CN105542308A - Preparation method of polypropylene composite material used for shell cover of storage battery - Google Patents
Preparation method of polypropylene composite material used for shell cover of storage battery Download PDFInfo
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- CN105542308A CN105542308A CN201610058523.0A CN201610058523A CN105542308A CN 105542308 A CN105542308 A CN 105542308A CN 201610058523 A CN201610058523 A CN 201610058523A CN 105542308 A CN105542308 A CN 105542308A
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/02—Flame or fire retardant/resistant
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- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a preparation method of a polypropylene composite material used for a shell cover of a storage battery. The preparation method is characterized by comprising the following steps: taking the following raw materials in parts by weight: 10 to 20 parts of dried raw material PP (Polypropylene) powder, 70 to 85 parts of high-transparency homopolymerized PP, 5 to 15 parts of ethylene propylene diene monomer, 0.1 to 0.3 part of a nucleating agent of the raw materials, 0.5 to 1 part of a silicon flame retardant and 1 to 2 parts of an antimony oxide flame retardant; mixing all the raw materials to obtain a mixture; pouring the mixture into a mixing machine, and stirring and mixing for 5 to 10 minutes; then adding the mixture into a double-screw extruder, and fusing, extruding, cooling, dicing and drying; injecting and molding to prepare the polypropylene composite material used for the shell cover of the storage battery. The composite material prepared by the invention has good mechanical properties and high-temperature-resisting and low-temperature-resisting stability properties, is particularly suitable for the shell cover of the storage battery, and also can be used for fields including packages with high transparency requirements, medical equipment, household articles, common industries and the like.
Description
Technical field
The invention belongs to the preparation of macromolecular compound, relate to a kind of preparation method of the polypropylene composite material for storage battery shell and cover.The polypropylene composite material that the present invention obtains is particularly useful as storage battery shell and cover, also may be used for the transparency and requires the fields etc. such as high packaging, medicine equipment, household supplies, general industry.
Background technology
Edison battery has been widely used in startup, traction, illumination, communication equal energy source system, its cap material many employings polypropylene (being called for short PP) sill, and other thermoplastic, polymeric materials, as ethylene-propylene copolymer, acrylonitrile-butadiene-styrol copolymer, nylon, acrylonitrile-styrol copolymer, methyl methacrylate vinegar-butadiene-styrene copolymer etc.In prior art, PP resin selected by storage battery factory is generally middle and high anti-impact injection grade PP Pipe Compound (as more domestic battery cell case factory adopts AY564, B3001 to do battery cell case), its production cost is higher, and most of dependence on import, annual at substantial foreign exchange.Because battery in use will often be subject to larger impact shock, and need the test of the environment for use temperature variation facing the annual four seasons, thus require higher to cap material normal temperature and low temperature impact properties; Along with the upgrading of product, to the transparency of battery cell case and flame-retardancy requirements more and more higher.Existing co-polypropylene EPF30R (7% ethene and PP multipolymer) has good processing characteristics and rigidity, but its normal temperature and low temperature impact strength lower, flame retardant resistance and the transparency poor, the requirement from battery cell case PP Pipe Compound (as AY-564) still has larger gap (as shown in table 1)
Table 1:PP anti-impact level Performance comparision
| Performance | Testing standard | EPF30R | AY-564 |
| MI/g(10min) -1≥ | GB3682-1988 | 12 | 15 |
| Tensile yield strength MPa >= | GB1040-1992 | 25 | 23 |
| Tensile yield elongation % >= | GB1040-1992 | 380 | 100 |
| Modulus in flexure/M Pa >= | GB9341-1988 | 1111 | 1000 |
| Izod notched impact strength 23 DEG C | GB9432-1988 | 46 | 70 |
| Flame retardant rating | DIN5510-2-2009 | S1 | HB |
| Transmittance | GB/T2410-2008 | —— | —— |
Summary of the invention
Object of the present invention is intended to overcome deficiency of the prior art, provides a kind of preparation method of the polypropylene composite material for storage battery shell and cover.The polypropylene composite material adopting the present invention to obtain has good flame retardant resistance, the transparency, and low-temperature impact resistance.
Content of the present invention is: a kind of preparation method of the polypropylene composite material for storage battery shell and cover, it is characterized in that step is:
A, raw materials pretreatment and batching:;
By raw material PP powder, high transparency homopolymerization PP and terpolymer EP rubber, dry 1 ~ 2h at temperature 70 ~ 80 DEG C respectively; PP is polyacrylic abbreviation;
Get dried raw material PP powder 10 ~ 20 weight part, high transparency homopolymerization PP 70 ~ 85 weight part, terpolymer EP rubber 5 ~ 15 weight part, get raw material nucleator 0.1 ~ 0.3 weight part, silicon-series five-retardant 0.5 ~ 1 weight part and antimony oxide flame retardant 1 ~ 2 weight part, whole raw material is mixed, obtains compound;
B, compound is poured into (at a high speed) (velocity range is preferably 100 ~ 300r/min) mixing machine, (at a high speed) after being uniformly mixed 5 ~ 10min, polypropylene is made to evenly spread in other raw material, again compound is joined in (rotating speed is 10 ~ 15r/min's preferably) twin screw extruder feed hopper, under the processing temperature of the screw speed of 170 ~ 190r/min and 180 ~ 195 DEG C, melting was entered to compound, extrude, cooling, pelletizing, dry 1 ~ 4h (hopper-type drying machine can be placed in dry) at 80 ~ 90 DEG C of temperature again, i.e. obtained (translucent) polypropylene composite material,
C, shaping: by obtained (translucent) polypropylene composite material (on request or require) injection molding, to obtain the polypropylene composite material for storage battery shell and cover.
In content of the present invention: the powder of PP described in step a can be the PP powder etc. of the trade mark 085 that the trade mark 085 that provides of the trade mark 075, SINOPEC Jingmen Company that Tianli Hi-New Tech Co., Ltd., Dushanzi, Xinjiang provides or SINOPEC Shijiazhuang Refining & Chemical Co., Ltd. provide, the trade mark and model, rear same.
