CN106700389A - Super tough ABS masterbatch composite material - Google Patents
Super tough ABS masterbatch composite material Download PDFInfo
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- CN106700389A CN106700389A CN201610998657.0A CN201610998657A CN106700389A CN 106700389 A CN106700389 A CN 106700389A CN 201610998657 A CN201610998657 A CN 201610998657A CN 106700389 A CN106700389 A CN 106700389A
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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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- 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
The invention provides a super tough ABS masterbatch composite material, which comprises the following raw materials by weight: 40-70 parts of ABS high rubber powder, 10-40 parts of modified ABS, 1-10 parts of an EMA compatilizer, 1-5 parts of a light stabilizer and 5-16 parts of titanium dioxide, wherein the modified ABS is functionalized ABS grafted sulfonated polyphenylene sulfide, and the functionalized ABS is glycidyl methacrylate, butadiene, styrene and acrylonitrile quadripolymer.
Description
Technical field
Polymeric material field the present invention relates to be applied to bathroom field, more particularly it relates to a kind of ultra-toughness
ABS masterbatch composite.
Background technology
Acrylonitrile-butadiene-styrene copolymer (ABS) resin is one of five big general synthetic resins, is widely applied
In fields such as automobile, household electrical appliances and office appliances.Different from other four big general synthetic resins, ABS is rubber toughened styrene-the third
A class non-crystalline type blend polymer obtained by alkene lonitrile copolymer (SAN), some characteristics with engineering plastics, as excellent
Rigidity, heat resistance and impact resistance.
With the development of society, people are to the demand of functionalization sanitaryware also more and more higher, and current sanitaryware is general
It is that base uses ceramic material, cover plate to use PP or ABS material.The exigent bending strength of connector of cover plate and base,
The world-famous enterprises such as section's Le are that bending number of times will not be broken more than more than 25000 times to connector requirement.Common flexibilizing ABS
Requirement can not be met.
It is not low temperature resistant in addition, the ABS material product that obtains of processing is easily aging, and then people can not be met functionalization is defended
Bath product life requirement.
Therefore, a kind of ABS composite material is needed badly, with toughness very high, weatherability, low temperature resistant, impact strength and bending
Intensity meets people to functionalization sanitaryware life requirement.
The content of the invention
In order to solve the above-mentioned technical problem, the first aspect of the invention provides a kind of ultra-toughness ABS masterbatch composite,
Calculate by weight, including following raw material：
Wherein, the modified ABS is functionalization ABS graft sulfonation polyphenylene sulfides, and the functionalization ABS is methacrylic acid
Ethylene oxidic ester, butadiene, styrene, acrylonitrile quadripolymer.
In one embodiment, calculate by weight, including following raw material：
In one embodiment, monomer methacrylic acid ethylene oxidic ester, butadiene, benzene second in the functionalization ABS
Alkene, the weight ratio of acrylonitrile are (0.01~0.05)：(45~63)：(20~40)：(5~20).
In one embodiment, monomer methacrylic acid ethylene oxidic ester, butadiene, benzene second in the functionalization ABS
Alkene, the weight ratio of acrylonitrile are (0.02~0.04)：(52~56)：(20~32)：(8~16).
In one embodiment, calculate by weight, the ultra-toughness ABS masterbatch composite also changes including 1~10 part
Property nano-calcium carbonate.
In one embodiment, the modified nano calcium carbonate includes acrylate/nano calcium carbonate grafted chitosan.
In one embodiment, the grafting rate of the acrylate/nano calcium carbonate grafted chitosan is 1~5%.
In one embodiment, the grafting rate of the acrylate/nano calcium carbonate grafted chitosan is 1~3%.
In one embodiment, the light stabilizer includes one kind in benzophenone, benzotriazole, hindered amines
Or various mixtures.
Another aspect provides the preparation method of ultra-toughness ABS masterbatch composite, at least comprise the following steps：
(1) each component raw material is weighed according to parts by weight, after ABS high glue powders, modified ABS, EMA compatilizers are mixed, plus
Enter in homogenizer, at 60~100 DEG C, stir 30~80min；
(2) added in step (1), addition modified nano calcium carbonate, light stabilizer and titanium dioxide, continuation stirring 20~
60min, obtains mixed material；
(3) step (2) mixed material is added into double screw extruder, controls screw speed for 200~350r/min, temperature
It it is 180~250 DEG C, while carrying out vacuumize process to machine barrel, vacuum is 0.04~0.08MPa, and melting extrusion granulation is obtained
Ultra-toughness ABS masterbatch composite.
The above-mentioned of the application and other features, aspect and advantage is more readily understood with reference to described further below.
Specific embodiment
The participation in the election detailed description for being preferable to carry out method of the invention below 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, " including ",
" 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, and can be including not expressly listed other key elements or
This kind of 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 the material that those are described, but relative normal
Except rule impurity.When phrase " Consists of " is appeared in be rather than immediately following after theme in the clause of claim main body,
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 is appreciated that and 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 that plural number discusses object, unless the context clearly dictates otherwise.It is " optional " or " any
It is a kind of " refer to that the item that describes thereafter or event 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, also including the acceptable part without cause the amendment of the change of related basic function close to the quantity.Phase
Answer, a numerical value is modified with " about ", " about " etc., mean 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.
