CN101985509B - Thermoplastic resin composition with excellent metal electroplated coating bonding force and preparation method thereof - Google Patents
Thermoplastic resin composition with excellent metal electroplated coating bonding force and preparation method thereof Download PDFInfo
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- CN101985509B CN101985509B CN2010102651808A CN201010265180A CN101985509B CN 101985509 B CN101985509 B CN 101985509B CN 2010102651808 A CN2010102651808 A CN 2010102651808A CN 201010265180 A CN201010265180 A CN 201010265180A CN 101985509 B CN101985509 B CN 101985509B
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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Abstract
The invention relates to a thermoplastic resin composition with excellent metal electroplated coating bonding force and a preparation method thereof, and the composition comprises the following components in parts by weight: 20 to 50 part of unsaturated nitrile-unsaturated alkadiene-vinyl arene grafting copolymerization, 50 to 80 parts of unsaturated nitrile-vinyl arene grafting copolymerization, 0.1 to 3 parts of lubricating agent, and 0.05 to 0.8 part of antioxidant. After the premixing of the raw materials above, the raw materials are melted and extruded through a double screw extrusion machine, cooled and pelletized to obtain the product. Compared with the prior art, the unsaturated nitrile-unsaturated alkadiene-vinyl arene grafting copolymerization prepared by the invention not only has excellent impact resistance strength, size stability and good manufacturing performance, but also has excellent electroplated coating bonding force.
Description
Technical field
The present invention relates to a kind of resin combination and preparation method thereof, especially relate to electrodeposition of metals bonding force thermoplastic resin excellent composition and method of making the same.
Background technology
Along with the appearance of the plastic and the overall plasticization automobile of automotive industry, the application of plastic electroplating is increasingly extensive, and the various coating of plating can satisfy the requirement of aspects such as protection, decoration, specific function on the plastic substrate.
Plastics after the plating have following advantage: improve solvent resistance, improve anti-ultraviolet aging and performance such as heat-resisting; Good decorative property not only has the metal sense, and wear-resisting; Improved the commodity class; Erosion resistance, electroconductibility and thermal conductivity all obviously improve.Give plastics good metal outward appearance through the processing of electroplating technology surface metalation, the substitute of Chang Zuowei metal is widely used in such as aspects such as automobile, wireless, Business Machine, industrial art, nameplate, decorations.
Usually unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer can be used in plating, has also had such numerous special-purpose plated materials on the market.Yet; Because the difference that various products itself exist; And product in moulding, electroplate the front surface pre-treatment, when electroplating and the difference of electroplating post-heat-treated; Usually some unfavorable conditions can occur, situation such as electrolytic coating is peeled off when comprising electrolytic coating foaming, surperficial pit, thermal treatment, shrinking percentage is bigger than normal, these situation generally resistance toheat with the bonding force of electroplating technology, material and electrolytic coating and material itself are relevant.The electrolytic coating that occurs when particularly electroplating product later stage thermal treatment is peeled off problem, and except that need suitably increased the resistance toheat of material, main considered strengthened the bonding force of body material and electrodeposition of metals.
For addressing this problem; Can improve the resistance toheat of material through the interpolation heat-resistant agent; Or adding mineral filler strengthens dimensional stability, also or add and have and the compatible compounds of metallic substance reactive activity group strengthens the bonding force of body material and metal level.Yet all there is weak point in these methods:
As add heat-resistant agent, and peel off problem though electrolytic coating occurs can effectively avoid electroplating product later stage thermal treatment the time, heat-resistant agent is generally the N-phenylmaleimide analog copolymer; The flexible extreme difference of its molecular weight; Second-order transition temperature is higher, and difficulty is uniformly dispersed in matrix resin, causes the impact strength decreased of material bigger; Mobile decline obviously, processing characteristics is relatively poor.
If add mineral filler, though favourable to the resistance toheat of raising material, the dimensional stability of material improves simultaneously, and shock strength can descend obviously, the difficult requirement of satisfying plating product high impact.
If add the compatible compounds that has with metallic substance reactive activity group, can strengthen the bonding force of matrix and electrodeposition of metals to a certain extent, reduce the poor plating rate, but also can be bigger to the shock strength and the flowability affects of material.
