CN106046589A - High-rigidity, high-melt-strength and low-temperature-impact-resistant thermo-plastic ABS resin composition used for blow molding - Google Patents
High-rigidity, high-melt-strength and low-temperature-impact-resistant thermo-plastic ABS resin composition used for blow molding Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
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- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention relates to a high-rigidity, high-melt-strength and low-temperature-impact-resistant thermo-plastic ABS resin composition used for blow molding. The resin composition includes: 20-60 parts of an acrylonitrile-butadiene-styrene stem-grafted copolymer, 30-70 parts of an acrylonitrile-styrene copolymer, 5-25 parts of a heat resistance modifier, 1-20 parts of a melt enhancer, 0.1-10.0 parts of a fluorine-containing polymer additive, and 0.5-3.0 parts of a processing aid. The thermo-plastic ABS resin composition has ultrahigh melt strength, ultrahigh rigidity and excellent low-temperature-impact resistance, and solves the problems that the melt strength, rigidity and low-temperature toughness of an ABS resin composition for blow molding in the prior art cannot be balanced well. The ABS resin composition is very suitable for large-size automobile parts (e.g. spoilers, seat backs, bumpers, etc,).
Description
Technical field
The present invention relates to technical field of polymer materials, specifically, be a kind of high rigidity for blow molding, Gao Rong
Body intensity and the thermoplastic abs resin composition of low-temperature impact resistance.
Background technology
ABS resin has excellent combination property, can by being molded, extrude, be blow molded and the multiple method molding such as roll-in, quilt
It is widely used in the fields such as electronic apparatus, building materials, automobile interior exterior decorations.And in blow-moulding process, polymer is by narrow and small
During mouth die, acted on by high shear force, it is easy to occur that parison sag phenomenon, excessive vertical meeting cause the wall thickness of product not
All, even can not molding time serious.Therefore, for blow molding ABS resin, it is desirable to the melt strength of resin is sufficiently high.
And for some automobile large parts, such as flow spoiler, the seat back of the body, bumper etc., need goods to bear the loading force of some strength,
And typically having the low-temperature impact requirement of experiment of-30 DEG C or-40 DEG C, it is desirable to can not there is the outward appearance such as crackle, cracking not in goods itself
Good.Therefore, for blow molding ABS resin, it is desirable to have higher intensity, rigidity and low-temperature flexibility.
Existing document has been disclosed for by increasing the rubber content in ABS resin, to improve the melt strength of ABS resin
And resistance to impact, but the rigidity of prepared resin combination, thermostability all can reduce, and on the other hand, the size of material is steady
Qualitative also can be deteriorated.As Chinese patent CN103013025 discloses the ABS of a kind of excellent combination property that can be used for blow molding
Resin, it improves toughness by improving rubber-phase content in ABS resin, but improves and melt index reduction in impact strength
Meanwhile, material stiffness can reduce.Existing document discloses by being blended by polymer prepared by different polymerization methodses, changes
The resistance to impact of kind material.Such as patent US4430478, US5605963, US5696204, by what emulsion polymerization technique was produced
The polymer that polymer produces with bulk technique carries out mixing the impact property improving material, but uses this kind of method
Obtained material melt intensity is low, is blow molded poor performance；And the room temperature toughness of material the most not necessarily becomes corresponding pass with low-temperature flexibility
System, when room temperature toughness improves, low-temperature flexibility improves limited.Existing document discloses and adds super high molecular weight in ABS resin
3rd component, improves the melt strength of material.Such as Chinese patent CN101250314, disclose a kind of for blow molding
Heat-proof ABS resin composition and preparation method thereof, it improves ABS resin by adding ultrahigh molecular weight polypropylene acid copolymer
The method of melt strength；But the low-temperature flexibility of said composition is relatively low.Existing document discloses raising SAN content in ABS resin
Or molecular weight, improves the rigidity of ABS resin, but uses this kind of method can reduce toughness and the melt strength of material.In as
State's patent CN101250314 discloses a kind of heat-proof ABS resin composition for blow molding, embodiment 1 and embodiment 6
Compared for by improving the impact on physical property of the SAN content in ABS resin, result shows: SAN content promotes, and material stiffness carries
Height, but melt strength and toughness all reduce.
