CN106046589B - A kind of thermoplastic abs resin composition for the high rigidity of blow molding, high fondant-strength and low-temperature impact resistance - Google Patents
A kind of thermoplastic abs resin composition for the high rigidity of blow molding, high fondant-strength and low-temperature impact resistance Download PDFInfo
- Publication number
- CN106046589B CN106046589B CN201610685304.5A CN201610685304A CN106046589B CN 106046589 B CN106046589 B CN 106046589B CN 201610685304 A CN201610685304 A CN 201610685304A CN 106046589 B CN106046589 B CN 106046589B
- Authority
- CN
- China
- Prior art keywords
- abs resin
- acrylonitrile
- strength
- styrene
- copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- 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
-
- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
Abstract
The present invention relates to a kind of thermoplastic abs resin compositions for the high rigidity of blow molding, high fondant-strength and low-temperature impact resistance, including following components and content: 20~60 parts of acrylonitrile-butadiene-phenylethene grafted copolymer, 30~70 parts of acrylonitritrile-styrene resin, 5~25 parts of heat-proof modifier, 1~20 part of melt reinforcing agent, 0.1~10.0 part of fluoropolymer additive, 0.5~3.0 part of processing aid.Thermoplastic ABS resin prepared by the present invention, have the advantages that superelevation melt strength, ultrahigh rigidity and excellent low-temperature impact resistance, the problem of melt strength, rigidity and low-temperature flexibility existing for current blow molding ABS resin composition cannot balance is well solved, especially suitable for some automobile large parts (e.g., the products such as flow spoiler, seat back, bumper).
Description
Technical field
The present invention relates to technical field of polymer materials, specifically, being a kind of high rigidity for blow molding, Gao Rong
The thermoplastic abs resin composition of body intensity and low-temperature impact resistance.
Background technique
ABS resin has excellent comprehensive performance, can be formed by a variety of methods such as injection molding, extrusion, blow molding and 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 passes through narrow
Effect when mouth mold, by high shear force, it is easy to parison sag phenomenon occur, excessive vertical contracting will lead to the wall thickness of product not
, it cannot even be formed when serious.Therefore, for blow molding ABS resin, it is desirable that the melt strength of resin wants sufficiently high.
And for some automobile large parts, such as flow spoiler, seat back, bumper, need product to bear the loading force of some strength,
And generally there is -30 DEG C or -40 DEG C of low-temperature impact requirement of experiment, it is desirable that there can be no the appearances such as crackle, cracking for product itself not
It is good.Therefore, for blow molding ABS resin, it is desirable that intensity, rigidity and low-temperature flexibility with higher.
Existing literature has been disclosed by increasing the rubber content in ABS resin, to improve the melt strength of ABS resin
And impact resistance, but the rigidity of prepared resin combination, heat resistance can all reduce, on the other hand, the size of material is steady
It is qualitative to be also deteriorated.As Chinese patent CN103013025 discloses a kind of ABS of excellent combination property that can be used for blow molding
Resin is improved toughness by rubber-phase content in raising ABS resin, but improved and melt index reduction in impact strength
Meanwhile material stiffness can reduce.Existing literature is disclosed to be blended by the polymer for preparing different polymerization methods, to change
The impact resistance of kind material.Such as patent US4430478, US5605963, US5696204, pass through produce emulsion polymerization technique
Polymer is mixed to improve the impact property of material with the polymer that bulk technique produces, however uses this kind of method
Obtained material melt intensity is low, and blow molding performance is poor；And the room temperature toughness and low-temperature flexibility of material are also not necessarily closed at corresponding
System, when room temperature toughness improves, low-temperature flexibility improves limited.Existing literature is disclosed adds super high molecular weight in ABS resin
Third component, the melt strength of Lai Tigao material.Such as Chinese patent CN101250314, disclose a kind of for blow molding
Heat-proof ABS resin composition and preparation method thereof improves ABS resin by addition ultrahigh molecular weight polypropylene acid copolymer
The method of melt strength；But the low-temperature flexibility of the composition is lower.Existing literature is disclosed improves SAN content in ABS resin
Or molecular weight, the rigidity of Lai Tigao ABS resin, but this kind of method of use can reduce the toughness and melt strength of material.As in
State patent CN101250314 discloses a kind of heat-proof ABS resin composition for blow molding, embodiment 1 and embodiment 6
It compared the influence by improving the SAN content in ABS resin to physical property, the results showed that SAN content is promoted, and material stiffness mentions
Height, but melt strength and toughness all reduce.