Though aforesaid method can solve certain aspect problem to a certain extent, can cause new problem to produce simultaneously.Therefore; Still exist for a kind of both to have had excellent resistance to impact shock, dimensional stability and an excellent machinability, have more the needs of unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer of the improved unsaturated diolefine-vinyl-arene copolymer rubber stratum nucleare of excellent electrodeposition of metals bonding force.
Summary of the invention
The object of the invention is exactly for the defective that overcomes above-mentioned prior art existence a kind of thermoplastic resin composition with excellent resistance to impact shock, dimensional stability, good processing properties and electrodeposition of metals bonding force and preparation method thereof to be provided.
The object of the invention can be realized through following technical scheme:
Electrodeposition of metals bonding force thermoplastic resin excellent compsn is characterized in that, said composition comprises following component and weight part content:
Unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer 20～50;
Unsaturated nitrile-vinyl-arene copolymer 50～80;
Lubricant 0.1～3;
Oxidation inhibitor 0.05～0.8.
The weight part content of described unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer is preferred 30～40, the weight part content preferred 60～70 of unsaturated nitrile-vinyl-arene copolymer.
Described unsaturated nitrile comprises acetonitrile or vinyl cyanide, and described unsaturated diolefine comprises divinyl or isoprene, and described vinyl-arene comprises vinylbenzene or vinyl toluene.
The structure of described unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer is the rubber stratum nucleare of unsaturated diolefine-vinyl-arene copolymer and is grafted to the vinyl-arene-unsaturated nitrile multipolymer shell on the above-mentioned stratum nucleare rubber polymer that weight-average molecular weight is 80000～500000.
Described unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer comprises the big or small unsaturated diolefine-vinyl-arene copolymer rubber stratum nucleare of two kinds of different-grain diameters:
Wherein, the unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer that contains big particle diameter rubber stratum nucleare accounts for 50～90wt% of unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer, preferred 70～80wt%;
Unsaturated nitrile-unsaturated diolefine-vinyl-arene the graft copolymer that contains small particle size rubber stratum nucleare accounts for the about 10～50wt% of ratio of unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer, preferred 20～30wt%.
The particle diameter of rubber stratum nucleare is 110～600nm in the described unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer that contains big particle diameter rubber stratum nucleare, preferred 200～400nm; Weight-average molecular weight is 80000～500000, preferred 150000～200000.
The rubber stratum nucleare accounts for 20～60%, preferred 40～55% by weight percentage in the described unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer that contains big particle diameter rubber stratum nucleare.
The particle diameter of rubber stratum nucleare is less than 80nm in the described unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer that contains small particle size rubber stratum nucleare, preferred 60nm to 80nm; Weight-average molecular weight is 80000～500000, preferred 150000～200000.
The rubber stratum nucleare accounts for 20～60%, preferred 40～55% by weight percentage in the described unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer that contains small particle size rubber stratum nucleare.
Described unsaturated nitrile-vinyl-arene copolymer is the multipolymer of 10～40% vinyl aromatic (co) hydrocarbon compound and 60～90% unsaturated nitrile compound by weight percentage, and the weight-average molecular weight of unsaturated nitrile-vinyl-arene copolymer is 80000～400000.
Described lubricant comprises one or more in pentaerythritol stearate, polyethylene wax, ethylene bis stearamide, stearate or the dimethylsilane.
Described oxidation inhibitor comprises phosphite ester kind antioxidant or Hinered phenols antioxidant, comprises commercially available oxidation inhibitor 168, antioxidant 1010, antioxidant 1076 or oxidation inhibitor 245.
A kind of electrodeposition of metals bonding force thermoplastic resin excellent preparation of compositions method is characterized in that this method may further comprise the steps:
(1) prepare raw material according to following component and weight part content:
Unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer 20～50,
Unsaturated nitrile-vinyl-arene copolymer 50～80,
Lubricant 0.1～3,
Oxidation inhibitor 0.05～0.8;
(2) above raw material is placed super mixer premix 3～10min, obtain Preblend;
(3) twin screw extruder is passed through in Preblend; Controlled temperature is 190～240 ℃; Screw speed is that 200～600rpm melt extrudes; Through cooling granulation, promptly obtain the excellent unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer thermoplastic resin composition of electrodeposition of metals bonding force then.
