CN107189323A - A kind of high abrasion sisal fiber modified SBS composite and preparation method thereof - Google Patents

A kind of high abrasion sisal fiber modified SBS composite and preparation method thereof Download PDF

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CN107189323A
CN107189323A CN201710550676.1A CN201710550676A CN107189323A CN 107189323 A CN107189323 A CN 107189323A CN 201710550676 A CN201710550676 A CN 201710550676A CN 107189323 A CN107189323 A CN 107189323A
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sisal fiber
sbs
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spermine
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刘钰馨
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Guangxi Teachers College
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Guangxi Teachers College
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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
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/08—Epoxidation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2401/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2415/00—Characterised by the use of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to a kind of SBS composites, and in particular to a kind of high abrasion sisal fiber modified SBS composite, by weight, includes following components：Include following component：50~70 parts of SBS, 20~30 parts of natural rubber, modified 5~10 parts of sisal fiber, 0.01~0.05 part of spermine NO, 0.01~0.03 part of citric acid, 2~5 parts of methyl diphenylene diisocyanate, N, 0.01~0.05 part of N dimethylanilines, 0.03~0.07 part of dibutyl tin laurate, 3~7 parts of carbon black, 2~5 parts of magnesia, 0.5~2 part of antioxidant, 0.5~1 part of lubricant.Present invention also offers the preparation method of above-mentioned SBS composites.The features such as SBS composites prepared by the inventive method have rub resistance, shock resistance is excellent.

Description

A kind of high abrasion sisal fiber modified SBS composite and preparation method thereof
Technical field
The present invention relates to a kind of SBS composite modifications technical field, in particular, it is related to a kind of high abrasion sisal hemp fine Tie up modified SBS composite.
Background technology
Sisal hemp belongs to Agavaceae, is a kind of perennial crudefiber crop economic plants planted extensively, and the sisal hemp for being derived from its blade is fine Dimension is pure white with color and luster, and seawater corrosion resistance is strong but pliable in texture, and density is small, and tensile strength and modulus are high, and wide material sources are cheap, Therefore, sisal fiber has a clear superiority for preparing the inexpensive fiber-reinforced polymer-matrix compound of high-strength and high-modulus.
SBS (SBS) is the block copolymer using styrene as monomer, is had concurrently The characteristic of plastics and rubber, low temperature performance excellent good with chemical stability, the advantage such as cheap and processing is convenient, is work One of important general-purpose plastics in industry, but its impact strength is not high, it is yielding, it is not wear-resisting etc., so that its application is received Limitation..
The content of the invention
The technical problem to be solved in the present invention is to provide the SBS composites that a kind of high abrasion sisal fiber is modified.
In order to solve the above-mentioned technical problem, the present invention is achieved by the following technical solutions：A kind of high abrasion sisal hemp is fine Modified SBS composite is tieed up, by weight, it includes following component：50~70 parts of SBS, 20~30 parts of natural rubber, changes Property 5~10 parts of sisal fiber, 0.01~0.05 part of spermine-NO, 0.01~0.03 part of citric acid, diphenylmethane diisocyanate 2~5 parts of ester, 0.01~0.05 part of DMA, 0.03~0.07 part of dibutyl tin laurate, 3~7 parts of carbon black, 2~5 parts of magnesia, 0.5~2 part of antioxidant, 0.5~1 part of lubricant, the high abrasion sisal fiber modified SBS composite wood The preparation method of material, comprises the following steps：
1) spermine is dissolved in absolute ethyl alcohol, adds nano aluminium oxide, is passed through nitrogen and is excluded after air, is passed through high pressure NO progress Reaction, rotary evaporation obtains spermine-NO after drying；
2) 50~70 parts of SBS and 20~30 part of natural rubbers are dissolved in hexamethylene, 0.01~0.05 part of spermine of addition- NO, 0.01~0.03 part of citric acid, 0.1~0.3 part of dioxane is stirred reaction under constant temperature, obtains ring Oxide；
3) after 3~7 parts of carbon blacks are well mixed with 0.5~2 part of magnesia, with step 2) in epoxides, 5~10 parts Modified sisal fiber, 2~5 parts of methyl diphenylene diisocyanates, 0.01~0.05 part of DMA, tin dilaurate two 0.03~0.07 part of butyl tin, 0.5~2 part of antioxidant, 0.5~1 part of mix lubricant simultaneously stirs, and is placed in banbury Internally mix is carried out under the protection of nitrogen, is granulated after cooling through pelleter, is dried, the SBS for obtaining high heat-resisting sisal fiber modification is answered Condensation material.