It is well known that the hydrogen being connected in fluoropolymer-containing high polymer main chain or side chain with carbon atom direct covalent bonds is former
After son is replaced in whole or in part by fluorine atom, fluorine atom is in spiral distribution along carbochain, other molecules or reactive group are difficult to
Insertion, effective protection carbon carbon backbone chain；Therefore, polymer has the series of advantages such as high, the big, good toughness of melt strength of rigidity.
Patent CN 101360786B discloses the method that fluoropolymer improves polymer weatherability and modulus, but the patent is
The system without rubber components and filler is had studied, is not made a search to the polymeric system comprising rubber components；Patent
US5962587 discloses the modulus of the thermoplastic compounds of polytetrafluoroethylene (PTFE) (PTFE) Lai Gaijin modified rubber, but does not grind
The high heat resistance ABS system for blow molding is studied carefully, also without the low-temperature flexibility situation of report product.Above-mentioned prior art is all
Be not carried out improvement while to rigidity, melt strength and low-temperature flexibility, i.e., while improving wherein a certain performance, other property
It can not promoted equally.As performance requirement of the automobile industry to material is more and more harsh, this three aspects performance is taken into account
The developing direction of prospective material requirement will be become by being blow molded ABS.
Summary of the invention
There is superelevation melt strength, super for blow molding the technical problem to be solved by the invention is to provide a kind of
The heat-proof ABS resin composition and preparation method of high rigidity and good low-temperature toughness.Using the resin combination, not only it was blow molded
Melt strength is high in journey, and parison sagging is few；The rigidity and low-temperature flexibility of product are improved significantly simultaneously, solve well
The problem of melt strength, rigidity and low-temperature flexibility existing for blow molding ABS resin composition in the prior art of having determined cannot balance.
The first purpose of this invention is aiming at the shortcomings in the prior art, to provide a kind of Gao Gang for blow molding
The thermoplastic abs resin composition of property, high fondant-strength and low-temperature impact resistance.
Second object of the present invention is to provide the preparation method of ABS resin composition as described above.
To achieve the above object, the technical solution adopted by the present invention is that:
A kind of thermoplastic ABS resin's combination for the high rigidity of blow molding, high fondant-strength and low-temperature impact resistance
Object, the ABS resin composition is to be made from the following raw materials in parts by weight:
Further, the ABS resin composition is to be made from the following raw materials in parts by weight:
Further, the weight average molecular weight of the acrylonitrile-butadiene-phenylethene grafted copolymer is 100,000~200,
000, relative density is 1.0~1.04, and average diameter range is 100~600nm, the butadiene rubber weight percent content
For 40~70wt%.
Further, the average grain diameter of the 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 the acrylonitritrile-styrene resin is 100,000~500,000, acrylonitrile
Weight percent content is 15~40wt%.
Further, the weight average molecular weight of the acrylonitritrile-styrene resin is preferably 200,000~400,000, propylene
The weight percentage of nitrile is preferably 25~35wt%.
Further, the heat-proof modifier is the copolymer of N- aryl maleimide copolymers, α-methylstyrene
One or more of mixtures.
Further, the heat-proof modifier is preferably N- aryl maleimide copolymers；More excellent is N- phenyl Malaysia acyl
The terpolymer or N-phenylmaleimide and maleic anhydride of imines and maleic anhydride and styrene, α-methylstyrene,
The multiple copolymer of acrylonitrile.
Further, the melt reinforcing agent is acrylic acid esters co-polymer, the styrene-maleic anhydride copolymer of core-shell structure
The mixture of object, acrylonitrile-styrene-glycidyl methacrylate copolymer one or more.
Further, the melt reinforcing agent is acrylic acid esters co-polymer, acrylonitrile-styrene-Glycidyl methacrylate
The compounding of glycerol ester copolymer.
Further, the acrylic acid esters co-polymer, acrylonitrile-styrene-glycidyl methacrylate quality
Than for 1:1.
Further, the fluoropolymer additive, fluoropolymer and 70~30wt% comprising 30~70wt%
Carrier polymer.
Further, the fluoropolymer be poly- Fluorine containing olefine, be selected from polytetrafluoroethylene (PTFE), Kynoar, tetrafluoroethene/
Hexafluoropropylene copolymer, tetrafluoroethylene/ethylene copolymer, tetrafluoroethylene/perfluoro alkyl ether copolymer, polyvinyl fluoride, trifluoro chlorine
Ethylene/vinyl copolymer, polytrifluorochloroethylene.
Further, the fluoropolymer is preferably polytetrafluoroethylene (PTFE) (FA-1).