In content of the present invention: the homopolymerization PP of high transparency described in step a can be the high transparency homopolymerization PP etc. of the trade mark RP344R that the trade mark ST868M that provides of trade mark 1100N, Lee Chang Yung Chemical Indust that Ningxia Coal Industry Group company limited of Shenhua provides or great Lin company of Korea S provide.
In content of the present invention: terpolymer EP rubber described in step a can be the terpolymer EP rubber etc. of the trade mark Keltan4506 that the trade mark 3720P that provides of the trade mark 4045, LG-DOW company that granary Kai Erda plastic material company limited provides or Dutch DSM N. V. provide.
In content of the present invention: nucleator described in step a can be the nucleator etc. that Dongguan City space profit field and the Chemical Co., Ltd. trade mark NX8000K, the Yuyao City Ou Li that provide plastify the trade mark 3988 that company limited provides or the trade mark 900A that the industrial chemical materials company limited of marine origin provides.
In content of the present invention: silicon-series five-retardant described in step a can be the trade mark SFR-100 organic silicon fibre retardant that the trade mark SFR-1000 organic silicon fibre retardant that provides of trade mark SFR-100 organic silicon fibre retardant, General Electric Apparatus Co.(U.S.A.) that General Electric Apparatus Co.(U.S.A.) provides or Guangzhou sky million Chemical Co., Ltd.s provide.
In content of the present invention: antimony oxide flame retardant described in step a can be the antimony oxide flame retardant etc. of the trade mark AT3-CN (TM) that the trade mark GX-2005 that provides of trade mark FR-5099, Jinan Guang Xun trade Co., Ltd that Dongguan City Calvin plastic cement Science and Technology Ltd. provides or bright and industry (Shanghai) Co., Ltd. provide.
Compared with prior art, the present invention has features and beneficial effect:
(1) adopt the present invention, add powder PP, add the mobility of blend components; By adding heat-resistant powder filler material, it can be used as toughening element to be dispersed in PP matrix, can be used as stress concentration thing, produce crazing and shear yielding deformation when product is subject to impacting, consume a large amount of striking energys, improve the low temperature impact strength of material; By adding nucleator, the crystallization that the heterogeneous nucleating effect of nucleator is PP is utilized to provide a large amount of β nucleus, and be conducive to spherulite size reduction and homogenization, visible rays then can be allowed to pass through when size is less than visible wavelength, thus improve glossiness and the transparency of PP, make the inventive method have the easy feature of simple process; Add silicon-series five-retardant and weisspiessglanz halogen-free flame retardants, by increasing rich char residue or layer of charcoal plays fire-retardant effect; Under high temperature, fire retardant forms condensed phase at polymer surfaces, by isolated air, stops the effect such as heat trnasfer, reduction inflammable gas burst size to reach fire-retardant object; By the cooperative flame retardant system of silicon-series five-retardant and antimony oxide flame retardant, make the present invention have low-mix, Halogen, low cigarette, low toxicity, flame retarding efficiency are high, and the feature such as environmental friendliness;
(2) adopt the present invention, PP, as the fastest kind of rate of growth in five large general synthetic resins, after transparent, fire-retardant, impact modification, not only can improve its low-temperature impact resistance, and the ratio of performance to price is very high; Rubber type of material is dispersed in matrix PP as toughness reinforcing body, can be used as stress concentration thing, produce crazing and shear yielding deformation when product is subject to impacting, consume a large amount of striking energys, improve the low temperature impact strength of material; Transparent nucleater has promotion Resin crystallization, the crystallization behavior changing resin and crystal habit and makes the effect of spherulite size refinement, by changing crystallization behavior and the crystal habit of PP, the transparency of goods, rigidity, toughness can be improved, and improve heat resisting temperature etc.; Silicon-series five-retardant, except giving the flame retardant properties of base material excellence, can also improve mechanical property and the processed-type of base material effectively; Therefore, by selecting fire-retardant, translucent, the shock resistance type PP modified plastics of nucleator, fire retardant, toughness reinforcing body and polypropene blended processability excellence, have important practical significance;
(3) the present invention is by adding the silicon-series five-retardant and antimony oxide flame retardant, nucleator that do not affect the transparency, and use terpolymer EP rubber, prepare the PP intermingling material translucent, fire-retardant, low-temperature impact resistance is excellent, by refinement and the homogenization method of PP spherocrystal, (translucent) polypropylene composite material obtained is particularly useful as storage battery shell and cover, also may be used for the transparency and requires the fields etc. such as high packaging, medicine equipment, household supplies, general industry;
(4) preparation technology of the present invention is simple, and operation is easy, easily operates, and obtained (translucent) Properties of Polypropylene Composite is good, practical.
Accompanying drawing explanation
Fig. 1 X-ray diffraction that PP is material modified prepared by the embodiment of the present invention (XRD) collection of illustrative plates; In Fig. 1, X-coordinate be diffraction angle 2 θ/°, ordinate zou is diffraction peak intensity/(a.u.); 2 θ are that 14.0 °, 16.8 °, 18.4 °, 21.0 °, the 21.8 ° diffraction peaks located correspond respectively to (110), (040), (130) of the alpha-crystal form of PP and the diffraction of overlapping (131), (111) face generation from left to right; 2 θ are the diffraction peak of (300) crystal face of typical beta crystal feature at 16 ° of places and peak value is high, illustrate that adding of nucleator creates a large amount of β crystalline substance;
The Fourier transform infrared collection of illustrative plates that the PP of Fig. 2 prepared by the embodiment of the present invention is material modified; As shown in Figure 1, at 973.63cm
-1and 1151.25cm
-1there is [the CH of PP in place
2(CHCH
3)]
ncharacteristic peak; And at 2922.20cm
-1appearance-CH
2stretching vibration peak, 1377.04cm
-1place's appearance-CH
3absorption peak, 1453.95cm
-1there is obvious absorption peak in place, illustrates containing CH
3-C, i.e. CH
3angle vibration; At 1637.37cm
-1there is the stretching vibration peak of C=C in terpolymer EP rubber in place;
Thermogravimetric (TG) curve that the PP of Fig. 3 prepared by the embodiment of the present invention is material modified; Be 350 DEG C with the decomposition temperature of pure PP, and by after blended with terpolymer EP rubber, consistency significantly improve, and thus, this decomposed sample temperature is increased;
Differential scanning calorimetry (DSC) curve of Fig. 4 sample prepared by the embodiment of the present invention; As can be seen from Figure, there is obvious melting peak at 150 DEG C of places in sample, and the melt temperature of pure PP is generally 152 DEG C ~ 165.Show adding of terpolymer EP rubber, destroy the perfect crystalline degree of homopolymerization, reduce the degree of crystallinity of homopolymerization, degree of crystallinity declines and just means the decline of the intermolecular forces of molecule, and Van der Waals force reduces just to result in fusing point and have dropped.