Compared with prior art; The present invention contains the unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer of unsaturated diolefine-vinyl-arene copolymer stratum nucleare particle diameter as 50-80nm through using; Can reach following purpose: on the basis of identical rubber content, use small particle size stratum nucleare rubber components, make that the surface-area of rubber phase is bigger in the unit mass resin; Like this can be so that the rubber grain distributed points of resin surface unit surface is more; And distribution area is bigger, therefore except that having excellent resistance to impact shock, dimensional stability and good processing properties, has more excellent electrodeposition of metals bonding force.
Embodiment
Below in conjunction with specific embodiment the present invention is elaborated.
Embodiment 1
26.25kg is contained the unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer of big particle diameter stratum nucleare rubber, unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer, 65kg unsaturated nitrile-vinyl-arene copolymer, 1.1kg lubricant, 0.4kg oxidation inhibitor that 8.75kg contains small particle size stratum nucleare rubber to join and stirs discharging after 10 minutes in the high-speed mixer; Extruding pelletization in the twin screw extruder that be 36 in length-to-diameter ratio then, diameter is 35mm; The barrel zone temperature of forcing machine is 190-240 ℃, and screw speed is 400rpm.
Embodiment 2
For the ratio that embodies the unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer that contains small particle size stratum nucleare rubber for the influence of electroplating bonding force, present embodiment will improve its component ratio and verify.17.5kg is contained the unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer of big particle diameter stratum nucleare rubber, unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer, 65kg unsaturated nitrile-vinyl-arene copolymer, 1.1kg lubricant, the 0.4kg oxidation inhibitor that 17.5kg contains small particle size stratum nucleare rubber; Join and stir discharging after 10 minutes in the high-speed mixer; Extruding pelletization in the twin screw extruder that be 36 in length-to-diameter ratio then, diameter is 35mm; The barrel zone temperature of forcing machine is 190-240 ℃, and screw speed is 400rpm.
Embodiment 3
For the ratio that embodies the unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer that contains small particle size stratum nucleare rubber for the influence of electroplating bonding force, present embodiment will reduce its component ratio and verify.31.5kg is contained the unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer of big particle diameter stratum nucleare rubber, unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer, 65kg unsaturated nitrile-vinyl-arene copolymer, 1.1kg lubricant, the 0.4kg oxidation inhibitor that 3.5kg contains small particle size stratum nucleare rubber; Join and stir discharging after 10 minutes in the high-speed mixer; Extruding pelletization in the twin screw extruder that be 36 in length-to-diameter ratio then, diameter is 35mm; The barrel zone temperature of forcing machine is 190-240 ℃, and screw speed is 400rpm.
Embodiment 4
Unsaturated nitrile-unsaturated diolefine-vinyl-arene the graft copolymer of small particle size stratum nucleare rubber can effectively improve unit surface etching density and etching surface is long-pending owing to contain, and therefore possibly reduce its content can reach same etching effect.24kg is contained the unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer of big particle diameter stratum nucleare rubber, unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer, 68kg unsaturated nitrile-vinyl-arene copolymer, 1.1kg lubricant, the 0.4kg oxidation inhibitor that 8kg contains small particle size stratum nucleare rubber; Join and stir discharging after 10 minutes in the high-speed mixer; Extruding pelletization in the twin screw extruder that be 36 in length-to-diameter ratio then, diameter is 35mm; The barrel zone temperature of forcing machine is 190-240 ℃, and screw speed is 400rpm.
Embodiment 5
Improve overall unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer content, should can reach the effect that improves etching effect equally, therefore, present embodiment will improve its content and verify.30kg is contained the unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer of big particle diameter stratum nucleare rubber, unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer, 60kg unsaturated nitrile-vinyl-arene copolymer, 1.1kg lubricant, 0.4kg oxidation inhibitor that 10kg contains small particle size stratum nucleare rubber to join and stirs discharging after 10 minutes in the high-speed mixer; Extruding pelletization in the twin screw extruder that be 36 in length-to-diameter ratio then, diameter is 35mm; The barrel zone temperature of forcing machine is 190-240 ℃, and screw speed is 400rpm.
Comparative Examples 1
In order to embody above-mentioned characteristics preferably, use Comparative Examples 1 at this with unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer thermoplastic resin composition of excellent electrodeposition of metals bonding force.In this Comparative Examples, do not use the unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer that contains small particle size stratum nucleare rubber, this also is traditional plating scheme.The concrete making as follows: the unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer, 65kg unsaturated nitrile-vinyl-arene copolymer, 1.1kg lubricant, the 0.4kg oxidation inhibitor that 35kg are contained big particle diameter stratum nucleare rubber join stirring discharging after 10 minutes in the high-speed mixer; Extruding pelletization in the twin screw extruder that be 36 in length-to-diameter ratio then, diameter is 35mm; The barrel zone temperature of forcing machine is 190-240 ℃, and screw speed is 400rpm.