Further, the carrier polymer is polymethyl methacrylate, polystyrene, poly- alpha-alkyl phenylethylene, Malaysia
Anhydride modified styrenic polymer, phenylethylene/maleic anhydride copolymer, Maleimide-modified phenylethylene polymerization
Object, styrene-N aryl maleimide copolymers, styrene/acrylonitrile copolymer, alpha-alkyl phenylethylene/acrylonitrile compolymer
Object, 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, the carrier polymer is preferably styrene/acrylonitrile copolymer or polymethyl methacrylate.
Further, the processing aid includes one or more of mixtures of antioxidant, lubricant, release agent.
Further, the antioxidant is preferably Hinered phenols antioxidant or phosphite ester antioxidant.
Further, the lubricant is preferably pentaerythritol stearate or ethylene bis stearic acid amide.
Further, the release agent is preferably silicone release agent.
To realize above-mentioned second purpose, the technical solution adopted by the present invention is that:
The system of the thermoplastic abs resin composition of any high rigidity, high fondant-strength and low-temperature impact resistance as above
Preparation Method, the preparation method include the following steps:
(1) proportion weighs raw material as described above；
(2) raw material got ready in step (1) is premixed in super mixer；
(3) by premix obtained in step (2) through metering device be sent into double screw extruder in, screw rod conveying,
Shearing and under being kneaded, it is material melting, compound, then through extrusion, tie rod, cooling, pelletizing step, obtain the Gao Gang for blow molding
Property high tenacity high melt strength thermoplastic ABS resin composition；Wherein the screw slenderness ratio of double screw extruder is 36~44, and
And have temperature control device and vacuum evacuation device；The extrusion temperature of the double screw extruder is screw rod between 180~250 DEG C
Revolving 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 are compounded, and preparing has superelevation melt strength, super for blow molding
The thermoplastic abs resin composition of high rigidity and excellent low-temperature impact resistance.Using the resin combination, not only in blow-molding process
Melt strength is high, and parison sagging is few；The rigidity and low-temperature flexibility of product are improved significantly simultaneously, well solve
The problem of melt strength, rigidity and low-temperature flexibility existing for blow molding ABS resin composition cannot balance in the prior art.
2, the present invention screens through a large number of experiments, and melt reinforcing agent selects acrylic acid esters co-polymer and acrylonitrile-benzene
Ethylene-methyl methacrylate glycidyl ester copolymer compounding, prepared ABS resin properties increase, especially
Melt flow rate (MFR) and shear viscosity improve the most obvious.
3, the present invention is by the way that specific group dtex is added into the styrene resin composite comprising specific components specific quantity
Quantitative heat-resistant agent, melt reinforcing agent, fluoropolymer additive, and synergistic effect occurs with the component in resin combination,
And then it solves blow molding heat-resisting ABS resin in the prior art and is deposited in terms of blow molding, mechanical performance, product
The problem of；The present invention is prepared for that blow molding property is strong, mechanical rigid is high, the high heat resistance of the high and low temperature excellent tenacity of melt strength
ABS resin composition is effectively improved the melt sagging of parison, and -40 DEG C of cantilever beam unnotched impact strengths of low temperature
Up to the low-temp storage requirement for constantly, meeting auto parts and components product, and the heat resistance of blow-molded article is high, also meets blow-molded article
High temperature storage requirement.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after having read the content of the invention recorded, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
Raw materials used in embodiment, parameter and the trade mark are as follows:
The acrylonitrile-butadiene-phenylethene grafted copolymer is polybutadiene rubber graft phenylethene-acrylonitrile compolymer
Object, weight average molecular weight 100,000~200,000, relative density be 1.0~1.04, average diameter range be 100~
600nm, wherein butadiene rubber weight percent content is 40~70wt%.The weight of the acrylonitritrile-styrene resin is equal
Molecular weight is 100,000~500,000, and the weight percent content of acrylonitrile is 15~40wt%.The heat-proof modifier is
N-phenylmaleimide-maleic anhydride-styrene terpolymer (HR-1), α-methylstyrene (HR-2).The melt
Reinforcing agent is the acrylic acid esters co-polymer (MR-1) of core-shell structure, weight average molecular weight 1000,000~5000,000；Propylene
Nitrile-styrene-t glycidyl ester copolymer (MR-2).The fluorochemical additive is (styrene/acrylonitrile copolymerization
Object carrier)/50wt% polytetrafluoroethylene (PTFE) (FA-1), (styrene/acrylonitrile copolymer carrier)/30wt% polytetrafluoroethylene (PTFE) (FA-