It is known that it is former with the hydrogen that carbon atom direct covalent bonds is connected in the high polymer main chain of fluoropolymer or side chain
After son is replaced in whole or in part by fluorine atom, fluorine atom is in spiral distribution along carbochain, and other molecules or reactive group are difficult to
Insert, effectively protect carbon carbon backbone chain；Therefore, polymer has the series of advantages such as high, big, the good toughness of melt strength of rigidity.
Patent CN 101360786B discloses fluoropolymer and improves polymer weatherability and the method for modulus, but this patent is simply
Have studied the system without rubber components and filler, the polymeric system comprising rubber components is not made a search；Patent
US5962587 discloses the modulus that politef (PTFE) improves the thermoplastic compounds of modified rubber, but does not grind
Study carefully the high heat-proof ABS system for blow molding, the most do not report the low-temperature flexibility situation of goods.Above-mentioned prior art is all
It is not carried out improving while rigidity, melt strength and low-temperature flexibility, i.e. while improving the most a certain performance, other property
Can be promoted the most equally.Along with automobile industry is more and more harsh to the performance requirement of material, take into account this three aspects performance
Blowing ABS will become the developing direction of prospective material requirement.
Summary of the invention
The technical problem to be solved is to provide a kind of has superelevation melt strength, super for blow molding
High rigidity and the heat-proof ABS resin composition of good low-temperature toughness and preparation method.Use this resin combination, be not only blow molded
In journey, melt strength is high, and parison sagging is few；Rigidity and the low-temperature flexibility of product is improved significantly simultaneously, solves well
The problem that melt strength, rigidity and the low-temperature flexibility that in prior art of having determined, blowing ABS resin compositions exists can not balance.
First purpose of the present invention is for deficiency of the prior art, it is provided that a kind of Gao Gang for blow molding
Property, high fondant-strength and the thermoplastic abs resin composition of low-temperature impact resistance.
Second object of the present invention is to provide the preparation method of ABS resin compositions described above.
For achieving the above object, the present invention adopts the technical scheme that:
A kind of thermoplastic ABS resin combination of high rigidity, high fondant-strength and low-temperature impact resistance for blow molding
Thing, described ABS resin compositions is to be prepared by the raw materials in:
Further, described ABS resin compositions is to be prepared by the raw materials in:
Further, the weight average molecular weight of described acrylonitrile-butadiene-phenylethene grafted copolymer is 100,000～200,
000, relative density is 1.0～1.04, and average diameter range is 100～600nm, described butadiene rubber weight percent content
It is 40～70wt%.
Further, the mean diameter of described acrylonitrile-butadiene-phenylethene grafted copolymer is preferably 200～300nm,
The weight percent content of butadiene rubber is preferably 45～55wt%.
Further, the weight average molecular weight of described acrylonitritrile-styrene resin is 100,000～500,000, acrylonitrile
Weight percent content is 15～40wt%.
Further, the weight average molecular weight of described acrylonitritrile-styrene resin is preferably 200,000～400, and 000, propylene
The weight percentage of nitrile is preferably 25～35wt%.
Further, described heat-proof modifier is the copolymer of N-aryl maleimide copolymers, α-methyl styrene
The mixture of one or more.
Further, described heat-proof modifier is preferably N-aryl maleimide copolymers；More excellent for N-phenyl maleoyl
Imines and maleic anhydride and cinnamic terpolymer or N-phenylmaleimide and maleic anhydride, α-methyl styrene,
The multiple copolymer of acrylonitrile.
Further, described melt reinforcing agent is the acrylic acid esters co-polymer of nucleocapsid structure, styrene-maleic anhydride copolymer
Thing, the mixture of one or more of acrylonitrile-styrene-glycidyl methacrylate copolymer.
Further, described melt reinforcing agent is acrylic acid esters co-polymer, acrylonitrile-styrene-Glycidyl methacrylate
Compounding of glyceride copolymer.
Further, described acrylic acid esters co-polymer, the quality of acrylonitrile-styrene-glycidyl methacrylate
Ratio is 1:1.
Further, described fluoropolymer additive, comprise the fluoropolymer and 70～30wt% of 30～70wt%
Carrier polymer.