Comparative Examples 2
In order to embody above-mentioned characteristics preferably, use Comparative Examples 2 at this with unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer thermoplastic resin composition of excellent electrodeposition of metals bonding force.In this Comparative Examples, do not use the unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer that contains big particle diameter stratum nucleare rubber.The concrete making as follows: the unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer, 65kg unsaturated nitrile-vinyl-arene copolymer, 1.1kg lubricant, the 0.4kg oxidation inhibitor that 35kg are contained small particle size stratum nucleare rubber join stirring discharging after 10 minutes in the high-speed mixer; Extruding pelletization in the twin screw extruder that be 36 in length-to-diameter ratio then, diameter is 35mm; The barrel zone temperature of forcing machine is 190-240 ℃, and screw speed is 400rpm.
For the above unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer thermoplastic resin composition who prepares according to embodiment and Comparative Examples, prepare test bars according to same injecting condition, concrete physicals test item is following:
Tensile strength: measure tensile strength according to ASTM D 178 (50mm/min), unit is MPa;
Flexural strength and modulus in flexure: detect flexural strength and modulus in flexure according to standard A STM D790 (3mm/min), unit is MPa;
The beam type notched Izod impact strength: measure according to ASTM D256 (1/8 " breach, 23 ℃) and to lack the beam type notched Izod impact strength, unit is J/m;
Melt flow rate(MFR): according to ASTM D1238 (220 ℃, 10kg) measure melt flow rate(MFR), unit is g/10min;
Heat-drawn wire (HDT): under the condition of 1.82MPa, according to ASTM D648 (1/4 ", 120 ℃/hr) measure heat-drawn wire, unit is ℃.
The electrolytic coating bonding force: detect the electrolytic coating bonding force according to TSM0501G, unit is N/cm.
The unsaturated nitrile that concrete embodiment 1-5 and Comparative Examples 1-2 prepare-unsaturated diolefine-vinyl-arene graft copolymer thermoplastic resin composition's detailed performance is seen table 1.
The performance comparison of table 1 embodiment and Comparative Examples
Comparison through embodiment in the table 1 and Comparative Examples; After can finding out that introducing contains the unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer of particle diameter less than the small particle size stratum nucleare rubber of 80nm, embodiments of the invention all show excellent more electrodeposition of metals bonding force.
Through comparative example 1, embodiment 2, embodiment 3, Comparative Examples 1, Comparative Examples 2; Can find out; Contain ratio that the ratio of the unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer of small particle size stratum nucleare rubber accounts for unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer when 25% left and right sides; Electroplate etching hole dot density and reached an optimal balance point for the influence of electroplating bonding force with the hole point degree of depth; Electroplate the bonding force optimum this moment, continue increase or reduce the unsaturated nitrile-ratio of unsaturated diolefine-vinyl-arene graft copolymer that contains small particle size stratum nucleare rubber all to cause electroplating the reduction of bonding force.
Through comparative example 1, embodiment 4 and Comparative Examples 1, can find out, reduce glue content and can reach good plating bonding force effect equally, show that the density distribution of etching hole point is very important, but the impact strength decreased amplitude is bigger.
Through comparative example 1, embodiment 5 and Comparative Examples 1, can find out, increase glue content and can effectively increase the electrolytic coating bonding force; But the viscosity of matrix resin is higher; Stress relief when being unfavorable for the product moulding, and the increase of glue content means that cost rises, practical feasibility is not as embodiment 1.