Additionally, 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 the polymerizable compound prepared by the monomer by the identical or different type that is polymerized.Generic term
" polymer " includes term " homopolymers ", " copolymer ", " terpolymer " and " EVA ".
" EVA " means the polymer prepared by least two different monomers that are polymerized.Generic term " EVA " includes
(its is general with term " terpolymer " for term " copolymer " (it is typically used to refer to the polymer prepared by two kinds of different monomers)
It is used to refer to the polymer prepared by three kinds of different monomers).Its polymerization for also being manufactured comprising monomer is planted by polymerization four or more
Thing." blend " means the polymerization that two or more polymer is mixed and formed jointly by physics or chemistry method
Thing.
The first aspect of the invention provides a kind of ultra-toughness ABS masterbatch composite, calculates by weight, including following
Raw material：
Wherein, the modified ABS is functionalization ABS graft sulfonation polyphenylene sulfides, and the functionalization ABS is methacrylic acid
Ethylene oxidic ester, butadiene, styrene, acrylonitrile quadripolymer.
In one embodiment, calculate by weight, including following raw material：
ABS high glue powders
ABS high glue powders (ABSHR) are a kind of excellent rubber-like toughener, the rubber (fourth two with superior quality fraction
65%) mass fraction of alkene is more than, and containing the poly- NBR latex that mass fraction is 5%~8%, has with ABS resin fine
Compatibility.
ABS resin
ABS resin is acrylonitrile, butadiene, three kinds of copolymers of monomer copolymerization of styrene, is a kind of excellent performance
Engineering plastics.
In one embodiment, the sulfonation degree of the Sulfonated Polyphenylene Sulfide is 1~10%；Preferably, the sulfonation gathers
The sulfonation degree of diphenyl sulfide is 3~6%.
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 the reaction for introducing sulphonyl halogen can be defined as halogen sulfonating reaction again.According to sulfonating reaction institute
The substitution base 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 the atom being connected in sulphur atom in sulfonic group and organic molecule, the product for obtaining 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 species of sulfonating agent is more, and reaction mechanism is also different.Have plenty of electrophilic reaction, such as sulfuric acid, sulfur trioxide, smoke
Sulfuric acid etc.；Have plenty of necleophilic reaction, such as sodium sulfite, sodium hydrogensulfite；Have plenty of radical reaction, such as sulfur dioxide and chlorine
Gas, sulfur dioxide and oxygen etc..Sulfonation on phenyl ring is electrophilic reaction.First be electrophilic reagent attack phenyl ring, generation carbon just from
Son, then loses a proton, generates benzene sulfonic acid or substituted benzenesulfonic acid.
Conventional sulfonating agent has sulfur trioxide, the concentrated sulfuric acid, oleum, chlorosulfonic acid.
Sulfur trioxide is a kind of colourless easy-sublimation solid, with three kinds of thing phases.Reacted using sulfur trioxide as sulfonating agent
Speed is fast, and volume of equipment is small, and need not additionally heat.Because the activity of sulfur trioxide is big, respond is strong, and will not give birth to
Cheng Shui, the consumption of sulfur trioxide can not need concentrating waste acid close to theoretical amount after sulfonation, be produced without neutralizing spent acid
Unnecessary neutral salt, has the advantages that other sulfonating agents are incomparable.But it has the disadvantage that sulfonating reaction heat release acutely, is easily led
The accessory substance such as Substrate hydrolysis or generation sulfone class is caused, and the viscosity of reactant is high, comes difficult to heat transmission belt.
The concentrated sulfuric acid is a kind of strong mineral acid with high corrosiveness, and the concentrated sulfuric acid has strong oxidizing property, dehydration property, deep-etching
Property, difficult volatility, acidity, water imbibition.When the concentrated sulfuric acid is as sulfonating agent, the side reaction of generation is less, but sulfonating reaction is anti-
Answer speed slower.Often generation 1mol sulfonated products can generate 1mol water simultaneously, can decline the concentration of the concentrated sulfuric acid, while in order that
Sulfonating reaction is smoothed out, it is necessary to add excessive sulfuric acid to be dehydrated.
Oleum is the product that sulfur trioxide is dissolved in the concentrated sulfuric acid, generally there is two kinds of specifications, i.e., be containing free sulfur trioxide
20%-25% and 60%-65%.The freezing point of both oleums is low, is liquid under normal temperature, is easy to use and transports.Hair
When cigarette sulfuric acid is as sulfonating agent, reaction speed is fast, and reaction temperature is relatively low, while having process is simple, equipment investment low, easy to operate
The advantages of.Have the disadvantage excessively violent to the effect of organic matter, be often accompanied by oxidation, the generation byproduct such as sulfone.Additionally, can be produced after sulfonation
Unboiled water.
