The assistant crosslinking agent is sulfonation octaphenyl-POSS, eight (aminophenyls
Three oxosilanes)；The weight ratio of the sulfonation octaphenyl-POSS and described eight (oxosilanes of aminophenyl three) is 1：0.6；Described point
Powder is vinyl bis-stearamides；The antioxidant is antioxidant 1010, antioxidant 1035；Resist described in the antioxidant
The weight ratio of oxygen agent 1010 and the antioxidant 1035 is 1：1.2；The light stabilizer is light stabilizer 770, light stabilizer
944；The weight ratio of light stabilizer 770 described in the light stabilizer and the light stabilizer 944 is 1：0.2；The ultraviolet
Absorbent is 2- (2- hydroxyl -5- butyl phenyls) BTAs and 2- (2- hydroxyl -5- octyl phenyls) BTA；The 2-
The weight ratio of (2- hydroxyl -5- butyl phenyls) BTA and the 2- (2- hydroxyl -5- octyl phenyls) BTA is 1：
1.3；The weight ratio of the antioxidant and the light stabilizer, the ultraviolet absorber is 1：3.5：1；The toughener is sulfonation
The weight ratio of graphene and barium sulfate, the sulfonated graphene and the barium sulfate is 1：0.32；
High durable exempts to spray the preparation method of imitative metal ABS composite material, at least comprises the following steps：
(1) by weight by ABS, modified ABS, exempt to spray imitative metal master batch, silane coupler, assistant crosslinking agent, dispersant,
Add in homogenizer, at 70 DEG C, stir 80min；
(2) toughener, antioxidant, light stabilizer, ultraviolet absorber are added into step (1) to continue to stir 60min, are obtained
Mixed material；
(3) mixed material in step (2) is added into double screw extruder, it is 200r/min, screw rod to control screw speed
Combination is using 21 cutouts, and the area of extrusion temperature the 1st is that the 0, the 2nd area to the 6th area is 260 degree, and the-the 10 area of the 7th area is 230 degree,
Melting extrusion is granulated, and is obtained the high durable and is exempted to spray imitative metal ABS composite material.
The preparation method of the modified ABS is as follows：
By weight addition ABS, 4- [2- (3,5- dihydroxy phenyls) vinyl] -1,2- benzenediols, two into reactor
Methacrylaldehyde contracting pentaerythrite, is warming up to 90 DEG C, divides 3 batches to sequentially add initiator, reacts 8h, obtain the modified ABS；It is described
The weight ratio of ABS and the initiator is 1：0.002, the initiator is azodiisobutyronitrile.
The preparation method for exempting to spray imitative metal master batch is as follows：
Silver powder (being less than 600 mesh), pearl essence HK111, orange pigment, diffusant, silane coupler are mixed with masterbatch
Even, dual-screw-stem machine extruding pelletization obtains silver color and imitates metal master batch；The diffusant is stearic amide and EBS, by weight 3：
1 mixture is made；Masterbatch is modified ABS, and the modified ABS is ABS and 4- [2- (3,5- dihydroxy phenyl) vinyl] -1,2- benzene
Diphenol, two methacrylaldehyde contracting pentaerythrite copolymers；Institute's silane coupler be KH560 and vinyl silanes A-171 by weight
3:1 mixed at high speed is made；The silane coupler accounts for the 1% of silver powder weight.
The preparation method of the sulfonation octaphenyl-POSS is as follows：
By the dissolving of the silsesquioxane of octaphenyl eight in concentrated sulfuric acid, it is warming up to after 95 DEG C, insulation reaction 9h, is down to room temperature,
Pour into deionized water, fully after washing to neutrality, filter and dry 12h at 120 DEG C in vacuum drying oven, obtain the benzene of sulfonation eight
The silsesquioxane of base eight；The weight ratio of the silsesquioxane of octaphenyl eight and the concentrated sulfuric acid is 1：18.
The preparation method of the sulfonated graphene is as follows：
(1) graphene oxide：The concentrated sulfuric acid and sodium nitrate of mass concentration 98%, ice-water bath are added in dry reactor
Lower cooling, under the conditions of 0-5 DEG C, stirring adds crystalline flake graphite, it is well mixed after be slowly added to potassium permanganate, controlling reaction temperature is
10-15 DEG C, continuation stirring reaction 2h under the conditions of 2h, 35 DEG C is reacted, deionized water is added, reacting liquid temperature is controlled at 98 DEG C, after
Continuous stirring 0.5h, adds the hydrogen peroxide that mass concentration is 30%, filters while hot, and product is carried out with watery hydrochloric acid (1mol/L)
Washing is dried under reduced pressure 24h, that is, the graphene oxide arrived to neutrality under the conditions of 60 DEG C；The crystalline flake graphite and the sodium nitrate, institute
The weight ratio for stating potassium permanganate is 1：0.6：2.1；The crystalline flake graphite and the concentrated sulfuric acid of the mass concentration 98%, the quality
Hydrogen peroxide that concentration is 30%, the mass volume ratio of the deionized water are 1：25：2.8：25；
(2) sulfonated graphene：The graphene oxide that step (1) is obtained is added in DMF (DMF),
Ultrasonically treated 1h, is obtained after finely dispersed graphene oxide, is separately added into (the dimethylamino of BTA -1- bases epoxide three
Base) phosphorus hexafluorophosphate and n-hydroxysuccinimide, after stirring reaction 2h, p-aminobenzene sulfonic acid is added, at room temperature continuously
After the completion of stirring reaction 24h, question response, it is washed with water repeatedly, ultrasound is dried under reduced pressure 24h under the conditions of peeling off 1h, 60 DEG C again, obtains
To sulfonated graphene；The graphene oxide and (dimethylamino) phosphorus hexafluoro phosphorus of BTA -1- bases epoxide three
Hydrochlorate, the n-hydroxysuccinimide, the weight ratio of the p-aminobenzene sulfonic acid are 1：7.2：4：5；The graphene oxide
Mass volume ratio with the DMF is 1：1.
