CN103554581A - Reinforcing illite/montmorillonite clay filler-containing rubber and preparation method thereof - Google Patents
Reinforcing illite/montmorillonite clay filler-containing rubber and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a reinforcing illite/montmorillonite clay filler-containing rubber and a preparation method thereof, which belong to the field of rubber applications. The rubber is composed of the following components in parts by mass: 100 parts of a crude styrene-butadiene rubber, 2 parts of an antiager 4020, 1.2 parts of an accelerant CZ, 3 parts of zinc oxide, 1 part of a stearic acid, 1.8 parts of sulfur, and 40-60 parts of modified illite/montmorillonite clay nano-powder. The preparation method of the rubber comprises the following steps of: 1, the preparation of dry illite/montmorillonite clay powder: including the steps of dry crushing, soaking, pulp mashing, screening, deironing, chemical bleaching, grinding, dispersing treatment, swelling treatment, evaporation drying, mechanical grinding and coating modification; 2, mixing; and 3, vulcanizing. Sine the rubber takes modified illite/montmorillonite clay nano-powder as a filler, the production cost is greatly reduced; and the rubber is good in mechanical properties and reinforcing effect.
Description
Technical field
The present invention relates to a kind of rubber of using Iraq/Mongolia clay filler containing reinforcement and preparation method thereof, relate in particular to the applied research for styrene-butadiene rubber(SBR) reinforcement as filler of a kind of Iraq/Mongolia clay nano powder, belong to rubber applications field.
Background technology
At present, product as loading material of rubber mainly contains: carbon black, white carbon black, nano-calcium carbonate, nanoclay (kaolin, polynite, attapulgite hybrid etc.), nano silicon, carbon black/white carbon black diphase nano-filler, nano zine oxide, nano aluminium oxide, nano ferriferrous oxide, nanometer acrylate metal salt, carbon nanotube and nano-scale fiber etc., of a great variety, very different, but its complex manufacturing, expend mass energy and resource, production cost is high, the economic interests that obtain are relatively less, and reinforcing effect does not reach perfect condition completely yet.Now need badly and seek a kind of rubber new packing and can play good strengthening action to rubber, can make up above-mentioned deficiency again.
Summary of the invention
High for existing loading material of rubber production cost, the undesirable problem of reinforcing effect of its filler, the object of the present invention is to provide a kind of rubber of using Iraq/Mongolia clay filler containing reinforcement, described rubber adopts modification Iraq/Mongolia clay nano powder as filler, greatly reduce production cost, and mechanical property is good, reinforcing effect is good.
Object of the present invention is realized by following technical scheme:
A rubber containing reinforcement with Iraq/Mongolia clay filler, described rubber composed as follows:
The described preparation method who uses the rubber of Iraq/Mongolia clay filler containing reinforcement, step is as follows:
1. the preparation of Iraq/Mongolia clay nano dry powder
1) dry milling: become particle diameter to be less than the Iraq/Mongolia clay pit fritter of 5cm natural Iraq/Mongolia clay mineral Mechanical Crushing;
2) soak: the Iraq/Mongolia clay pit fritter that step 1) is obtained is soaked 12～24h, obtains Iraq/Mongolia clay slip; Wherein, solids in pulp amount is 45wt%;
3) smash slurry: regulating the pH value of Iraq/Mongolia clay slip is 8～10, adds dispersion agent, and adopt sand milling dispersion machine to smash slurry dispersion; Wherein, the add-on of dispersion agent is 1～3wt% of solid content in described slip; The rotating speed of sand milling dispersion machine is 700～1000rpm, and churning time is 30～60min;
4) screening: the slip that step 3) is smash after slurry disperses is crossed 500 mesh sieves, obtains minus mesh slurry;
5) deironing: the slip that adopts high gradient magnetic separator to obtain step 4) carries out deironing, and slip circulates 2～5 times in high gradient magnetic separator, and the magneticstrength of high gradient magnetic separator is 8000～10000Gs;
6) chemical bleaching: the slip after deironing is bleached under 700～1000rpm, the condition of 65 ℃, be specially: first adopt H