Embodiment 6
A kind of electrodeposition of metals bonding force thermoplastic resin excellent preparation of compositions method, this method may further comprise the steps:
(1) prepare raw material according to following component and content: acetonitrile-butadiene-styrene graft copolymer 20kg, unsaturated nitrile-vinyl-arene copolymer 80kg, lubricant pentaerythritol stearate 0.1kg, oxidation inhibitor 168 are 0.05kg; Wherein the structure of acetonitrile-butadiene-styrene graft copolymer is the rubber stratum nucleare of acetonitrile-styrol copolymer and is grafted to the vinylbenzene-acetonitrile multipolymer shell on the above-mentioned stratum nucleare rubber polymer; Weight-average molecular weight is 80000; The mixture of acetonitrile-butadiene-styrene graft copolymer of the rubber stratum nucleare that contains small particle size of acetonitrile-butadiene-styrene graft copolymer and particle diameter 50nm that by particle diameter is the rubber stratum nucleare that contains big particle diameter of 100nm is formed; The content of rubber stratum nucleare is 20wt%; The multipolymer content 50wt% of big particle diameter in the mixture, the multipolymer content 50wt% of small particle size; Acetonitrile-styrol copolymer is the vinylbenzene of 10wt% and the acetonitrile multipolymer of 90wt%, and weight-average molecular weight is 80000;
(2) above raw material is placed super mixer premix 3min, obtain Preblend;
(3) twin screw extruder is passed through in Preblend; Controlled temperature is 190 ℃; Screw rod machine rotating speed is that 200rpm melt extrudes, and then through cooling granulation, promptly obtains the excellent unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer thermoplastic resin composition of electrodeposition of metals bonding force.
Embodiment 7
A kind of electrodeposition of metals bonding force thermoplastic resin excellent preparation of compositions method, this method may further comprise the steps:
(1) prepare raw material according to following component and content: vinyl cyanide-isoprene-vinyl toluene graft copolymer 30kg, unsaturated nitrile-vinyl-arene copolymer 70kg, lubricant 1kg, antioxidant 1010 are 0.2kg; Wherein the structure of vinyl cyanide-isoprene-vinyl toluene graft copolymer is the rubber stratum nucleare of isoprene-methylstyrene copolymer and is grafted to the isoprene-acrylonitrile copolymer shell on the above-mentioned stratum nucleare rubber polymer; Weight-average molecular weight is 150000; The mixture of vinyl cyanide-isoprene-vinyl toluene graft copolymer of the rubber stratum nucleare that contains small particle size of vinyl cyanide-isoprene-vinyl toluene aromatic hydrocarbons graft copolymer and particle diameter 60nm that by particle diameter is the rubber stratum nucleare that contains big particle diameter of 200nm is formed; The content of rubber stratum nucleare is 40wt%; The multipolymer content 70wt% of big particle diameter in the mixture, the multipolymer content 30wt% of small particle size; Unsaturated nitrile-vinyl-arene copolymer is the multipolymer of vinyl cyanide of vinyl toluene and the 60wt% of 40wt%, and weight-average molecular weight is 100000, and lubricant is the mixture of polyethylene wax and ethylene bis stearamide;
(2) above raw material is placed super mixer premix 5min, obtain Preblend;
(3) twin screw extruder is passed through in Preblend; Controlled temperature is 210 ℃; Screw rod machine rotating speed is that 400rpm melt extrudes, and then through cooling granulation, promptly obtains the excellent unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer thermoplastic resin composition of electrodeposition of metals bonding force.
Embodiment 8
A kind of electrodeposition of metals bonding force thermoplastic resin excellent preparation of compositions method, this method may further comprise the steps:
(1) prepare raw material according to following component and content: vinyl cyanide-isoprene-vinyl toluene graft copolymer 40kg, unsaturated nitrile-vinyl-arene copolymer 60kg, lubricant 2kg, antioxidant 1010 are 0.5kg; Wherein the structure of vinyl cyanide-isoprene-vinyl toluene graft copolymer is the rubber stratum nucleare of isoprene-methylstyrene copolymer and is grafted to the vinyl toluene-acrylonitrile copolymer shell on the above-mentioned stratum nucleare rubber polymer; Weight-average molecular weight is 200000; The mixture of vinyl cyanide-isoprene-vinyl toluene graft copolymer of the rubber stratum nucleare that contains small particle size of vinyl cyanide-isoprene-vinyl toluene graft copolymer and particle diameter 60nm that by particle diameter is the rubber stratum nucleare that contains big particle diameter of 400nm is formed; The content of rubber stratum nucleare is 55wt%; The multipolymer content 80wt% of big particle diameter in the mixture, the multipolymer content 20wt% of small particle size; Unsaturated nitrile-vinyl-arene copolymer is the multipolymer of vinyl cyanide of vinyl toluene and the 60wt% of 40wt%, and weight-average molecular weight is 200000, and lubricant is the mixture of polyethylene wax and ethylene bis stearamide;
(2) above raw material is placed super mixer premix 5min, obtain Preblend;
(3) twin screw extruder is passed through in Preblend; Controlled temperature is 210 ℃; Screw rod machine rotating speed is that 400rpm melt extrudes, and then through cooling granulation, promptly obtains the excellent unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer thermoplastic resin composition of electrodeposition of metals bonding force.