Embodiment 2
The high durable exempts to spray imitative metal ABS composite material, calculates by weight, including following raw material：
Wherein, the modified ABS is ABS and 4- [2- (3,5- dihydroxy phenyl) vinyl] -1,2- benzenediols, two propylene
Aldehyde contracting pentaerythrite copolymer, it is the ABS and the 4- [2- (3,5- dihydroxy phenyl) vinyl] -1,2- benzenediols, described
The weight ratio of two methacrylaldehyde contracting pentaerythrites is 1：0.8：0.16；It is described that to exempt to spray imitative metal master batch be modified ABS cladding
Pearly-lustre metallic pigments；The silane coupler is KH570；The assistant crosslinking agent is sulfonation octaphenyl-POSS, eight (aminophenyls
Three oxosilanes)；The weight ratio of the sulfonation octaphenyl-POSS and described eight (oxosilanes of aminophenyl three) is 1：0.6；Described point
Powder is vinyl bis-stearamides；The antioxidant is antioxidant 1010, antioxidant 1035；Resist described in the antioxidant
The weight ratio of oxygen agent 1010 and the antioxidant 1035 is 1：1.2；The light stabilizer is light stabilizer 770, light stabilizer
944；The weight ratio of light stabilizer 770 described in the light stabilizer and the light stabilizer 944 is 1：0.2；The ultraviolet
Absorbent is 2- (2- hydroxyl -5- butyl phenyls) BTAs and 2- (2- hydroxyl -5- octyl phenyls) BTA；The 2-
The weight ratio of (2- hydroxyl -5- butyl phenyls) BTA and the 2- (2- hydroxyl -5- octyl phenyls) BTA is 1：
1.3；The weight ratio of the antioxidant and the light stabilizer, the ultraviolet absorber is 1：3.5：1；The toughener is sulfonation
The weight ratio of graphene and barium sulfate, the sulfonated graphene and the barium sulfate is 1：0.32；
High durable is exempted to spray the preparation method of imitative metal ABS composite material, the preparation method of the modified ABS, described exempted from
The preparation method of the imitative metal master batch of spraying, the preparation method of the sulfonation octaphenyl-POSS, the preparation side of the sulfonated graphene
Method be the same as Example 1.
Embodiment 3
The high durable exempts to spray imitative metal ABS composite material, calculates by weight, including following raw material：
Wherein, the modified ABS is ABS and 4- [2- (3,5- dihydroxy phenyl) vinyl] -1,2- benzenediols, two propylene
Aldehyde contracting pentaerythrite copolymer, it is the ABS and the 4- [2- (3,5- dihydroxy phenyl) vinyl] -1,2- benzenediols, described
The weight ratio of two methacrylaldehyde contracting pentaerythrites is 1：0.8：0.16；It is described that to exempt to spray imitative metal master batch be modified ABS cladding
Pearly-lustre metallic pigments；The silane coupler is KH570；The assistant crosslinking agent is sulfonation octaphenyl-POSS, eight (aminophenyls
Three oxosilanes)；The weight ratio of the sulfonation octaphenyl-POSS and described eight (oxosilanes of aminophenyl three) is 1：0.6；Described point
Powder is vinyl bis-stearamides；The antioxidant is antioxidant 1010, antioxidant 1035；Resist described in the antioxidant
The weight ratio of oxygen agent 1010 and the antioxidant 1035 is 1：1.2；The light stabilizer is light stabilizer 770, light stabilizer
944；The weight ratio of light stabilizer 770 described in the light stabilizer and the light stabilizer 944 is 1：0.2；The ultraviolet
Absorbent is 2- (2- hydroxyl -5- butyl phenyls) BTAs and 2- (2- hydroxyl -5- octyl phenyls) BTA；The 2-
The weight ratio of (2- hydroxyl -5- butyl phenyls) BTA and the 2- (2- hydroxyl -5- octyl phenyls) BTA is 1：
1.3；The weight ratio of the antioxidant and the light stabilizer, the ultraviolet absorber is 1：3.5：1；The toughener is sulfonation
The weight ratio of graphene and barium sulfate, the sulfonated graphene and the barium sulfate is 1：0.32；
High durable is exempted to spray the preparation method of imitative metal ABS composite material, the preparation method of the modified ABS, described exempted from
The preparation method of the imitative metal master batch of spraying, the preparation method of the sulfonation octaphenyl-POSS, the preparation side of the sulfonated graphene
Method be the same as Example 1.