2sO
4it is 4～5 that solution regulates the pH value of slip, and the powder that then takes a policy, reacts 45～60min, then adds oxalic acid, reacts 45～60min; Again slip is carried out to separation afterwards and obtain yellow solid, gained yellow solid is washed to white, then adding water, to make solids in pulp amount be 45wt%, the slip after can being bleached; Wherein, the add-on of vat powder is the 1wt% of solid content in slip, and the add-on of oxalic acid is 1.5～3.5wt% of solid content in slip;
7) grind: adopt high-energy-density to stir mill the slip after bleaching is ground, wherein, the delivery rate of pump is 1～3L/min, and grinding medium is the ZrO of diameter 0.7～0.8mm
2ceramic fine bead, grinding medium filling ratio is 85%, and mill speed is 1000～1400rpm, and milling time is 2～6h; After grinding, obtain nanometer slurry;
8) dispersion treatment: add dispersion agent in the nanometer slurry obtaining to step 7), and adopt sand milling dispersion machine dispersed with stirring; Wherein, adding the amount of dispersion agent is 1～2wt% of solid content in described slip; The rotating speed of sand milling dispersion machine is 1000～3000rpm, and churning time is 5～10min;
9) swollenization processed: in the slip after step 8) dispersion treatment, add properties-correcting agent, then, adopt sand milling dispersion machine to stir, rotating speed 2000～5000rpm, churning time 10～30min; Wherein, adding the amount of properties-correcting agent is 2.0～4.0wt% of solid content in slip;
10) evaporation drying: the slip after swollenization processed is dried, and obtains nanometer siccative; Wherein, drying temperature is 120～150 ℃, and be 6～12h time of drying;
11) mechanical disintegration: the nanometer siccative that step 10) is obtained carries out mechanical disintegration, grinding time is 30～90s;
12) coated modification: add containing hydrogen silicone oil or γ-aminopropyl triethoxysilane (KH550) in the nanometer siccative after mechanical disintegration, dispersed with stirring is carried out in continuation in high speed pulverization dispersion machine, churning time is 15～60s, obtains modification Iraq/Mongolia clay nano powder; Wherein the add-on of containing hydrogen silicone oil or γ-aminopropyl triethoxysilane is 2～6% of nanometer siccative quality after mechanical disintegration;
2. mixing: in the open mixing roll of twin-roll, first styrene-butadiene rubber(SBR) (SBR) rubber to be plasticated 3～5 times in minimum roll spacing, rubber molecular weight is reduced; Then add respectively in order antioxidant 4020, accelerant CZ, zinc oxide, stearic acid; Until above-mentioned substance and SBR mixing evenly after, obtain mixing system, then divide and add modification Iraq/Mongolia clay nano powder for 3～5 times, guarantee that modification Iraq/Mongolia clay nano powder mixes in mixing system, add again sulphur, thin-pass, mixing 20min is until evenly, smash sheet under glue, obtain rubber unvulcanizate;
3. sulfuration: vulcanize 5～8min in vulcanizer, obtain the rubber with Iraq/Mongolia clay filler containing reinforcement.
Step 3) preferably adopts NaOH or H while regulating the pH value of Iraq/Mongolia clay slip
2sO
4solution;
Described in step 3) and step 8), dispersion agent is all preferably WF-211 dispersion agent (polycarboxylate sodium's multipolymer);
Described in step 9), properties-correcting agent is polyoxyethylenated alcohol sodium sulfate (AES), AMONYL 380LC (CAB), one or more in γ-aminopropyl triethoxysilane (KH550) and sodium lauryl sulphate (K12).
Beneficial effect
1. pair powder carries out dry method modification, when realizing enhancing inorganic powder particle and organic matrix bonding force, has increased homogeneity and the dispersiveness of powder granule.
2. modification Iraq/Mongolia clay nano powder, as styrene-butadiene rubber(SBR) filler, only needs reinforced filling seldom can make matrix material have higher intensity, Young's modulus and toughness.
3. modification Iraq/Mongolia clay nano powder has good thermostability and dimensional stability as styrene-butadiene rubber(SBR) filler.
4. modification Iraq/Mongolia clay nano powder is as styrene-butadiene rubber(SBR) filler, and the mechanical property of its matrix material is better than white carbon black, nano-calcium carbonate, fiber-reinforced polymer system etc., because clay can play strengthening action in two dimension.