Further, described fluoropolymer is poly-Fluorine containing olefine, selected from politef, Kynoar, tetrafluoroethene/
Hexafluoropropylene copolymer, tetrafluoroethylene/ethylene copolymer, tetrafluoroethylene/perfluoro alkyl ether copolymer, polyvinyl fluoride, trifluoro chlorine
Ethylene/vinyl copolymer, polytrifluorochloroethylene.
Further, described fluoropolymer is preferably politef (FA-1).
Further, described carrier polymer is polymethyl methacrylate, polystyrene, poly-alpha-alkyl phenylethylene, Malaysia
The polymerization of anhydride modified styrenic polymer, phenylethylene/maleic anhydride copolymer, Maleimide-modified phenylethylene
Thing, styrene-N aryl maleimide copolymers, styrene/acrylonitrile copolymer, alpha-alkyl phenylethylene/acrylonitrile compolymer
Thing, styrene/alpha-alkyl phenylethylene/acrylonitrile copolymer, styrene/acrylonitrile/methylmethacrylate copolymer, benzene second
Alkene/alpha-alkyl phenylethylene/acrylonitrile/methylmethacrylate copolymer and alpha-alkyl phenylethylene/acrylonitrile/methyl methacrylate
Ester copolymer.
Further, described carrier polymer is preferably styrene/acrylonitrile copolymer or polymethyl methacrylate.
Further, described processing aid includes the mixture of one or more of antioxidant, lubricant, releasing agent.
Further, described antioxidant is preferably Hinered phenols antioxidant or phosphite ester kind antioxidant.
Further, described lubricant is preferably pentaerythritol stearate or ethylene bis stearic acid amide.
Further, described releasing agent is preferably silicone releasing agent.
For realizing above-mentioned second purpose, the present invention adopts the technical scheme that:
The system of the thermoplastic abs resin composition of arbitrary described high rigidity, high fondant-strength and low-temperature impact resistance
Preparation Method, described preparation method comprises the steps:
(1) proportioning weighs raw material as described above；
(2) raw material got ready in step (1) is premixed in super mixer；
(3) by the premix material that obtains in step (2) in double screw extruder sent into by metering device, screw rod conveying,
Under shearing and being mixing, material melting, compound more extruded, tie rod, cooling, pelletizing step, obtain the Gao Gang for blow molding
Property high tenacity high melt strength thermoplastic ABS resin compositions；Wherein the screw slenderness ratio of double screw extruder is 36～44, and
And with attemperating unit and vacuum extractor；The extrusion temperature of described double screw extruder is between 180～250 DEG C, screw rod
Rotating speed is 200～500 revs/min.
The invention has the advantages that:
1, compared with prior art, the present invention is by using fluoropolymer additive and strong with a certain proportion of melt
Degree reinforcing agent, a certain proportion of heat-proof modifier compound, and prepare and have superelevation melt strength, super for blow molding
High rigidity and the thermoplastic abs resin composition of excellent low-temperature impact resistance.Use this resin combination, not only in blow-molding process
Melt strength is high, and parison sagging is few；Rigidity and the low-temperature flexibility of product is improved significantly simultaneously, solves well
The problem that melt strength, rigidity and the low-temperature flexibility that in prior art, blowing ABS resin compositions exists can not balance.
2, the present invention passes through substantial amounts of experiment screening, and melt reinforcing agent selects acrylic acid esters co-polymer and acrylonitrile-benzene
Ethylene-methyl methacrylate glycidyl ester copolymer compounds, and prepared ABS resin properties all increases, especially
Melt flow rate (MFR) and shear viscosity are improved the most obvious.
3, the present invention is special by adding specific components in the styrene resin composite comprising specific components specified quantitative
Quantitative heat-resistant agent, melt reinforcing agent, fluoropolymer additive, and with the component generation synergistic effect in resin combination,
And then solve blow molding heat-resisting ABS resin in prior art and deposit at aspects such as blow molding, mechanical performance, product experiments
Problem；The present invention is prepared for that blowing property is strong, mechanical rigid is high, melt strength is high and the height of excellent in low temperature toughness is heat-resisting
ABS resin compositions, is effectively improved the melt sagging of parison, and-40 DEG C of cantilever beam unnotched impact strengths of low temperature
Up to constantly, meet the low-temp storage requirement of auto parts and components goods, and the thermostability of blow-molded article is high, also meets blow-molded article
High temperature storage requirement.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate this
Bright rather than limit the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention records, art technology
The present invention can be made various changes or modifications by personnel, and these equivalent form of values fall within the application appended claims equally and limited
Fixed scope.