Embodiment 4
The high durable exempts to spray imitative metal ABS composite material, calculates by weight, including following raw material：
Wherein, the modified ABS is ABS and 4- [2- (3,5- dihydroxy phenyl) vinyl] -1,2- benzenediols, two propylene
Aldehyde contracting pentaerythrite copolymer, it is the ABS and the 4- [2- (3,5- dihydroxy phenyl) vinyl] -1,2- benzenediols, described
The weight ratio of two methacrylaldehyde contracting pentaerythrites is 1：0.8：0.16；It is described that to exempt to spray imitative metal master batch be modified ABS cladding
Pearly-lustre metallic pigments；The silane coupler is KH570；The assistant crosslinking agent is sulfonation octaphenyl-POSS, eight (aminophenyls
Three oxosilanes)；The weight ratio of the sulfonation octaphenyl-POSS and described eight (oxosilanes of aminophenyl three) is 1：0.6；Described point
Powder is vinyl bis-stearamides；The antioxidant is antioxidant 1010, antioxidant 1035；Resist described in the antioxidant
The weight ratio of oxygen agent 1010 and the antioxidant 1035 is 1：1.2；The light stabilizer is light stabilizer 770, light stabilizer
944；The weight ratio of light stabilizer 770 described in the light stabilizer and the light stabilizer 944 is 1：0.2；The ultraviolet
Absorbent is 2- (2- hydroxyl -5- butyl phenyls) BTAs and 2- (2- hydroxyl -5- octyl phenyls) BTA；The 2-
The weight ratio of (2- hydroxyl -5- butyl phenyls) BTA and the 2- (2- hydroxyl -5- octyl phenyls) BTA is 1：
1.3；The weight ratio of the antioxidant and the light stabilizer, the ultraviolet absorber is 1：3.5：1；The toughener is sulfonation
The weight ratio of graphene and barium sulfate, the sulfonated graphene and the barium sulfate is 1：0.32；
High durable is exempted to spray the preparation method of imitative metal ABS composite material, the preparation method of the modified ABS, described exempted from
The preparation method of the imitative metal master batch of spraying, the preparation method of the sulfonation octaphenyl-POSS, the preparation side of the sulfonated graphene
Method be the same as Example 1.
Embodiment 5
The high durable exempts to spray imitative metal ABS composite material, calculates by weight, including following raw material：
Wherein, the modified ABS is ABS and 4- [2- (3,5- dihydroxy phenyl) vinyl] -1,2- benzenediols, two propylene
Aldehyde contracting pentaerythrite copolymer, it is the ABS and the 4- [2- (3,5- dihydroxy phenyl) vinyl] -1,2- benzenediols, described
The weight ratio of two methacrylaldehyde contracting pentaerythrites is 1：1：0.1；It is described to exempt to spray imitative metal master batch and coat pearly-lustre for the modified ABS
Metallic pigments；The silane coupler is KH570；The assistant crosslinking agent is sulfonation octaphenyl-POSS, the eight (oxygen of aminophenyl three
Silane)；The weight ratio of the sulfonation octaphenyl-POSS and described eight (oxosilanes of aminophenyl three) is 1：0.6；The dispersant
For vinyl bis-stearamides；The antioxidant is antioxidant 1010, antioxidant 1035；Antioxidant described in the antioxidant
1010 be 1 with the weight ratio of the antioxidant 1035：1.2；The light stabilizer is light stabilizer 770, light stabilizer 944；Institute
The weight ratio for stating light stabilizer 770 described in light stabilizer and the light stabilizer 944 is 1：0.2；The ultra-violet absorber
For 2- (2- hydroxyl -5- butyl phenyls) BTAs and 2- (2- hydroxyl -5- octyl phenyls) BTA；The 2- (2- hydroxyls-
5- butyl phenyls) the weight ratio of BTA and the 2- (2- hydroxyl -5- octyl phenyls) BTA is 1：1.3；It is described anti-
The weight ratio of oxygen agent and the light stabilizer, the ultraviolet absorber is 1：3.5：1；The toughener is sulfonated graphene and sulphur
The weight ratio of sour barium, the sulfonated graphene and the barium sulfate is 1：0.32；
High durable is exempted to spray the preparation method of imitative metal ABS composite material, the preparation method of the modified ABS, described exempted from
The preparation method of the imitative metal master batch of spraying, the preparation method of the sulfonation octaphenyl-POSS, the preparation side of the sulfonated graphene
Method be the same as Example 1.