Chlorosulfonic acid is a kind of colourless or flaxen liquid, and with acrid odors, smoke in atmosphere is of sulfuric acid
The compound that hydroxyl is formed after being replaced by chlorine.When chlorosulfonic acid is used as sulfonating agent, respond is strong, and reaction condition is gentle, obtains
The product for arriving is purer.Accessory substance is hydrogen chloride, can be discharged under negative pressure, is conducive to reaction to carry out completely.Have the disadvantage price compared with
Height, and molecular weight is big, introduces a sulfonic sulfonating agent consumption and sees many.Additionally, the hydrogen chloride produced in reaction has strong corruption
Corrosion.
In one embodiment, the sulfonating agent of the sulfonating reaction be it is a kind of in the concentrated sulfuric acid, oleum, chlorosulfonic acid or
It is various；Preferably, the sulfonating agent is the concentrated sulfuric acid.
The preparation method of the modified ABS is as follows：
(1) functionalization ABS
Sodium pyrophosphate, DEXTROSE ANHYDROUS and FeSO are quantified to being added in reactor4Fully polybutadiene glue is added after dissolving
Breast, adjustment pH value is 10, and agitating device is opened after nitrogen purging, is warming up to 65 DEG C, and styrene, acrylonitrile, first is continuously added dropwise
The monomer mixture of base glycidyl acrylate, cumyl hydroperoxide and tert-dodecylmercaotan, continues after completion of dropwise addition
After reaction 1.5h, antioxidant 1010 is added, after demulsification, washing, filtering, 100 DEG C of drying under reduced pressure 12h；
(2) functionalization ABS graft sulfonations polyphenylene sulfide
Sulfonated Polyphenylene Sulfide：By polyphenylene sulfide dissolving in concentrated sulfuric acid, the weight of the polyphenylene sulfide and the concentrated sulfuric acid
Than being 1：(10-20), after reacting 5-10h at 80 DEG C -120 DEG C, is down to room temperature, pours into deionized water, fully washs to neutrality
Afterwards, filter and dry 12h at 120 DEG C in vacuum drying oven, obtain partly sulfonated polyphenylene sulfide；
Functionalization ABS graft sulfonation polyphenylene sulfides：Partly sulfonated polyphenylene sulfide obtained above, functionalization ABS is molten
In polyphosphoric acids, the functionalization ABS, the Sulfonated Polyphenylene Sulfide, the weight ratio of the polyphosphoric acids are 1 to solution：(1-2)：
(10-15), after reacting 5-10h at 180 DEG C, is down to room temperature, pours into acetone, fully after washing, filters and in vacuum drying oven
16h is dried at 120 DEG C, functionalization ABS graft sulfonation polyphenylene sulfides are obtained.
In one embodiment, monomer methacrylic acid ethylene oxidic ester, butadiene, benzene second in the functionalization ABS
Alkene, the weight ratio of acrylonitrile are (0.01~0.05)：(45~63)：(20~40)：(5~20).
In one embodiment, monomer methacrylic acid ethylene oxidic ester, butadiene, benzene second in the functionalization ABS
Alkene, the weight ratio of acrylonitrile are (0.02~0.04)：(52~56)：(20~32)：(8~16)；Preferably, the functionalization
Monomer methacrylic acid ethylene oxidic ester, butadiene, styrene, the weight ratio of acrylonitrile are 0.025 in ABS：53：26：12.
Functionalization ABS graft sulfonations polyphenylene sulfide mainly improves resin and is asked with toner, the compatible of inorganic powder in the present invention
Topic, reduces material hardness, improves the pliability and buckle resistance of product.New monomer first is introduced by by ABS functionalizations
Base glycidyl acrylate, improves the balancing moment value during blend melt blending and rises, and two interphase interfaces are combined
Power increases, and reduces ABS material fragility；Polyphenylene sulfide has high mechanical strength, high temperature resistant, chemical proofing, fire retardant, hot steady
The advantages of qualitative good, excellent electrical properties, but polyphenylene sulfide is a kind of crystalline polymer, with very strong rigid structure,
Poly-p-phenylene sulfide ether will carry out sulfonation, introduce polar group sulfonic group, then be reacted with functionalization ABS, obtain functionalization ABS and connect
Branch Sulfonated Polyphenylene Sulfide, makes to generate substantial amounts of micro-crack inside polymeric matrix, portion of energy is dissipated, due to fine fisssure
The presence of line, makes the stress of polymeric inner be evenly distributed state and changes, the stress in subrange near micro-crack
Rapid increase, considerably beyond original stress average value, formation causes the stress concentration at micro-crack, so as to trigger local surrender
With crazing process, the toughness of material is improve, while the compatibility with toner, inorganic powder is also improved, also with resistance to height
Warm, low temperature resistant excellent properties.
EMA
Ethylene-methyl acrylate copolymer (EMA) is a kind of good mechanical performance, environmental stress crack resistance good and electrically
Resin material that can be very excellent.
EMA solves ABS resin and toner, the compatible problem of inorganic powder well in the present invention, reduce material hardness,
Improve the pliability and buckle resistance of product.