In embodiment, raw materials used, parameter and the trade mark are as follows:
Described acrylonitrile-butadiene-phenylethene grafted copolymer is polybutadiene rubber graft phenylethene-acrylonitrile compolymer
Thing, its weight average molecular weight is 100,000～200,000, and relative density is 1.0～1.04, average diameter range be 100～
600nm, wherein butadiene rubber weight percent content is 40～70wt%.The weight average of described acrylonitritrile-styrene resin
Molecular weight is 100,000～500,000, and the weight percent content of acrylonitrile is 15～40wt%.Described heat-proof modifier is
N-phenylmaleimide-maleic anhydride-styrene terpolymer (HR-1), α-methyl styrene (HR-2).Described melt
Reinforcing agent is the acrylic acid esters co-polymer (MR-1) of nucleocapsid structure, and weight average molecular weight is 1000,000～5000,000；Propylene
Nitrile-styrene-t glycidyl ester copolymer (MR-2).Described fluorochemical additive is (styrene/acrylonitrile copolymerization
Thing carrier)/50wt% politef (FA-1), (styrene/acrylonitrile copolymer carrier)/30wt% politef (FA-
2), polymethyl methacrylate carrier/50wt% politef (FA-3).Described processing aid is the IG-of antioxidant Ciba
1076。
Embodiment 1
Acrylonitrile-butadiene-phenylethene grafted copolymer 40 parts, acrylonitritrile-styrene resin 50 parts, heat-proof modifier
(HR-2) 10 parts, melt reinforcing agent (MR-1) 5 parts, fluoropolymer additive (FA-1) 3 parts, processing aid 0.6 part.According to upper
State component part and weigh raw material, adopt and prepare described blowing ABS resin compositions with the following method:
(1) raw material prepared is sufficiently mixed 30min in super mixer；
(2) premix material step 1 prepared is in double screw extruder sent into by metering device, in conveying, the shearing of screw rod
Under mixing, material melting, compound more extruded, tie rod, cooling, pelletizing step, obtain the high rigidity for blow molding high
Toughness high melt strength thermoplastic ABS resin compositions.Wherein the screw slenderness ratio of double screw extruder is 36～44, vacuum
Control at 0.09Ma；The extrusion temperature of described double screw extruder is between 180～250 DEG C, and screw speed is 200～500
Rev/min.
Embodiment 2-7, comparative example 1-3
For the ease of being embodied the creativeness of the present invention by contrast, embodiment 2-7 proportioning, on the basis of embodiment 1, is divided
Do not compare variety classes heat-proof modifier (α-methyl styrene), fluoropolymer additive Different adding amount, variety classes
Melt reinforcing agent, variety classes melt reinforcing agent are compounding, the compounding shadow to material property of variety classes fluoropolymer additive
Ringing, concrete preparation method is same as in Example 1, and proportioning raw materials is as shown in table 1.Additionally, the processing aid in embodiment 2～7 can
Be the arbitrary value in 0.5～3.0, and material component can be antioxidant, lubricant, releasing agent one or more, in order to strengthen
With the comparability of embodiment 1, the weight fraction selected at this is 0.6.
Table 1 embodiment 1-7 and the composition of raw materials of comparative example 1-3
Note: in table, "/" represents without this component.