Preferably, step 1) in, described spermine is 0.05~0.1 part, and nano aluminium oxide is 0.01~0.05 part, nitrogen Gas is passed through the time after 3~5min, to be passed through the high pressure NO reaction time for 30~60min.
Preferably, NO pressure is 2~3MPa, and the rotating speed of rotary evaporation is 50~80r/min, and temperature is 50~70 DEG C, vacuum is more than 0.01MPa.
The temperature of constant temperature in preferably, it is characterised in that step 2) is 50~60 DEG C, the rotating speed of stirring for 50~ 80r/min。
Preferably, the preparation method of modified sisal fiber is：It is 1~3cm by sisal fiber Mechanical Crushing, is soaked in 5~10h in sodium hydroxide solution, is placed in pressure pan, carries out steam explosion treatment, cooling, washing to neutrality.
Preferably, in the tank of explosion treatment temperature be 150~200 DEG C, in tank pressure be 3~5MPa, keep 2~ 5min, pressure inside the tank release time is 0.01~0.1s.
Preferably, described antioxidant is that mass ratio is (0.5~1):(1~2):The p-phenylenediamine of (0.5~1), Three (2,4- di-tert-butyl-phenyl) phosphite esters and stearoylketene tannate, described lubricant is zinc stearate, calcium stearate, One or more in paraffin.
Preferably, the internally mix temperature in banbury is 200~250 DEG C, and screw speed is 50~80r/min, and the time is 4 ~7h, internally mix is transferred in mould after terminating, temperature be 180~200 DEG C, pressure be 10~15MPa under conditions of, insulation 15 ~30min.
Advantages of the present invention：SBS is aoxidized the epoxy bond to be formed by dioxane with the double bond on natural rubber, has Oxidation rate is fast, the characteristics of oxidation efficiency is high；NO is provided by spermine-NO, dioxane is effectively converted SBS and day Unsaturated double-bond in right rubber structure is epoxy bond, and conversion ratio is up to more than 99.7%；Citric acid and nanoscale reactive aluminum The water of generation makes citric acid dissociate proton, and when spermine-NO runs into proton, fast decoupled discharges NO, by adding nanoscale Aluminum oxide, can be such that release NO speed more relaxes, it is to avoid NO spilling, improve its utilization rate；The ratio of nano magnesia Surface area is big, and good dispersion is mixed by it with carbon black, can not only improve dispersiveness of the carbon black in SBS and natural rubber, also Good filler, lubricant can be played a part of, make SBS composites determines Shen stress, tensile strength, tearing strength and resistance to Mill property is significantly improved；SBS, natural rubber and sisal fiber are crosslinked by methyl diphenylene diisocyanate, with crosslink density Height, the covalent bond effect power of formation is stronger, strengthens the wearability of SBS composites；Sisal fiber is after soaking with sodium hydroxide Steam explosion is carried out again, and content of cellulose is up to more than 99%, and the flexible modulus of modification sisal fiber of acquisition is big, face crack More, specific surface area improves more than 16%；By adding a certain proportion of antioxidant, the chain reaction of free radical can be blocked, Good antioxidation can be played, the service life of SBS composites is extended；SBS composite woods prepared by the inventive method Material, Akron abrasion experiment is carried out according to GB/T1689-1998, and Akron abrasion loss is reduced than common SBS composites More than 30%.