Material when high elongation region reaches critical elasticity deformation, the process of the strain softening for occurring to strain hardening
It is a primary condition of its toughness.Material does not soften, surrenders and stretches the substantial amounts of energy that cannot dissipate；Even if occurring
Surrender and stretch, but finally strain hardening does not occur, stress concentration will cause material in deformation early fracture.EMA is in material
The effect of stress concentration point is served during material stress, the circumference stress of biaxial stretch-formed generation makes to generate cavity inside it, EMA
The Voiding extension of son and its final rupture are heavily dependent on the energy in cavity.
The Voiding resistance for weakening particle to material deformation of EMA particles, base has been triggered in the case of stress reduction
The surrender of body, surrender tends to the result to form that shear band is strain softening that localizes.Under the continuous action of external force, per surely
There is strain softening in the elastic deformation material on planar band periphery, thus cause the planar expanded of yield band, EMA particles and matrix
Rubber particle in resin etc. has equally triggered crazing effect under external force, and the hardening produced by crazing chain orientation is final
Degree to straining is limited, and is presented as that crazing spontaneous termination and crazing terminate yield band.Meanwhile, crazing end and fiber draw
The strain softening of surrounding high polymer is sent out, has been expanded and is related to the volume of energy absorbing material, material is reached drawing very high
Ratio is stretched, material hardness is reduced, is improve the pliability and buckle resistance of product.
Titanium dioxide
Titanium dioxide (English name：Titanium dioxide), main component is titanium dioxide (TiO2) Chinese white.
Scientific name is titanium dioxide (titanium dioxide), and molecular formula is TiO2It is a kind of polycrystalline compounds, its particle is arranged in rule
Row, with grid system.
The chemical property of titanium dioxide is extremely stablized, and is a kind of amphoteric oxide of slant acidity.Under normal temperature hardly with its
His element and compound reaction, all do not work to oxygen, ammonia, nitrogen, hydrogen sulfide, carbon dioxide, sulfur dioxide, water insoluble, fat
Fat, is also insoluble in olefin(e) acid and inorganic acid, alkali, is dissolved only in hydrofluoric acid.But under light action, titanium dioxide can occur continuous oxidation also
Original reaction, with photochemical activity.Titanium dioxide has three kinds of crystal habits in nature：Rutile-type, anatase titanium dioxide and plate titanium-type.
In one embodiment, the titanium dioxide is anatase thpe white powder.
Anatase thpe white powder belongs to pigment-level titanium dioxide, and with strong covering power, tinting strength, tinting power is high, the features such as good weatherability.
Light stabilizer
Light stabilizer (English name Light stabilizer；Photostabilizer it is) that high molecular products (are for example moulded
Material, rubber, coating, synthetic fibers) a kind of additive, it can shield or absorb the energy of ultraviolet, quenching singlet oxygen and
Hydroperoxides are resolved into the functions such as inert matter, makes high molecular polymer under the radiation of light, can exclude or slow down light
Chemical reaction possibility, prevents or postpones the process of light aging, so as to reach extension high polymer product service life
Purpose.
In one embodiment, the light stabilizer includes one kind in benzophenone, benzotriazole, hindered amines
Or various mixtures.
Wherein, the benzophenone include 2,2 ', 4,4 '-tetrahydroxybenzophenone, 2,4 ,-dihydroxy benaophenonel,
2,2 '-dihydroxy -4,4 '-dimethoxy-benzophenone, ESCALOL 567；The benzotriazole includes
2- (2'- hydroxyl -5'- aminomethyl phenyls) BTA, 2- (the 2'- hydroxyl -3'- tert-butyl group -5'- aminomethyl phenyls) -5- chloro benzos
Triazole, 2- (2'- hydroxyls -3', 5'- di-tert-butyl-phenyl) -5- chlorinated benzotriazoles, 2- (2'- hydroxyls -3', 5'- diamyl benzene
Base) BTA, 2- (2'- hydroxyl 5'- t-octyls phenyl) BTA；The hindered amines includes double (2,2,6,6- tetramethyls
Phenylpiperidines base) sebacate (CAS NO.：41556-26-7), double (1,2,2,6,6- pentamethyl -4- piperidyls) sebacates
(CAS NO：52829-07-9), poly-succinic (4-hydroxyl-2,2,6,6--1-piperidine ethanols of tetramethyl) ester (CAS NO：
65447-77-0), poly- { [6- [(1,1,3,3- tetramethyl butyl) amino]] -1,3,5-triazines -2,4- double [(2,2,6,6,-four
Methyl-piperidyl) imino group] -1,6- oneself two support [(2,2,6,6- tetramethyl -4- piperidyls) imino group] (CAS NO：
70624-18-9)。
In the present invention, the light stabilizer preferably 2,2 ', 4,4 '-tetrahydroxybenzophenone and 2- (2'- hydroxyl -5'- methyl
Phenyl) BTA mixture；Described 2,2 ', 4,4 '-tetrahydroxybenzophenone and 2- (2'- hydroxyl -5'- aminomethyl phenyls) benzene
And the weight ratio of triazole is 1：0.3.
In one embodiment, calculate by weight, the ultra-toughness ABS masterbatch composite also changes including 1~10 part
Property nano-calcium carbonate.
In one embodiment, the modified nano calcium carbonate includes acrylate/nano calcium carbonate grafted chitosan.