Performance test
ABS resin compositions above-described embodiment 1-7 and comparative example 1-2 prepared, according to identical injecting condition
Preparation test bars, concrete physical property and rheological property detection project are as follows:
Hot strength: test according to ISO527 standard, test speed is 50mm/min,
Bending strength: test according to ISO178 standard, test speed is 2mm/min；
Bending modulus: test according to ISO178 standard, test speed is 1mm/min；
23 DEG C of cantilever beam unnotched impact strengths: test according to ISO180 standard, batten thickness is 4mm；
-40 DEG C of cantilever beam unnotched impact strengths: test according to ISO180 standard, batten thickness is 4mm., test
Condition is-40 DEG C/4h；
Heat distortion temperature: test according to ISO75 standard, test condition is 0.45MPa；
Melt flow rate (MFR): test according to ISO1183 standard, test condition is 220 DEG C/10kg；
Shear viscosity: use the test of Malvern monotubular capillary rheometer, choose draw ratio 16/1, a diameter of 0.5mm, enter
Bicker is the mouth die of 180 °.Setting test temperature 240 DEG C, range of shear rate 200～50000s-1, raw material plastic phase sets
For being pressurized to 1MPa, then it is incubated 6min, after repressurization to 1MPa, again preheats 4min.After design temperature is stable, weigh
The material about 35g being fully dried, is separately added in barrel and compresses compacting, then starts test, records under each shear rate
Shear viscosity.Wherein the shear viscosity 1 in table 2 is viscosity during 200/s shear rate, and shear viscosity 2 is cut for 50000/s
Viscosity during cutting speed rate.
Table 2 embodiment 1-7 and the performance test of comparative example 1-3
Note: in table, No Fracture represents unbroken, under the conditions of being i.e. somebody's turn to do, notch strength value is more than the maximum tested at present
Value.
From the results shown in Table 2, by select α-methyl styrene type heat-proof modifier system, low temperature cantilever beam without
Notch impact strength is wanted with maleic anhydride and cinnamic terpolymer heat-proof modifier system than N-phenylmaleimide
Height, but material is heat-resisting, rigidity and melt viscosity on the low side.Add melt strength enhancers and sterically hindered bigger fluoropolymer
Thing additive, all can be effectively improved the rigidity of material, low-temperature flexibility and melt viscosity.Increase fluoropolymer additive further
Consumption, the rigidity of material, melt flow rate (MFR) and shear viscosity continue to lift up.By the acrylic acid esters co-polymer of nucleocapsid structure
Melt strength enhancers and acrylonitrile-styrene-glycidyl methacrylate copolymer melt that reaction can be crosslinked
Intensity reinforcing agent is compounding to be used, and the rigidity of material, low-temperature flexibility, melt flow rate (MFR) and shear viscosity are improved significantly；
In fluoropolymer additive, polytetrafluoroethylene content improves, and performance improvement efficiency is the highest.
The preparation of the thermoplastic ABS resin of the high rigidity of embodiment 8, high fondant-strength and low-temperature impact resistance
Acrylonitrile-butadiene-phenylethene grafted copolymer 40 parts, acrylonitritrile-styrene resin 50 parts, heat-proof modifier
(HR-1) 10 parts, melt reinforcing agent (MR-1) 10 parts, fluoropolymer additive (FA-3) 6 parts, processing aid 0.6 part.According to
Above-mentioned component part weighs raw material, adopts and prepares described blowing ABS resin compositions with the following method:
(1) raw material prepared is sufficiently mixed 30min in super mixer；
(2) premix material step 1 prepared is in double screw extruder sent into by metering device, in conveying, the shearing of screw rod
Under mixing, material melting, compound more extruded, tie rod, cooling, pelletizing step, obtain the high rigidity for blow molding high
Toughness high melt strength thermoplastic ABS resin compositions.Wherein the screw slenderness ratio of double screw extruder is 36～44, vacuum
Control at 0.09Ma；The extrusion temperature of described double screw extruder is between 180～250 DEG C, and screw speed is 200～500
Rev/min.
The preparation of the thermoplastic ABS resin of the high rigidity of embodiment 9, high fondant-strength and low-temperature impact resistance
Acrylonitrile-butadiene-phenylethene grafted copolymer 40 parts, acrylonitritrile-styrene resin 50 parts, heat-proof modifier
(HR-1) 10 parts, melt reinforcing agent (MR-2) 10 parts, fluoropolymer additive (FA-3) 6 parts, processing aid 0.6 part.According to
Above-mentioned component part weighs raw material, adopts and prepares described blowing ABS resin compositions with the following method:
(1) raw material prepared is sufficiently mixed 30min in super mixer；
(2) premix material step 1 prepared is in double screw extruder sent into by metering device, in conveying, the shearing of screw rod
Under mixing, material melting, compound more extruded, tie rod, cooling, pelletizing step, obtain the high rigidity for blow molding high
Toughness high melt strength thermoplastic ABS resin compositions.Wherein the screw slenderness ratio of double screw extruder is 36～44, vacuum
Control at 0.09Ma；The extrusion temperature of described double screw extruder is between 180～250 DEG C, and screw speed is 200～500
Rev/min.
