CN103613877B - High heat-proof ABS resin composition suitable for blow molding and preparation method thereof - Google Patents
High heat-proof ABS resin composition suitable for blow molding and preparation method thereof Download PDFInfo
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- CN103613877B CN103613877B CN201310590377.2A CN201310590377A CN103613877B CN 103613877 B CN103613877 B CN 103613877B CN 201310590377 A CN201310590377 A CN 201310590377A CN 103613877 B CN103613877 B CN 103613877B
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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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- 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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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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
- C08L25/16—Homopolymers or copolymers of alkyl-substituted styrenes
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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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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Abstract
The present invention relates to a kind of suitable for high heat-proof ABS resin composition of blow molding and preparation method thereof；Styrene resin composite A of the composition comprising 100 parts by weight and 20~40 parts by weight heat-resistant agent B；The heat-resistant agent B is N phenyl maleimide α-methylstyrene acrylonitrile styrene quadripolymers；The preparation method of the ABS resin composition comprises the following steps：Each component is weighed according to parts by weight；Each component is sufficiently mixed in high-speed mixer, mixture is obtained；Mixture is entered from the main feeding of double screw extruder, by melting extrusion, cooling, drying, pelletizing, the ABS resin composition is produced.Blow-molded article prepared by the present invention has good surface quality and heat resistance, vicat softening temperature is up to more than 110 DEG C, the heat resistant requirements and more harsh use environment of auto parts and components spray painting after-processing technology can be met, and the impact resistance of blow-molded article is good.
Description
Technical field
The invention belongs to technical field of macromolecules, and in particular to a kind of high heat-resisting ABS resin suitable for blow molding is combined
Thing and preparation method thereof.
Background technology
ABS resin has excellent combination property, can be applied to be molded, extrude, vacuum, a variety of shapings such as blowing and roll-in
Method.In blow-moulding process, when polymer is by narrow and small mouth mold, due to by high shear, the type of extrusion
Sag phenomenon can be presented in base under Gravitative Loads, and excessive vertical contracting can cause the wall unevenness of product even, even can not when serious
Shaping.Therefore, when selection is adapted to the polymer of blowing, it is necessary to understand fully the viscous-elastic behaviour of its shearing.Suitable for blow molding
ABS resin is in addition to high fondant-strength, it is desirable to which the sensitiveness of its melt viscosity is small to shear rate, i.e. melt viscosity is with cutting
The change of cutting speed rate is small.
The ABS resin of blow molding is widely used in automobile large-scale product, such as flow spoiler, the seat back of the body, bumper system
Product.For manufacturing the ABS resins of auto parts and components except that must have good physical and mechanical properties (especially impact property),
There must also be high-fire resistance energy, to meet the after-processing technology requirements such as spray painting and more harsh use environment.Such as, meet
The vicat softening temperature requirement of the high heat-resisting extrusion-grade ABS product of Ford WSK-M4D906-A1/A2 standards is more than 105 DEG C；Cause
This, it is desirable to suitable for auto parts and components blow molding ABS resin except with good blowing property, it is necessary to simultaneously improve
The heat resistance and impact property of resin, and heat resistance and the surface quality of impact resistance and product are contradiction；Existing skill
In art, achievable vicat softening temperature reaches more than 105 DEG C, but the surface quality of product and impact resistance can become very
Difference.
The heat-proof modifier for being presently used for ABS resin is mainly based upon the copolymer of maleimide and based on alpha-alkyl
The copolymer of styrene.Due to the limitation of synthetic method, be used alone this two classes heat-resistant agent be used for prepare be blow molded ABS resin all
In the presence of more or less deficiency：(1) patent CN101250314 and CN103013025A, which are disclosed, uses N- benzyl maleimides
The terpolymer of amine (PMI) and maleic anhydride (MAH), styrene (St) is prepared for suitable for the resistance to of blow molding as heat-resistant agent
Hot ABS resin composition.It must be noted that in order to improve the heat resistance of resin, based on the heat-resisting of maleimide copolymer
It is (general that agent contains a large amount of maleimide amine components>40 parts by weight), the glass transition temperature of heat-resistant agent is very high,
The glass transition temperature for the PMI-St-MAH copolymers that CN101250314 is selected is up to 160-210 DEG C, and during ABS blow moldings
Processing temperature is general at 180-210 DEG C.Therefore, it is very easy to cause Plastic bad, the defect such as product surface finish difference increases
The cost of follow-up sand milling is added；Secondly, the labile maleic anhydride component of heat/chance water electrode is introduced simultaneously in heat-resistant agent, caused
Make the heat endurance of resin tends to be unstable with the increase of MAH contents；3rd, seriously undermined due to introducing a large amount of NPMI components
The shock resistance of ABS resin, CN103013025A patents have compounded rubber powder simultaneously, for toughness reinforcing, further increased
Material cost；4th, when the copolymer based on maleimide has high maleimide content, due at a relatively high melt
Viscosity, is generally prepared using solution polymerization process, and manufacturing cost is very high, therefore, the heat-resistant agent based on maleimide copolymer
Price all costly；(2) the heat resistance modified limited extent of the heat-resistant agent of the copolymer based on alpha-alkyl phenylethylene.Meanwhile,
The copolymer for preparing alpha-alkyl phenylethylene generally utilizes free-radical emulsion polymerization, and building-up process is difficult that low molecule amount breast is completely eliminated
The impurity that other additives such as agent, flocculating agent are brought to product, the VOC content of product is higher, and blow-molding process resin is easily produced
Raw decomposition gas, influence product surface outward appearance and follow-up spray painting yield.In addition, also having engineering plastics of resistance to thermal level such as ABS and PC
Expect blending and modifying, ABS heat resistances and shock resistance can be improved simultaneously, but shortcoming is to reduce being blow molded for ABS resin
Property, and easily hydrolysis causes product unstable to PC.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of high heat-proof ABS tree suitable for blow molding
Oil/fat composition and preparation method thereof.The method of the present invention is prepared suitable by the heat-resistant agent and high glue powder of compounding use special ratios
In the high heat-resisting ABS resin of blow molding, with solve to prepare in the prior art blow molding with during the ABS resin of resistance to thermal level into
The deficiency caused in terms of sheet, shaping, surface quality, heat resistance/impact property and product post-processing.