2), polymethyl methacrylate carrier/50wt% polytetrafluoroethylene (PTFE) (FA-3).The processing aid is the IG- of antioxidant Ciba
1076。
Embodiment 1
40 parts of acrylonitrile-butadiene-phenylethene grafted copolymer, 50 parts of acrylonitritrile-styrene resin, heat-proof modifier
(HR-2) 10 parts, 5 parts of melt reinforcing agent (MR-1), 3 parts of fluoropolymer additive (FA-1), 0.6 part of processing aid.According to upper
It states component part and weighs raw material, prepare the blow molding ABS resin composition with the following method:
(1) raw material prepared is sufficiently mixed 30min in super mixer；
(2) premix for preparing step 1 is sent into double screw extruder through metering device, conveying, shearing in screw rod
It is material melting, compound under mixing, then through extrusion, tie rod, cooling, pelletizing step, obtain high for the high rigidity of blow molding
Toughness high melt strength thermoplastic ABS resin composition.Wherein the screw slenderness ratio of double screw extruder is 36~44, vacuum degree
Control is in 0.09Ma；The extrusion temperature of the 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 embodying creativeness of the invention by comparison, embodiment 2-7 is matched on the basis of embodiment 1, point
Variety classes heat-proof modifier (α-methylstyrene), fluoropolymer additive Different adding amount, variety classes are not compared
Melt reinforcing agent, variety classes melt reinforcing agent compounding, variety classes fluoropolymer additive compound the shadow to material property
It rings, specific preparation method is same as Example 1, and raw material proportioning is as shown in table 1.In addition, the processing aid in embodiment 2~7 can
For the arbitrary value in 0.5~3.0, and material component can be the one or more of antioxidant, lubricant, release agent, in order to enhance
With the comparativity of embodiment 1, the weight fraction selected herein is 0.6.
The composition of raw materials of table 1 embodiment 1-7 and comparative example 1-3
Note: "/" indicates to be free of the component in table.
Performance test
The ABS resin composition that above-described embodiment 1-7 and comparative example 1-2 are prepared, according to identical injecting condition
Test bars are prepared, specific physical property and rheological property detection project are as follows:
Tensile strength: being tested according to ISO527 standard, test speed 50mm/min,
Bending strength: being tested according to ISO178 standard, test speed 2mm/min；
Bending modulus: being tested according to ISO178 standard, test speed 1mm/min；
23 DEG C of cantilever beam unnotched impact strengths: it is tested according to ISO180 standard, batten is with a thickness of 4mm；
- 40 DEG C of cantilever beam unnotched impact strengths: being tested according to ISO180 standard, and batten is with a thickness of 4mm., test
Condition is -40 DEG C/4h；
Heat distortion temperature: being tested according to ISO75 standard, test condition 0.45MPa；
Melt flow rate (MFR): being tested according to ISO1183 standard, and test condition is 220 DEG C/10kg；
Shear viscosity: being tested using Malvern monotubular capillary rheometer, is chosen draw ratio 16/1, diameter 0.5mm, is entered
The mouth mold that bicker is 180 °.240 DEG C of test temperature, 200~50000s-1 of range of shear rate of setting, the setting of raw material plastic phase
To be pressurized to 1MPa, 6min is then kept the temperature, preheats 4min again after repressurization to 1MPa.After set temperature is stablized, weigh
Sufficiently dry material about 35g, is separately added into barrel and compresses compacting, then start to test, record under each shear rate
Shear viscosity.Viscosity when wherein the shear viscosity 1 in table 2 is 200/s shear rate, and shear viscosity 2 is cut for 50000/s
Viscosity when cutting speed rate.
The performance test of table 2 embodiment 1-7 and comparative example 1-3
Note: No Fracture is indicated unbroken in table, i.e., notch strength value is greater than the maximum tested at present under this condition
Value.
From the results shown in Table 2, by select α-methylstyrene type heat-proof modifier system, low temperature cantilever beam without
Notch impact strength is than the terpolymer heat-proof modifier system of N-phenylmaleimide and maleic anhydride and styrene
Height, but material is heat-resisting, rigidity and melt viscosity are relatively low.Add melt strength enhancers and the biggish fluoropolymer of steric hindrance
Object additive can all be effectively improved the rigidity, low-temperature flexibility and melt viscosity of material.Further increase fluoropolymer additive
Dosage, rigidity, melt flow rate (MFR) and the shear viscosity of material continue to lift up.By the acrylic acid esters co-polymer of core-shell structure
Melt strength enhancers and acrylonitrile-styrene-glycidyl methacrylate copolymer melt that reaction can be crosslinked
Intensity reinforcing agent is used in compounding, and rigidity, low-temperature flexibility, melt flow rate (MFR) and the shear viscosity of material are improved significantly；
Polytetrafluoroethylene content improves in fluoropolymer additive, and performance improvement efficiency is higher.