The preparation of the thermoplastic ABS resin of the high rigidity of embodiment 10, high fondant-strength and low-temperature impact resistance
Acrylonitrile-butadiene-phenylethene grafted copolymer 40 parts, acrylonitritrile-styrene resin 50 parts, heat-proof modifier
(HR-1) 10 parts, melt reinforcing agent (MR-1) 5 parts, melt reinforcing agent (styrene-maleic anhydride copolymer) 5 parts, fluoropolymer
Thing additive (FA-3) 6 parts, processing aid 0.6 part.Weigh raw material according to above-mentioned component part, adopt and blow described in preparing with the following method
Mould and use ABS resin compositions:
(1) raw material prepared is sufficiently mixed 30min in super mixer；
(2) premix material step 1 prepared is in double screw extruder sent into by metering device, in conveying, the shearing of screw rod
Under mixing, material melting, compound more extruded, tie rod, cooling, pelletizing step, obtain the high rigidity for blow molding high
Toughness high melt strength thermoplastic ABS resin compositions.Wherein the screw slenderness ratio of double screw extruder is 36～44, vacuum
Control at 0.09Ma；The extrusion temperature of described double screw extruder is between 180～250 DEG C, and screw speed is 200～500
Rev/min.
The preparation of the thermoplastic ABS resin of the high rigidity of embodiment 11, high fondant-strength and low-temperature impact resistance
Acrylonitrile-butadiene-phenylethene grafted copolymer 40 parts, acrylonitritrile-styrene resin 50 parts, heat-proof modifier
(HR-1) 10 parts, melt reinforcing agent (MR-2) 5 parts, melt reinforcing agent (styrene-maleic anhydride copolymer) 5 parts, fluoropolymer
Thing additive (FA-3) 6 parts, processing aid 0.6 part.Weigh raw material according to above-mentioned component part, adopt and blow described in preparing with the following method
Mould and use ABS resin compositions:
(1) raw material prepared is sufficiently mixed 30min in super mixer；
(2) premix material step 1 prepared is in double screw extruder sent into by metering device, in conveying, the shearing of screw rod
Under mixing, material melting, compound more extruded, tie rod, cooling, pelletizing step, obtain the high rigidity for blow molding high
Toughness high melt strength thermoplastic ABS resin compositions.Wherein the screw slenderness ratio of double screw extruder is 36～44, vacuum
Control at 0.09Ma；The extrusion temperature of described double screw extruder is between 180～250 DEG C, and screw speed is 200～500
Rev/min.
Performance test
The ABS resin compositions prepared by above-described embodiment 8-11, prepares test specimens according to identical injecting condition
Bar, concrete physical property and rheological property detection project are as follows:
Hot strength: test according to ISO527 standard, test speed is 50mm/min,
Bending strength: test according to ISO178 standard, test speed is 2mm/min；
Bending modulus: test according to ISO178 standard, test speed is 1mm/min；
23 DEG C of cantilever beam unnotched impact strengths: test according to ISO180 standard, batten thickness is 4mm；
-40 DEG C of cantilever beam unnotched impact strengths: test according to ISO180 standard, batten thickness is 4mm., test
Condition is-40 DEG C/4h；
Heat distortion temperature: test according to ISO75 standard, test condition is 0.45MPa；
Melt flow rate (MFR): test according to ISO1183 standard, test condition is 220 DEG C/10kg；
Shear viscosity: use the test of Malvern monotubular capillary rheometer, choose draw ratio 16/1, a diameter of 0.5mm, enter
Bicker is the mouth die of 180 °.Setting test temperature 240 DEG C, range of shear rate 200～50000s-1, raw material plastic phase sets
For being pressurized to 1MPa, then it is incubated 6min, after repressurization to 1MPa, again preheats 4min.After design temperature is stable, weigh
The material about 35g being fully dried, is separately added in barrel and compresses compacting, then starts test, records under each shear rate
Shear viscosity.Wherein the shear viscosity 1 in table 2 is viscosity during 200/s shear rate, and shear viscosity 2 is cut for 50000/s
Viscosity during cutting speed rate.