The present invention is realized by following technical scheme, the present invention relates to a kind of suitable for the high heat-resisting of blow molding
ABS resin composition and preparation method thereof：
In a first aspect, the present invention relates to a kind of high heat-proof ABS resin composition suitable for blow molding, the composition bag
Contain：The styrene resin composite A of the 100 parts by weight and heat-resistant agent B of 20~40 parts by weight；
(a) component and part of the styrene resin composite A is as follows, based on 100 parts by weight：
The parts by weight of graft copolymer A-1 10~40；
The parts by weight of graft copolymer A-2 0~30；
The parts by weight of copolymer A -3 55~80；
(b) preparation method of the graft copolymer A-1 comprises the following steps：Based on 100 parts by weight, in 10~70 weight
Part rubber polymer in the presence of, prepared by being polymerize by the monomer mixture of 90~30 parts by weight graft copolymer；
Wherein, the component and part of the monomer mixture is as follows, based on 100 parts by weight：35~75 parts by weight
α-methylstyrene, the styrene of 5~45 parts by weight, the acrylonitrile component of 10~25 parts by weight；
(c) preparation method of the graft copolymer A-2 comprises the following steps：Based on 100 parts by weight, in 10~70 weight
Part rubber polymer in the presence of, prepared by being polymerize by the monomer mixture of 90~30 parts by weight graft copolymer；
Wherein, the component and part of the monomer mixture is as follows, based on 100 parts by weight：10~30 parts by weight
The styrenic component of acrylonitrile and 70~90 parts by weight；
(d) preparation method of the copolymer A -3 comprises the following steps：Prepared by being polymerize by monomer mixture copolymerization
Thing；Wherein, the component and part of the monomer mixture is as follows, based on 100 parts by weight：The acrylonitrile of 18~48 parts by weight
The styrene monomer of monomer and 52~82 parts by weight.
Preferably, heat-resisting component α in heat-resistant agent B and graft copolymer A-1 compound proportion and graft copolymer A-1-
The parts by weight of methyl styrene can be adjustable according to the specific heat resistant requirements of product；Preferably, heat-resisting component in graft copolymer A-1
α-methylstyrene component selects 50~75 parts by weight, now, and high heat-proof ABS resin composition includes the graft copolymer A-
120~40 parts by weight, the parts by weight of heat-resistant agent B20~35；It thereby may be ensured that and production is taken into account while product has excellent heat resistance
The surface quality and impact property of product.
Preferably, the rubber polymer that the graft copolymer A-1 and graft copolymer A-2 are used in preparing is poly-
One or more of mixing in butadiene rubber, butadiene-styrene rubber, ACM, nitrile rubber.
Preferably, the gel content of the graft copolymer A-1 and graft copolymer A-2 are all higher than being equal to 85%.
Preferably, the gel content of the graft copolymer A-1 and graft copolymer A-2 are all higher than being equal to 90%.
Preferably, the rubber size of the graft copolymer A-1 and graft copolymer A-2, which are respectively less than, is equal to 400nm.
Preferably, the rubber size of the graft copolymer A-1 and graft copolymer A-2, which are respectively less than, is equal to 300nm.
Preferably, the molecular weight of the copolymer A -3 is 100,000~300,000.
Preferably, the molecular weight of the copolymer A -3 is 180,000~300,000.
Preferably, the heat-resistant agent B is common for N-phenylmaleimide-α-methylstyrene-acrylonitrile-styrene quaternary
Polymers, is synthesized using continuous bulk polymerization method.
Preferably, the component and part of the heat-resistant agent B is as follows, based on 100 parts by weight, wherein, N- phenyl Malaysia
The parts by weight of acid imide component 20~30, the parts by weight of α-methylstyrene component 30~50, the parts by weight of styrenic component 10~40, third
The parts by weight of alkene nitrile component 20~40.
Preferably, the glass transition temperature of the heat-resistant agent B is 140~160 DEG C.
