Summary of the invention
The present invention seeks to develop a kind of high rigidity, high heat-stable mar-proof talc powder filled polypropylene, that is: provide that a kind of anti-zoned trace, outward appearance are beautiful, good rigidly, easily processing, the inexpensive mar-proof talc powder filled polypropylene composition and method of making the same of light weight.
For realizing above purpose, technical scheme of the present invention provides a kind of mar-proof talc powder filled polypropylene to be formed, and with high crystalline polypropylene, it is made by following materials of weight proportions:
A. high crystallization high isotatic polypropylene 60-90
B. talcum powder 10-40
C. coupling agent 3-10
D. stablizer 0.1-1.0
E. talcum powder surface passivation agent 0.2-1.5
Wherein, A+B (high crystallization high isotatic polypropylene and talcum powder gross weight) is 100 weight parts, described stablizer is acid absorber, thermal oxidation stabilizer and photostabilizer, wherein, thermal oxidation stabilizer is 1010 (" β-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester) and Irganox PS 802 (thio-2 acid 2 stearyl ester), consumption is respectively 0.1%-1.0%, is preferably 0.1%-0.5%; Photostabilizer is 770 (two (2,2,6,6-tetramethyl--4-piperidyl) sebate) and Chimassorb 944, and consumption is the 0.1-1.0 weight part; Acid absorber is a stearate, and as calcium stearate and Zinic stearas, its consumption is 0.05%-0.5%; Described talcum powder is the talcum powder of sheet structure, and length/thickness rate is 100~500, and particle size range is 1~10 micron; Described talcum powder surface passivation agent is higher fatty acid or Resins, epoxy Araltide 7072; Described coupling agent is a maleic anhydride inoculated polypropylene; Also comprise ethylene bis stearamide, its consumption is 0.05~1.0 weight part; Degree of crystallinity is not less than 70% in the described high crystallization high isotatic polypropylene, and degree of isotacticity is greater than 99%.
On the such scheme basis, described polypropylene is high crystallization homo-polypropylene and block copolymerization propylene, wherein the comonomer of block copolymerization propylene is an ethene, its content is in the scope of 4-10mol%, polyacrylic melt flow rate (MFR) is 5-50g/10min under 230 ℃, 2.16kg loading condiction, and more commonly used is 5-30g/10min.
On the such scheme basis, described talcum powder particle size range is preferably the 1-10 micron for the talcum powder particle diameter is the 0.5-10 micron.
On the such scheme basis, degree of crystallinity is not less than 70% in the described high crystallization high isotatic polypropylene, and degree of isotacticity is greater than 99%.
The preparation method of a kind of high rigidity, high heat-stable mar-proof talc powder filled polypropylene, its method is as follows:
(1) takes by weighing raw material by weight ratio;
(2) polypropylene, talcum powder, stablizer, coupling agent and ethylene bis stearamide were mixed in homogenizer 10~20 minutes;
(3) mixed raw material is put into twin screw extruder, material residence time in screw rod is 1~2 minute, and temperature is in the screw rod: 185~195 ℃ in a district, 190~210 ℃ in two districts, 190~210 ℃ in three districts, 195~215 ℃ in four districts; The twin screw extruder rotating speed is 300-700 rev/min;
(4) discharging melt extrudes in twin screw extruder, extrudes postcooling, drying, pelletizing and gets product.
Advantage of the present invention is:
1. the present invention adopts high crystalline polypropylene and talcum powder blend, has improved polyacrylic rigidity greatly.
2. thermotolerance, intensity, hardness and mar-proof performance can satisfy the requirement of automobile component to material.
3. owing to the use of high crystallization PP, under same inflexible situation, just can reach requirement with more a spot of talcum powder, this helps reducing the density of material, thereby reduces the weight of automobile component.
4. the various material sources that use among the present invention are extensive, are easy to get.
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment
The polypropylene of mentioning among the present invention is high degree of isotacticity, high crystalline homopolymerization or block copolymerization propylene, and wherein the comonomer of block copolymerization propylene is that ethene, butylene are to 20 carbon olefins.Typical comonomer is ethene in the co-polypropylene that uses in the present invention, and its content is no more than 15mol%, the more common 5mol% that is no more than.