5. modification Iraq/Mongolia clay nano powder is as styrene-butadiene rubber(SBR) filler, and it has aboundresources and cheap, and production cost reduces greatly.
Embodiment
Below in conjunction with specific embodiment in detail the present invention is described in detail, but is not limited to this.
In following examples, equipment used is as follows:
Sand milling dispersion machine: Shenzhen SDF-400 of San Xingfeirong Machinery Co., Ltd. type;
High gradient magnetic separator: Foshan Wanda's industry mechanical means WD of company limited series electromagnetism high gradient magnetic separator;
High-energy-density stirs mill: Switzerland Bulher (Bu Le) SuperFlow12 of company type;
High speed pulverization dispersion machine: the accurate RT-04 of the Science and Technology Ltd. type of Taiwan Rong Cong.
The open mixing roll of twin-roll: the two roller mills of rubber machinery plant, Shanghai SK-1608 type;
XLB vulcanizing press: east, Huzhou XLB-D of Machinery Co., Ltd. (Q) is from die sinking vulcanizing press;
In following examples, curing time is measured and is adopted GT-M2000A type to measure without rotor vulkameter (Taiwan high ferro Science and Technology Co., Ltd.); Elastomeric mechanical property records according to GB/T528-1998 standard.
In embodiment, containing hydrogen silicone oil used is that Guangzhou auspicious sign Chemical Co., Ltd. produces.
In embodiment, dispersion agent WF-211 used is that Shanghai Xin Yang Chemical Co., Ltd. produces.
Embodiment 1
1. the preparation of Iraq/Mongolia clay nano dry powder
1) dry milling: become particle diameter to be less than the illite/smectite mixed layer clay pit fritter of 5cm natural Iraq/Mongolia clay mineral Mechanical Crushing;
2) soak: the illite/smectite mixed layer clay pit fritter that step 1) is obtained is soaked 12h, obtains Iraq/Mongolia clay slip; Wherein, in slip, solid content is 45wt%;
3) smash slurry: adopting the pH value of the NaOH solution adjusting Iraq/Mongolia clay slip of 0.1mol/L is 8, adds WF-211 dispersion agent, and adopts sand milling dispersion machine to smash slurry dispersion; Wherein, the add-on of WF-211 dispersion agent is the 3wt% of solid content in described slip; The rotating speed of sand milling dispersion machine is 1000rpm, and churning time is 60min;
4) screening: the slip that step 3) is smash after slurry disperses is crossed 500 mesh sieves, obtains minus mesh slurry;
5) deironing: the slip that adopts high gradient magnetic separator to obtain step 4) carries out deironing, and slip circulates 2 times in high gradient magnetic separator, and the magneticstrength of high gradient magnetic separator is 8000Gs;
6) chemical bleaching: the slip after deironing is bleached under 1000rpm, the condition of 65 ℃, be specially: the H that first adopts 0.1mol/L
2sO
4it is 4 that solution regulates the pH value of slip, the powder that then takes a policy, and reaction 45min, then add oxalic acid, reaction 45min; Again slip is carried out to separation afterwards and obtain yellow solid, gained yellow solid is washed to white, then adding water, to make solid content in slip be 45wt%, the slip after can being bleached; Wherein, the add-on of vat powder is the 1wt% of solid content in slip, and the add-on of oxalic acid is the 1.5wt% of solid content in slip;
7) grind: adopt high-energy-density to stir mill and grind, wherein, the delivery rate of pump is 1L/min, and grinding medium is the ZrO of diameter 0.7mm
2ceramic fine bead, grinding medium filling ratio is 85%, and mill speed is 1000rpm, and milling time is 2h; After grinding, obtain Iraq/Mongolia clay nano slip;
8) dispersion treatment: add WF-211 dispersion agent in the nanometer slurry obtaining to step 7), and adopt sand milling dispersion machine dispersed with stirring; Wherein, adding the amount of WF-211 dispersion agent is the 2wt% of solid content in described slip; The rotating speed of sand milling dispersion machine is 3000rpm, and churning time is 5min;