It is further preferred that in the heat-resistant agent B, the content of each monomer can be adjusted according to specific heat resistant requirements
It is whole, it is preferable that N-phenylmaleimide component in 20~30 parts by weight, α-methylstyrene component in 35~45 parts by weight,
Styrenic component is in 10~40 parts by weight, and acrylonitrile component is in 20~40 parts by weight；And then, the glass transition of the heat-resistant agent
Temperature is preferably 145~155 DEG C.
As needed, composition of the invention can also add conventional filler or processing aid；As a preferred embodiment, described
ABS resin composition also includes each component of following parts by weight：The polyene of the talcum of 0.1~5 parts by weight, 0.1~5 parts by weight
The antioxidant of hydrocarbon wax, 0.1~1 parts by weight.
Second aspect, the invention further relates to the preparation method of the foregoing high heat-proof ABS resin composition suitable for blow molding,
Comprise the following steps：
Step 1, each component is weighed according to parts by weight；
Step 2, each component is sufficiently mixed in high-speed mixer, obtains mixture；
Step 3, mixture is entered from the main feeding of double screw extruder, by melting extrusion, cooling, drying, pelletizing,
Produce the ABS resin composition.
Preferably, the screw slenderness ratio of described double screw extruder is 30~70, and machine barrel must be provided with true at least two
Empty exhaust device, screw rod material machine barrel feed zone temperature is 180~210 DEG C, fluxing zone temperature is 230~250 DEG C, homogenizing zone temperature
For 220~240 DEG C, screw speed is 200~500rpm.
The present invention compared with the existing technology, with advantages below and beneficial effect：
(1) present invention is closed by adding ad hoc approach into the styrene resin composite comprising specific components specified quantitative
Into the heat-resistant agent with specific components specified quantitative, and acted synergistically with the component in resin combination, and then solve
In the prior art blow molding with the ABS resin of resistance to thermal level in terms of cost, shaping, surface quality, heat resistance/impact property
The problem of existing；
(2) present invention is prepared for blowing property and the high heat-proof ABS resin composition of all good blow molding of heat resistance, blows
Modeling product has good surface quality and impact resistance；
(3) melt strength of resin combination of the invention is high and melt viscosity is small to the sensitiveness of shear rate, can be with
Reduce the melt sagging of parison, and the surface quality of blow-molded article is good；
(4) the heat-resisting height of resin combination of the invention, vicat softening temperature can meet automobile zero up to more than 110 DEG C
The heat resistant requirements and more harsh use environment of part spray painting after-processing technology, and the impact resistance of blow-molded article is good.
Corresponding principle to the present invention is analyzed as follows, and what heat-resistant agent B was selected is N-phenylmaleimide-Alpha-Methyl
Styrene-acrylonitrile-styrene quadripolymer, is synthesized using continuous bulk polymerization method；Have using continuous bulk polymerization process
It is prepared by high yield and low cost beneficial to polymerizate；Do not reported in the prior art is used to be blow molded into using such heat-resistant agent
The preparation of the type ABS resin of resistance to thermal level composition；
In order to avoid the problem of bulk polymerisation process melt viscosity is too high causes implode, while realizing the height of quadripolymer
The comprehensive expression of of stability and heat resistance, processing characteristics and blending property is warmed, the ratio of four kinds of components of polymerization process will be controlled rationally
System, therefore, the component of each monomer is by special selection, specially N- substituted maleimides amine in heat-resistant agent B in the present invention
Component is in 20~30 parts by weight, and α-methylstyrene component is in 30~50 parts by weight, and styrenic component is in 10~40 parts by weight, third
Alkene nitrile component is in 20~40 parts by weight so that the glass transition temperature of quadripolymer is controlled at 140~160 DEG C：
Glass transition temperature relatively low heat-resistant agent B in the present invention so that it can be highly suitable to be applied for processing temperature
The blow molding ABS resin of relatively low (being specially 190~210 DEG C), while also determining its raising heat-resisting to ABS resin
The finiteness of amplitude；Therefore, want to realize invention effect of the invention, it is necessary to by the heat-resistant agent B and graft copolymer A-1
Compounding use, plays its synergy；
In the present invention, the α-methylstyrene component being grafted in used graft copolymer A-1 significantly improves grafting
The heat resistance of copolymer, so that in heat-resistant agent B prepared by continuous bulk polymerization process, in order to solve relatively low Malaysia acyl
Imines content causes the problem of heat resistance reduction is caused, except by introducing appropriate α-methylstyrene simultaneously in quadripolymer
Component is outer to make up, and selects the graft copolymer A-1 that heat resistance is improved to be compounded with heat-resistant agent B also in ABS resin preparation process
Using further improving the heat resistance of ABS resin；However, the content of the α-methylstyrene in graft copolymer A-1 is necessary
In right amount, in order that the vicat softening temperature for obtaining ABS resin composition of the invention reaches 110 DEG C, the graft copolymer A-1
In, α-methylstyrene component must be controlled in 35~75 parts by weight；
To improve graft copolymer A-1 and graft copolymer A- in ABS resin melt strength and blowing property, the present invention
2 gel content need to reach more than 85%, preferably more than 90%；Meanwhile, rubber size size is in below 400nm, preferably
Below 300nm；Rubber gels content is too low or rubber size is excessive, is all unfavorable for improving the melt strength of ABS resin, and is blowing
Mould in ABS, high fondant-strength is the necessary condition for preventing parison sagging.