Table 3 embodiment 5-11 performance test
By the result of table 3 it can be seen that the ABS resin compositions of the present invention have superelevation melt strength, ultrahigh rigidity and
The advantage of excellent low-temperature impact resistance.Using this resin combination, not only in blow-molding process, melt strength is high, parison sagging
Few；Rigidity and the low-temperature flexibility of product is improved significantly simultaneously, solves blowing ABS resin in prior art well
The problem that melt strength, rigidity and the low-temperature flexibility that compositions exists can not balance.Right by embodiment 7 and embodiment 8-11
Than it can be seen that in the case of other constituent contents are constant, melt reinforcing agent select acrylic acid esters co-polymer and acrylonitrile-
Styrene-t glycidyl ester copolymer compounds, and prepared ABS resin properties all increases, especially
It is that melt flow rate (MFR) and shear viscosity are improved the most obvious.
In sum, the present invention is specific by adding in the styrene resin composite comprising specific components specified quantitative
The heat-resistant agent of component specified quantitative, melt reinforcing agent, fluoropolymer additive, and with the component generation synergistic in resin combination
Effect, and then solve in prior art blow molding heat-resisting ABS resin in blow molding, mechanical performance, product experiment etc.
The problem that aspect exists；The present invention is prepared for that blowing property is strong, mechanical rigid is high and the high heat-resisting ABS resin of excellent in low temperature toughness
Compositions；The melt strength of the resin combination of the present invention is high, can be effectively improved the melt sagging of parison, this
Bright resin combination low-temperature flexibility is high, and-40 DEG C of cantilever beam unnotched impact strengths, up to constantly, can meet auto parts and components
The low-temp storage requirement of goods, and the thermostability of blow-molded article is high, it is possible to meet the high temperature storage requirement of blow-molded article.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
Member, on the premise of without departing from the inventive method, it is also possible to makes some improvement and supplements, and these improve and supplement and also should be regarded as
Protection scope of the present invention.
Claims (10)
1. it is used for a thermoplastic abs resin composition for high rigidity, high fondant-strength and the low-temperature impact resistance of blow molding,
It is characterized in that, described ABS resin compositions is to be prepared by the raw materials in:
Thermoplastic ABS resin's combination of high rigidity the most according to claim 1, high fondant-strength and low-temperature impact resistance
Thing, it is characterised in that the weight average molecular weight of described acrylonitrile-butadiene-phenylethene grafted copolymer is 100,000～200,
000, relative density is 1.0～1.04, and average diameter range is 100～600nm, described butadiene rubber weight percent content
It is 40～70wt%；The weight average molecular weight of described acrylonitritrile-styrene resin is 100,000～500,000, the weight of acrylonitrile
Amount degree is 15～40wt%.
Thermoplastic ABS resin's combination of high rigidity the most according to claim 2, high fondant-strength and low-temperature impact resistance
Thing, it is characterised in that the average diameter range of described acrylonitrile-butadiene-phenylethene grafted copolymer is 200～300nm, institute
The weight percent content stating butadiene rubber is 45～55wt%；The weight average molecular weight of described acrylonitritrile-styrene resin
Preferably 200,000～400,000, the weight percentage of acrylonitrile preferably 25～35wt%.
Thermoplastic ABS resin's combination of high rigidity the most according to claim 1, high fondant-strength and low-temperature impact resistance
Thing, it is characterised in that described heat-proof modifier is the one of the copolymer of N-aryl maleimide copolymers, α-methyl styrene
Kind or several mixture.
Thermoplastic ABS resin's combination of high rigidity the most according to claim 4, high fondant-strength and low-temperature impact resistance
Thing, it is characterised in that described heat-proof modifier is N-phenylmaleimide copolymer and maleic anhydride and cinnamic ternary
Copolymer or described heat-proof modifier are α-methyl styrene.