In one embodiment, the preparation method of the modified nano calcium carbonate is as follows：
(1) nano-calcium carbonate is added into barrel temperature in 50 DEG C of high-speed mixers, by weight acrylic acid is added, to stir
After 0.5~2h, discharging after high-speed mixer barrel temperature is risen to 120 DEG C, above-mentioned material is refunded in high-speed mixer, high
Discharged after 0.5~1h of speed stirring, obtain acrylic acid coated caco3；The acrylic acid is with the weight ratio of the nano-calcium carbonate
1：(10~20)；
(2) it is that 120 DEG C of high speeds are mixed acrylate/nano calcium carbonate in step (1) and P-hydroxybenzoic acid to be added into barrel temperature
In conjunction machine, discharged after 0.5~2h of high-speed stirred；The acrylate/nano calcium carbonate is with the weight ratio of the P-hydroxybenzoic acid
1：(0.2~0.6)；
(3) the acrylate/nano dissolution of calcium carbonate of the grafting P-hydroxybenzoic acid that will be obtained in step (2) is in 90% ethanol
In solution, shitosan is added, after reacting 8h at 70 DEG C, be down to room temperature, poured into acetone, fully after washing, filtered and in vacuum
In baking oven 12h is dried at 60 DEG C；The acrylate/nano calcium carbonate of the grafting P-hydroxybenzoic acid and the middle weight of the shitosan
Amount is than being 1：(1~3).
In one embodiment, the grafting rate of the acrylate/nano calcium carbonate grafted chitosan is 1~5%.
In one embodiment, the grafting rate of the acrylate/nano calcium carbonate grafted chitosan is 1~3%；It is preferred that
Ground, the grafting rate of the acrylate/nano calcium carbonate grafted chitosan is 2%.
In one embodiment, the particle diameter of the modified nano calcium carbonate is 100~200nm.
Shitosan
Shitosan has the antibacterial activity of wide spectrum, has bright to various bacterias such as gram-positive bacteria and Gram-negative bacterias
Aobvious suppression and killing action.Its Antibacterial mechanism is broadly divided into two classes：For macromolecular shitosan, mainly by macromolecule
The intensive surface in bacterium of chain forms a floor height molecular film, influences external nutriment to intracellular transport, prevents metabolin
Excretion, make the metabolic disturbance of microorganism, so as to reach the effect of bactericidal；For small molecule shitosan, can be with
Reached inside bacterium by osmosis, the cytoplasm with anion in adherent cell body, and bring it about flocculation, denaturation,
The normal physiological activity of bacterium is upset, plays a part of antibacterial sterilizing.
In one embodiment, the weight average molecular mass of the shitosan is 2000~30000；Preferably, the shell
The weight average molecular mass of glycan is 5000~12000.
The measure of weight average molecular weight：When incident light electromagnetic wave passes through medium, make the small particles (such as macromolecule) in medium
In electronics produce forced vibration so that produce secondary wave source to all directions launch it is same with oscillating electric field (incident light electromagnetic wave)
The scattering light wave of frequency.And the high score power of this scattered wave is related to the dipole quantum count in small particles (macromolecule), i.e.,
The quality or molal weight of son are relevant.According to above-mentioned principle, macromolecule alkene solution is determined using laser light scattering instrument and incident
Light is in low-angle (2 ° -7 °) scattered light intensity, so as to calculate high molecular absolute weight average molecular (MW) value in alkene solution.Adopt
The distribution of the hydrodynamic radius of particle (macromolecule) can be determined with the measure of dynamic light scattering, and then is calculated macromolecule
The distribution curve of molecular weight.
Another aspect provides the preparation method of ultra-toughness ABS masterbatch composite, at least comprise the following steps：
(1) each component raw material is weighed according to parts by weight, after ABS high glue powders, modified ABS, EMA compatilizers are mixed, plus
Enter in homogenizer, at 60~100 DEG C, stir 30~80min；
(2) added in step (1), addition modified nano calcium carbonate, light stabilizer and titanium dioxide, continuation stirring 20~
60min, obtains mixed material；
(3) step (2) mixed material is added into double screw extruder, controls screw speed for 200~350r/min, temperature
It it is 180~250 DEG C, while carrying out vacuumize process to machine barrel, vacuum is 0.04~0.08MPa, and melting extrusion granulation is obtained
Ultra-toughness ABS masterbatch composite.
Acrylic acid reactivity in the present invention is very high, and its one end is the carboxyl of highly acid, can be with CaCO3Surface occurs
Chemical bonding, under the reaction condition of solid phase grafting, product propylene acid calcium is still with CaCO3Surface, modified Nano CaCO3's
Surface can occur greatly to reduce, so as to be not susceptible to reunite between particle；Other modified Nano CaCO3Particle can trigger
Hole is formed, and during impact fracture, the formation of cavitation can absorb part energy, but substantial amounts of hole also reduces
Along the surrender that the fracture path and local extending stress band of base material come.Acrylate/nano carbonic acid is added in toughness polymer matrix
Calcium grafted chitosan, can trigger a large amount of cavitations, and the crazing that cavitation brings can effectively be terminated, therefore
Toughness is greatly improved, and the introducing of shitosan in addition serves the effect of antibacterial, in solution daily life, suitable temperature
The external environment conditions such as degree, humidity easily make bacterium that the problem of infection is grown in ABS plastic product.