Copolymer A -3 is the SAN with HMW, molecular weight control 100,000~
300,000, preferably 180,000~300,000.Compounding use HMW SAN is also the important of raising ABS resin melt strength
Approach.But SAN molecular weight is too high, also easily cause the phase that ABS resin plasticizing is bad and it is with rubber-type graft polymers
Capacitive problem.
Embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that to the ordinary skill of this area
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
Embodiment 1~5
(1) in all embodiments and comparative example, the raw material used for：
Graft copolymer A-1a is polybutadiene rubber graft phenylethene-acrylonitrile-α-methylstyrenecopolymer, gel
Content is 85%, rubber size about 150nm；
The preparation method of the graft copolymer A-1a comprises the following steps：Exist in the polybutadiene rubber of 45 parts by weight
Under, prepared by being polymerize by the monomer mixture of 55 parts by weight graft copolymer；
Wherein, the component and part that the monomer mixture is included is as follows, based on 100 parts by weight：60 parts by weight
α-methylstyrene, the styrene of 16 parts by weight, the acrylonitrile component of 24 parts by weight；
Graft copolymer A-1b is polybutadiene rubber graft phenylethene-acrylonitrile-α-methylstyrenecopolymer, gel
Content is 90%, rubber size about 200nm；
The preparation method of the graft copolymer A-1b comprises the following steps：Exist in the polybutadiene rubber of 50 parts by weight
Under, prepared by being polymerize by the monomer mixture of 50 parts by weight graft copolymer；
Wherein, the component and part that the monomer mixture is included is as follows, based on 100 parts by weight：70 parts by weight
α-methylstyrene, the styrene of 20 parts by weight, the acrylonitrile component of 10 parts by weight；
Graft copolymer A-1c is polybutadiene rubber graft phenylethene-acrylonitrile-α-methylstyrenecopolymer, gel
Content is 93%, rubber size about 250nm；
The preparation method of the graft copolymer A-1c comprises the following steps：Exist in the polybutadiene rubber of 50 parts by weight
Under, prepared by being polymerize by the monomer mixture of 50 parts by weight graft copolymer；
Wherein, the component and part that the monomer mixture is included is as follows, based on 100 parts by weight：50 parts by weight
α-methylstyrene, the styrene of 35 parts by weight, the acrylonitrile component of 15 parts by weight；
Graft copolymer A-2a is polybutadiene rubber graft phenylethene-acrylonitrile copolymer, and gel content is 85%, rubber
Micelle footpath about 300nm；
The preparation method of the graft copolymer A-2a comprises the following steps：Exist in the polybutadiene rubber of 50 parts by weight
Under, prepared by being polymerize by the monomer mixture of 50 parts by weight graft copolymer；
Wherein, the component and part of the monomer mixture is as follows, based on 100 parts by weight：The benzene second of 76 parts by weight
The acrylonitrile component of olefinic constituent and 24 parts by weight；
Graft copolymer A-2b is polybutadiene rubber graft phenylethene-acrylonitrile copolymer, and gel content is 92%, rubber
Micelle footpath about 300nm；
The preparation method of the graft copolymer A-2b comprises the following steps：Exist in the polybutadiene rubber of 60 parts by weight
Under, prepared by being polymerize by the monomer mixture of 40 parts by weight graft copolymer；
Wherein, the component and part of the monomer mixture is as follows, based on 100 parts by weight：The benzene second of 70 parts by weight
The acrylonitrile component of olefinic constituent and 30 parts by weight；
Copolymer A -3a is SAN, and AN ingredients weight parts are 26%, and molecular weight is 210,000.
Copolymer A -3b is SAN, and AN ingredients weight parts are 32%, and molecular weight is 250,000.
Heat-resistant agent B-1a is N-phenylmaleimide-α-methylstyrene-acrylonitrile-benzene second that continuous bulk is synthesized
Alkene quadripolymer；Based on 100 parts by weight, wherein N-phenylmaleimide ingredients weight parts are 20 parts by weight, Alpha-Methyl benzene
Ethylene component parts by weight are 40 parts by weight, the parts by weight of styrenic component 18, the parts by weight of acrylonitrile component 22；Glass transition temperature
For 145 DEG C.
Heat-resistant agent B-1b is N-phenylmaleimide-α-methylstyrene-acrylonitrile-benzene second that continuous bulk is synthesized
Alkene quadripolymer；Based on 100 parts by weight, wherein N-phenylmaleimide ingredients weight parts are 30 parts by weight, Alpha-Methyl benzene
Ethylene component parts by weight are 30 parts by weight, the parts by weight of styrenic component 25, the parts by weight of acrylonitrile component 15；Glass transition temperature
For 155 DEG C.
Talcum powder C mesh number is 2500~5000 mesh.
TPO wax D is commercially available Tissuemat E.