9) swollenization processed: in the slip after step 8) dispersion treatment, add AES and KH550, then, adopt sand milling dispersion machine to stir, rotating speed 2000rpm, churning time 30min; Wherein, add the amount of AES and KH550 to be respectively the 1.0wt% of solid content in slip;
10) evaporation drying: it is dry that the slip after swollenization processed is placed in common exhausting loft drier, obtains nanometer siccative; Wherein, drying temperature is 120 ℃, and be 6h time of drying;
11) mechanical disintegration: the nanometer siccative that step 10) is obtained carries out mechanical disintegration, grinding time is 90s;
12) coated modification: add containing hydrogen silicone oil in the nanometer siccative after mechanical disintegration, continue to carry out dispersed with stirring in high speed pulverization dispersion machine, churning time is 15s, obtains modification Iraq/Mongolia clay nano powder; Wherein the add-on of containing hydrogen silicone oil is 2% of nanometer siccative quality after mechanical disintegration;
2. mixing: in the open mixing roll of twin-roll, first styrene-butadiene rubber(SBR) (SBR) rubber to be plasticated 3 times in minimum roll spacing, rubber molecular weight is reduced; Then add respectively in order antioxidant 4020, accelerant CZ, zinc oxide, stearic acid; Until above-mentioned substance and SBR mixing evenly after, obtain mixing system, then minute add modification Iraq/Mongolia clay nano powder for 5 times, the Iraq/Mongolia clay nano powder of guaranteeing modification mixes in mixing system, then adds sulphur, thin-pass, mixing 20min until evenly, smash sheet under glue, obtains rubber unvulcanizate.Wherein styrene-butadiene rubber(SBR) rubber is 100 mass parts, and antioxidant 4020 is 2 mass parts, and accelerant CZ is 1.2 mass parts, zinc oxide 3 mass parts, and stearic acid is 1 mass parts, and modification Iraq/Mongolia clay nano powder is 40 mass parts, and sulphur is 1.8 mass parts.
3. sulfuration: get 7g rubber unvulcanizate and measure vulcanization curve in GT-M2000A type on without rotor vulkameter, the rubber plateau cure stage recording according to vulcanization characteristics curve is determined compressing tablet curing time, then in XLB vulcanizing press, vulcanize, curing time is 5min, obtains the rubber with Iraq/Mongolia clay filler containing reinforcement.The rubber preparing is cut into dumbbell-shaped specimen and (determines four specimen, be designated as respectively sample 1, sample 2, sample 3 and sample 4), according to GB/T528-1998 standard testing, carry out mechanical property (tension test) test: draw speed is 15mm/min.Test-results is as shown in table 1.Various mineral fillers are as shown in table 4 on the impact of styrene-butadiene rubber(SBR) mechanical property.
Contrast table 1 can obviously draw with table 4, the prepared modification Iraq/Mongolia clay nano powder of the present embodiment has very strong strengthening action as loading material of rubber, its tensile strength has reached 10.63MPa, be greater than the 7.2MPa of VN3 white carbon black, 100% tensile modulus is 1.62MPa, is also greater than the 1.1MPa of VN3 white carbon black.Contrast other mineral fillers, also can draw, the modification Iraq/Mongolia clay nano powder strengthening action of this experiment preparation is better than the fillers such as calcined kaolin, VN3 white carbon black, can be used as and replace VN3 white carbon black etc. as a kind of layered clay mineral filler of styrene-butadiene rubber(SBR), its rubber performance as strengthening agent is good.
Table 1 is the rubber mechanical experimental results with Iraq/Mongolia clay filler containing reinforcement
Remarks: the tensile stress when working portion that 100% tensile modulus is defined as sample is stretched to 100% elongation.