The polypropylene that uses among the present invention can adopt different polymerization processs to obtain, as suspension polymerization and solution polymerization, the state of propylene monomer can be gas phase or slurries attitude, the catalyzer that uses is common to be Ziegler-Natta type, certainly comprise that also other any catalyzer can prepare the polypropylene of high regularity structure, its degree of isotacticity should be greater than 99%.
The polyacrylic flowability of using among the present invention melt flow rate (MFR) (MFR) commonly used represents that its test block is: 230 ℃, 2.16kg loading condiction; Melt flow rate (MFR) and polyacrylic molecular weight are inverse ratio, and promptly the polypropylene molecule amount is big more, and flowability is poor more, and MFR is more little.Select the MFR size, mainly need to consider physics, the mechanical property of moulding processability and material, MFR is too small, and flowability is too poor, is unsuitable for injection molding, and MFR is excessive, and polyacrylic toughness is too poor, and material is too crisp.Polyacrylic MFR scope is 0.5-100g/10min, and more common MFR scope is 0.5-50g/10min.
The filler of mentioning among the present invention is a talcum powder, is typical sheet structure, and length/thickness rate (L/T) is 100-500, and particle size range is the 1-10 micron.In order significantly to improve polyacrylic rigidity, talcous consumption generally is not less than 10% in modified polypropene, and is too low, and the rigidity of material is too poor; But amount of talc is also too much unsuitable, as surpassing 40%, then can the polyacrylic processing characteristics of remarkably influenced, therefore general amount of talc (wt%) is 10,15,20,25,30 and 35 etc., also can be any natural number between the 10-35, more common be 15-25wt%.
In order further to strengthen the interaction of talcum powder and polypropylene surface, need to add coupling agent usually.Coupling agent is some low molecule or macromolecular compounds of containing active function groups, low molecule coupling agent is common silane coupling agent, titanate coupling agent, aluminate coupling agent etc., and polymer coupler some graft copolymers normally, maleic anhydride inoculated polypropylene, toxilic acid graft polypropylene, maleic anhydride grafted polyethylene, toxilic acid grafted polyethylene etc. are typically arranged, relatively, the polymer coupler better effects if, so the present invention adopts maleic anhydride inoculated polypropylene.
The method of graft polypropylene is a lot, can be divided into fusion-grafting, solution graft copolymerization, solid phase grafting etc. from reaction form branch, fusion-grafting because of the preparation method simply again no coupling product be widely used, the present invention adopts the maleic anhydride inoculated polypropylene of fusion-grafting method preparation.
Owing to have tertiary carbon atom in the polypropylene molecule, easier to be more aging than polyethylene, particularly under the effect of high temperature and UV-light, the polypropylene that does not add stablizer is in a short time just with embrittlement, lose use value, so the adding of stablizer is even more important to modified polypropene.General polyacrylic stabilising system comprises: phenols primary antioxidant, phosphorous acid esters or thioesters class are worked in coordination with oxidation inhibitor, acid absorber, UV light absorber, hydrogen peroxide decomposition agent etc.
In polyacrylic stabilising system, the phenols primary antioxidant is common to be had, the Irganox 1010 of Switzerland Ciba company (four [β-(3, the 5--di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester) and Irganox 1076 (2,6-two (1-phenyl) ethyl-4 one nonylphenol), wherein 1010 is more commonly used, and consumption is generally 0.1-1.0%, and more commonly used is 0.1-0.5%.
Phosphorous acid esters and thioesters class auxiliary antioxidant, with above-mentioned primary antioxidant synergy is arranged, common kind has: the Irgafos 168 (three (2 of Switzerland Ciba company, phosphorous acid ester) and Irganox PS 802 (thio-2 acid 2 stearyl ester) the 4-di-tert-butyl-phenyl), because the former is easy to hydrolysis in talc powder filled polypropylene, so the latter is more commonly used.Its consumption is 0.1-1.0%, and more commonly used is 0.1-0.5%.
In polyacrylic stabilising system, also need add acid absorber, common kind has stearates, and this class material plays the effect of internal lubricant simultaneously, and as calcium stearate and Zinic stearas etc., its consumption is 0.05-0.5%, and more commonly used is 0.05-0.2%.