Antioxidant E is the mixture of commercially available be obstructed single phenol, bis-phenol or polyphenolic substance and phosphite ester compound.
Each component is taken according to the parts by weight shown in table 1, adopts prepare the ABS resin composition with the following method afterwards：
Step 1, each component is weighed according to parts by weight；
Step 2, each component is sufficiently mixed 20min in high-speed mixer, obtains mixture；
Step 3, mixture is entered from the main feeding of double screw extruder, by melting extrusion, cooling, drying, pelletizing,
Produce the ABS resin composition；The screw diameter of double screw extruder is 35mm, and draw ratio is 44.Extruder is from charge door
10 temperature controlled regions are had to mouth mold, wherein the 1st~3 area (feed zone) temperature control is 180~210 DEG C；4th~7 area's (fluxing zone) temperature
Control as 230~250 DEG C；8th~10 area (homogenizing zone) temperature control is 220~240 DEG C；Two of extruder vacuumize position and set respectively
The the 4th and the 9th area is placed in, vacuum is 0.06~0.094MPa, and screw speed is set to 300~500rpm.
(2) comparative example 1
The characteristics of in order to preferably embody above-mentioned heat-proof ABS resin composition for blow molding, herein using contrast
Example 1.In the comparative example into, heat-resistant agent (B) component is changed to N-phenylmaleimide-styrene-Malaysia of solwution method synthesis
Acid anhydrides terpolymer (B1), N-phenylmaleimide component weight percent content is 55%, and the vitrifying of copolymer turns
Temperature is 196 DEG C.Raw material weight ratio is shown in Table 1, preparation method be the same as Example 1.
(3) comparative example 2
The characteristics of in order to preferably embody above-mentioned heat-proof ABS resin composition for blow molding, herein using contrast
Example 2.In the comparative example, heat-resistant agent (B) component is changed into phenylethylene-maleic anhydride bipolymer (B2), maleic anhydride group
The weight percent content divided is 23%, and the glass transition temperature of copolymer is 150 DEG C.Raw material weight ratio is shown in Table 1, preparation
Method be the same as Example 1.
(4) comparative example 3
The characteristics of in order to preferably embody above-mentioned heat-proof ABS resin composition for blow molding, herein using contrast
Example 2.In the comparative example, heat-resistant agent (B-1c) N-phenylmaleimide-α-methylstyrene-acrylonitrile-styrene quaternary
Copolymer；Based on 100 parts by weight, wherein N-phenylmaleimide ingredients weight parts are 40 parts by weight, α-methylstyrene group
It is 20 parts by weight, the parts by weight of styrenic component 30, the parts by weight of acrylonitrile component 10 to divide parts by weight；Glass transition temperature is 165
℃.Raw material weight ratio is shown in Table 1, preparation method be the same as Example 1.
(5) comparative example 4
The characteristics of in order to preferably embody above-mentioned heat-proof ABS resin composition for blow molding, herein using contrast
Example 2.In the comparative example, heat-resistant agent (B) component is changed into α-methylstyrene-acrylonitrile copolymer (B3), ingredients weight parts
α-methylstyrene is 70 parts by weight, the parts by weight of acrylonitrile component 30；Glass transition temperature is 135 DEG C.Raw material weight ratio
It is shown in Table 1, preparation method be the same as Example 1.
(6) comparative example 5
The characteristics of in order to preferably embody above-mentioned heat-proof ABS resin composition for blow molding, herein using contrast
Example 2.In the comparative example, graft copolymer A-1 is that polybutadiene rubber graft phenylethene-acrylonitrile-α-methylstyrene is common
Polymers (A-1d), gel content is 80%, rubber size about 350nm；
The preparation method of the graft copolymer A-1d comprises the following steps：Exist in the polybutadiene rubber of 45 parts by weight
Under, prepared by being polymerize by the monomer mixture of 55 parts by weight graft copolymer；
Wherein, the component and part that the monomer mixture is included is as follows, based on 100 parts by weight：60 parts by weight
α-methylstyrene, the styrene of 16 parts by weight, the acrylonitrile component of 24 parts by weight；Raw material weight ratio is shown in Table 1, preparation method
Be the same as Example 1.
(7) comparative example 6
The characteristics of in order to preferably embody above-mentioned heat-proof ABS resin composition for blow molding, herein using contrast
Example 2.In the comparative example, graft copolymer A-2 is polybutadiene rubber graft phenylethene-acrylonitrile copolymer (A-2c), is coagulated
Glue content is 75%, rubber size about 250nm；
The preparation method of the graft copolymer A-2c comprises the following steps：Exist in the polybutadiene rubber of 50 parts by weight
Under, prepared by being polymerize by the monomer mixture of 50 parts by weight graft copolymer；
Wherein, the component and part of the monomer mixture is as follows, based on 100 parts by weight：The benzene second of 76 parts by weight
The acrylonitrile component of olefinic constituent and 24 parts by weight；Raw material weight ratio is shown in Table 1, preparation method be the same as Example 1.