High resolution cold field emission flying-spot microscope (FESEM) photo of the sample fracture of Fig. 5 prepared by the embodiment of the present invention; Sample fracture is more smooth as seen from the figure, terpolymer EP rubber particle is better dispersed in matrix PP, formed " sea-island structure ", and distribute with some dimples, these terpolymer EP rubbers added can be used as stress concentration thing, produce crazing and shear yielding deformation when being hit, consume a large amount of striking energys, improve normal temperature and the low temperature impact strength of material.
Embodiment
The invention will be further described for embodiment plan given below; but can not be interpreted as it is limiting the scope of the invention; some nonessential improvement and adjustment that person skilled in art makes the present invention according to the content of the invention described above, still belong to protection scope of the present invention.
Embodiment 1:
A kind of preparation method of the polypropylene composite material for storage battery shell and cover, step is: take at 75 DEG C temperature carry out powder PP (10g), high transparency homopolymerization PP (85g), the terpolymer EP rubber (5g) of dry 2h, add nucleator (0.1g), silicon-series five-retardant (1.0g) and antimony oxide flame retardant (1.5g), then mix.At room temperature mixture is poured into high-speed mixer, carry out 5min high-speed stirring mixing, make polypropylene and various additive dispersed.Then the compound mixed is joined the twin screw extruder feed hopper that rotating speed is 12r/min, under the processing temperature of the screw speed of 178r/min and 180 ~ 195 DEG C, melting entered to compound, extruded, cooled, pelletizing, drying in 4 hours is carried out, obtained transparent polypropylene matrix material at 85 DEG C, hopper-type drying machine; By obtained transparent polypropylene matrix material (on request or require) injection molding, obtain the polypropylene composite material for storage battery shell and cover.By the obtained polypropylene composite material being used for storage battery shell and cover after temperature 23 ± 2 DEG C, relative humidity 50 ± 5% deposit 24h, ambient temperature 23 ± 2 DEG C, relative humidity 50 ± 5% carries out Mechanics Performance Testing.Record experimental result as follows: sample flow (GB/T3682-2000) is 3.4g/10mim; Density is for being 0.902g/cm
3; Tensile strength (GB/T1040-1992) is 31.8MPa, and tensile modulus is 1631MPa; Elongation (GB/T1040-1992) is 30.0%; Flexural strength (GB/T9341-2000) is 32.1MPa, and modulus in flexure is 1462MPa; Notch shock (GB/T1843-1996) is 3.8KJ/m
2; Ball falling impact test (-40 DEG C of .0.85kg iron ball 1m height ball falling impacts): sample burst; The transparency (GB/T2410-2008) transmittance is 49.2%; Flame retardant resistance (DIN5510-2-2009) is burnt, and grade is S1, level of smoke is SR2, drippage grade is ST2.
Embodiment 2:
A kind of preparation method of the polypropylene composite material for storage battery shell and cover, step is: take at 75 DEG C temperature carry out powder PP (10g), high transparency homopolymerization PP (84g), the terpolymer EP rubber (10g) of dry 2h, add nucleator (0.1g), silicon-series five-retardant (1.0g) and antimony oxide flame retardant (1.0g), then mix.At room temperature mixture is poured into high-speed mixer, carry out 5min high-speed stirring mixing, make polypropylene and various additive dispersed.Then the compound mixed is joined the twin screw extruder feed hopper that rotating speed is 12r/min, under the processing temperature of the screw speed of 178r/min and 180 ~ 195 DEG C, melting entered to compound, extruded, cooled, pelletizing, drying in 4 hours is carried out, obtained transparent polypropylene matrix material at 85 DEG C, hopper-type drying machine; By obtained transparent polypropylene matrix material (on request or require) injection molding, obtain the polypropylene composite material for storage battery shell and cover.By the obtained polypropylene composite material being used for storage battery shell and cover after temperature 23 ± 2 DEG C, relative humidity 50 ± 5% deposit 24h, ambient temperature 23 ± 2 DEG C, relative humidity 50 ± 5% carries out Mechanics Performance Testing.Record experimental result as follows: sample flow (GB/T3682-2000) is 4.2g/10mim; Density is 0.904g/cm
3; Tensile strength (GB/T1040-1992) is 28.3MPa, and tensile modulus is 1598MPa; Elongation (GB/T1040-1992) is 35.0%; Flexural strength (GB/T9341-2000) is 28.6MPa, and modulus in flexure is 1385MPa; Notch shock (GB/T1843-1996) is 5.6KJ/m
2; Ball falling impact test (-40 DEG C of .0.85kg iron ball 1m height ball falling impacts): sample does not break; The transparency (GB/T2410-2008) transmittance is 57.2%; Flame retardant resistance (DIN5510-2-2009) is burnt, and grade is S2, level of smoke is SR2, drippage grade is ST2.