Embodiment 2
1) dry milling: become particle diameter to be less than the illite/smectite mixed layer clay pit fritter of 5cm natural Iraq/Mongolia clay mineral Mechanical Crushing;
2) soak: the illite/smectite mixed layer clay pit fritter that step 1) is obtained is soaked 24h, obtains Iraq/Mongolia clay slip; Wherein, in slip, solid content is 45wt%;
3) smash slurry: adding the pH value of the NaOH solution adjusting Iraq/Mongolia clay slip of 0.1mol/L is 10, adds WF-211 dispersion agent, and adopts sand milling dispersion machine to smash slurry dispersion; Wherein, the add-on of WF-211 dispersion agent is the 1wt% of solid content in described slip; The rotating speed of sand milling dispersion machine is 700rpm, and churning time is 30min;
4) screening: the slip that step 3) is smash after slurry disperses is crossed 500 mesh sieves, obtains minus mesh slurry;
5) deironing: the slip that adopts high gradient magnetic separator to obtain step 4) carries out deironing, and slip circulates 5 times in high gradient magnetic separator, and the magneticstrength of high gradient magnetic separator is 10000Gs;
6) chemical bleaching: the slip after deironing is bleached under 700rpm, the condition of 65 ℃, be specially: the H that first adopts 0.1mol/L
2sO
4it is 5 that solution regulates the pH value of slip, the powder that then takes a policy, and reaction 60min, then add oxalic acid, reaction 60min; Again slip is carried out to separation afterwards and obtain yellow solid, gained yellow solid is washed to white, then adding water, to make solid content in slip be 45wt%, the slip after can being bleached; Wherein, the add-on of vat powder is the 1wt% of solid content in slip, and the add-on of oxalic acid is the 3.5wt% of solid content in slip;
7) grind: adopt high-energy-density to stir mill and grind, wherein, the delivery rate of pump is 2L/min, and grinding medium is the ZrO of diameter 0.8mm
2ceramic fine bead, grinding medium filling ratio is 85%, and mill speed is 1400rpm, and milling time is 3h; After grinding, obtain Iraq/Mongolia clay nano slip;
8) dispersion treatment: add dispersion agent WF-211 in the nanometer slurry obtaining to step 7), and adopt sand milling dispersion machine dispersed with stirring; Wherein, adding the amount of dispersion agent is the 2wt% of solid content in described slip; The rotating speed of sand milling dispersion machine is 1000rpm, and churning time is 10min;
9) swollenization processed: in the slip after step 8) dispersion treatment, add AES and CAB, then, adopt sand milling dispersion machine to stir, rotating speed 5000rpm, churning time 10min; Wherein, adding the amount of AES is the 1wt% of solid content in slip, and the amount that adds CAB is the 2.5wt% of solid content in slip;
10) evaporation drying: it is dry that the slip after swollenization processed is placed in common exhausting loft drier, obtains nanometer siccative; Wherein, drying temperature is 130 ℃, and be 8h time of drying;
11) mechanical disintegration: the nanometer siccative that step 10) is obtained carries out mechanical disintegration, grinding time is 60s;
12) coated modification: add γ-aminopropyl triethoxysilane (KH550) in the nanometer siccative after mechanical disintegration, continue to carry out dispersed with stirring in high speed pulverization dispersion machine, churning time is 60s, obtains modification Iraq/Mongolia clay nano powder; Wherein the add-on of KH550 is 2% of nanometer siccative quality after mechanical disintegration;
2. mixing: in the open mixing roll of twin-roll, first styrene-butadiene rubber(SBR) (SBR) rubber to be plasticated 5 times in minimum roll spacing, rubber molecular weight is reduced; Then add respectively in order antioxidant 4020, accelerant CZ, zinc oxide, stearic acid; Until above-mentioned substance and SBR mixing evenly after, obtain mixing system, then divide and add the Iraq/Mongolia clay nano powder after modification for 5 times, the Iraq/Mongolia clay nano powder of guaranteeing modification mixes in mixing system, add again sulphur, thin-pass, mixing 20min is until evenly, smash sheet under glue, obtain rubber unvulcanizate.Wherein styrene-butadiene rubber(SBR) rubber is 100 mass parts, and antioxidant 4020 is 2 mass parts, and accelerant CZ is 1.2 mass parts, zinc oxide 3 mass parts, and stearic acid is 1 mass parts, and modification Iraq/Mongolia clay nano powder is 50 mass parts, and sulphur is 1.8 mass parts.
3. sulfuration: get 7g sample and measure vulcanization curve in GT-M2000A type on without rotor vulkameter, the rubber plateau cure stage recording according to vulcanization characteristics curve is determined compressing tablet curing time, then in XLB vulcanizing press, vulcanize, curing time is 8min, obtains the rubber with Iraq/Mongolia clay filler containing reinforcement.The rubber preparing is cut into dumbbell-shaped specimen and (determines four specimen, be designated as respectively sample 1, sample 2, sample 3 and sample 4), according to GB/T528-1998 standard testing, carry out mechanical property (tension test) test: draw speed is 15mm/min.Test-results is as shown in table 2.
Contrast table 2 and table 4, can obviously draw, the prepared modification Iraq/Mongolia clay nano powder of the present embodiment has very strong strengthening action as loading material of rubber, its tensile strength has reached 9.42MPa, be greater than the 7.2MPa of VN3 white carbon black, 100% tensile modulus is the 1.1MPa that 1.74MPa is also greater than VN3 white carbon black.Contrast other, also can draw, the modification Iraq/Mongolia clay nano powder strengthening action of this experiment preparation is better than the fillers such as calcined kaolin, VN3 white carbon black, can be used as and replaces VN3 white carbon black etc. as a kind of layered clay mineral filler of styrene-butadiene rubber(SBR), and its rubber performance as strengthening agent is good.
Table 2 is the rubber mechanical experimental results with Iraq/Mongolia clay filler containing reinforcement
Embodiment 3
1) dry milling: become particle diameter to be less than the illite/smectite mixed layer clay pit fritter of 5cm natural Iraq/Mongolia clay mineral Mechanical Crushing;
2) soak: the illite/smectite mixed layer clay pit fritter that step 1) is obtained is soaked 20h, obtains Iraq/Mongolia clay slip; Wherein, in slip, solid content is 45wt%;
3) smash slurry: adding the pH value of the NaOH solution adjusting Iraq/Mongolia clay slip of 0.1mol/L is 9, adds WF-211 dispersion agent, and adopts sand milling dispersion machine to smash slurry dispersion; Wherein, the add-on of WF-211 dispersion agent is the 2wt% of solid content in described slip; The rotating speed of sand milling dispersion machine is 800rpm, and churning time is 45min;
4) screening: the slip that step 3) is smash after slurry disperses is crossed 500 mesh sieves, obtains minus mesh slurry;
5) deironing: the slip that adopts high gradient magnetic separator to obtain step 4) carries out deironing, and slip circulates 3 times in high gradient magnetic separator, and the magneticstrength of high gradient magnetic separator is 9000Gs;
6) chemical bleaching: the slip after deironing is bleached under 900rpm, the condition of 65 ℃, be specially: the H that first adds 0.1mol/L
2sO
4it is 5 that solution regulates the pH value of slip, the powder that then takes a policy, and reaction 60min, then add oxalic acid, reaction 60min; Again slip is carried out to separation afterwards and obtain yellow solid, gained yellow solid is washed to white, then adding water, to make solid content in slip be 45wt%, the slip after can being bleached; Wherein, the add-on of vat powder is the 1wt% of solid content in slip, and the add-on of oxalic acid is the 2.5wt% of solid content in slip;
7) grind: adopt high-energy-density to stir mill and grind, wherein, the delivery rate of pump is 3L/min, and grinding medium is the ZrO of diameter 0.7mm
2ceramic fine bead, grinding medium filling ratio is 85%, and mill speed is 1200rpm, and milling time is 6h; After grinding, obtain Iraq/Mongolia clay nano slip;
8) dispersion treatment: add dispersion agent WF-211 in the nanometer slurry obtaining to step 7), and adopt sand milling dispersion machine dispersed with stirring; Wherein, adding the amount of dispersion agent is the 1wt% of solid content in described slip; The rotating speed of sand milling dispersion machine is 2000rpm, and churning time is 10min;
9) swollenization processed: in the slip after step 8) dispersion treatment, add AES, K12 and CAB, then, adopt sand milling dispersion machine to stir, rotating speed 3000rpm, churning time 20min; Wherein, adding the amount of AES is the 1wt% of solid content in slip, and adding the amount of K12 is the 1wt% of solid content in slip, and the amount that adds CAB is the 2wt% of solid content in slip;
10) evaporation drying: it is dry that the slip after swollenization processed is placed in common exhausting loft drier, obtains nanometer siccative; Wherein, drying temperature is 150 ℃, and be 12h time of drying;
11) mechanical disintegration: the nanometer siccative that step 10) is obtained carries out mechanical disintegration, grinding time is 30s;
12) coated modification: add γ-aminopropyl triethoxysilane (KH550) in the nanometer siccative after mechanical disintegration, continue to carry out dispersed with stirring in high speed pulverization dispersion machine, churning time is 45s, obtains modification Iraq/Mongolia clay nano powder; Wherein the add-on of KH550 is 6% of nanometer siccative quality after mechanical disintegration;
2. mixing: in the open mixing roll of twin-roll, first styrene-butadiene rubber(SBR) (SBR) rubber to be plasticated 3 times in minimum roll spacing, rubber molecular weight is reduced; Then add respectively in order antioxidant 4020, accelerant CZ, zinc oxide, stearic acid; Until above-mentioned substance and SBR mixing evenly after, obtain mixing system, then divide and add the Iraq/Mongolia clay nano powder after modification for 3 times, the Iraq/Mongolia clay nano powder of guaranteeing modification mixes in mixing system, add again sulphur, thin-pass, mixing 20min is until evenly, smash sheet under glue, obtain rubber unvulcanizate.Wherein styrene-butadiene rubber(SBR) rubber is 100 mass parts, and antioxidant 4020 is 2 mass parts, and accelerant CZ is 1.2 mass parts, zinc oxide 3 mass parts, and stearic acid is 1 mass parts, and modification Iraq/Mongolia clay nano powder is 60 mass parts, and sulphur is 1.8 mass parts.
3. sulfuration: get 7g sample and measure vulcanization curve in GT-M2000A type on without rotor vulkameter, the rubber plateau cure stage recording according to vulcanization characteristics curve is determined compressing tablet curing time, then in XLB vulcanizing press, vulcanize, curing time is 8min, obtains the rubber with Iraq/Mongolia clay filler containing reinforcement.The rubber preparing is cut into dumbbell-shaped specimen and (determines four specimen, be designated as respectively sample 1, sample 2, sample 3 and sample 4), according to GB/T528-1998 standard testing, carry out mechanical property (tension test) test: draw speed is 15mm/min.Test-results is as shown in table 3.
Contrast table 3 and table 4, can obviously draw, the prepared modification Iraq/Mongolia clay nano powder of the present embodiment has very strong strengthening action as loading material of rubber, its tensile strength has reached 10.48MPa, be greater than the 7.2MPa of VN3 white carbon black, 100% tensile modulus is the 1.1MPa that 1.4MPa is also greater than VN3 white carbon black.Contrast other, also can draw, the modification Iraq/Mongolia clay nano powder strengthening action of this experiment preparation is better than the fillers such as calcined kaolin, VN3 white carbon black, can be used as and replaces VN3 white carbon black etc. as a kind of layered clay mineral filler of styrene-butadiene rubber(SBR), and its rubber performance as strengthening agent is good.
Table 3 is the rubber mechanical experimental results with Iraq/Mongolia clay filler containing reinforcement
The impact of the various mineral fillers of table 4 on styrene-butadiene rubber(SBR) mechanical property
The present invention includes but be not limited to above embodiment, every any being equal to of carrying out under the principle of spirit of the present invention, replaces or local improvement, all will be considered as within protection scope of the present invention.
Claims (4)
1. the rubber with Iraq/Mongolia clay filler containing reinforcement, is characterized in that, described rubber composed as follows:
Wherein, described modification Iraq/Mongolia clay nano powder is to obtain through one or more modifier modifications in polyoxyethylenated alcohol sodium sulfate, AMONYL 380LC, γ-aminopropyl triethoxysilane and sodium lauryl sulphate.