Embodiment 9
A kind of electrodeposition of metals bonding force thermoplastic resin excellent preparation of compositions method, this method may further comprise the steps:
(1) prepare raw material according to following component and content: acetonitrile-butadiene-styrene graft copolymer 50kg, unsaturated nitrile-vinyl-arene copolymer 50kg, lubricant dimethylsilane 32kg, antioxidant 1076 are 0.8kg; Wherein the structure of acetonitrile-butadiene-styrene graft copolymer is the rubber stratum nucleare of BS and is grafted to the divinyl-acetonitrile multipolymer shell on the above-mentioned stratum nucleare rubber polymer; Weight-average molecular weight is 500000; The mixture of acetonitrile-butadiene-styrene graft copolymer of the rubber stratum nucleare that contains small particle size of acetonitrile-butadiene-styrene graft copolymer and particle diameter 80nm that by particle diameter is the rubber stratum nucleare that contains big particle diameter of 600nm is formed; The content of rubber stratum nucleare is 60wt%; The multipolymer content 90wt% of big particle diameter in the mixture, the multipolymer content 10wt% of small particle size; Unsaturated nitrile-vinyl-arene copolymer is the multipolymer of acetonitrile of vinylbenzene and the 70wt% of 30wt%, and weight-average molecular weight is 400000, and lubricant is the mixture of polyethylene wax and ethylene bis stearamide;
(2) above raw material is placed super mixer premix 10min, obtain Preblend;
(3) twin screw extruder is passed through in Preblend; Controlled temperature is 240 ℃; Screw rod machine rotating speed is that 600rpm melt extrudes, and then through cooling granulation, promptly obtains the excellent unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer thermoplastic resin composition of electrodeposition of metals bonding force.
For person of ordinary skill in the field of the present invention, after knowing the instruction that aforementioned description provides, can expect many modifications of the present invention and other embodiments.Therefore, be to be understood that the present invention should not be limited to the specific embodiment of disclosure, in the appended claim scope that these modifications and other embodiments comprise.Although used specific term in the text, they only are used with general and descriptive meaning and are not used in the purpose of restriction, and the scope of the present invention claim of having the right limits.
Claims (10)
1. electrodeposition of metals bonding force thermoplastic resin excellent compsn is characterized in that, said composition comprises following component and weight part content:
Unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer 20～50;
Unsaturated nitrile-vinyl-arene copolymer 50～80;
Lubricant 0.1～3;
Oxidation inhibitor 0.05～0.8;
Described unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer is that particle diameter is the mixture of the unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer of the unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer of the rubber stratum nucleare that contains big particle diameter of 100～600nm and the rubber stratum nucleare that contains small particle size that particle diameter is 50～80nm;
Described unsaturated nitrile-unsaturated diolefine-vinyl-arene the graft copolymer that contains the rubber stratum nucleare of big particle diameter by weight the percentage meter account for unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer ratio 50～90%;
Described unsaturated nitrile-unsaturated diolefine-vinyl-arene the graft copolymer that contains the rubber stratum nucleare of small particle size by weight the percentage meter account for unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer ratio 10～50%.
2. electrodeposition of metals bonding force thermoplastic resin excellent compsn according to claim 1; It is characterized in that; The weight part content of described unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer is preferred 30～40, the weight part content preferred 60～70 of unsaturated nitrile-vinyl-arene copolymer.
3. electrodeposition of metals bonding force thermoplastic resin excellent compsn according to claim 1; It is characterized in that; Described unsaturated nitrile is a vinyl cyanide, and described unsaturated diolefine is divinyl or isoprene, and described vinyl-arene is vinylbenzene or vinyl toluene.
4. electrodeposition of metals bonding force thermoplastic resin excellent compsn according to claim 1; It is characterized in that; The structure of described unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer is the rubber stratum nucleare of unsaturated diolefine-vinyl-arene copolymer and is grafted to the vinyl-arene-unsaturated nitrile multipolymer shell on the above-mentioned rubber stratum nucleare that weight-average molecular weight is 80000～500000.
5. electrodeposition of metals bonding force thermoplastic resin excellent compsn according to claim 1; It is characterized in that the described rubber stratum nucleare that contains the unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer of the rubber stratum nucleare of big particle diameter is 20～60% by weight percentage.
6. electrodeposition of metals bonding force thermoplastic resin excellent compsn according to claim 1; It is characterized in that the described rubber stratum nucleare that contains the unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer of the rubber stratum nucleare of small particle size is 20～60% by weight percentage.
7. electrodeposition of metals bonding force thermoplastic resin excellent compsn according to claim 1; It is characterized in that; Described unsaturated nitrile-vinyl-arene copolymer is the multipolymer of 10～40% vinyl aromatic (co) hydrocarbon compound and 60～90% unsaturated nitrile compound by weight percentage, and the weight-average molecular weight of unsaturated nitrile-vinyl-arene copolymer is 80000～400000.
8. electrodeposition of metals bonding force thermoplastic resin excellent compsn according to claim 1; It is characterized in that described lubricant comprises one or more in pentaerythritol stearate, polyethylene wax, ethylene bis stearamide, stearate or the dimethylsilane.
9. electrodeposition of metals bonding force thermoplastic resin excellent compsn according to claim 1 is characterized in that described oxidation inhibitor comprises commercial anti oxygen agent 168, antioxidant 1010, antioxidant 1076 or oxidation inhibitor 245.
10. electrodeposition of metals bonding force thermoplastic resin excellent preparation of compositions method as claimed in claim 1 is characterized in that this method may further comprise the steps:
(1) prepare raw material according to following component and weight part content:
Unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer 20～50,
Unsaturated nitrile-vinyl-arene copolymer 50～80,
Lubricant 0.1～3,
Oxidation inhibitor 0.05～0.8,
Described unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer is that particle diameter is the mixture of the unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer of the unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer of the rubber stratum nucleare that contains big particle diameter of 100～600nm and the rubber stratum nucleare that contains small particle size that particle diameter is 50～80nm
Described unsaturated nitrile-unsaturated diolefine-vinyl-arene the graft copolymer that contains the rubber stratum nucleare of big particle diameter by weight the percentage meter account for unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer ratio 50～90%,
Described unsaturated nitrile-unsaturated diolefine-vinyl-arene the graft copolymer that contains the rubber stratum nucleare of small particle size by weight the percentage meter account for unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer ratio 10～50%;
(2) above raw material is placed super mixer premix 3～10min, obtain Preblend;
(3) twin screw extruder is passed through in Preblend; Controlled temperature is 190～240 ℃; Screw speed is that 200～600rpm melt extrudes; Through cooling granulation, promptly obtain the excellent unsaturated nitrile-unsaturated diolefine-vinyl-arene graft copolymer thermoplastic resin composition of electrodeposition of metals bonding force then.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1101651A (en) * | 1993-09-28 | 1995-04-19 | 电气化学工业株式会社 | Thermoplastic resin composition and its synthetic resin composite |
| CN1156736A (en) * | 1995-10-04 | 1997-08-13 | 巴斯福股份公司 | Shaped articles comprising thermoplastic molding materials |
| CN1298427A (en) * | 1998-04-24 | 2001-06-06 | 美国拜尔公司 | Compatibilized ABS-polycarbonate molding composition |
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| DE19961894A1 (en) * | 1999-12-20 | 2001-06-21 | Basf Ag | Transparent, high-impact thermoplastic moulding material, used for film, fibres and mouldings, contains acrylic polymer, styrene-acrylonitrile copolymer and graft copolymer with bimodal particle size distribution |
| KR100396402B1 (en) * | 2000-12-21 | 2003-09-02 | 제일모직주식회사 | Thermoplastic Resin Composition Having Excellent Chemical Resistance And Easy Vacuum Formability |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1101651A (en) * | 1993-09-28 | 1995-04-19 | 电气化学工业株式会社 | Thermoplastic resin composition and its synthetic resin composite |
| CN1156736A (en) * | 1995-10-04 | 1997-08-13 | 巴斯福股份公司 | Shaped articles comprising thermoplastic molding materials |
| CN1298427A (en) * | 1998-04-24 | 2001-06-06 | 美国拜尔公司 | Compatibilized ABS-polycarbonate molding composition |
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