Embodiment 6
The high durable exempts to spray imitative metal ABS composite material, calculates by weight, including following raw material：
Wherein, the modified ABS is ABS and 4- [2- (3,5- dihydroxy phenyl) vinyl] -1,2- benzenediols, two propylene
Aldehyde contracting pentaerythrite copolymer, it is the ABS and the 4- [2- (3,5- dihydroxy phenyl) vinyl] -1,2- benzenediols, described
The weight ratio of two methacrylaldehyde contracting pentaerythrites is 1：0.2：0.3；It is described to exempt to spray imitative metal master batch and coat pearl for the modified ABS
Light metallic pigments；The silane coupler is KH570；The assistant crosslinking agent is sulfonation octaphenyl-POSS, eight (aminophenyls three
Oxosilane)；The weight ratio of the sulfonation octaphenyl-POSS and described eight (oxosilanes of aminophenyl three) is 1：0.6；It is described scattered
Agent is vinyl bis-stearamides；The antioxidant is antioxidant 1010, antioxidant 1035；Antioxygen described in the antioxidant
The weight ratio of agent 1010 and the antioxidant 1035 is 1：1.2；The light stabilizer is light stabilizer 770, light stabilizer 944；
The weight ratio of light stabilizer 770 described in the light stabilizer and the light stabilizer 944 is 1：0.2；The ultraviolet radiation absorption
Agent is 2- (2- hydroxyl -5- butyl phenyls) BTAs and 2- (2- hydroxyl -5- octyl phenyls) BTA；2- (the 2- hydroxyls
Base -5- butyl phenyls) the weight ratio of BTA and the 2- (2- hydroxyl -5- octyl phenyls) BTA is 1：1.3；It is described
The weight ratio of antioxidant and the light stabilizer, the ultraviolet absorber is 1：3.5：1；The toughener be sulfonated graphene and
The weight ratio of barium sulfate, the sulfonated graphene and the barium sulfate is 1：0.32；
High durable is exempted to spray the preparation method of imitative metal ABS composite material, the preparation method of the modified ABS, described exempted from
The preparation method of the imitative metal master batch of spraying, the preparation method of the sulfonation octaphenyl-POSS, the preparation side of the sulfonated graphene
Method be the same as Example 1.
Embodiment 7
The high durable exempts to spray imitative metal ABS composite material, calculates by weight, including following raw material：
Wherein, the modified ABS is ABS and 4- [2- (3,5- dihydroxy phenyl) vinyl] -1,2- benzenediols, two propylene
Aldehyde contracting pentaerythrite copolymer, it is the ABS and the 4- [2- (3,5- dihydroxy phenyl) vinyl] -1,2- benzenediols, described
The weight ratio of two methacrylaldehyde contracting pentaerythrites is 1：0.8：0.16；It is described that to exempt to spray imitative metal master batch be modified ABS cladding
Pearly-lustre metallic pigments；The silane coupler is KH570；The assistant crosslinking agent is sulfonation octaphenyl-POSS, eight (aminophenyls
Three oxosilanes)；The weight ratio of the sulfonation octaphenyl-POSS and described eight (oxosilanes of aminophenyl three) is 1：0.5；Described point
Powder is vinyl bis-stearamides；The antioxidant is antioxidant 1010, antioxidant 1035；Resist described in the antioxidant
The weight ratio of oxygen agent 1010 and the antioxidant 1035 is 1：1.2；The light stabilizer is light stabilizer 770, light stabilizer
944；The weight ratio of light stabilizer 770 described in the light stabilizer and the light stabilizer 944 is 1：0.2；The ultraviolet
Absorbent is 2- (2- hydroxyl -5- butyl phenyls) BTAs and 2- (2- hydroxyl -5- octyl phenyls) BTA；The 2-
The weight ratio of (2- hydroxyl -5- butyl phenyls) BTA and the 2- (2- hydroxyl -5- octyl phenyls) BTA is 1：
1.3；The weight ratio of the antioxidant and the light stabilizer, the ultraviolet absorber is 1：3.5：1；The toughener is sulfonation
The weight ratio of graphene and barium sulfate, the sulfonated graphene and the barium sulfate is 1：0.32；
High durable is exempted to spray the preparation method of imitative metal ABS composite material, the preparation method of the modified ABS, described exempted from
The preparation method of the imitative metal master batch of spraying, the preparation method of the sulfonation octaphenyl-POSS, the preparation side of the sulfonated graphene
Method be the same as Example 1.
Embodiment 8
The high durable exempts to spray imitative metal ABS composite material, calculates by weight, including following raw material：
Wherein, the modified ABS is ABS and 4- [2- (3,5- dihydroxy phenyl) vinyl] -1,2- benzenediols, two propylene
Aldehyde contracting pentaerythrite copolymer, it is the ABS and the 4- [2- (3,5- dihydroxy phenyl) vinyl] -1,2- benzenediols, described
The weight ratio of two methacrylaldehyde contracting pentaerythrites is 1：0.8：0.16；It is described that to exempt to spray imitative metal master batch be modified ABS cladding
Pearly-lustre metallic pigments；The silane coupler is KH570；The assistant crosslinking agent is sulfonation octaphenyl-POSS, eight (aminophenyls
Three oxosilanes)；The weight ratio of the sulfonation octaphenyl-POSS and described eight (oxosilanes of aminophenyl three) is 1：1；It is described scattered
Agent is vinyl bis-stearamides；The antioxidant is antioxidant 1010, antioxidant 1035；Antioxygen described in the antioxidant
The weight ratio of agent 1010 and the antioxidant 1035 is 1：1.2；The light stabilizer is light stabilizer 770, light stabilizer 944；
The weight ratio of light stabilizer 770 described in the light stabilizer and the light stabilizer 944 is 1：0.2；The ultraviolet radiation absorption
Agent is 2- (2- hydroxyl -5- butyl phenyls) BTAs and 2- (2- hydroxyl -5- octyl phenyls) BTA；2- (the 2- hydroxyls
Base -5- butyl phenyls) the weight ratio of BTA and the 2- (2- hydroxyl -5- octyl phenyls) BTA is 1：1.3；It is described
The weight ratio of antioxidant and the light stabilizer, the ultraviolet absorber is 1：3.5：1；The toughener be sulfonated graphene and
The weight ratio of barium sulfate, the sulfonated graphene and the barium sulfate is 1：0.32；
High durable is exempted to spray the preparation method of imitative metal ABS composite material, the preparation method of the modified ABS, described exempted from
The preparation method of the imitative metal master batch of spraying, the preparation method of the sulfonation octaphenyl-POSS, the preparation side of the sulfonated graphene
Method be the same as Example 1.