Embodiment
Further advantage, target and the feature of the present invention embodies part by following explanation, and part will also be by this The research and practice of invention and be understood by the person skilled in the art.
Following embodiments are used to further illustrate but be not limited to the present invention.
Embodiment 1
A kind of high abrasion sisal fiber modified SBS composite, by weight, it includes following component：50 parts of SBS, 20 parts of natural rubber, modified 5 parts of sisal fiber, 0.01 part of spermine-NO, 0.01 part of citric acid, methyl diphenylene diisocyanate 2 parts, 0.01 part of DMA, 0.03 part of dibutyl tin laurate, 3 parts of carbon black, 2 parts of magnesia, antioxidant 0.5 Part, 0.5 part of lubricant, the preparation method of the high abrasion sisal fiber modified SBS composite comprises the following steps：
1) spermine is dissolved in absolute ethyl alcohol, adds nano aluminium oxide, is passed through nitrogen and is excluded after air, is passed through high pressure NO progress Reaction, rotary evaporation obtains spermine-NO after drying；
2) 50 parts of SBS and 20 part of natural rubbers are dissolved in hexamethylene, 0.01 part of spermine-NO of addition, 0.01 part of citric acid, 0.1 part of dioxane, is stirred reaction under constant temperature, obtains epoxides；
3) after the carbon black that 3 parts of particle diameters are 10~20nm is well mixed with the magnesia that 0.5 part of particle diameter is 20~40nm, with Step 2) in epoxides, 5 parts of modified sisal fibers, 2 parts of methyl diphenylene diisocyanates, 0.01 part of N, N- dimethyl benzenes Amine, 0.07 part of dibutyl tin laurate, 0.5 part of antioxidant, 0.5 part of mix lubricant simultaneously stirs, and is placed in banbury In internally mix is carried out under the protection of nitrogen, granulate, dry through pelleter after cooling, obtain the SBS that high heat-resisting sisal fiber is modified Composite.
SBS is aoxidized the epoxy bond to be formed by dioxane with the double bond on natural rubber, fast with oxidation rate, oxygen The characteristics of changing efficiency high；NO is provided by spermine-NO, dioxane is effectively converted in SBS and natural rubber structure Unsaturated double-bond be epoxy bond, conversion ratio is up to more than 99.7%；Citric acid and the water of oxidation reactive aluminum generation make lemon acidolysis Proton is separated out, when spermine-NO runs into proton, fast decoupled discharges NO, by adding alumina in Nano level, can make release NO's Speed more relaxes, it is to avoid NO spilling, improves its utilization rate；The specific surface area of nano magnesia is big, good dispersion, and With stronger absorption property, mixed by it with carbon black, dispersiveness of the carbon black in SBS and natural rubber can not only be improved, Good filler, lubricant can also be played a part of, make SBS composites determines Shen stress, tensile strength, tearing strength and Wearability is significantly improved；N, accelerine can be catalyzed methyl diphenylene diisocyanate with being formed on SBS, natural rubber Epoxy bond reaction, dibutyl tin laurate can be catalyzed methyl diphenylene diisocyanate and sisal fiber, on carbon black Hydroxyl reaction, forms the stronger covalent bond of active force, enhances the wearability of SBS composites；Sisal fiber passes through hydroxide Steam explosion is carried out after sodium immersion again, content of cellulose is up to more than 99%, and the flexible modulus of modification sisal fiber of acquisition is big, Face crack is more, and specific surface area improves more than 16%；By adding a certain proportion of antioxidant, the chain of free radical can be blocked Formula is reacted, and can be played good antioxidation, be extended the service life of SBS composites；By manufactured in the present embodiment SBS composites and common SBS materials, Akron abrasion experiment is carried out according to GB/T1689-1998 respectively, prepared by the present embodiment SBS composites reduce more than 30% than common SBS materials Akron abrasion loss.
Embodiment 2
A kind of high abrasion sisal fiber modified SBS composite, by weight, it includes following component：70 parts of SBS, 30 parts of natural rubber, modified 10 parts of sisal fiber, 0.05 part of spermine-NO, 0.03 part of citric acid, diphenylmethane diisocyanate 5 parts of ester, 0.05 part of DMA, 0.07 part of dibutyl tin laurate, 7 parts of carbon black, 5 parts of magnesia, antioxidant 2 Part, 1 part of lubricant, the preparation method of the high abrasion sisal fiber modified SBS composite comprises the following steps：
1) 0.05 part of spermine is dissolved in absolute ethyl alcohol, adds 0.01 part of nano aluminium oxide, is passed through nitrogen 3min and is excluded air Afterwards, it is passed through high pressure NO and carries out reaction 30min, rotary evaporation obtains spermine-NO after drying；
2) 70 parts of SBS and 30 part of natural rubbers are dissolved in hexamethylene, 0.05 part of spermine-NO of addition, 0.03 part of citric acid, 0.3 part of dioxane, is stirred reaction under constant temperature, obtains epoxides；
3) after 7 parts of carbon blacks are well mixed with 2 parts of magnesia, with step 2) in epoxides, 10 parts of modified sisal hemps it is fine Dimension, 5 parts of methyl diphenylene diisocyanates, 0.05 part of DMA, 0.07 part of dibutyl tin laurate, 2 parts resist Oxidant, 1 part of mix lubricant simultaneously stirs, and is placed in banbury and internally mix is carried out under the protection of nitrogen, through cutting after cooling Grain machine granulation, drying obtains the SBS composites that high heat-resisting sisal fiber is modified.
When spermine-NO runs into proton, the NO of quick release can change the double bond with steric hindrance, make it easier to by dioxa Cyclohexane oxidation formation epoxy bond, improves the efficiency more than 8% of double bond epoxidation.
Embodiment 3
A kind of high abrasion sisal fiber modified SBS composite, by weight, it includes following component：70 parts of SBS, 30 parts of natural rubber, modified 10 parts of sisal fiber, 0.05 part of spermine-NO, 0.03 part of citric acid, diphenylmethane diisocyanate 5 parts of ester, 0.05 part of DMA, 0.07 part of dibutyl tin laurate, 7 parts of carbon black, 5 parts of magnesia, antioxidant 2 Part, 1 part of lubricant, the preparation method of the high abrasion sisal fiber modified SBS composite comprises the following steps：
1) 0.05 part of spermine is dissolved in absolute ethyl alcohol, adds 0.05 part of nano aluminium oxide, is passed through nitrogen 3min and is excluded air Afterwards, high pressure NO is passed through, the pressure for making NO is 2MPa, carries out reaction 30min, rotary evaporation is dried, and the rotating speed of rotary evaporation is 50r/min, temperature is 50 DEG C, and vacuum is 0.05MPa, obtains spermine-NO；
2) 70 parts of SBS and 30 part of natural rubbers are dissolved in hexamethylene, 0.05 part of spermine-NO of addition, 0.03 part of citric acid, 0.3 part of dioxane, is stirred reaction under constant temperature, obtains epoxides；
3) after 7 parts of carbon blacks are well mixed with 2 parts of magnesia, with step 2) in epoxides, 10 parts of modified sisal hemps it is fine Dimension, 5 parts of methyl diphenylene diisocyanates, 0.05 part of DMA, 0.07 part of dibutyl tin laurate, 2 parts resist Oxidant, 1 part of mix lubricant simultaneously stirs, and is placed in banbury and internally mix is carried out under the protection of nitrogen, through cutting after cooling Grain machine granulation, drying obtains the SBS composites that high heat-resisting sisal fiber is modified.
Embodiment 4
A kind of high abrasion sisal fiber modified SBS composite, by weight, it includes following component：70 parts of SBS, 30 parts of natural rubber, modified 10 parts of sisal fiber, 0.05 part of spermine-NO, 0.03 part of citric acid, diphenylmethane diisocyanate 5 parts of ester, 0.05 part of DMA, 0.07 part of dibutyl tin laurate, 7 parts of carbon black, 5 parts of magnesia, antioxidant 2 Part, 1 part of lubricant, the preparation method of the high abrasion sisal fiber modified SBS composite comprises the following steps：
1) 0.05 part of spermine is dissolved in absolute ethyl alcohol, adds 0.05 part of nano aluminium oxide, is passed through nitrogen 3min and is excluded air Afterwards, high pressure NO is passed through, the pressure for making NO is 2MPa, carries out reaction 30min, rotary evaporation is dried, and the rotating speed of rotary evaporation is 50r/min, temperature is 50 DEG C, and vacuum is 0.05MPa, obtains spermine-NO；
2) 70 parts of SBS and 30 part of natural rubbers are dissolved in hexamethylene, 0.05 part of spermine-NO of addition, 0.03 part of citric acid, 0.3 part of dioxane, under 50 DEG C of constant temperatures, speed of agitator is that 50r/min is stirred reaction, obtains epoxidation Thing；
3) after 7 parts of carbon blacks are well mixed with 2 parts of magnesia, with step 2) in epoxides, 10 parts of modified sisal hemps it is fine Dimension, 5 parts of methyl diphenylene diisocyanates, 0.05 part of DMA, 0.07 part of dibutyl tin laurate, 2 parts resist Oxidant, 1 part of mix lubricant simultaneously stirs, and is placed in banbury and internally mix is carried out under the protection of nitrogen, through cutting after cooling Grain machine granulation, drying obtains the SBS composites that high heat-resisting sisal fiber is modified.
Embodiment 5
A kind of high abrasion sisal fiber modified SBS composite, by weight, it includes following component：70 parts of SBS, 30 parts of natural rubber, modified 10 parts of sisal fiber, 0.05 part of spermine-NO, 0.03 part of citric acid, diphenylmethane diisocyanate 5 parts of ester, 0.05 part of DMA, 0.07 part of dibutyl tin laurate, 7 parts of carbon black, 5 parts of magnesia, antioxidant 2 Part, 1 part of lubricant, the preparation method of the high abrasion sisal fiber modified SBS composite comprises the following steps：
1) 0.05 part of spermine is dissolved in absolute ethyl alcohol, adds 0.05 part of nano aluminium oxide, is passed through nitrogen 3min and is excluded air Afterwards, high pressure NO is passed through, the pressure for making NO is 3MPa, carries out reaction 30min, rotary evaporation is dried, and the rotating speed of rotary evaporation is 50r/min, temperature is 50 DEG C, and vacuum is 0.05MPa, obtains spermine-NO；
2) 70 parts of SBS and 30 part of natural rubbers are dissolved in hexamethylene, 0.05 part of spermine-NO of addition, 0.03 part of citric acid, 0.3 part of dioxane, under 50 DEG C of constant temperatures, speed of agitator is that 50r/min is stirred reaction, obtains epoxidation Thing；
3) after 7 parts of carbon blacks are well mixed with 2 parts of magnesia, with step 2) in epoxides, 10 parts of modified sisal hemps it is fine Dimension, 5 parts of methyl diphenylene diisocyanates, 0.05 part of DMA, 0.07 part of dibutyl tin laurate, 2 parts resist Oxidant, 1 part of mix lubricant simultaneously stirs, and is placed in banbury and internally mix is carried out under the protection of nitrogen, through cutting after cooling Grain machine granulation, drying obtains the SBS composites that high heat-resisting sisal fiber is modified, wherein, the preparation side of modified sisal fiber Method is：It is 3cm by sisal fiber Mechanical Crushing, is soaked in 10h in sodium hydroxide solution, is placed in pressure pan, carries out steam quick-fried Tear is managed, cooling, washing to neutrality, obtains modified sisal fiber.
Embodiment 6
A kind of high abrasion sisal fiber modified SBS composite, by weight, it includes following component：70 parts of SBS, 30 parts of natural rubber, modified 10 parts of sisal fiber, 0.05 part of spermine-NO, 0.03 part of citric acid, diphenylmethane diisocyanate 5 parts of ester, 0.05 part of DMA, 0.07 part of dibutyl tin laurate, 7 parts of carbon black, 5 parts of magnesia, antioxidant 2 Part, 1 part of lubricant, the preparation method of the high abrasion sisal fiber modified SBS composite comprises the following steps：
1) 0.05 part of spermine is dissolved in absolute ethyl alcohol, adds 0.05 part of nano aluminium oxide, is passed through nitrogen 3min and is excluded air Afterwards, high pressure NO is passed through, the pressure for making NO is 2MPa, carries out reaction 30min, rotary evaporation is dried, and the rotating speed of rotary evaporation is 50r/min, temperature is 50 DEG C, and vacuum is 0.05MPa, obtains spermine-NO；
2) 70 parts of SBS and 30 part of natural rubbers are dissolved in hexamethylene, 0.05 part of spermine-NO of addition, 0.03 part of citric acid, 0.3 part of dioxane, under 50 DEG C of constant temperatures, speed of agitator is that 50r/min is stirred reaction, obtains epoxidation Thing；
3) after 7 parts of carbon blacks are well mixed with 2 parts of magnesia, with step 2) in epoxides, 10 parts of modified sisal hemps it is fine Dimension, 5 parts of methyl diphenylene diisocyanates, 0.05 part of DMA, 0.07 part of dibutyl tin laurate, 2 parts resist Oxidant, 1 part of mix lubricant simultaneously stirs, and is placed in banbury and internally mix is carried out under the protection of nitrogen, through cutting after cooling Grain machine granulation, drying obtains the SBS composites that high heat-resisting sisal fiber is modified, wherein, the preparation side of modified sisal fiber Method is：It is 3cm by sisal fiber Mechanical Crushing, is soaked in 10h in sodium hydroxide solution, is placed in pressure pan, carries out steam quick-fried Tear is managed, and temperature is 200 DEG C in the tank of explosion treatment, and pressure is 5MPa in tank, keeps 5min, and pressure inside the tank release time is 0.1s, cooling, washing to neutrality obtains modified sisal fiber.
Embodiment 7
A kind of high abrasion sisal fiber modified SBS composite, by weight, it includes following component：70 parts of SBS, 30 parts of natural rubber, modified 10 parts of sisal fiber, 0.05 part of spermine-NO, 0.03 part of citric acid, diphenylmethane diisocyanate 5 parts of ester, 0.05 part of DMA, 0.07 part of dibutyl tin laurate, 7 parts of carbon black, 5 parts of magnesia, antioxidant 2 Part, 1 part of lubricant, the preparation method of the high abrasion sisal fiber modified SBS composite comprises the following steps：
1) 0.05 part of spermine is dissolved in absolute ethyl alcohol, adds 0.05 part of nano aluminium oxide, is passed through nitrogen 3min and is excluded air Afterwards, high pressure NO is passed through, the pressure for making NO is 2MPa, carries out reaction 30min, rotary evaporation is dried, and the rotating speed of rotary evaporation is 50r/min, temperature is 50 DEG C, and vacuum is 0.05MPa, obtains spermine-NO；
2) 70 parts of SBS and 30 part of natural rubbers are dissolved in hexamethylene, 0.05 part of spermine-NO of addition, 0.03 part of citric acid, 0.3 part of dioxane, under 50 DEG C of constant temperatures, speed of agitator is that 50r/min is stirred reaction, obtains epoxidation Thing；
3) after 7 parts of carbon blacks are well mixed with 2 parts of magnesia, with step 2) in epoxides, 10 parts of modified sisal hemps it is fine Dimension, 5 parts of methyl diphenylene diisocyanates, 0.05 part of DMA, 0.07 part of dibutyl tin laurate, 2 parts resist Oxidant, 1 part of zinc stearate lubricant is mixed and stirred for uniformly, wherein, described antioxidant is p-phenylenediamine, three (2,4- Di-tert-butyl-phenyl) phosphite ester and stearoylketene tannate are in mass ratio 0.5:1:0.5 mixing composition, cooling, washing is extremely Neutrality is placed in banbury carries out internally mix under the protection of nitrogen, is granulated after cooling through pelleter, drying, obtains high heat-resisting sisal hemp The SBS composites of fibre modification.
Embodiment 8
A kind of high abrasion sisal fiber modified SBS composite, it includes by weight, including following component：SBS 70 parts, 30 parts of natural rubber, modified 10 parts of sisal fiber, 0.05 part of spermine-NO, 0.03 part of citric acid, diphenyl methane two is different 5 parts of cyanate, 0.05 part of DMA, 0.07 part of dibutyl tin laurate, 7 parts of carbon black, 5 parts of magnesia, antioxygen 2 parts of agent, 1 part of lubricant, the preparation method of the high abrasion sisal fiber modified SBS composite comprises the following steps：
1) 0.05 part of spermine is dissolved in absolute ethyl alcohol, adds 0.05 part of nano aluminium oxide, is passed through nitrogen 3min and is excluded air Afterwards, high pressure NO is passed through, the pressure for making NO is 2MPa, carries out reaction 30min, rotary evaporation is dried, and the rotating speed of rotary evaporation is 50r/min, temperature is 50 DEG C, and vacuum is 0.05MPa, obtains spermine-NO；
2) 70 parts of SBS and 30 part of natural rubbers are dissolved in hexamethylene, 0.05 part of spermine-NO of addition, 0.03 part of citric acid, 0.3 part of dioxane, under 50 DEG C of constant temperatures, speed of agitator is that 50r/min is stirred reaction, obtains epoxidation Thing；
3) after 7 parts of carbon blacks are well mixed with 2 parts of magnesia, with step 2) in epoxides, 10 parts of modified sisal hemps it is fine Dimension, 5 parts of methyl diphenylene diisocyanates, 0.05 part of DMA, 0.07 part of dibutyl tin laurate, 2 parts resist Oxidant, 1 part of zinc stearate lubricant is mixed and stirred for uniformly, wherein, described antioxidant is that mass ratio is
0.5:1:0.5 p-phenylenediamine, three (2,4- di-tert-butyl-phenyls) phosphite esters are mixed with stearoylketene tannate Composition is placed in banbury carries out internally mix under the protection of nitrogen, and internally mix temperature is 200 DEG C, and screw speed is 50r/min, time For 4h, internally mix is transferred in mould after terminating, and is 180 DEG C in temperature, pressure cools down under conditions of 10MPa, to be incubated 30min Granulate, dry by pelleter, obtain the SBS composites that high heat-resisting sisal fiber is modified.
The reactions such as hydroxyl, the carboxyl that each component passes through on internally mix, methyl diphenylene diisocyanate and carbon black, with epoxidation Hydroxyl reaction on thing forms strong covalent bond, the SBS composite properties being prepared into more is stablized, the degree of cross linking is higher, more Plus it is wear-resisting.
Although embodiment of the present invention is disclosed as above, it is not restricted in specification and embodiment listed With it can be applied to various suitable the field of the invention completely, can be easily for those skilled in the art Other modification is realized, therefore under the universal limited without departing substantially from claim and equivalency range, the present invention is not limited In specific details and shown here as the embodiment with description.

Claims (8)

1. a kind of high abrasion sisal fiber modified SBS composite, it is characterised in that including by weight, comprising with the following group Part：50~70 parts of SBS, 20~30 parts of natural rubber, modified 5~10 parts of sisal fiber, 0.01~0.05 part of spermine-NO, lemon 0.01~0.03 part of lemon acid, 2~5 parts of methyl diphenylene diisocyanate, 0.01~0.05 part of DMA, two bays Sour 0.03~0.07 part of dibutyl tin, 3~7 parts of carbon black, 2~5 parts of magnesia, 0.5~2 part of antioxidant, lubricant 0.5~1 Part, the preparation method of the high abrasion sisal fiber modified SBS composite comprises the following steps：
1) spermine is dissolved in absolute ethyl alcohol, adds nano aluminium oxide, is passed through nitrogen and is excluded after air, is passed through high pressure NO and is carried out instead Should, rotary evaporation obtains spermine-NO after drying；
2) 50~70 parts of SBS and 20~30 part of natural rubbers are dissolved in hexamethylene, add 0.01~0.05 part of spermine-NO, lemon 0.01~0.03 part of lemon acid, 0.1~0.3 part of dioxane is stirred reaction under constant temperature, obtains epoxidation Thing；
3) after 3~7 parts of carbon blacks are well mixed with 0.5~2 part of magnesia, with step 2) in epoxides, 5~10 parts of modifications Sisal fiber, 2~5 parts of methyl diphenylene diisocyanates, 0.01~0.05 part of DMA, di lauric dibutyl 0.03~0.07 part of tin, 0.5~2 part of antioxidant, 0.5~1 part of mix lubricant simultaneously stirs, and is placed in banbury in nitrogen Internally mix is carried out under the protection of gas, is granulated after cooling through pelleter, is dried, the SBS composite woods that high heat-resisting sisal fiber is modified are obtained Material.
2. high abrasion sisal fiber modified SBS composite according to claim 1, it is characterised in that step 1) in, institute The spermine stated is 0.05~0.1 part, and nano aluminium oxide is 0.01~0.05 part, and nitrogen is passed through the time after 3~5min, to be passed through height The pressure NO reaction time is 30~60min.
3. high abrasion sisal fiber modified SBS composite according to claim 1 or 2, it is characterised in that NO pressure For 2~3MPa, the rotating speed of rotary evaporation is 50~80r/min, and temperature is 50~70 DEG C, and vacuum is more than 0.01MPa.
4. high abrasion sisal fiber modified SBS composite according to claim 1, it is characterised in that characterized in that, Step 2) in the temperature of constant temperature be 50~60 DEG C, the rotating speed of stirring is 50~80r/min.
5. high abrasion sisal fiber modified SBS composite according to claim 1, it is characterised in that modified sisal hemp is fine The preparation method of dimension is：It is 1~3cm by sisal fiber Mechanical Crushing, is soaked in 5~10h in sodium hydroxide solution, is placed in height Press in tank, carry out steam explosion treatment, cooling, washing to neutrality.
6. high abrasion sisal fiber modified SBS composite according to claim 5, it is characterised in that explosion treatment In tank temperature be 150~200 DEG C, in tank pressure be 3~5MPa, keep 2~5min, pressure inside the tank release time be 0.01~ 0.1s。
7. high abrasion sisal fiber modified SBS composite according to claim 1, it is characterised in that described antioxygen Agent is that mass ratio is (0.5~1):(1~2):The p-phenylenediamine of (0.5~1), three (2,4- di-tert-butyl-phenyls) phosphite esters With stearoylketene tannate, described lubricant is the one or more in zinc stearate, calcium stearate, paraffin.
8. high abrasion sisal fiber modified SBS composite according to claim 1, it is characterised in that in banbury Internally mix temperature is 200~250 DEG C, and screw speed is 50~80r/min, and the internally mix time is 4~7h, and internally mix is transferred to mould after terminating In tool, temperature be 180~200 DEG C, pressure be 10~15MPa under conditions of, be incubated 15~30min.
CN201710550676.1A 2017-07-07 2017-07-07 A kind of high abrasion sisal fiber modified SBS composite and preparation method thereof Pending CN107189323A (en)

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