The present invention is combined by modified ABS and the synergy of modified nano calcium carbonate and EMA compatilizers, the ABS for obtaining
Material has toughness very high, weatherability, low temperature resistant, impact strength and buckling strength excellent properties.
The present invention is specifically described below by embodiment.Be necessary it is pointed out here 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 nonessential modifications and adaptations that content according to the invention described above is made, still fall within protection scope of the present invention.
The ABS high glue powders are purchased from South Korea Jin Hu.
In addition, if without other explanation, it is raw materials used be all it is commercially available, be purchased from traditional Chinese medicines chemical reagent.
Embodiment 1
A kind of ultra-toughness ABS masterbatch composite, calculates by weight, including following raw material：
The preparation method of the ultra-toughness ABS masterbatch composite is as follows：
(1) each component raw material is weighed according to parts by weight, after ABS high glue powders, modified ABS, EMA compatilizers are mixed, plus
Enter in homogenizer, at 90 DEG C, stir 60min；
(2) added in step (1), add modified nano calcium carbonate, light stabilizer and titanium dioxide, continue to stir 40min,
Obtain mixed material；The light stabilizer is 2,2 ', 4,4 '-tetrahydroxybenzophenone and 2- (2'- hydroxyl -5'- aminomethyl phenyls)
BTA, described 2,2 ', 4, the weight of 4 '-tetrahydroxybenzophenone and 2- (2'- hydroxyl -5'- aminomethyl phenyls) BTA
Than being 1：0.3；
(3) step (2) mixed material is added into double screw extruder, controls screw speed for 240r/min, temperature is 220
DEG C, while carrying out vacuumize process to machine barrel, vacuum is 0.05MPa, and melting extrusion granulation obtains ultra-toughness ABS masterbatch composite wood
Material.
The preparation method of the modified ABS is as follows：
(1) functionalization ABS
Quantitative sodium pyrophosphate, DEXTROSE ANHYDROUS and FeSO will be added in reactor4Fully polybutadiene glue is added after dissolving
Breast, adjustment pH value is 10, and agitating device is opened after nitrogen purging, is warming up to 65 DEG C, and styrene, acrylonitrile, first is continuously added dropwise
The monomer mixture of base glycidyl acrylate, cumyl hydroperoxide and tert-dodecylmercaotan, continues after completion of dropwise addition
After reaction 1.5h, antioxidant 1010 is added, after demulsification, washing, filtering, 100 DEG C of drying under reduced pressure 12h；In the functionalization ABS
Monomer methacrylic acid ethylene oxidic ester, butadiene, styrene, the weight ratio of acrylonitrile are 0.025：53：26：12；It is described poly-
Butadiene and the sodium pyrophosphate, the DEXTROSE ANHYDROUS, the FeSO4Weight ratio be 1：0.1：10：0.06；The benzene second
Alkene is 1 with the weight ratio of the cumyl hydroperoxide, the tert-dodecylmercaotan：0.02：0.07；
(2) functionalization ABS graft sulfonations polyphenylene sulfide
Sulfonated Polyphenylene Sulfide：By polyphenylene sulfide dissolving in concentrated sulfuric acid, the weight of the polyphenylene sulfide and the concentrated sulfuric acid
Than being 1：After reacting 9h at 11,90 DEG C, room temperature is down to, poured into deionized water, fully after washing to neutrality, filtered and in vacuum
12h is dried at 120 DEG C in baking oven, partly sulfonated polyphenylene sulfide is obtained；
Functionalization ABS graft sulfonation polyphenylene sulfides：Partly sulfonated polyphenylene sulfide obtained above, functionalization ABS is molten
In polyphosphoric acids, the functionalization ABS, the Sulfonated Polyphenylene Sulfide, the weight ratio of the polyphosphoric acids are 1 to solution：1.3：14,
After reacting 8h at 180 DEG C, room temperature is down to, poured into acetone, fully after washing, filtered and dried at 120 DEG C in vacuum drying oven
16h, obtains functionalization ABS graft sulfonation polyphenylene sulfides.
Following (the grafting of the acrylate/nano calcium carbonate grafted chitosan of the preparation method of the modified nano calcium carbonate
2.3%) rate is：
(1) nano-calcium carbonate is added into barrel temperature in 50 DEG C of high-speed mixers, by weight acrylic acid is added, to stir
After 1h, discharging after high-speed mixer barrel temperature is risen to 120 DEG C, above-mentioned material is refunded in high-speed mixer, high-speed stirred
Discharged after 1h, obtain acrylic acid coated caco3；The acrylic acid is 1 with the weight ratio of the nano-calcium carbonate：12；
(2) it is that 120 DEG C of high speeds are mixed acrylate/nano calcium carbonate in step (1) and P-hydroxybenzoic acid to be added into barrel temperature
In conjunction machine, discharged after high-speed stirred 1h；The acrylate/nano calcium carbonate is 1 with the weight ratio of the P-hydroxybenzoic acid：
0.45；
(3) the acrylate/nano dissolution of calcium carbonate of the grafting P-hydroxybenzoic acid that will be obtained in step (2) is in 90% ethanol
In solution, shitosan is added, after reacting 8h at 70 DEG C, be down to room temperature, poured into acetone, fully after washing, filtered and in vacuum
In baking oven 12h is dried at 60 DEG C；The acrylate/nano calcium carbonate of the grafting P-hydroxybenzoic acid and the middle weight of the shitosan
Amount is than being 1：2.1.