It is as shown in table 1 below, have 6 formulas and carry out melting extrusion according to above-mentioned preparation method, draw grain cooling, granulation to prepare
ABS resin composition, by material in 80 DEG C of dry 12h, it is ensured that the water absorption rate of resin before injection<0.05%, then marked according to ISO
Standard, batten is molded under same injecting condition, tests the physical property of each resin combination.Wherein, marked based on ISO179
Standard determines the simply supported beam notch impact strength of batten；Vicat softening temperature (VST) based on ISO306 standard test battens, load
For 5kg, heating rate is 50 DEG C/h.
Rheology testing：Using Malvern monotubular capillary rheometer, choose draw ratio be 16/1, a diameter of 0.5mm,
Inlet angle is 180 ° of mouth mold.240 DEG C of test temperature is set, range of shear rate 200-50000s-1, raw material plastic phase is set
It is set to and is pressurized to 1Mpa and then preheats 4min again after being incubated 6min, repressurization to 1Mpa.After design temperature is stable, weigh
Fully dry material about 35g, adds in charging basket and compresses compacting by several times, then starts test, records under each shear rate
Shear viscosity.Viscosity when shear viscosity 1 wherein in table 1 is 200s-1 shear rates, and shear viscosity 2 is 50000s-1
Viscosity during shear rate.
Blow-molded article surface quality：The circle that a diameter of 100mm, length are 500mm and thickness is 5mm is prepared using blow moulding machine
Cylindricality blow-molded article.Blowing conditions are that parison temperature is 240 DEG C, screw speed 50rpm, and mold temperature is 70 DEG C.By visual observation
The surface appearance of above-mentioned whole cylindrical blow-molded article is observed, the uneven position to surface is that (count pit size is pit
0.02mm or bigger) quantity counted.Evaluated based on following standard：
○：The quantity of pit is less than 10；
△：The quantity of pit is not less than 10 but less than 20；
◇：The quantity of pit is not less than 20；
Evaluation result is：Pit quantity is small, shows product surface excellent performance.
Table 1
The blow molding prepared according to the present invention is can be seen that from the experimental result of embodiment 1~4 to be combined with ABS resin
Thing, with excellent blowing property and high-fire resistance, and blow-molded article has good surface quality and impact resistance.Pass through
Compounding use graft copolymer (A-1) and heat-resistant agent (B), can be up to the vicat softening temperature of the ABS resin composition of preparation
More than 110 DEG C, the heat resistant requirements and more harsh use environment of auto parts and components spray painting after-processing technology can be met completely；
Moreover, the initial melt viscosity of resin combination prepared by the present invention is low, melt viscosity is small to the sensitiveness of shear rate, can be with
Melt is sagging caused by reducing parison due to causing melt viscosity decline by high shear force during narrow extrusion neck ring mold
Phenomenon.
It is prepared by comparative example 1, the heat-resistant agent R1 based on high content N-phenylmaleimide component prepared using solwution method
Resin combination, heat-resisting raising clearly, but be due to heat-resistant agent glass transition temperature it is very high, composition it is initial
Melt viscosity is very big, easily cause plasticizing it is bad, have a strong impact on the surface quality of product；Melt shear viscosity is with shear rate
Change is big, easily causes parison sagging；And Charpy impact properties are decreased obviously.
Similarly, comparative example 3, heat-resistant agent N-phenylmaleimide-α-methylstyrene-acrylonitrile-styrene quaternary
When N-phenylmaleimide content in copolymer reaches 40 parts by weight, blow-molded article shows that quality is affected significantly.
Comparative example 2, the resin combination prepared by the use of styrene-maleic anhydride copolymer (B2) as heat-resistant agent is heat-resisting
Improve very limited, vicat softening temperature is low；The heat endurance for being additionally, since maleic anhydride component is poor, and blow-molded article into
The type cycle is long, and heat endurance poor SMA easily causes product surface quality not good.
Comparative example 4, resin combination is prepared using into α-methylstyrene-acrylonitrile copolymer (B3) as heat-resistant agent
When, heat-resisting raising is also very limited, and vicat softening temperature is low, does not reach use requirement.
Comparative example 5,6, when being respectively 80%, 75% A-1 and A-2 graft copolymers using gel content, the thing of resin
Rationality can be reasonable with surface pit.It will be appreciated, however, that product of the resin combination of its preparation in blow molding
Thickness distribution is uneven.
Embodiment 6~9
(1) in embodiment 6~9, the raw material used for：The styrene resin composite A and 20 weight of 100 parts by weight
The heat-resistant agent B of part；
The component and part of the styrene resin composite A is as follows, based on 100 parts by weight：
The parts by weight of graft copolymer A-1c 30；
The parts by weight of graft copolymer A-2b 10；
The parts by weight of copolymer A -3a 60；
Wherein, graft copolymer A-1c is polybutadiene rubber graft phenylethene-acrylonitrile-α-methylstyrene copolymerization
Thing, the proportioning (parts by weight) of each monomer is as shown in table 2；
Graft copolymer A-2b is polybutadiene rubber graft phenylethene-acrylonitrile copolymer, the proportioning (weight of each monomer
Part) as shown in table 2；
Copolymer A -3a is SAN, and the proportioning (parts by weight) of each monomer is as shown in table 2；
Heat-resistant agent is N-phenylmaleimide-α-methylstyrene-acrylonitrile-benzene that B-1a is continuous bulk synthesis
Ethene quadripolymer, the proportioning (parts by weight) of each monomer is as shown in table 2；
The mesh number of talcum powder (C) is 2500~5000 mesh, 1 parts by weight；
TPO wax (D) is commercially available Tissuemat E, 1 parts by weight；
Antioxidant (E) is the mixture of commercially available be obstructed single phenol, bis-phenol or polyphenolic substance and phosphite ester compound,
1 parts by weight.