In order to improve the weather resistance of modified polypropene, often need to add photostabilizer.Photostabilizer commonly used is divided into according to the mechanism of action: UV light absorber, quencher, hydrogen peroxide decomposition agent and radical scavenger, common several photostabilizers are also used the weather resistance that can improve material by a relatively large margin.Ultraviolet absorbers in the composition has; Benzophenone, phenyl methyl ketone amine, benzotriazole category, triazines, wherein PP the most common be benzophenone and phenyl methyl ketone amine; Above-mentioned ultraviolet absorbers consumption is at 0.1-1.0%, and the most suitable consumption is 0.1-0.5%; Typical UV light absorber product is the Sanduvor PR-25 and the Sanduvor VSU of Switzerland Clariant company.
Free radical quencher in the composition has: hindered amines and nickel huge legendary turtle compound class, the latter now seldom uses because of environmental issue.Common hindered amine light stabilizer has Switzerland Ciba company ' rinuvin 770 (two (2,2,6, sebate) and Chimassorb 944 (a kind of high molecular weight hindered amine light stabilizer 6-tetramethyl--4-piperidyl), it has good heat endurance, resistant to extraction, and lower volatility and transport property have good consistency with polypropylene simultaneously), its consumption is 0.1-2.0 (mass parts), and the most suitable consumption is 0.1-1.0 (mass parts).In polyacrylic smooth stabilising system, be generally multiple photostabilizer and usefulness, its total consumption is no more than 2%.
General packing specific area is than higher, and easily therefore various low molecule auxiliary agent, particularly oxidation inhibitor and the anti UV agent of absorption adding must carry out surface treatment.Except that adopting some conventional surface treatment methods, as adopt higher fatty acid, titanate coupling agent, aluminate coupling agent and silane coupling agent, also need add some surface passivation agent such as some epoxy compoundss, Resins, epoxy is typically arranged, present embodiment adopts the solid epoxy Araltide 7072 of Switzerland Ciba company, its consumption is 0.2-1.5%, and the optimum consumption is 0.5-1.0%.
In order to improve talcous dispersion, need to add processing aid usually, it is common that its consumption is generally 0.1-1.0% as stearate, fatty amide, fluorine-containing or siliceous compound, and the most suitable consumption is 0.1-0.5%, and more suitable consumption is 0.2-0.4%.
The materials used explanation:
The present invention has contrasted multiple high crystallization homopolymerization or copolymerization PP, wherein be typical for melt flow rate (MFR) and be homopolymerization and block copolymerization propylene about 10g/10min, its degree of isotacticity is 99.5%, and the present invention adopts the high normal block copolymerization propylene CB5108 (melt flow rate (MFR) is 8) of high degree of isotacticity homo-polypropylene HJ700 that Korea S Hyosung Corporation produces (melt flow rate (MFR) is 10) and the production of company of Korea S Kpic under 230 ℃, 2.16kg loading condiction under 230 ℃, 2.16kg loading condiction.As a comparison, the homo-polypropylene Y1600 that we adopt Shanghai petro-chemical corporation to produce, degree of isotacticity is 95%, melt flow rate (MFR) is 16 and the general block copolymerization propylene SB9310 that produces of company of Korea S Kpic (melt flow rate (MFR) is 10 under 230 ℃, 2.16kg loading condiction) under 230 ℃, 2.16kg loading condiction.
The talcum powder that uses among the present invention produces as Guangxi China, and its size is the 1-10 micron, and whiteness is more than 95%.Glass fibre is the ER-13 that Chinese Zhejiang megalith company produces, and adopts silane coupling agent to handle.
In order to strengthen the interaction of talcum powder and polypropylene surface, need to add coupling agent.The present invention adopts maleic anhydride inoculated polypropylene (GPP), and percentage of grafting is 0.5% (adopting method of infrared spectrophotometry to obtain).
The various auxiliary agents that use among the present invention are: acid-acceptor is calcium stearate; Talcum powder surface passivation agent is the Resins, epoxy 7072 that Switzerland Ciba company produces; Thermal oxidation stabilizer is the Irganox 1010 ([β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester) and the IrganoxPS 802 (thio-2 acid 2 stearyl ester) of Switzerland Ciba company; Photostabilizer is the Tinuvin770 (two (2,2,6,6-tetramethyl--4 one piperidyl) sebate) and the Chimassorb 944 of Switzerland Ciba company; Processing aid is an ethylene bis stearamide.