Embodiment 2
A kind of ultra-toughness ABS masterbatch composite, calculates by weight, including following raw material：
The preparation method of the ultra-toughness ABS masterbatch composite, the preparation method of the modified ABS and the modified Nano
The preparation method of calcium carbonate is with embodiment 1；The grafting rate of the acrylate/nano calcium carbonate grafted chitosan is 2.3%.
Embodiment 3
A kind of ultra-toughness ABS masterbatch composite, calculates by weight, including following raw material：
The preparation method of the ultra-toughness ABS masterbatch composite, the preparation method of the modified ABS and the modified Nano
The preparation method of calcium carbonate is with embodiment 1；The grafting rate of the acrylate/nano calcium carbonate grafted chitosan is 2.3%.
Embodiment 4
A kind of ultra-toughness ABS masterbatch composite, calculates by weight, including following raw material：
The preparation method of the ultra-toughness ABS masterbatch composite, the preparation method of the modified ABS and the modified Nano
The preparation method of calcium carbonate is with embodiment 1；The grafting rate of the acrylate/nano calcium carbonate grafted chitosan is 2.3%.
Embodiment 5
A kind of ultra-toughness ABS masterbatch composite, calculates by weight, including following raw material：
The preparation method of the ultra-toughness ABS masterbatch composite, the preparation method of the modified ABS and the modified Nano
The preparation method of calcium carbonate is with embodiment 1；The grafting rate of the acrylate/nano calcium carbonate grafted chitosan is 2.3%.
Embodiment 6
A kind of ultra-toughness ABS masterbatch composite, calculates by weight, including following raw material：
The preparation method of the ultra-toughness ABS masterbatch composite, the preparation method of the modified ABS and the modified Nano
The preparation method of calcium carbonate is with embodiment 1；Difference be the modified ABS preparation method described in monomer in functionalization ABS
GMA, butadiene, styrene, the weight ratio of acrylonitrile are 0.01：53：30：20；The acrylic acid is received
The grafting rate of rice calcium carbonate grafted chitosan is 2.3%.
Embodiment 7
A kind of ultra-toughness ABS masterbatch composite, calculates by weight, including following raw material：
The preparation method of the ultra-toughness ABS masterbatch composite, the preparation method of the modified ABS and the modified Nano
The preparation method of calcium carbonate is with embodiment 1；Difference be the modified ABS preparation method described in monomer in functionalization ABS
GMA, butadiene, styrene, the weight ratio of acrylonitrile are 0.05：63：30：20；The acrylic acid is received
The grafting rate of rice calcium carbonate grafted chitosan is 2.3%.
Embodiment 8
A kind of ultra-toughness ABS masterbatch composite, calculates by weight, including following raw material：
The preparation method of the ultra-toughness ABS masterbatch composite, the preparation method of the modified ABS and the modified Nano
The preparation method of calcium carbonate is with embodiment 1；Difference be the modified nano calcium carbonate preparation method described in acrylic acid receive
Rice calcium carbonate is 1 with the weight ratio of the P-hydroxybenzoic acid：0.2, the acrylate/nano carbon of the grafting P-hydroxybenzoic acid
Sour calcium is 1 with the middle weight ratio of the shitosan：1；The grafting rate of the acrylate/nano calcium carbonate grafted chitosan is
1.2%.
Comparative example 1
A kind of ultra-toughness ABS masterbatch composite, calculates by weight, including following raw material：
The preparation method of the ultra-toughness ABS masterbatch composite and the preparation method of the modified nano calcium carbonate are with implementation
Example 1；Difference is that the ABS replaces modified ABS.
Comparative example 2
A kind of ultra-toughness ABS masterbatch composite, calculates by weight, including following raw material：
Wherein, the particle diameter of the nano-calcium carbonate is 100~200nm, the preparation side of the ultra-toughness ABS masterbatch composite
The preparation method of method and the modified ABS is with embodiment 1；Difference is that nano-calcium carbonate replaces modified nano calcium carbonate.
Comparative example 3
A kind of ultra-toughness ABS masterbatch composite, calculates by weight, including following raw material：
Wherein, the particle diameter of the nano-calcium carbonate is 100~200nm, the preparation side of the ultra-toughness ABS masterbatch composite
Method is with embodiment 1；Difference is that ABS replaces modified ABS, nano-calcium carbonate to replace modified nano calcium carbonate.
Performance test
1st, tensile strength：It is measured according to ISO-527/2.
2nd, elongation at break：It is measured according to ISO-527/2.
3rd, normal temperature and low temperature notched impact strength：Be measured according to ISO-180, test environment temperature be respectively 23 DEG C ,-
40℃。
4th, bending strength, bending modulus：It is measured according to ISO-178.
5th, biocidal property：With the representative strain Staphylococcus aureus of gram-positive bacteria, the representative strain of Ge Shi negative bacteriums is big
Enterobacteria is cooked tested strain, does biocidal property experiment.It is blank with the bacteria suspension for being not added with any antibacterial material, to add ultra-toughness
The bacteria suspension of ABS composite material is experimental group.The sample of certain mass is added to respectively in the fluid nutrient medium for preparing, configured
Sample concentration is the solution 20mL of 1mg/mL, accurate to add 0.2mL bacteria suspensions, and 37 DEG C of culture 12h, will train in earthquake incubator
Solution after supporting dilutes 10 times, takes one after another drop of on blood counting chamber, examines under a microscope counting indoor bacteria, according to thanking to row
Formula calculates bacterial concentration：Bacterium number/mL=80 lattice TCS/80 × 400 × 10000 × extension rate；
Bacteriostasis rate=(experimental group clump count/control group clump count) × 100%.
The performance test results of table 1
From above-mentioned test result as can be seen that compared with unmodified ABS, unmodified nano-calcium carbonate, the present invention
The ultra-toughness ABS masterbatch composite of offer has toughness very high, weatherability, low temperature resistant, impact strength and buckling strength excellent
Performance.
Foregoing example is merely illustrative, some features for explaining the method for the invention.Appended right will
The scope as wide as possible for being intended to require to be contemplated that is sought, and embodiments as presented herein is only according to all possible implementation
The explanation of the implementation method of the selection of the combination of example.Therefore, the purpose of applicant is that appended claim is not illustrated this hair
The selectional restriction of the example of bright feature.Some number ranges used also include sub- model within the claims
Enclose, the change in these scopes should also be construed to be covered by appended claim in the conceived case.
Claims (10)
1. a kind of ultra-toughness ABS masterbatch composite, it is characterised in that calculate by weight, including following raw material：
Wherein, the modified ABS is functionalization ABS graft sulfonation polyphenylene sulfides, and the functionalization ABS contracts for methacrylic acid
Water glyceride, butadiene, styrene, acrylonitrile quadripolymer.
2. ultra-toughness ABS masterbatch composite according to claim 1, it is characterised in that calculate by weight, including following original
Material：
3. ultra-toughness ABS masterbatch composite according to claim 1, it is characterised in that monomer methyl in the functionalization ABS
Glycidyl acrylate, butadiene, styrene, the weight ratio of acrylonitrile are (0.01~0.05)：(45~63)：(20~
40)：(5~20).
4. ultra-toughness ABS masterbatch composite according to claim 3, it is characterised in that monomer methyl in the functionalization ABS
Glycidyl acrylate, butadiene, styrene, the weight ratio of acrylonitrile are (0.02~0.04)：(52~56)：(20~
32)：(8~16).
5. ultra-toughness ABS masterbatch composite according to claim 1, it is characterised in that calculate by weight, the ultra-toughness
ABS masterbatch composite also includes 1~10 part of modified nano calcium carbonate.
6. ultra-toughness ABS masterbatch composite according to claim 5, it is characterised in that the modified nano calcium carbonate includes
Acrylate/nano calcium carbonate grafted chitosan.
7. ultra-toughness ABS masterbatch composite according to claim 6, it is characterised in that the acrylate/nano calcium carbonate connects
The grafting rate of branch shitosan is 1~5%.
8. ultra-toughness ABS masterbatch composite according to claim 7, it is characterised in that the acrylate/nano calcium carbonate connects
The grafting rate of branch shitosan is 1~3%.
9. ultra-toughness ABS masterbatch composite according to claim 1, it is characterised in that the light stabilizer includes hexichol first
One or more mixture in ketone, benzotriazole, hindered amines.
10. the preparation method of ultra-toughness ABS masterbatch composite according to claims 1 to 9, it is characterised in that at least include
Following steps：
(1) each component raw material is weighed according to parts by weight, after ABS high glue powders, modified ABS, EMA compatilizers are mixed, is added high
In fast mixer, at 60~100 DEG C, 30~80min is stirred；
(2) added in step (1), add modified nano calcium carbonate, light stabilizer and titanium dioxide, continue to stir 20~60
Min, obtains mixed material；
(3) step (2) mixed material is added into double screw extruder, controls screw speed for 200~350r/min, temperature is
180~250 DEG C, while carrying out vacuumize process to machine barrel, vacuum is 0.04~0.08MPa, and melting extrusion granulation is surpassed
Tough ABS masterbatch composite.
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Effective date of registration: 20230417 Address after: No. 3 Jingjiu Road, Changping Town, Dongguan City, Guangdong Province, 523581 Patentee after: BAIFU PLASTICS TECHNOLOGY (DONGGUAN) CO.,LTD. Address before: 528427, Sheng Hui North Industrial Zone, Nantou Town, Zhongshan, Guangdong Patentee before: ZHONGSHAN DOLEUNGCHOI PLASTIC TECHNOLOGY CO.,LTD. |