Thermoplastic ABS resin's combination of high rigidity the most according to claim 1, high fondant-strength and low-temperature impact resistance
Thing, it is characterised in that described melt reinforcing agent is that the acrylic acid esters co-polymer of nucleocapsid structure, phenylethylene-maleic anhydride are common
Polymers, the mixture of one or more of acrylonitrile-styrene-glycidyl methacrylate copolymer.
Thermoplastic ABS resin's combination of high rigidity the most according to claim 6, high fondant-strength and low-temperature impact resistance
Thing, it is characterised in that described melt reinforcing agent is acrylic acid esters co-polymer and acrylonitrile-styrene-Glycidyl methacrylate
Compounding of glyceride.
Thermoplastic ABS resin's combination of high rigidity the most according to claim 1, high fondant-strength and low-temperature impact resistance
Thing, it is characterised in that described fluoropolymer additive, comprises the fluoropolymer and 70～30wt% of 30～70wt%
Carrier polymer；Described fluoropolymer is poly-Fluorine containing olefine, selected from politef, Kynoar, tetrafluoroethene/hexafluoro
Propylene copolymer, tetrafluoroethylene/ethylene copolymer, tetrafluoroethylene/perfluoro alkyl ether copolymer, polyvinyl fluoride, CTFE/
Ethylene copolymer, polytrifluorochloroethylene；Described carrier polymer is selected from polymethyl methacrylate, polystyrene, poly-alpha-alkyl
Styrene, maleic anhydride modified styrenic polymer, phenylethylene/maleic anhydride copolymer, Maleimide-modified benzene
Polyvinyls, styrene-N aryl maleimide copolymers, styrene/acrylonitrile copolymer, alpha-alkyl phenylethylene/the third
Alkene lonitrile copolymer, styrene/alpha-alkyl phenylethylene/acrylonitrile copolymer, styrene/acrylonitrile/methyl methacrylate copolymer
Thing, styrene/alpha-alkyl phenylethylene/acrylonitrile/methylmethacrylate copolymer and alpha-alkyl phenylethylene/acrylonitrile/methyl
Methyl acrylate copolymer.
Thermoplastic ABS resin's combination of high rigidity the most according to claim 1, high fondant-strength and low-temperature impact resistance
Thing, it is characterised in that described processing aid includes the mixture of one or more of antioxidant, lubricant, releasing agent；Described anti-
Oxygen agent is Hinered phenols antioxidant or phosphite ester kind antioxidant；Described lubricant is that pentaerythritol stearate or ethylene are double hard
Fat acid amide；Described releasing agent is silicone releasing agent.
10. thermoplastic ABS resin's combination of the arbitrary described high rigidity of claim 1-9, high fondant-strength and low-temperature impact resistance
The preparation method of thing, it is characterised in that described preparation method comprises the steps:
(1) raw material is weighed by proportioning；
(2) raw material got ready in step (1) is premixed in super mixer；
(3) by the premix material that obtains in step (2) in double screw extruder sent into by metering device, in conveying, the shearing of screw rod
Under mixing, material melting, compound more extruded, tie rod, cooling, pelletizing step, obtain the high rigidity for blow molding high
Toughness high melt strength thermoplastic ABS resin compositions；Wherein the screw slenderness ratio of double screw extruder is 36～44, and carries
There are attemperating unit and vacuum extractor；The extrusion temperature of described double screw extruder is between 180～250 DEG C, screw speed
It it is 200～500 revs/min.
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| CN108164856A (en) * | 2017-12-27 | 2018-06-15 | 浙江普利特新材料有限公司 | A kind of superelevation is heat-resisting, high fondant-strength is blow molded ABS material and preparation method thereof |
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| CN114034605B (en) * | 2021-10-28 | 2024-01-16 | 国高材高分子材料产业创新中心有限公司 | Melt flow rate standard substance and preparation method thereof |
| CN115894808A (en) * | 2022-11-17 | 2023-04-04 | 北方华锦化学工业股份有限公司 | Low-crystal-point plate-grade ABS material and preparation method thereof |
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| CN115819916B (en) * | 2022-12-20 | 2024-03-22 | 金发科技股份有限公司 | Modified ABS composition and preparation method and application thereof |
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