The preparation of the thermoplastic ABS resin of 8 high rigidity of embodiment, high fondant-strength and low-temperature impact resistance
40 parts of acrylonitrile-butadiene-phenylethene grafted copolymer, 50 parts of acrylonitritrile-styrene resin, heat-proof modifier
(HR-1) 10 parts, 10 parts of melt reinforcing agent (MR-1), 6 parts of fluoropolymer additive (FA-3), 0.6 part of processing aid.According to
Above-mentioned component part weighs raw material, prepares the blow molding ABS resin composition with the following method:
(1) raw material prepared is sufficiently mixed 30min in super mixer；
(2) premix for preparing step 1 is sent into double screw extruder through metering device, conveying, shearing in screw rod
It is material melting, compound under mixing, then through extrusion, tie rod, cooling, pelletizing step, obtain high for the high rigidity of blow molding
Toughness high melt strength thermoplastic ABS resin composition.Wherein the screw slenderness ratio of double screw extruder is 36~44, vacuum degree
Control is in 0.09Ma；The extrusion temperature of the 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 9 high rigidity of embodiment, high fondant-strength and low-temperature impact resistance
40 parts of acrylonitrile-butadiene-phenylethene grafted copolymer, 50 parts of acrylonitritrile-styrene resin, heat-proof modifier
(HR-1) 10 parts, 10 parts of melt reinforcing agent (MR-2), 6 parts of fluoropolymer additive (FA-3), 0.6 part of processing aid.According to
Above-mentioned component part weighs raw material, prepares the blow molding ABS resin composition with the following method:
(1) raw material prepared is sufficiently mixed 30min in super mixer；
(2) premix for preparing step 1 is sent into double screw extruder through metering device, conveying, shearing in screw rod
It is material melting, compound under mixing, then through extrusion, tie rod, cooling, pelletizing step, obtain high for the high rigidity of blow molding
Toughness high melt strength thermoplastic ABS resin composition.Wherein the screw slenderness ratio of double screw extruder is 36~44, vacuum degree
Control is in 0.09Ma；The extrusion temperature of the 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 10 high rigidity of embodiment, high fondant-strength and low-temperature impact resistance
40 parts of acrylonitrile-butadiene-phenylethene grafted copolymer, 50 parts of acrylonitritrile-styrene resin, heat-proof modifier
(HR-1) 10 parts, 5 parts of melt reinforcing agent (MR-1), 5 parts of melt reinforcing agent (styrene-maleic anhydride copolymer), fluoropolymer
6 parts of object additive (FA-3), 0.6 part of processing aid.Raw material is weighed according to above-mentioned component part, prepares described blow with the following method
Modeling ABS resin composition:
(1) raw material prepared is sufficiently mixed 30min in super mixer；
(2) premix for preparing step 1 is sent into double screw extruder through metering device, conveying, shearing in screw rod
It is material melting, compound under mixing, then through extrusion, tie rod, cooling, pelletizing step, obtain high for the high rigidity of blow molding
Toughness high melt strength thermoplastic ABS resin composition.Wherein the screw slenderness ratio of double screw extruder is 36~44, vacuum degree
Control is in 0.09Ma；The extrusion temperature of the 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 11 high rigidity of embodiment, high fondant-strength and low-temperature impact resistance
40 parts of acrylonitrile-butadiene-phenylethene grafted copolymer, 50 parts of acrylonitritrile-styrene resin, heat-proof modifier
(HR-1) 10 parts, 5 parts of melt reinforcing agent (MR-2), 5 parts of melt reinforcing agent (styrene-maleic anhydride copolymer), fluoropolymer
6 parts of object additive (FA-3), 0.6 part of processing aid.Raw material is weighed according to above-mentioned component part, prepares described blow with the following method
Modeling ABS resin composition:
(1) raw material prepared is sufficiently mixed 30min in super mixer；
(2) premix for preparing step 1 is sent into double screw extruder through metering device, conveying, shearing in screw rod
It is material melting, compound under mixing, then through extrusion, tie rod, cooling, pelletizing step, obtain high for the high rigidity of blow molding
Toughness high melt strength thermoplastic ABS resin composition.Wherein the screw slenderness ratio of double screw extruder is 36~44, vacuum degree
Control is in 0.09Ma；The extrusion temperature of the double screw extruder is between 180~250 DEG C, and screw speed is 200~500
Rev/min.