The preparation method and the equal be the same as Example 1 of method for testing performance of corresponding resin combination.
Table 2
In heat-resistant agent B prepared by continuous bulk polymerization process, cause heat-resisting to solve relatively low maleimide content
Property reduction the problem of cause, introduce appropriate α-methylstyrene component simultaneously in by quadripolymer making up in addition to, and also
The graft copolymer A-1 for selecting heat resistance to improve in ABS resin preparation process is further improved with heat-resistant agent B compounding uses
The heat resistance of ABS resin.
In addition, the content of the α-methylstyrene in graft copolymer A-1 must be appropriate, in order that obtaining ABS of the invention
The vicat softening temperature of resin combination reaches 110 DEG C, and blow-molded article has excellent surface quality, the graft copolymer
In A-1, α-methylstyrene component must be controlled in 35~75 parts by weight；Further on the basis of embodiment 6, other are kept
Part is constant, only adjusts each component proportion relation of monomer mixture in graft copolymer A-1, and α-methylstyrene is adjusted respectively
Parts by weight are 25 and 80 parts by weight, and its result is as shown in table 3.It can be seen that, in graft copolymer A-1, α-methylstyrene<35 weights
Part is measured, then the vicat softening temperature of ABS resin composition is difficult to reach 110 DEG C；And work as α-methylstyrene>75 parts by weight, then
ABS resin composition is heat-resisting preferable accordingly, but the surface quality of corresponding blow-molded article is poor.
Table 3
Above in the description of embodiment, the rubber in rubber-type graft copolymer A-1 and A-2 only lists polybutadiene
Rubber, other a few class rubber：Butadiene-styrene rubber, ACM, nitrile rubber are also applied for the present invention, and different rubber can
Bring other different effects：Butadiene-styrene rubber can improve the mobility of resin combination；ACM can improve tree
The weatherability of oil/fat composition；Nitrile rubber can improve the oil resistivity of resin combination.
In summary, the present invention is specific by being added into the styrene resin composite comprising specific components specified quantitative
The heat-resistant agent with specific components specified quantitative of method synthesis, and acted synergistically with the component in resin combination, and then
Solve blow molding in the prior art with the ABS resin of resistance to thermal level cost, shaping, surface quality, thickness distribution heat resistance/
The problem of existing in terms of impact property；The present invention is prepared for blowing property and all good blow molding of heat resistance is heat-resisting with height
ABS resin composition, blow-molded article has good surface quality and impact resistance；The melt of the resin combination of the present invention
Intensity is high and melt viscosity is small to the sensitiveness of shear rate, can reduce the melt sagging of parison, and blowing system
The surface quality of product is good；The heat-resisting height of the resin combination of the present invention, vicat softening temperature can meet vapour up to more than 110 DEG C
The heat resistant requirements and more harsh use environment of car parts spray painting after-processing technology, and the impact resistance of blow-molded article
It is good.
It is only the detailed description carried out to presently preferred embodiments of the present invention and comparative example above, but the present invention is not limited
In above example and comparative example.It should be understood that in the case of the spirit and scope of claims hereof are not departed from,
The various modifications that those skilled in the art makes, still fall within the scope of the present invention.
Claims (9)
1. a kind of high heat-proof ABS resin composition suitable for blow molding, it is characterised in that the composition is included：100 weight
The styrene resin composite A of part and heat-resistant agent B of 20~40 parts by weight；
(a) component and part of the styrene resin composite A is as follows, based on 100 parts by weight：
The parts by weight of graft copolymer A-1 10~40；
The parts by weight of graft copolymer A-2 0~30；
The parts by weight of copolymer A -3 55~80；
(b) preparation method of the graft copolymer A-1 comprises the following steps：Based on 100 parts by weight, in 10~70 parts by weight
In the presence of rubber polymer, prepared by being polymerize by the monomer mixture of 90~30 parts by weight graft copolymer；Wherein, institute
The component and part for stating monomer mixture is as follows, based on 100 parts by weight：The α-methylstyrene of 35~75 parts by weight, 5~
The acrylonitrile component of the styrene of 45 parts by weight, 10~25 parts by weight；
(c) preparation method of the graft copolymer A-2 comprises the following steps：Based on 100 parts by weight, in 10~70 parts by weight
In the presence of rubber polymer, prepared by being polymerize by the monomer mixture of 90~30 parts by weight graft copolymer；Wherein, institute
The component and part for stating monomer mixture is as follows, based on 100 parts by weight：The acrylonitrile of 10~30 parts by weight and 70~90 weights
Measure the styrenic component of part；
(d) preparation method of the copolymer A -3 comprises the following steps：Prepared by being polymerize by monomer mixture copolymer；
Wherein, the component and part of the monomer mixture is as follows, based on 100 parts by weight：The acrylonitrile list of 18~48 parts by weight
The styrene monomer of body and 52~82 parts by weight；
The gel content of the graft copolymer A-1 and graft copolymer A-2 are all higher than being equal to 85%；The graft copolymer
A-1 and graft copolymer A-2 rubber size, which are respectively less than, is equal to 400nm；
The heat-resistant agent B is N-phenylmaleimide-α-methylstyrene-acrylonitrile-styrene quadripolymer, using even
Continuous mass polymerization synthesis；The component and part of the heat-resistant agent B is as follows, based on 100 parts by weight, wherein, N- phenyl horses
Carry out the parts by weight of acid imide component 20~30, the parts by weight of α-methylstyrene component 30~50, the parts by weight of styrenic component 10~40,
The parts by weight of acrylonitrile component 20~40.
2. it is suitable to the high heat-proof ABS resin composition of blow molding as claimed in claim 1, it is characterised in that the grafting
The rubber polymer that copolymer A -1 and graft copolymer A-2 are used in preparing is polybutadiene rubber, butadiene-styrene rubber, third
One or more of mixing in olefin(e) acid ester rubber, nitrile rubber.
3. it is suitable to the high heat-proof ABS resin composition of blow molding as claimed in claim 1, it is characterised in that the grafting
Copolymer A -1 and graft copolymer A-2 gel content are all higher than being equal to 90%.
4. it is suitable to the high heat-proof ABS resin composition of blow molding as claimed in claim 1, it is characterised in that the grafting
Copolymer A -1 and graft copolymer A-2 rubber size, which are respectively less than, is equal to 300nm.
5. it is suitable to the high heat-proof ABS resin composition of blow molding as claimed in claim 1, it is characterised in that the copolymerization
Thing A-3 molecular weight is 100,000~300,000.
6. it is suitable to the high heat-proof ABS resin composition of blow molding as claimed in claim 1, it is characterised in that the copolymerization
Thing A-3 molecular weight is 180,000~300,000.
7. it is suitable to the high heat-proof ABS resin composition of blow molding as claimed in claim 1, it is characterised in that described heat-resisting
Agent B glass transition temperature is 140~160 DEG C.
8. a kind of preparation method of the high heat-proof ABS resin composition as claimed in claim 1 suitable for blow molding, its feature
It is, comprises the following steps：
Step 1, each component is weighed according to parts by weight；
Step 2, each component is sufficiently mixed in high-speed mixer, obtains mixture；
Step 3, mixture is entered from the main feeding of double screw extruder, by melting extrusion, cooling, drying, pelletizing, produced
The ABS resin composition.
9. preparation method as claimed in claim 8, it is characterised in that in step 3, the screw rod of described double screw extruder is long
Footpath ratio is 30~70, and machine barrel must be provided with vacuum exhaust device at least two, and screw rod material machine barrel feed zone temperature is 180~210
DEG C, fluxing zone temperature be 230~250 DEG C, homogenizing zone temperature be 220~240 DEG C, screw speed is 200~500rpm.
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| CN201310590377.2A CN103613877B (en) | 2013-11-20 | 2013-11-20 | High heat-proof ABS resin composition suitable for blow molding and preparation method thereof |
| JP2016533619A JP6364490B2 (en) | 2013-11-20 | 2013-12-04 | High heat resistant ABS resin composition suitable for blow molding and method for preparing the same |
| PCT/CN2013/088527 WO2015074297A1 (en) | 2013-11-20 | 2013-12-04 | Heat-resistant abs resin composition formed by blow molding and preparation method therefor |
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| TWI573710B (en) * | 2016-05-18 | 2017-03-11 | Vehicle rear fender guardrail | |
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| KR102210030B1 (en) | 2017-12-11 | 2021-02-01 | 주식회사 엘지화학 | Heat-resistant resin composition |
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| CN110498890A (en) * | 2019-08-26 | 2019-11-26 | 江苏宝源高新电工有限公司 | One kind having Weatherproof ageing-resistant nitrile rubber graft polymers and preparation method thereof |
| KR102493671B1 (en) * | 2019-10-23 | 2023-02-06 | 주식회사 엘지화학 | Thermoplastic resin composition |
| WO2021080211A1 (en) | 2019-10-23 | 2021-04-29 | 주식회사 엘지화학 | Thermoplastic resin composition |
| KR102639153B1 (en) * | 2021-12-01 | 2024-02-21 | 금호석유화학 주식회사 | Low odor acrylonitrile-butadiene-styrene based resin composition with excellent antibacterial property |
| CN115044165B (en) * | 2022-08-17 | 2022-10-28 | 山东东临新材料股份有限公司 | ABS resin composition and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| JP2017502106A (en) | 2017-01-19 |
| JP6364490B2 (en) | 2018-07-25 |
| WO2015074297A1 (en) | 2015-05-28 |
| CN103613877A (en) | 2014-03-05 |
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