Performance test
(1) mar-proof performance test: the injection molding size of sample is 150 * 100 * 3.2mm, with hand-held hardness test pen load is 10N, the nib diameter is that 0.75mm carries out scratch test on the model surface, cut is 2mm at interval, each stroke of vertical and horizontal 10-20 bar line, the color and luster that grid material is drawn in the color measurement system testing of adopting Japanese Minolta company to produce changes, the Δ L value of recording materials, thereby the anti-scratch performance of discriminating material.
(2) melt flow rate (MFR) (MFR) is measured: undertaken by ISO 1183 standards, think in Shanghai and reach and carry out 230 ℃ of probe temperatures, load 2.16kg on the fusion index instrument of scientific instrument company;
(3) tensile property is measured: undertaken by ISO 527 standards, carry out on the German Zwick Z010 of company universal testing machine, rate of extension is 50mm/min:
(4) bending property is measured: undertaken by ISO 178 standards, on the German Zwick Z010 of company universal testing machine, carry out, and span 64mm, speed 2mm/min, modulus in flexure is calculated and is undertaken by tangential way:
(5) impact property is measured: undertaken by ISO 179 standards, carry out on the impact experiment machine of German Zwick company, batten is 80 * 10 * 4mm, v-notch, and bottom radius is 0.25mm.
(6) hardness test: carry out on the hardness-testing device of German Zwick company by ISO 2039-1 standard, loading is 358N, 30 seconds readings.
(7) heat-drawn wire: undertaken by ISO 75 standards, carry out on the HDT 300 that Italian Ceast company produces, batten is 120 * 10 * 4, loads to be 0.45MPa
Table 1 and table 2 have contrasted the influence of polypropylene kind to modified polypropylene material mechanical property and mar-proof performance respectively.Basic recipe in the experiment is as follows: the major ingredient prescription sees Table 1 and table 2, and auxiliary formula is: 10100.1, and PS 8020.3, and EBS 0.2, calcium stearate 0.1,7700.2,9440.2.
Concrete preparation method is as follows:
(1) weighs raw material by weight ratio;
(2) polypropylene, talcum powder, coupling agent GPP, stablizer, talcum powder surface passivation agent and processing aid were mixed in homogenizer 1.5 minutes;
(3) (material residence time in screw rod is 1.5 minutes for diameter 34mm, length-to-diameter ratio 40/1, and temperature is in the screw rod: 190 ℃ in a district, 205 ℃ in two districts, 210 ℃ in three districts, 210 ℃ in four districts mixed raw material to be put into twin screw extruder; It is 300 rev/mins that twin screw squeezes the forcing machine rotating speed:
(4) discharging melt extrudes in twin screw extruder, extrudes postcooling, drying, pelletizing and gets product.
(5) will extrude pellet and on 100 tons of sea day injection moulding machines, prepare sample.The injection moulding machine temperature is set at 200 ℃, and 220 ℃, 230 ℃, melt temperature is 230 ℃, and the forming process time is 60 seconds.
As can be seen from Table 1, under the situation of identical amount of talc, high crystalline modified polyacrylic ball indentation hardness and modulus in flexure are all apparently higher than general homo-polypropylene, and the rigidity of illustrative material has obtained obvious improvement.Heat-drawn wire especially under the high loading situation (1.82MPa) high-crystallinity polypropylene also want high more than 20 to spend, the thermotolerance of illustrative material also is significantly improved.In addition, because material surface hardness improves, mar-proof performance also has certain improvement.E1 is compared with C3, and glass-reinforced polypropylene has higher flexural strength and modulus in flexure, hardness and heat-resisting sex change, but the mar-proof performance of material is relatively poor relatively, and this main and glass fibre expose relevant, simultaneously the also obvious variation of the visual appearance of goods.
Table 2 has contrasted talcum powder and has filled the performance that high crystallization co-polypropylene and talcum powder are filled general co-polypropylene.Can see that under the situation of identical amount of talc, the rigidity of high-crystallinity polypropylene is better.Compare with the general filling homo-polypropylene of table 1, the rigidity of high crystallization co-polypropylene is suitable with general homo-polypropylene, but notched Izod impact strength is higher, and the toughness of material is better.
Table 1 embodiment 1-3 and comparative example 1-3
Table 2 embodiment 4-7 and comparative example 4-5