Performance test
The ABS resin composition that above-described embodiment 8-11 is prepared prepares test specimens according to identical injecting condition
Item, specific physical property and rheological property detection project are as follows:
Tensile strength: being tested according to ISO527 standard, test speed 50mm/min,
Bending strength: being tested according to ISO178 standard, test speed 2mm/min；
Bending modulus: being tested according to ISO178 standard, test speed 1mm/min；
23 DEG C of cantilever beam unnotched impact strengths: it is tested according to ISO180 standard, batten is with a thickness of 4mm；
- 40 DEG C of cantilever beam unnotched impact strengths: being tested according to ISO180 standard, and batten is with a thickness of 4mm., test
Condition is -40 DEG C/4h；
Heat distortion temperature: being tested according to ISO75 standard, test condition 0.45MPa；
Melt flow rate (MFR): being tested according to ISO1183 standard, and test condition is 220 DEG C/10kg；
Shear viscosity: being tested using Malvern monotubular capillary rheometer, is chosen draw ratio 16/1, diameter 0.5mm, is entered
The mouth mold that bicker is 180 °.240 DEG C of test temperature, 200~50000s-1 of range of shear rate of setting, the setting of raw material plastic phase
To be pressurized to 1MPa, 6min is then kept the temperature, preheats 4min again after repressurization to 1MPa.After set temperature is stablized, weigh
Sufficiently dry material about 35g, is separately added into barrel and compresses compacting, then start to test, record under each shear rate
Shear viscosity.Viscosity when wherein the shear viscosity 1 in table 2 is 200/s shear rate, and shear viscosity 2 is cut for 50000/s
Viscosity when cutting speed rate.
3 embodiment 5-11 performance test of table
It can be seen from the result of table 3 ABS resin composition of the invention have superelevation melt strength, ultrahigh rigidity and
The advantages of excellent low-temperature impact resistance.Using the resin combination, not only melt strength is high in blow-molding process, parison sagging
It is few；The rigidity and low-temperature flexibility of product are improved significantly simultaneously, have well solved blow molding ABS resin in the prior art
The problem of melt strength, rigidity existing for composition and low-temperature flexibility cannot balance.Pass through embodiment 7 and pair of embodiment 8-11
Than can be seen that in the case where other components content is constant, melt reinforcing agent selects acrylic acid esters co-polymer and acrylonitrile-
Styrene-t glycidyl ester copolymer compounding, prepared ABS resin properties increase, especially
It is that melt flow rate (MFR) and shear viscosity improvement are the most obvious.
In conclusion the present invention is specific by being added into the styrene resin composite comprising specific components specific quantity
Heat-resistant agent, the melt reinforcing agent, fluoropolymer additive of component specific quantity, and synergistic occurs with the component in resin combination
Effect, so solve in the prior art blow molding heat-resisting ABS resin blow molding, mechanical performance, product experiment etc.
Aspect there are the problem of；The present invention is prepared for that blow molding property is strong, the high heat resistance ABS resin of the high and low temperature excellent tenacity of mechanical rigid
Composition；The melt strength of resin combination of the invention is high, can be effectively improved the melt sagging of parison, this hair
Bright resin combination low-temperature flexibility is high, and -40 DEG C of cantilever beam unnotched impact strengths can satisfy auto parts and components up to constantly
The low-temp storage requirement of product, and the heat resistance of blow-molded article is high, can also meet the high temperature storage requirement of blow-molded article.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
Member, under the premise of not departing from the method for the present invention, can also make several improvement and supplement, these are improved and supplement also should be regarded as
Protection scope of the present invention.
Claims (6)
1. a kind of thermoplastic abs resin composition for the high rigidity of blow molding, high fondant-strength and low-temperature impact resistance,
It is characterized in that, the ABS resin composition is to be made from the following raw materials in parts by weight:
The fluoropolymer additive, the supported polymerisation of fluoropolymer and 70~30wt% comprising 30~70wt%
Object；The fluoropolymer be selected from polytetrafluoroethylene (PTFE), Kynoar, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethene/
Ethylene copolymer, tetrafluoroethylene/perfluoro alkyl ether copolymer, polyvinyl fluoride, chlorotrifluoroethylene/ethylene copolymer, poly- trifluoro chlorine
Ethylene；The carrier polymer is selected from polymethyl methacrylate, polystyrene, poly- alpha-alkyl phenylethylene, maleic anhydride modified
Styrenic polymer, Maleimide-modified styrenic polymer, styrene-N aryl maleimide copolymers,
Styrene/acrylonitrile copolymer, alpha-alkyl phenylethylene/acrylonitrile copolymer, styrene/alpha-alkyl phenylethylene/acrylonitrile compolymer
Object, styrene/acrylonitrile/methylmethacrylate copolymer, styrene/alpha-alkyl phenylethylene/acrylonitrile/methyl methacrylate
Ester copolymer and alpha-alkyl phenylethylene/acrylonitrile/methylmethacrylate copolymer；
The heat-proof modifier is N-phenylmaleimide-maleic anhydride-styrene terpolymer；
The melt reinforcing agent is acrylic acid esters co-polymer, the acrylonitrile-styrene-Glycidyl methacrylate of core-shell structure
One or more of mixtures of glycerol ester copolymer.