Embodiment 9
The high durable exempts to spray imitative metal ABS composite material, calculates by weight, including following raw material：
Wherein, the modified ABS is ABS and 4- [2- (3,5- dihydroxy phenyl) vinyl] -1,2- benzenediols, two propylene
Aldehyde contracting pentaerythrite copolymer, it is the ABS and the 4- [2- (3,5- dihydroxy phenyl) vinyl] -1,2- benzenediols, described
The weight ratio of two methacrylaldehyde contracting pentaerythrites is 1：0.8：0.16；It is described that to exempt to spray imitative metal master batch be modified ABS cladding
Pearly-lustre metallic pigments；The silane coupler is KH570；The assistant crosslinking agent is sulfonation octaphenyl-POSS, eight (aminophenyls
Three oxosilanes)；The weight ratio of the sulfonation octaphenyl-POSS and described eight (oxosilanes of aminophenyl three) is 1：0.6；Described point
Powder is vinyl bis-stearamides；The antioxidant is antioxidant 1010, antioxidant 1035；Resist described in the antioxidant
The weight ratio of oxygen agent 1010 and the antioxidant 1035 is 1：1.2；The light stabilizer is light stabilizer 770, light stabilizer
944；The weight ratio of light stabilizer 770 described in the light stabilizer and the light stabilizer 944 is 1：0.2；The ultraviolet
Absorbent is 2- (2- hydroxyl -5- butyl phenyls) BTAs and 2- (2- hydroxyl -5- octyl phenyls) BTA；The 2-
The weight ratio of (2- hydroxyl -5- butyl phenyls) BTA and the 2- (2- hydroxyl -5- octyl phenyls) BTA is 1：
1.3；The weight ratio of the antioxidant and the light stabilizer, the ultraviolet absorber is 1：3.5：1；The toughener is sulfonation
The weight ratio of graphene and barium sulfate, the sulfonated graphene and the barium sulfate is 1：0.2；
High durable is exempted to spray the preparation method of imitative metal ABS composite material, the preparation method of the modified ABS, described exempted from
The preparation method of the imitative metal master batch of spraying, the preparation method of the sulfonation octaphenyl-POSS, the preparation side of the sulfonated graphene
Method be the same as Example 1.
Embodiment 10
The high durable exempts to spray imitative metal ABS composite material, calculates by weight, including following raw material：
Wherein, the modified ABS is ABS and 4- [2- (3,5- dihydroxy phenyl) vinyl] -1,2- benzenediols, two propylene
Aldehyde contracting pentaerythrite copolymer, it is the ABS and the 4- [2- (3,5- dihydroxy phenyl) vinyl] -1,2- benzenediols, described
The weight ratio of two methacrylaldehyde contracting pentaerythrites is 1：0.8：0.16；It is described that to exempt to spray imitative metal master batch be modified ABS cladding
Pearly-lustre metallic pigments；The silane coupler is KH570；The assistant crosslinking agent is sulfonation octaphenyl-POSS, eight (aminophenyls
Three oxosilanes)；The weight ratio of the sulfonation octaphenyl-POSS and described eight (oxosilanes of aminophenyl three) is 1：0.6；Described point
Powder is vinyl bis-stearamides；The antioxidant is antioxidant 1010, antioxidant 1035；Resist described in the antioxidant
The weight ratio of oxygen agent 1010 and the antioxidant 1035 is 1：1.2；The light stabilizer is light stabilizer 770, light stabilizer
944；The weight ratio of light stabilizer 770 described in the light stabilizer and the light stabilizer 944 is 1：0.2；The ultraviolet
Absorbent is 2- (2- hydroxyl -5- butyl phenyls) BTAs and 2- (2- hydroxyl -5- octyl phenyls) BTA；The 2-
The weight ratio of (2- hydroxyl -5- butyl phenyls) BTA and the 2- (2- hydroxyl -5- octyl phenyls) BTA is 1：
1.3；The weight ratio of the antioxidant and the light stabilizer, the ultraviolet absorber is 1：3.5：1；The toughener is sulfonation
The weight ratio of graphene and barium sulfate, the sulfonated graphene and the barium sulfate is 1：0.5；
High durable is exempted to spray the preparation method of imitative metal ABS composite material, the preparation method of the modified ABS, described exempted from
The preparation method of the imitative metal master batch of spraying, the preparation method of the sulfonation octaphenyl-POSS, the preparation side of the sulfonated graphene
Method be the same as Example 1.
Comparative example 1
The high durable exempts to spray imitative metal ABS composite material, calculates by weight, including following raw material：
Wherein, it is described to exempt to spray imitative metal master batch and coat pearly-lustre metallic pigments for the ABS；The silane coupler is
KH570；The assistant crosslinking agent is sulfonation octaphenyl-POSS, eight (oxosilanes of aminophenyl three)；Sulfonation octaphenyl-the POSS
Weight ratio with described eight (oxosilanes of aminophenyl three) is 1：0.6；The dispersant is vinyl bis-stearamides；It is described anti-
Oxidant is antioxidant 1010, antioxidant 1035；The weight of antioxidant 1010 described in the antioxidant and the antioxidant 1035
Amount is than being 1：1.2；The light stabilizer is light stabilizer 770, light stabilizer 944；Light stabilizer described in the light stabilizer
770 be 1 with the weight ratio of the light stabilizer 944：0.2；The ultra-violet absorber is 2- (2- hydroxyl -5- butyl phenyls) benzene
And triazole and 2- (2- hydroxyl -5- octyl phenyls) BTA；2- (2- hydroxyl -5- butyl phenyls) BTAs with it is described
The weight ratio of 2- (2- hydroxyl -5- octyl phenyls) BTA is 1：1.3；The antioxidant and the light stabilizer, the purple
The weight ratio of outer absorbent is 1：3.5：1；The toughener be sulfonated graphene and barium sulfate, the sulfonated graphene with it is described
The weight ratio of barium sulfate is 1：0.32；
High durable exempts to spray the preparation method of imitative metal ABS composite material, the preparation side for exempting to spray imitative metal master batch
Method (modified ABS replaces with ABS), the preparation method of the sulfonation octaphenyl-POSS, the preparation side of the sulfonated graphene
Method be the same as Example 1.
Comparative example 2
The high durable exempts to spray imitative metal ABS composite material, calculates by weight, including following raw material：
Wherein, the modified ABS is ABS and 4- [2- (3,5- dihydroxy phenyl) vinyl] -1,2- benzenediols, two propylene
Aldehyde contracting pentaerythrite copolymer, it is the ABS and the 4- [2- (3,5- dihydroxy phenyl) vinyl] -1,2- benzenediols, described
The weight ratio of two methacrylaldehyde contracting pentaerythrites is 1：0.8：0.16；It is described that to exempt to spray imitative metal master batch be modified ABS cladding
Pearly-lustre metallic pigments；The silane coupler is KH570；The assistant crosslinking agent is eight (oxosilanes of aminophenyl three)；Described point
Powder is vinyl bis-stearamides；The antioxidant is antioxidant 1010, antioxidant 1035；Resist described in the antioxidant
The weight ratio of oxygen agent 1010 and the antioxidant 1035 is 1：1.2；The light stabilizer is light stabilizer 770, light stabilizer
944；The weight ratio of light stabilizer 770 described in the light stabilizer and the light stabilizer 944 is 1：0.2；The ultraviolet
Absorbent is 2- (2- hydroxyl -5- butyl phenyls) BTAs and 2- (2- hydroxyl -5- octyl phenyls) BTA；The 2-
The weight ratio of (2- hydroxyl -5- butyl phenyls) BTA and the 2- (2- hydroxyl -5- octyl phenyls) BTA is 1：
1.3；The weight ratio of the antioxidant and the light stabilizer, the ultraviolet absorber is 1：3.5：1；The toughener is sulfonation
The weight ratio of graphene and barium sulfate, the sulfonated graphene and the barium sulfate is 1：0.32；
High durable is exempted to spray the preparation method of imitative metal ABS composite material, the preparation method of the modified ABS, described exempted from
Preparation method, the preparation method be the same as Example 1 of the sulfonated graphene of the imitative metal master batch of spraying.
Comparative example 3
The high durable exempts to spray imitative metal ABS composite material, calculates by weight, including following raw material：
Wherein, the modified ABS is ABS and 4- [2- (3,5- dihydroxy phenyl) vinyl] -1,2- benzenediols, two propylene
Aldehyde contracting pentaerythrite copolymer, it is the ABS and the 4- [2- (3,5- dihydroxy phenyl) vinyl] -1,2- benzenediols, described
The weight ratio of two methacrylaldehyde contracting pentaerythrites is 1：0.8：0.16；It is described that to exempt to spray imitative metal master batch be modified ABS cladding
Pearly-lustre metallic pigments；The silane coupler is KH570；The assistant crosslinking agent is sulfonation octaphenyl-POSS, eight (aminophenyls
Three oxosilanes)；The weight ratio of the sulfonation octaphenyl-POSS and described eight (oxosilanes of aminophenyl three) is 1：0.6；Described point
Powder is vinyl bis-stearamides；The antioxidant is antioxidant 1010, antioxidant 1035；Resist described in the antioxidant
The weight ratio of oxygen agent 1010 and the antioxidant 1035 is 1：1.2；The light stabilizer is light stabilizer 770, light stabilizer
944；The weight ratio of light stabilizer 770 described in the light stabilizer and the light stabilizer 944 is 1：0.2；The ultraviolet
Absorbent is 2- (2- hydroxyl -5- butyl phenyls) BTAs and 2- (2- hydroxyl -5- octyl phenyls) BTA；The 2-
The weight ratio of (2- hydroxyl -5- butyl phenyls) BTA and the 2- (2- hydroxyl -5- octyl phenyls) BTA is 1：
1.3；The weight ratio of the antioxidant and the light stabilizer, the ultraviolet absorber is 1：3.5：1；The toughener is sulfuric acid
Barium；
High durable is exempted to spray the preparation method of imitative metal ABS composite material, the preparation method of the modified ABS, described exempted from
The preparation method of the imitative metal master batch of spraying, the preparation method of the sulfonation octaphenyl-POSS, the preparation side of the sulfonated graphene
Method be the same as Example 1.
Comparative example 4
The high durable exempts to spray imitative metal ABS composite material, calculates by weight, including following raw material：
Wherein, it is described to exempt to spray imitative metal master batch and coat pearly-lustre metallic pigments for the ABS；The silane coupler is
KH570；The assistant crosslinking agent is eight (oxosilanes of aminophenyl three)；The dispersant is vinyl bis-stearamides；It is described anti-
Oxidant is antioxidant 1010, antioxidant 1035；The weight of antioxidant 1010 described in the antioxidant and the antioxidant 1035
Amount is than being 1：1.2；The light stabilizer is light stabilizer 770, light stabilizer 944；Light stabilizer described in the light stabilizer
770 be 1 with the weight ratio of the light stabilizer 944：0.2；The ultra-violet absorber is 2- (2- hydroxyl -5- butyl phenyls) benzene
And triazole and 2- (2- hydroxyl -5- octyl phenyls) BTA；2- (2- hydroxyl -5- butyl phenyls) BTAs with it is described
The weight ratio of 2- (2- hydroxyl -5- octyl phenyls) BTA is 1：1.3；The antioxidant and the light stabilizer, the purple
The weight ratio of outer absorbent is 1：3.5：1；The toughener is barium sulfate；
High durable exempts to spray the preparation method of imitative metal ABS composite material, the preparation side for exempting to spray imitative metal master batch
Method be the same as Example 1.
Comparative example 5
The high durable exempts to spray imitative metal ABS composite material, calculates by weight, including following raw material：
Wherein, it is described to exempt to spray imitative metal master batch for pearly-lustre metallic pigments；The silane coupler is KH570；It is described to help
Crosslinking agent is eight (oxosilanes of aminophenyl three)；The dispersant is vinyl bis-stearamides；The antioxidant is antioxygen
Agent 1010, antioxidant 1035；The weight ratio of antioxidant 1010 described in the antioxidant and the antioxidant 1035 is 1：1.2；
The light stabilizer is light stabilizer 770, light stabilizer 944；Light stabilizer 770 described in the light stabilizer and the light are steady
The weight ratio for determining agent 944 is 1：0.2；The ultra-violet absorber is 2- (2- hydroxyl -5- butyl phenyls) BTAs and 2- (2-
Hydroxyl -5- octyl phenyls) BTA；2- (2- hydroxyl -5- butyl phenyls) BTAs and the 2- (2- hydroxyls -5-
Octyl phenyl) BTA weight ratio be 1：1.3；The antioxidant and the light stabilizer, the weight of the ultraviolet absorber
Amount is than being 1：3.5：1；The toughener is barium sulfate；
The preparation method be the same as Example 1 that high durable exempts to spray imitative metal ABS composite material is (described to exempt to spray imitative metal substitute
Exempt to spray imitative metal master batch).
Performance test
Tensile property：Tensile strength and elongation at break are measured according to JISK6251.
Weather resistance：According to the program of JISK6266 SA methods, to exempting to spray imitative metal ABS composite material product progress
Degenerate and test.The outer surface structure-oriented carbon lamp light source of imitative metal ABS composite material product, experimental temperature 63 will be exempted to spray
DEG C, the continuous irradiation light, and water is sprayed on the outer surface for exempting to spray imitative metal ABS composite material product, follow within every 102 minutes
Ring 18 minutes.Annealing time is 48 hours, 96 hours and 168 hours.Each after experiment of degenerating is exempted to spray imitative metal ABS
Composite product carries out constant strain fatigue experiment, and applying 40% to sample at 20 DEG C with 6.7Hz circulation repeats to extend
Strain, and evaluate its endurance quality.It is considered as what is evaluated when the surface for exempting to spray imitative metal ABS composite material product is split
Terminal.Terminated and evaluated with 10,000,000 repetition fatigue and cyclics.
The performance test results of table 1
It is seen from the above data that compared with addition modified ABS, sulfonation octaphenyl-POSS, sulfonated graphene, this hair
The high durable of bright offer, which exempts to spray imitative metal ABS composite material, can be obviously improved ABS xanthochromias, improve product gloss, impact property.
Foregoing example is merely illustrative, some features of the feature for explaining the disclosure.Appended claim
The scope as wide as possible for requiring to be contemplated that is intended to, and embodiments as presented herein is only according to all possible embodiment
Combination selection embodiment explanation.Therefore, the purpose of applicant is appended claim not by the explanation present invention
Feature example selectional restriction.And the progress in science and technology by formed language performance it is inaccurate due to and not
The possible equivalent or son being presently considered are replaced, and these changes should also be interpreted by appended in the conceived case
Claim is covered.
Claims (10)
1. a kind of high durable exempts to spray imitative metal ABS composite material, it is characterised in that calculate by weight, including following raw material：
Wherein, the modified ABS is that ABS contracts with 4- [2- (3,5- dihydroxy phenyl) vinyl] -1,2- benzenediols, two methacrylaldehyde
Pentaerythrite copolymer；It is described to exempt to spray imitative metal master batch and coat pearly-lustre metallic pigments for the modified ABS.
2. high durable exempts to spray imitative metal ABS composite material according to claim 1, it is characterised in that calculate by weight,
Including following raw material：
3. high durable exempts to spray imitative metal ABS composite material according to claim 2, it is characterised in that calculate by weight,
Including following raw material：
4. high durable exempts to spray imitative metal ABS composite material according to claim 1, it is characterised in that in the modified ABS
The ABS and the 4- [2- (3,5- dihydroxy phenyls) vinyl] -1,2- benzenediols, the two methacrylaldehyde contracting pentaerythrite
Weight ratio is 1：(0.2-1)：(0.1-0.3).
5. high durable exempts to spray imitative metal ABS composite material according to claim 1, it is characterised in that described silane coupled
Agent is one or more in KH560, KH570, vinyl silanes A-171.
6. high durable exempts to spray imitative metal ABS composite material according to claim 1, it is characterised in that the assistant crosslinking agent
Including one or more in sulfonation octaphenyl-POSS, eight (oxosilanes of aminophenyl three).
7. high durable exempts to spray imitative metal ABS composite material according to claim 6, it is characterised in that the assistant crosslinking agent
For sulfonation octaphenyl-POSS, eight (oxosilanes of aminophenyl three)；Sulfonation octaphenyl-the POSS and described eight (aminophenyls three
Oxosilane) weight ratio be 1：(0.5-1).
8. high durable exempts to spray imitative metal ABS composite material according to claim 1, it is characterised in that the dispersant bag
Include one or more in bisamide class dispersant, paraffin class dispersant, organic metal salt dispersant.
9. high durable exempts to spray imitative metal ABS composite material according to claim 1, it is characterised in that the high durable is exempted from
The imitative metal ABS composite material of spraying also includes 1-5 parts of antioxidant, 3-15 parts of light stabilizers, 1-5 parts of ultraviolet absorbers.
10. the high durable according to claim 1-9 exempts to spray the preparation method of imitative metal ABS composite material, it is characterised in that
At least comprise the following steps：
(1) by weight by ABS, modified ABS, exempt to spray imitative metal master batch, silane coupler, assistant crosslinking agent, dispersant, add
In homogenizer, at 40~100 DEG C, 60~120min is stirred；
(2) toughener, antioxidant, light stabilizer, ultraviolet absorber are added into step (1) to continue to stir 30~90min, are obtained
Mixed material；
(3) mixed material in step (2) is added into double screw extruder, it is 50~250r/min, temperature to control screw speed
For 150~260 DEG C, melting extrusion granulation obtains the high durable and exempts to spray imitative metal ABS composite material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109762293A (en) * | 2018-12-21 | 2019-05-17 | 上海长伟锦磁工程塑料有限公司 | A kind of metallic luster, superhigh tenacity and combined material with excellent weather resistance and preparation method thereof |
| CN111793317A (en) * | 2020-07-27 | 2020-10-20 | 五行科技股份有限公司 | High-density spraying-free metal-like ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof |
| CN113462115A (en) * | 2021-06-29 | 2021-10-01 | 上海艾镇新材料有限公司 | High-weather-resistance spraying-free ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof |
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| WO2001023449A1 (en) * | 1999-09-27 | 2001-04-05 | Mitsubishi Rayon Co., Ltd. | Graft copolymer and thermoplastic resin composition containing the same |
| CN101974197A (en) * | 2010-10-20 | 2011-02-16 | 深圳市科聚新材料有限公司 | Metal-imitated high-gloss ABS (Acrylonitrile Butadiene Styrene) alloy and preparation method thereof |
| CN104177756A (en) * | 2014-07-31 | 2014-12-03 | 青岛吉顺隆商贸有限公司 | Environment-friendly metal imitating modified composite plastic |
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| WO2001023449A1 (en) * | 1999-09-27 | 2001-04-05 | Mitsubishi Rayon Co., Ltd. | Graft copolymer and thermoplastic resin composition containing the same |
| CN101974197A (en) * | 2010-10-20 | 2011-02-16 | 深圳市科聚新材料有限公司 | Metal-imitated high-gloss ABS (Acrylonitrile Butadiene Styrene) alloy and preparation method thereof |
| CN104177756A (en) * | 2014-07-31 | 2014-12-03 | 青岛吉顺隆商贸有限公司 | Environment-friendly metal imitating modified composite plastic |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109762293A (en) * | 2018-12-21 | 2019-05-17 | 上海长伟锦磁工程塑料有限公司 | A kind of metallic luster, superhigh tenacity and combined material with excellent weather resistance and preparation method thereof |
| CN109762293B (en) * | 2018-12-21 | 2021-01-29 | 上海长伟锦磁工程塑料有限公司 | Combined material with metallic luster, ultrahigh toughness and excellent weather resistance and preparation method thereof |
| CN111793317A (en) * | 2020-07-27 | 2020-10-20 | 五行科技股份有限公司 | High-density spraying-free metal-like ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof |
| CN113462115A (en) * | 2021-06-29 | 2021-10-01 | 上海艾镇新材料有限公司 | High-weather-resistance spraying-free ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof |
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| CN107163493B (en) | 2019-08-02 |
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