Embodiment 3:
A kind of preparation method of the polypropylene composite material for storage battery shell and cover, step is: take at 75 DEG C temperature carry out powder PP (20g), high transparency homopolymerization PP (70g), the terpolymer EP rubber (15g) of dry 2h, add nucleator (0.2g), silicon-series five-retardant (1.0g) and antimony oxide flame retardant (1.0g), then mix.At room temperature mixture is poured into high-speed mixer, carry out 5min high-speed stirring mixing, make polypropylene and various additive dispersed.Then the compound mixed is joined the twin screw extruder feed hopper that rotating speed is 12r/min, under the processing temperature of the screw speed of 178r/min and 180 ~ 195 DEG C, melting entered to compound, extruded, cooled, pelletizing, drying in 4 hours is carried out, obtained translucent polypropylene composite material at 85 DEG C, hopper-type drying machine; By obtained translucent polypropylene composite material (on request or require) injection molding, obtain the polypropylene composite material for storage battery shell and cover.By the obtained polypropylene composite material being used for storage battery shell and cover after temperature 23 ± 2 DEG C, relative humidity 50 ± 5% deposit 24h, ambient temperature 23 ± 2 DEG C, relative humidity 50 ± 5% carries out Mechanics Performance Testing.Record experimental result as follows: sample flow (GB/T3682-2000) is 6.5g/10mim; Density is for being 0.912g/cm
3; Tensile strength (GB/T1040-1992) is 26.3MPa, and tensile modulus is 985MPa; Elongation (GB/T1040-1992) is 56.0%; Flexural strength (GB/T9341-2000) is 27.6MPa, and modulus in flexure is 1103MPa; Notch shock (GB/T1843-1996) is 15.8KJ/m
2; Ball falling impact test (-40 DEG C of .0.85kg iron ball 1m height ball falling impacts): sample does not break; The transparency (GB/T2410-2008) transmittance is 69.3%; Flame retardant resistance (DIN5510-2-2009) is burnt, and grade is S2, level of smoke is SR2, drippage grade is ST2.
Embodiment 4:
A kind of preparation method of the polypropylene composite material for storage battery shell and cover, step is: take at 75 DEG C temperature carry out powder PP (20g), high transparency homopolymerization PP (70g), the terpolymer EP rubber (12g) of dry 2h, add nucleator (0.1g), silicon-series five-retardant (1.0g) and antimony oxide flame retardant (1.0g), then mix.At room temperature mixture is poured into high-speed mixer, carry out 5min high-speed stirring mixing, make polypropylene and various additive dispersed.Then the compound mixed is joined the twin screw extruder feed hopper that rotating speed is 12r/min, under the processing temperature of the screw speed of 178r/min and 180 ~ 195 DEG C, melting entered to compound, extruded, cooled, pelletizing, drying in 4 hours is carried out, obtained translucent polypropylene composite material at 85 DEG C, hopper-type drying machine; By obtained translucent polypropylene composite material (on request or require) injection molding, obtain the polypropylene composite material for storage battery shell and cover.By the obtained polypropylene composite material being used for storage battery shell and cover after temperature 23 ± 2 DEG C, relative humidity 50 ± 5% deposit 24h, ambient temperature 23 ± 2 DEG C, relative humidity 50 ± 5% carries out Mechanics Performance Testing.Record experimental result as follows: sample flow (GB/T3682-2000) is 6.7g/10mim; Density is for being 0.911g/cm
3; Tensile strength (GB/T1040-1992) is 25.8MPa, and tensile modulus is 1003MPa; Elongation (GB/T1040-1992) is 54.0%; Flexural strength (GB/T9341-2000) is 27.8MPa, and modulus in flexure is 1098MPa; Notch shock (GB/T1843-1996) is 10.3KJ/m
2; Ball falling impact test (-40 DEG C of .0.85kg iron ball 1m height ball falling impacts): sample does not break; The transparency (GB/T2410-2008) transmittance is 64.5%; Flame retardant resistance (DIN5510-2-2009) is burnt, and grade is S2, level of smoke is SR2, drippage grade is ST2.
Embodiment 5:
A kind of preparation method of the polypropylene composite material for storage battery shell and cover, step is: take at 75 DEG C temperature carry out powder PP (20g), high transparency homopolymerization PP (71g), the terpolymer EP rubber (10g) of dry 2h, add, nucleator (0.2g), silicon-series five-retardant (1.0g) and antimony oxide flame retardant (1.5g), then mix.At room temperature mixture is poured into high-speed mixer, carry out 5min high-speed stirring mixing, make polypropylene and various additive dispersed.Then the compound mixed is joined the twin screw extruder feed hopper that rotating speed is 12r/min, under the processing temperature of the screw speed of 178r/min and 180 ~ 195 DEG C, melting entered to compound, extruded, cooled, pelletizing, drying in 4 hours is carried out, obtained translucent polypropylene composite material at 85 DEG C, hopper-type drying machine; By obtained translucent polypropylene composite material (on request or require) injection molding, obtain the polypropylene composite material for storage battery shell and cover.By the obtained polypropylene composite material being used for storage battery shell and cover after temperature 23 ± 2 DEG C, relative humidity 50 ± 5% deposit 24h, ambient temperature 23 ± 2 DEG C, relative humidity 50 ± 5% carries out Mechanics Performance Testing.Record experimental result as follows: mobility (GB/T3682-2000) is 7.2g/10mim; Density (GB/T1033.1-2008) is 0.904g/cm
3; Tensile strength (GB/T1040-2006) is 27.8MPa, and tensile modulus (GB/T1040-2006) is 1320MPa; Elongation (GB/T1040-2006) is 38%, and flexural strength (GB/T9341-2008) is 27.6MPa, and modulus in flexure (GB/T9341-2008) is 1233MPa; Izod notched impact (GB/T1843-2008) is 6.6KJ/m
2; Ball falling impact test (-40 DEG C of .0.85kg iron ball 1m height ball falling impacts): sample does not break; The transparency (GB/T2410-2008) transmittance is 56.4%; Flame retardant resistance (DIN5510-2-2009) is burnt, and grade is S4, level of smoke is SR2, drippage grade is ST2.
Embodiment 6:
A kind of preparation method of the polypropylene composite material for storage battery shell and cover, step is: take at 75 DEG C temperature carry out powder PP (15g), high transparency homopolymerization PP (73.5g), the terpolymer EP rubber (10g) of dry 2h, add nucleator (0.2g), silicon-series five-retardant (0.5g) and antimony oxide flame retardant (2.0g), then mix.At room temperature mixture is poured into high-speed mixer, carry out 5min high-speed stirring mixing, make polypropylene and various additive dispersed.Then the compound mixed is joined the twin screw extruder feed hopper that rotating speed is 12r/min, under the processing temperature of the screw speed of 178r/min and 180 ~ 95 DEG C, melting entered to compound, extruded, cooled, pelletizing, drying in 4 hours is carried out, obtained translucent polypropylene composite material at 85 DEG C, hopper-type drying machine; By obtained translucent polypropylene composite material (on request or require) injection molding, obtain the polypropylene composite material for storage battery shell and cover.By the obtained polypropylene composite material being used for storage battery shell and cover after temperature 23 ± 2 DEG C, relative humidity 50 ± 5% deposit 24h, ambient temperature 23 ± 2 DEG C, relative humidity 50 ± 5% carries out Mechanics Performance Testing.Record experimental result as follows: mobility (GB/T3682-2000) is 6.8g/10mim; Density (GB/T1033.1-2008) is 0.906g/cm
3; Tensile strength (GB/T1040-2006) is 28.1MPa, and tensile modulus (GB/T1040-2006) is 1136MPa; Elongation (GB/T1040-2006) is 20.5%, flexural strength (GB/T9341-2008) is 26.9MPa, modulus in flexure (GB/T9341-2008) is 1133MPa, and Izod notched impact (GB/T1843-2008) is 4.7KJ/m
2; Ball falling impact test (-40 DEG C of .0.85kg iron ball 1m height ball falling impacts): sample does not break; The transparency (GB/T2410-2008) transmittance is 56.7%; Flame retardant resistance (DIN5510-2-2009) is burnt, and grade is S4, level of smoke is SR2, drippage grade is ST2.
Embodiment 7:
A kind of preparation method of the polypropylene composite material for storage battery shell and cover, step is: take at 75 DEG C temperature carry out powder PP (20g), high transparency homopolymerization PP (72g), the terpolymer EP rubber (9.0g) of dry 2h, add nucleator (0.2g), silicon-series five-retardant (1.5g) and antimony oxide flame retardant (1.0g), then mix.At room temperature mixture is poured into high-speed mixer, carry out 5min high-speed stirring mixing, make polypropylene and various additive dispersed.Then the compound mixed is joined the twin screw extruder feed hopper that rotating speed is 12r/min, under the processing temperature of the screw speed of 178r/min and 180 ~ 195 DEG C, melting entered to compound, extruded, cooled, pelletizing, drying in 4 hours is carried out, obtained translucent polypropylene composite material at 85 DEG C, hopper-type drying machine; By obtained translucent polypropylene composite material (on request or require) injection molding, obtain the polypropylene composite material for storage battery shell and cover.By the obtained polypropylene composite material being used for storage battery shell and cover after temperature 23 ± 2 DEG C, relative humidity 50 ± 5% deposit 24h, ambient temperature 23 ± 2 DEG C, relative humidity 50 ± 5% carries out Mechanics Performance Testing.Record experimental result as follows: mobility (GB/T3682-2000) is 7.9g/10mim; Density (GB/T1033.1-2008) is 0.907g/cm
3; Tensile strength (GB/T1040-2006) is 27.6MPa, and tensile modulus (GB/T1040-2006) is 1226MPa; Elongation (GB/T1040-2006) is 32.8%, flexural strength (GB/T9341-2008) is 21.2MPa, modulus in flexure (GB/T9341-2008) is 1256MPa, and Izod notched impact (GB/T1843-2008) is 6.8KJ/m
2; Ball falling impact test (-40 DEG C of .0.85kg iron ball 1m height ball falling impacts): sample has vestige; The transparency (GB/T2410-2008) transmittance is 58.4%; Flame retardant resistance (DIN5510-2-2009) is burnt, and grade is S4, level of smoke is SR2, drippage grade is ST2.
Embodiment 8:
A kind of preparation method of the polypropylene composite material for storage battery shell and cover, step is: take at 75 DEG C temperature carry out powder PP (20g), high transparency homopolymerization PP (70.5g), the terpolymer EP rubber (8.0g) of dry 2h, add nucleator (0.2g), silicon-series five-retardant (0.5g) and antimony oxide flame retardant (1.0g), then mix.At room temperature mixture is poured into high-speed mixer, carry out 5min high-speed stirring mixing, make polypropylene and various additive dispersed.Then the compound mixed is joined the twin screw extruder feed hopper that rotating speed is 12r/min, under the processing temperature of the screw speed of 178r/min and 180 ~ 195 DEG C, melting entered to compound, extruded, cooled, pelletizing, drying in 4 hours is carried out, obtained translucent polypropylene composite material at 85 DEG C, hopper-type drying machine; By obtained translucent polypropylene composite material (on request or require) injection molding, obtain the polypropylene composite material for storage battery shell and cover.By the obtained polypropylene composite material being used for storage battery shell and cover after temperature 23 ± 2 DEG C, relative humidity 50 ± 5% deposit 24h, ambient temperature 23 ± 2 DEG C, relative humidity 50 ± 5% carries out Mechanics Performance Testing.Record experimental result as follows: mobility (GB/T3682-2000) is 8.2g/10mim; Density (GB/T1033.1-2008) is 0.908g/cm
3; Tensile strength (GB/T1040-2006) is 27.2MPa, and tensile modulus (GB/T1040-2006) is 1230MPa; Elongation (GB/T1040-2006) is 31.7%, flexural strength (GB/T9341-2008) is 20.7MPa, modulus in flexure (GB/T9341-2008) is 1168MPa, and Izod notched impact (GB/T1843-2008) is 6.3KJ/m
2; Ball falling impact test (-40 DEG C of .0.85kg iron ball 1m height ball falling impacts): sample does not break; The transparency (GB/T2410-2008) transmittance is 54.6%; Flame retardant resistance (DIN5510-2-2009) is burnt, and grade is S4, level of smoke is SR2, drippage grade is ST2.
Embodiment 9:
A kind of preparation method of the polypropylene composite material for storage battery shell and cover, step is: take at 75 DEG C temperature carry out powder PP (20g), high transparency homopolymerization PP (71.5g), the terpolymer EP rubber (7.0g) of dry 2h, add nucleator (0.3g), silicon-series five-retardant (0.5g) and antimony oxide flame retardant (1g), then mix.At room temperature mixture is poured into high-speed mixer, carry out 5min high-speed stirring mixing, make polypropylene and various additive dispersed.Then the compound mixed is joined the twin screw extruder feed hopper that rotating speed is 12r/min, under the processing temperature of the screw speed of 178r/min and 180 ~ 195 DEG C, melting entered to compound, extruded, cooled, pelletizing, drying in 4 hours is carried out, obtained translucent polypropylene composite material at 85 DEG C, hopper-type drying machine; By obtained translucent polypropylene composite material (on request or require) injection molding, obtain the polypropylene composite material for storage battery shell and cover.By the obtained polypropylene composite material being used for storage battery shell and cover after temperature 23 ± 2 DEG C, relative humidity 50 ± 5% deposit 24h, ambient temperature 23 ± 2 DEG C, relative humidity 50 ± 5% carries out Mechanics Performance Testing.Record experimental result as follows: mobility (GB/T3682-2000) is 8.6g/10mim; Density (GB/T1033.1-2008) is 0.905g/cm
3; Tensile strength (GB/T1040-2006) is 28.5MPa, and tensile modulus (GB/T1040-2006) is 1286MPa; Elongation (GB/T1040-2006) is 28.8%, flexural strength (GB/T9341-2008) is 21.5mpa, modulus in flexure (GB/T9341-2008) is 1263mpa, and Izod notched impact (GB/T1843-2008) is 5.8KJ/m
2; Ball falling impact test (-40 DEG C of .0.85kg iron ball 1m height ball falling impacts): sample does not break; The transparency (GB/T2410-2008) transmittance is 49.3%; Flame retardant resistance (DIN5510-2-2009) is burnt, and grade is S4, level of smoke is SR2, drippage grade is ST2.
Embodiment 10:
A kind of preparation method of the polypropylene composite material for storage battery shell and cover, step is: take at 75 DEG C temperature carry out powder PP (20g), high transparency homopolymerization PP (70.5g), the terpolymer EP rubber (8.0g) of dry 2h, add nucleator (0.3g), silicon-series five-retardant (0.5g) and antimony oxide flame retardant (1g), then mix.At room temperature mixture is poured into high-speed mixer, carry out 5min high-speed stirring mixing, make polypropylene and various additive dispersed.Then the compound mixed is joined the twin screw extruder feed hopper that rotating speed is 12r/min, under the processing temperature of the screw speed of 178r/min and 180 ~ 195 DEG C, melting entered to compound, extruded, cooled, pelletizing, drying in 4 hours is carried out, obtained translucent polypropylene composite material at 85 DEG C, hopper-type drying machine; By obtained translucent polypropylene composite material (on request or require) injection molding, obtain the polypropylene composite material for storage battery shell and cover.By the obtained polypropylene composite material being used for storage battery shell and cover after temperature 23 ± 2 DEG C, relative humidity 50 ± 5% deposit 24h, ambient temperature 23 ± 2 DEG C, relative humidity 50 ± 5% carries out Mechanics Performance Testing.Record experimental result as follows: mobility (GB/T3682-2000) is 8.4g/10mim; Density (GB/T1033.1-2008) is 0.908g/cm
3; Tensile strength (GB/T1040-2006) is 28.2MPa, and tensile modulus (GB/T1040-2006) is 1216MPa; Elongation (GB/T1040-2006) is 30.8%, flexural strength (GB/T9341-2008) is 20.6mpa, modulus in flexure (GB/T9341-2008) is 1156mpa, and Izod notched impact (GB/T1843-2008) is 6.2KJ/m
2; Ball falling impact test (-40 DEG C of .0.85kg iron ball 1m height ball falling impacts): sample does not break; The transparency (GB/T2410-2008) transmittance is 48.1%; Flame retardant resistance (DIN5510-2-2009) is burnt, and grade is S4, level of smoke is SR2, drippage grade is ST2.
Embodiment 11:
For a preparation method for the polypropylene composite material of storage battery shell and cover, step is:
A, raw materials pretreatment and batching:;
By raw material PP powder, high transparency homopolymerization PP and terpolymer EP rubber, dry 2h under temperature 70 C respectively;
Get dried raw material PP powder 10 weight part, high transparency homopolymerization PP 70 weight part, terpolymer EP rubber 5 weight part, get raw material nucleator 0.1 weight part, silicon-series five-retardant 0.5 weight part and antimony oxide flame retardant 1 weight part, whole raw material is mixed, obtains compound;
B, compound is poured into (speed is 100r/min) mixing machine, after being uniformly mixed 5min, polypropylene is made to evenly spread in other raw material, again compound is joined in (rotating speed is 10r/min's) twin screw extruder feed hopper, under the processing temperature of the screw speed of 170r/min and 180 DEG C, melting entered to compound, extruded, cooled, pelletizing, dry 4h (hopper-type drying machine can be placed in dry), i.e. obtained (translucent) polypropylene composite material at 80 ~ 90 DEG C of temperature again;
C, shaping: by obtained (translucent) polypropylene composite material (on request or require) injection molding, to obtain the polypropylene composite material for storage battery shell and cover.
Embodiment 12:
For a preparation method for the polypropylene composite material of storage battery shell and cover, step is:
A, raw materials pretreatment and batching:;
By raw material PP powder, high transparency homopolymerization PP and terpolymer EP rubber, dry 1h at temperature 80 DEG C respectively;
Get dried raw material PP powder 20 weight part, high transparency homopolymerization PP 85 weight part, terpolymer EP rubber 15 weight part, get raw material nucleator 0.3 weight part, silicon-series five-retardant 1 weight part and antimony oxide flame retardant 2 weight part, whole raw material is mixed, obtains compound;
B, compound is poured into (speed is 300r/min) mixing machine, after being uniformly mixed 10min, polypropylene is made to evenly spread in other raw material, again compound is joined in (rotating speed is 15r/min's) twin screw extruder feed hopper, under the processing temperature of the screw speed of 190r/min and 195 DEG C, melting entered to compound, extruded, cooled, pelletizing, dry 1h (hopper-type drying machine can be placed in dry), i.e. obtained (translucent) polypropylene composite material at 90 DEG C of temperature again;
C, shaping: by obtained (translucent) polypropylene composite material (on request or require) injection molding, to obtain the polypropylene composite material for storage battery shell and cover.
Embodiment 13:
For a preparation method for the polypropylene composite material of storage battery shell and cover, step is:
A, raw materials pretreatment and batching:;
By raw material PP powder, high transparency homopolymerization PP and terpolymer EP rubber, dry 1.5h at temperature 75 DEG C respectively;
Get dried raw material PP powder 15 weight part, high transparency homopolymerization PP 77 weight part, terpolymer EP rubber 10 weight part, get raw material nucleator 0.2 weight part, silicon-series five-retardant 0.7 weight part and antimony oxide flame retardant 1.5 weight part, whole raw material is mixed, obtains compound;
B, compound is poured into (speed is 200r/min) mixing machine, after being uniformly mixed 7min, polypropylene is made to evenly spread in other raw material, again compound is joined in (rotating speed is 12r/min's) twin screw extruder feed hopper, under the processing temperature of the screw speed of 180r/min and 187 DEG C, melting entered to compound, extruded, cooled, pelletizing, dry 3h (hopper-type drying machine can be placed in dry), i.e. obtained (translucent) polypropylene composite material at 85 DEG C of temperature again;
C, shaping: by obtained (translucent) polypropylene composite material (on request or require) injection molding, to obtain the polypropylene composite material for storage battery shell and cover.
Embodiment 14:
For a preparation method for the polypropylene composite material of storage battery shell and cover, step is:
A, raw materials pretreatment and batching:;
By raw material PP powder, high transparency homopolymerization PP and terpolymer EP rubber, dry 1.5h at temperature 80 DEG C respectively;
Get dried raw material PP powder 20 weight part, high transparency homopolymerization PP 70 weight part, terpolymer EP rubber 5 weight part, get raw material nucleator 0.1 weight part, silicon-series five-retardant 0.7 weight part and antimony oxide flame retardant 1.3 weight part, whole raw material is mixed, obtains compound;
B, compound is poured into (speed is 180r/min) mixing machine, after being uniformly mixed 6min, polypropylene is made to evenly spread in other raw material, again compound is joined in (rotating speed is 11r/min's) twin screw extruder feed hopper, under the processing temperature of the screw speed of 178r/min and 190 DEG C, melting entered to compound, extruded, cooled, pelletizing, dry 4h (hopper-type drying machine can be placed in dry), i.e. obtained (translucent) polypropylene composite material at 80 DEG C of temperature again;
C, shaping: by obtained (translucent) polypropylene composite material (on request or require) injection molding, to obtain the polypropylene composite material for storage battery shell and cover.
Embodiment 15 ~ 21:
For a preparation method for the polypropylene composite material of storage battery shell and cover, step is:
A, raw materials pretreatment and batching:;
By raw material PP powder, high transparency homopolymerization PP and terpolymer EP rubber, dry 1 ~ 2h at temperature 70 ~ 80 DEG C respectively;
Get dried raw material PP powder 10 ~ 20 weight part, high transparency homopolymerization PP 70 ~ 85 weight part, terpolymer EP rubber 5 ~ 15 weight part, get raw material nucleator 0.1 ~ 0.3 weight part, silicon-series five-retardant 0.5 ~ 1 weight part and antimony oxide flame retardant 1 ~ 2 weight part, whole raw material is mixed, obtains compound; In each embodiment, the concrete weight part consumption of each feed composition sees the following form:
B, compound is poured into (at a high speed) (velocity range is preferably 100 ~ 300r/min) mixing machine, (at a high speed) after being uniformly mixed 5 ~ 10min, polypropylene is made to evenly spread in other raw material, again compound is joined in (rotating speed is 10 ~ 15r/min's preferably) twin screw extruder feed hopper, under the processing temperature of the screw speed of 170 ~ 190r/min and 180 ~ 195 DEG C, melting was entered to compound, extrude, cooling, pelletizing, dry 1 ~ 4h (hopper-type drying machine can be placed in dry) at 80 ~ 90 DEG C of temperature again, i.e. obtained (translucent) polypropylene composite material,
C, shaping: by obtained (translucent) polypropylene composite material (on request or require) injection molding, to obtain the polypropylene composite material for storage battery shell and cover.
In above-described embodiment: the powder of PP described in step a can be the PP powder etc. of the trade mark 085 that the trade mark 085 that provides of the trade mark 075, SINOPEC Jingmen Company that Tianli Hi-New Tech Co., Ltd., Dushanzi, Xinjiang provides or SINOPEC Shijiazhuang Refining & Chemical Co., Ltd. provide, the trade mark and model, rear same.
In above-described embodiment: the homopolymerization PP of high transparency described in step a can be the high transparency homopolymerization PP etc. of the trade mark RP344R that the trade mark ST868M that provides of trade mark 1100N, Lee Chang Yung Chemical Indust that Ningxia Coal Industry Group company limited of Shenhua provides or great Lin company of Korea S provide.
In above-described embodiment: terpolymer EP rubber described in step a can be the terpolymer EP rubber etc. of the trade mark Keltan4506 that the trade mark 3720P that provides of the trade mark 4045, LG-DOW company that granary Kai Erda plastic material company limited provides or Dutch DSM N. V. provide.
In above-described embodiment: nucleator described in step a can be the nucleator etc. that Dongguan City space profit field and the Chemical Co., Ltd. trade mark NX8000K, the Yuyao City Ou Li that provide plastify the trade mark 3988 that company limited provides or the trade mark 900A that the industrial chemical materials company limited of marine origin provides.
In above-described embodiment: silicon-series five-retardant described in step a can be the trade mark SFR-100 organic silicon fibre retardant that the trade mark SFR-1000 organic silicon fibre retardant that provides of trade mark SFR-100 organic silicon fibre retardant, General Electric Apparatus Co.(U.S.A.) that General Electric Apparatus Co.(U.S.A.) provides or Guangzhou sky million Chemical Co., Ltd.s provide.
In above-described embodiment: antimony oxide flame retardant described in step a can be the antimony oxide flame retardant etc. of the trade mark AT3-CN (TM) that the trade mark GX-2005 that provides of trade mark FR-5099, Jinan Guang Xun trade Co., Ltd that Dongguan City Calvin plastic cement Science and Technology Ltd. provides or bright and industry (Shanghai) Co., Ltd. provide.
In above-described embodiment: each raw material adopted is commercially available prod.
In above-described embodiment: in the percentage adopted, do not indicate especially, be weight (quality) percentage or well known to a person skilled in the art percentage; Described weight (quality) part can be all gram or kilogram.
In above-described embodiment: the processing parameter (temperature, time, concentration etc.) in each step and each amounts of components numerical value etc. are scope, and any point is all applicable.
The concrete same prior art of technology contents described in content of the present invention and above-described embodiment.
The invention is not restricted to above-described embodiment, all can implement described in content of the present invention and there is described good result.
Claims (7)
1., for a preparation method for the polypropylene composite material of storage battery shell and cover, it is characterized in that step is:
A, raw materials pretreatment and batching:
By raw material PP powder, high transparency homopolymerization PP and terpolymer EP rubber, dry 1 ~ 2h at temperature 70 ~ 80 DEG C respectively;
Get dried raw material PP powder 10 ~ 20 weight part, high transparency homopolymerization PP 70 ~ 85 weight part, terpolymer EP rubber 5 ~ 15 weight part, get raw material nucleator 0.1 ~ 0.3 weight part, silicon-series five-retardant 0.5 ~ 1 weight part and antimony oxide flame retardant 1 ~ 2 weight part, whole raw material is mixed, obtains compound;
B, compound is poured into mixing machine, after being uniformly mixed 5 ~ 10min, again compound is joined in twin screw extruder feed hopper, under the processing temperature of the screw speed of 170 ~ 190r/min and 180 ~ 195 DEG C, melting entered to compound, extruded, cooled, pelletizing, dry 1 ~ 4h at 80 ~ 90 DEG C of temperature, i.e. obtained polypropylene composite material again;
C, shaping: by obtained polypropylene composite material injection molding, to obtain the polypropylene composite material for storage battery shell and cover.
2. by the preparation method for the polypropylene composite material of storage battery shell and cover described in claim 1, it is characterized in that: the powder of PP described in step a is the PP powder of the trade mark 085 that the trade mark 085 that provides of the trade mark 075, SINOPEC Jingmen Company that Tianli Hi-New Tech Co., Ltd., Dushanzi, Xinjiang provides or SINOPEC Shijiazhuang Refining & Chemical Co., Ltd. provide.
3. by the preparation method for the polypropylene composite material of storage battery shell and cover described in claim 1, it is characterized in that: the homopolymerization PP of high transparency described in step a is the high transparency homopolymerization PP of the trade mark RP344R that the trade mark ST868M that provides of trade mark 1100N, Lee Chang Yung Chemical Indust that Ningxia Coal Industry Group company limited of Shenhua provides or great Lin company of Korea S provide.
4. by the preparation method for the polypropylene composite material of storage battery shell and cover described in claim 1, it is characterized in that: terpolymer EP rubber described in step a is the terpolymer EP rubber of the trade mark Keltan4506 that the trade mark 3720P that provides of the trade mark 4045, LG-DOW company that granary Kai Erda plastic material company limited provides or Dutch DSM N. V. provide.
5. by the preparation method for the polypropylene composite material of storage battery shell and cover described in claim 1, it is characterized in that: nucleator described in step a is the nucleator that trade mark NX8000K, Yuyao City Ou Li that Dongguan City space profit field and Chemical Co., Ltd. provide plastify the trade mark 3988 that company limited provides or the trade mark 900A that the industrial chemical materials company limited of marine origin provides.
6. by the preparation method for the polypropylene composite material of storage battery shell and cover described in claim 1, it is characterized in that: silicon-series five-retardant described in step a is the trade mark SFR-100 organic silicon fibre retardant that the trade mark SFR-1000 organic silicon fibre retardant that provides of trade mark SFR-100 organic silicon fibre retardant, General Electric Apparatus Co.(U.S.A.) that General Electric Apparatus Co.(U.S.A.) provides or Guangzhou sky million Chemical Co., Ltd.s provide.
7. by the preparation method for the polypropylene composite material of storage battery shell and cover described in claim 1, it is characterized in that: antimony oxide flame retardant described in step a is the antimony oxide flame retardant of the trade mark AT3-CN (TM) that the trade mark GX-2005 that provides of trade mark FR-5099, Jinan Guang Xun trade Co., Ltd that Dongguan City Calvin plastic cement Science and Technology Ltd. provides or bright and industry (Shanghai) Co., Ltd. provide.
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