2. the thermoplastic ABS resin of high rigidity according to claim 1, high fondant-strength and low-temperature impact resistance combines
Object, which is characterized in that the weight average molecular weight of the acrylonitrile-butadiene-phenylethene grafted copolymer is 100,000~200,
000, relative density is 1.0~1.04, and average diameter range is 100~600nm, and butadiene rubber weight percent content is 40
~70wt%；The weight average molecular weight of the acrylonitritrile-styrene resin is 100,000~500,000, the weight hundred of acrylonitrile
Dividing than content is 15~40wt%.
3. the thermoplastic ABS resin of high rigidity according to claim 2, high fondant-strength and low-temperature impact resistance combines
Object, which is characterized in that the average diameter range of the acrylonitrile-butadiene-phenylethene grafted copolymer is 200~300nm, institute
The weight percent content for stating butadiene rubber is 45~55wt%；The weight average molecular weight of the acrylonitritrile-styrene resin
It is preferred that 200,000~400,000, the weight percentage of acrylonitrile preferably 25~35wt%.
4. the thermoplastic ABS resin of high rigidity according to claim 1, high fondant-strength and low-temperature impact resistance combines
Object, which is characterized in that the melt reinforcing agent is the acrylic acid esters co-polymer and acrylonitrile-styrene-methyl of core-shell structure
The compounding of glycidyl acrylate.
5. the thermoplastic ABS resin of high rigidity according to claim 1, high fondant-strength and low-temperature impact resistance combines
Object, which is characterized in that the processing aid includes one or more of mixtures of antioxidant, lubricant, release agent；It is described anti-
Oxygen agent is Hinered phenols antioxidant or phosphite ester antioxidant；The lubricant is that pentaerythritol stearate or ethylene are double hard
Resin acid amide；The release agent is silicone release agent.
6. the thermoplastic abs resin composition of any high rigidity of claim 1-5, high fondant-strength and low-temperature impact resistance
Preparation method, which is characterized in that the preparation method includes the following steps:
(1) raw material is weighed according to the ratio；
(2) raw material got ready in step (1) is premixed in super mixer；
(3) premix obtained in step (2) is sent into double screw extruder through metering device, conveying, shearing in screw rod
It is material melting, compound under mixing, then through extrusion, tie rod, cooling, pelletizing step, obtain high for the high rigidity of blow molding
Toughness high melt strength thermoplastic ABS resin composition；Wherein the screw slenderness ratio of double screw extruder is 36~44, and band
There are temperature control device and vacuum evacuation device；The extrusion temperature of the double screw extruder is screw speed between 180~250 DEG C
It is 200~500 revs/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610685304.5A CN106046589B (en) | 2016-08-18 | 2016-08-18 | A kind of thermoplastic abs resin composition for the high rigidity of blow molding, high fondant-strength and low-temperature impact resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610685304.5A CN106046589B (en) | 2016-08-18 | 2016-08-18 | A kind of thermoplastic abs resin composition for the high rigidity of blow molding, high fondant-strength and low-temperature impact resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106046589A CN106046589A (en) | 2016-10-26 |
| CN106046589B true CN106046589B (en) | 2019-08-02 |
Family
ID=57194731
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610685304.5A Active CN106046589B (en) | 2016-08-18 | 2016-08-18 | A kind of thermoplastic abs resin composition for the high rigidity of blow molding, high fondant-strength and low-temperature impact resistance |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106046589B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20210115244A1 (en) * | 2017-12-19 | 2021-04-22 | Ineos Styrolution Group Gmbh | Abs thermoplastic molding composition for blow molding |
| 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 |
| CN109135159B (en) * | 2018-08-09 | 2021-03-23 | 杭州师范大学 | Method for preparing ABS/PVDF alloy by utilizing in-situ self-assembly and product thereof |
| CN109762294B (en) * | 2018-12-30 | 2021-07-20 | 上海锦湖日丽塑料有限公司 | ABS composition suitable for laser welding and preparation method thereof |
| CN112226009A (en) * | 2020-09-09 | 2021-01-15 | 中广核俊尔（上海）新材料有限公司 | Blow molding ABS material with high melt strength and high toughness and preparation method thereof |
| CN112175388B (en) * | 2020-09-30 | 2023-08-18 | 上海金发科技发展有限公司 | Polyamide composition with high heat resistance and high melt strength |
| 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 |