2. containing reinforcement, use as claimed in claim 1 a preparation method for the rubber of Iraq/Mongolia clay filler, it is characterized in that, step is as follows:
The preparation of step 1. Iraq/Mongolia clay nano dry powder
1) dry milling: become particle diameter to be less than the Iraq/Mongolia clay pit fritter of 5cm natural Iraq/Mongolia clay mineral Mechanical Crushing;
2) soak: the Iraq/Mongolia clay pit fritter that step 1) is obtained is soaked 12～24h, obtains Iraq/Mongolia clay slip; Wherein, solids in pulp amount is 45wt%;
3) smash slurry: regulating the pH value of Iraq/Mongolia clay slip is 8～10, adds dispersion agent, and adopt sand milling dispersion machine to smash slurry dispersion; Wherein, the add-on of dispersion agent is 1～3wt% of solid content in described slip; The rotating speed of sand milling dispersion machine is 700～1000rpm, and churning time is 30～60min;
4) screening: the slip that step 3) is smash after slurry disperses is crossed 500 mesh sieves, obtains minus mesh slurry;
5) deironing: the slip that adopts high gradient magnetic separator to obtain step 4) carries out deironing, and slip circulates 2～5 times in high gradient magnetic separator, and the magneticstrength of high gradient magnetic separator is 8000～10000Gs;
6) chemical bleaching: the slip after deironing is bleached under 700～1000rpm, the condition of 65 ℃, be specially: first adopt H
2sO
4it is 4～5 that solution regulates the pH value of slip, and the powder that then takes a policy, reacts 45～60min, then adds oxalic acid, reacts 45～60min; Again slip is carried out to separation afterwards and obtain yellow solid, gained yellow solid is washed to white, then adding water, to make solids in pulp amount be 45wt%, the slip after can being bleached; Wherein, the add-on of vat powder is the 1wt% of solid content in slip, and the add-on of oxalic acid is 1.5～3.5wt% of solid content in slip;
7) grind: adopt high-energy-density to stir mill the slip after bleaching is ground, wherein, the delivery rate of pump is 1～3L/min, and grinding medium is the ZrO of diameter 0.7～0.8mm
2ceramic fine bead, grinding medium filling ratio is 85%, and mill speed is 1000～1400rpm, and milling time is 2～6h; After grinding, obtain nanometer slurry;
8) dispersion treatment: add dispersion agent in the nanometer slurry obtaining to step 7), and adopt sand milling dispersion machine dispersed with stirring; Wherein, adding the amount of dispersion agent is 1～2wt% of solid content in described slip; The rotating speed of sand milling dispersion machine is 1000～3000rpm, and churning time is 5～10min;
9) swollenization processed: in the slip after step 8) dispersion treatment, add properties-correcting agent, then, adopt sand milling dispersion machine to stir, rotating speed 2000～5000rpm, churning time 10～30min; Wherein, adding the amount of properties-correcting agent is the 2.0wt%～4.0wt% of solid content in slip;
10) evaporation drying: the slip after swollenization processed is dried, and obtains nanometer siccative; Wherein, drying temperature is 120～150 ℃, and be 6～12h time of drying;
11) mechanical disintegration: the nanometer siccative that step 10) is obtained carries out mechanical disintegration, grinding time is 30～90s;
12) coated modification: add containing hydrogen silicone oil or γ-aminopropyl triethoxysilane in the nanometer siccative after mechanical disintegration, continue to carry out dispersed with stirring in high speed pulverization dispersion machine, churning time is 15～60s, obtains modification Iraq/Mongolia clay nano powder; Wherein the add-on of containing hydrogen silicone oil or γ-aminopropyl triethoxysilane is 2～6% of nanometer siccative quality after mechanical disintegration;
Step 2. is mixing: in the open mixing roll of twin-roll, first styrene-butadiene rubber(SBR) rubber is plasticated 3～5 times in minimum roll spacing; Then add respectively in order antioxidant 4020, accelerant CZ, zinc oxide, stearic acid; Until above-mentioned substance and styrene-butadiene rubber(SBR) rubber mixing evenly after, obtain mixing system, then divide and add modification Iraq/Mongolia clay nano powder for 3～5 times, guarantee that modification Iraq/Mongolia clay nano powder mixes in mixing system, add again sulphur, thin-pass, mixing 20min is until evenly, smash sheet under glue, obtain rubber unvulcanizate;
Step 3. sulfuration: vulcanize 5～8min in vulcanizer, obtain the rubber with Iraq/Mongolia clay filler containing reinforcement;
Wherein, properties-correcting agent is polyoxyethylenated alcohol sodium sulfate described in step 9), AMONYL 380LC, one or more in γ-aminopropyl triethoxysilane and sodium lauryl sulphate.
3. the preparation method with the rubber of Iraq/Mongolia clay filler containing reinforcement according to claim 2, is characterized in that, step 3) adopts NaOH or H while regulating the pH value of Iraq/Mongolia clay slip
2sO
4solution.
4. the preparation method with the rubber of Iraq/Mongolia clay filler containing reinforcement according to claim 2, is characterized in that, dispersion agent is WF-211 dispersion agent described in step 3) and step 8).
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