| 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 |
| CN116218211B (en) * | 2023-04-24 | 2024-02-20 | 至正控股集团有限公司 | Photovoltaic panel frame resin and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5962587A (en) * | 1997-10-23 | 1999-10-05 | General Electric Company | High modulus thermoplastic resin composition |
| US6593404B1 (en) * | 1997-10-23 | 2003-07-15 | Cheil Industries, Inc. | Thermoplastic resin composition |
| CN101360786A (en) * | 2005-11-30 | 2009-02-04 | 通用电气公司 | Weatherable, high modulus polymer compositions and method |
| CN103333456A (en) * | 2013-07-19 | 2013-10-02 | 上海锦湖日丽塑料有限公司 | Heat-resisting ABS (Acrylonitrile Butadiene Styrene) resin with excellent blow-molded surface and preparation method of heat-resisting ABS resin |
| CN103483760A (en) * | 2013-08-21 | 2014-01-01 | 苏州润佳工程塑料股份有限公司 | Low-orientation extrusion-grade ABS (acrylonitrile-butadiene-styrene) material |
-
2016
- 2016-08-18 CN CN201610685304.5A patent/CN106046589B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5962587A (en) * | 1997-10-23 | 1999-10-05 | General Electric Company | High modulus thermoplastic resin composition |
| US6593404B1 (en) * | 1997-10-23 | 2003-07-15 | Cheil Industries, Inc. | Thermoplastic resin composition |
| CN101360786A (en) * | 2005-11-30 | 2009-02-04 | 通用电气公司 | Weatherable, high modulus polymer compositions and method |
| CN103333456A (en) * | 2013-07-19 | 2013-10-02 | 上海锦湖日丽塑料有限公司 | Heat-resisting ABS (Acrylonitrile Butadiene Styrene) resin with excellent blow-molded surface and preparation method of heat-resisting ABS resin |
| CN103483760A (en) * | 2013-08-21 | 2014-01-01 | 苏州润佳工程塑料股份有限公司 | Low-orientation extrusion-grade ABS (acrylonitrile-butadiene-styrene) material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106046589A (en) | 2016-10-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106046589B (en) | A kind of thermoplastic abs resin composition for the high rigidity of blow molding, high fondant-strength and low-temperature impact resistance | |
| CN106810809B (en) | Ultralow gloss, super low-temperature resistant ASA resin composition and preparation method thereof | |
| CN107082977A (en) | A kind of high-impact high fluidity PVC injected plastics materials formula and preparation method thereof | |
| JP6364490B2 (en) | High heat resistant ABS resin composition suitable for blow molding and method for preparing the same | |
| CN102391628B (en) | Polylactic acid/ polyamide 11 alloy material | |
| CN103333456A (en) | Heat-resisting ABS (Acrylonitrile Butadiene Styrene) resin with excellent blow-molded surface and preparation method of heat-resisting ABS resin | |
| CN114213794B (en) | Heat-resistant dimensionally stable styrene-based alloy composition and preparation method thereof | |
| CN103436012B (en) | Ultrahigh-molecular weight polyethylene modified nylon 66 and preparation method thereof | |
| Bagotia et al. | Excellent impact strength of ethylene-methyl acrylate copolymer toughened polycarbonate | |
| CN102153830B (en) | ACS (acrylonitrile-chlorinated polyethylene-styrene) resin composition and method for preparing same | |
| CN110734623A (en) | scratch-resistant ABS (acrylonitrile butadiene styrene) material and preparation method thereof | |
| CN106700253B (en) | A kind of low-contraction low-density PP material and preparation method thereof | |
| CN112063147A (en) | Two-dimensional organic metal framework MOF modified PC material | |
| CN106349675B (en) | A kind of hydrolysis, low temperature resistant PC/ABS composite material and preparation method thereof | |
| CN107815054A (en) | A kind of PA composites and preparation method thereof with low water absorption, strong thermal conductivity | |
| CN107964173A (en) | A kind of EPDM sulfuration thermoplastic elastomers of ultra-low-smell and preparation method thereof | |
| CN106810840A (en) | A kind of new low stress PC compositions | |
| CN105820496A (en) | Graphene/ glass fiber reinforced ABS composite and preparation method thereof | |
| CN112480646B (en) | Kaolin reinforced polyphenyl ether composition and preparation method and application thereof | |
| CN115703904A (en) | High-heat-resistance polyethylene pipe composition and preparation method thereof | |
| CN108610531A (en) | Polyvinyl piping materials composite assistant packet and preparation method thereof | |
| RU2674019C1 (en) | Extruded antifriction composite on basis of super-high-molecular polyethylene and method of its obtaining | |
| CN112646306A (en) | Weather-resistant antistatic ASA composite material and preparation method thereof | |
| CN114149636B (en) | Fatigue-resistant glass fiber reinforced polypropylene composite material and preparation method thereof | |
| CN104974419A (en) | Foamed polypropylene pre-mixed material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |