CN101524895A - Method of using super-cladodification polymer branch-connection inorganic nanometer powder for reinforcing surface rubber performance of engineering tyre - Google Patents
Method of using super-cladodification polymer branch-connection inorganic nanometer powder for reinforcing surface rubber performance of engineering tyre Download PDFInfo
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Abstract
The invention discloses a method of using super-cladodification polymer branch-connection inorganic nanometer powder for reinforcing the surface rubber performance of an engineering tyre, which is as follows: nanometer powder after super-cladodification surface process is added into the rubber mixed-smelting process; and under the condition that the original rubber production formula and technology are not changed, 1 to 20 parts of super-cladodification nanometer powder are added into 100 weight parts of rubber substrate. The terminal-group functional group of high density of the super-cladodification polymer and the defective cavity structure are helpful for the dispersion of nanometer granules, and have great potency for balancing the integrative performance of the nanometer composite material, thus the granules have excellent dispersing compatibility in the rubber substrate, the rubber displays excellent reinforcing synergy effect and interface compatible effect, and the tensile strength, the breakage elongation, the tearing strength and the wear resistance are greatly improved.
Description
Technical field
The present invention relates to the method for the collaborative enhancement engineering tire tread glue performance of a kind of dissaving polymer/nano-powder, belong to nano-material modified tread rubber and rubber compounding technical field.
Background technology
Rubber is being brought into play very important effect as strategic goods and materials in national economy.In traditional rubber process industry, carbon black nano-powder, white carbon powder are commonly used as the indispensable reinforcing agent of rubber.Along with to the improving constantly of rubber product performance requirement, the performance that how further to improve elastomeric material is when the key subjects of forward swing in the rubber industry technical field.Nanometer technology has boundless prospect in the modified rubber field.
Along with carrying out of the various highways of China, large hydraulic engineering, mining engineering and many Engineering Project Construction, need a large amount of various engineering machinery of using.Under the project implementations such as particularly development of the West Regions, the south water to north, transfering natural gas from the west to the east, market further enlarges the demand of large-scale engineering machinery.Off-the-road tyre is generally worked under rigorous environment, as: engineering trucks such as bull-dozer, excavator, road roller, the operation place is big, Uneven road is smooth and exacting terms such as foreign material such as sharp-pointed crushed stone, rock, nail and glass and acid or alkali environment are arranged, impacted by hard thing and regularly greatly again work continuously round the clock, tire tread is easily hurt or is pierced through or phenomenons such as using up piece occurred collapsing.Especially in the engineering machinery of work such as copper mine, iron ore, usually to contact a lot of corrosive substances, cause tyre life sharply to reduce.
Because the particularity of working environment, off-the-road tyre is big to Capability Requirements such as loading of tire and acid-alkali-corrosive-resistings, require tyre surface to have high strength, tear-resistant, splendid combination property tires such as good wear-resisting and strong acid and alkali-resistance, and conventional tire formula technique and external advanced technology barriers make the domestic very big obstacle that run into when exploitation high-performance engineering tire tread material, must take new technology to break through, the exploitation high-performance tire tread material that develops into of nano material and technology provides new way.
Compatibility is poor between at present most nano-powder and rubber molecule, form " island " structure, bring very big difficulty for dispersion and processing, be used with silane coupler on this basis and solve nano particle and rubber macromolecule consistency problem to a certain extent, but still can not reach ideal effect.
Summary of the invention
The object of the invention provides a kind of method of grafted by super branched polymer inorganic nanometer powder enhancement engineering tire tread glue performance.
In order to achieve the above object, the present invention adopts following technical scheme.
A kind of method of grafted by super branched polymer inorganic nanometer powder enhancement engineering tire tread glue performance is characterized in that having following technical process and step:
Step (a): in flask, add in following ratio, in every 100ml absolute ethyl alcohol, add 1-10g inorganic nanometer powder and 1-5ml gamma-amino propyl-triethoxysilicane oxygen alkane (KH550), γ-sulfydryl propyl-triethoxysilicane oxygen alkane (KH590) or γ-glycidyl ether oxygen propyl trimethoxy siloxanes (KH560), ultrasonic 30 minutes, stirring and refluxing 2-4h was up to whole suspensions, cyclic washing, suction filtration obtains the organic process nano-powder behind 110 ℃ of vacuum drying 10-24h;
Step (b): add a kind of direct grafting of step (a) (graft to) in flask: gained has amino, sulfydryl, hydroxyl, the nano-powder of epoxy radicals or do not pass through organically-modified nano-powder 1-10 weight portion, solvent 20-100 weight portion, with contain terminal hydroxy group, end carboxyl, the dissaving polymer 1-50 weight portion of the amino or end epoxy radicals of end, sealing, take out nitrogen repeatedly three times, ultrasonic processing 30-1000min reacts 1-24h down at 10-180 ℃, suction filtration, cyclic washing, 10-180 ℃ of vacuum drying obtains hyperbranched modified nano powder;
Step (c): the method that also can take situ-formed graft (graft from): to have amino in the step (a), sulfydryl, hydroxyl, the inorganic nanometer powder of epoxy radicals is 1 weight portion for nuclear, consumption, with the AB2 that can react with it is that monomer, consumption are the 0.1-50 weight portion, with other lewis acids such as p-methyl benzenesulfonic acid or BFEEs is that catalyst, consumption are the 0.1-10 weight portion, add the 1-50 parts by weight solvent, 0-180 ℃ is reacted 1min-500h down under argon gas or nitrogen protection, up to reacting completely, filter, drying obtains modified powder; Perhaps will react with 1-50 weight portion polyalcohol or polyamine after the 1-10 weight portion inorganic nanometer powder acidylate; react with 1-50 weight portion alpha-halogen carboxylic acid halides then; obtain the inorganic nanometer powder that the surface has initator functional group; be nuclear with it then; add the double bond containing monomer of 0.1-50 weight portion; the solvent that adds 0.1-5 weight portion catalyst or 0.1-5 weight portion part and 1-50 weight portion; 0-180 ℃ is reacted 1min-500h down under argon gas or nitrogen protection; after being significantly increased, viscosity stops reaction; in methyl alcohol, precipitate; the gained precipitation heavily is dissolved in solvent; suction filtration; washing, 20-180 ℃ of vacuum drying obtains the macromolecular grafted inorganic nanometer powder of in-situ polymerization.
Step (d): the grafted by super branched polymer inorganic nanometer powder that in 100 weight portion sizing materials, adds the 0.5-20 weight portion, after fully mixing, obtain rubber, behind sulfidization molding, make tread rubber and show excellent enhancing cooperative effect and interface co-operative effect, hot strength and elongation at break have had largely and to have improved, and anti-wear performance has also had and significantly improves.
Used inorganic nanometer powder be wherein any or several: nanometer Al
2O
3, nanometer SiO
2, nano-TiO
2, nano SiC, nanometer BaSO
4, nanometer BN, nano-MgO, nanometer CaCO
3Deng.
The preparation method of above-mentioned direct grafting (graft to) dissaving polymer, dissaving polymer used in the step (b) is for containing terminal hydroxy group, end carboxyl or the amino hyperbranched polyether of end, polyester, polyesteramine, polyamide, polyurethane, polysulfones amine, polyureas-ammonia ester.
The preparation method of above-mentioned direct grafting (graft to) dissaving polymer, used solvent is oxolane, dimethyl sulfoxide (DMSO), N among step (b), (c), dinethylformamide, N, N-dimethylacetylamide, chloroform, carrene, ethyl acetate, acetone, toluene, dimethylbenzene etc.
The preparation method of above-mentioned situ-formed graft (graft from) dissaving polymer, used AB in the step (c)
2The type monomer is 2, two (hydroxymethyl) propionic acid of 2-, the monobasic ester of trimellitic anhydride, trimesic acid or monobasic acid amides, dihydroxy-benzoic acid, dihydroxy-benzoic acid ester, hydroxy benzenes diacid and derivative thereof, as 5-phenoxy group isophthalic acid, a dihydroxy benzene halide, dihydroxy amine etc.
The preparation method of above-mentioned situ-formed graft (graft from) dissaving polymer, contain double bond monomer in the step (c) and comprise methyl acrylate, hydroxy-ethyl acrylate, acrylic acid ammonia ethyl ester, methacrylic acid hydroxy butyl ester and derivative thereof, styrene, methyl styrene and derivative thereof, Methacrylamide, ethyl acrylamide and derivative thereof etc.
The preparation method of above-mentioned situ-formed graft (graft from) dissaving polymer is characterized in that catalyst used in the step (c) is cuprous salt ferrous salt, inferior lead salt etc.; Part is tetramethylethylenediamine, pentamethyl-diethyl tetramine, hexamethyl-triethyl group tetramine, ethanedioic acid, malonic acid, succinic acid, phthalic acid etc.
Highdensity terminal functionality of dissaving polymer and the void structure with defective all help the dispersion of nano particle, and the combination property of balance nano composite material is had very big potentiality.Therefore particle has good decentralized photo capacitive in rubber matrix, and sizing material shows excellent enhancing cooperative effect and interface co-operative effect, and hot strength and elongation at break have had largely and improve, and anti-wear performance has also had and significantly improves.
The specific embodiment
After now embodiments of the invention being described in.
Embodiment 1
With the nano aluminium oxide is initial raw material, and 110 ℃ of vacuum drying 24h remove impurities in raw materials, surface modification grafted silane coupling agent KH550 then, and KH560, KH590 obtains the nano-powder of hyperbranched grafting again with the hyper-branched polyester reaction under catalyst action.
Step (a): in flask, add in the 100ml absolute ethyl alcohol, add 2g nano-powder and 1ml KH550, ultrasonic 30 minutes, stirring and refluxing 2-4h is up to whole suspensions, cyclic washing, suction filtration obtains organic process nano-powder KH550-Al behind 110 ℃ of vacuum drying 10-24h
2O
3
Step (b): in flask, add the nano-powder of step (a) or do not pass through organically-modified nano-powder 2g, the dissaving polymer tetrahydrofuran solution 25g of the end carboxyl of adding 10%, sealing, take out nitrogen repeatedly three times, ultrasonic processing 30-1000min reacts 4h down at 120 ℃, suction filtration, cyclic washing, 110 ℃ of vacuum drying obtain hyperbranched modified nano powder HBP-Al
2O
3
Embodiment 2
With the nano aluminium oxide is initial raw material, and 110 ℃ of vacuum drying 24h remove impurities in raw materials, surface modification grafted silane coupling agent KH550 then, and KH560, KH590 obtains the nano-powder of hyperbranched grafting again with the hyper-branched polyester reaction under catalyst action.
Step (a): add in flask in the 100ml absolute ethyl alcohol, add 2g powder and 1ml KH550, ultrasonic 30 minutes, stirring and refluxing 2-4h was up to whole suspensions, cyclic washing, and suction filtration obtains the organic process nano-powder behind 110 ℃ of vacuum drying 10-24h;
Step (b): in flask, add the 2g nano-powder of step (a) or do not pass through organically-modified nano-powder, add 5g 2, two (hydroxymethyl) propionic acid of 2-, 0.5g p-methyl benzenesulfonic acid and 50ml DMF are after ultrasonic 30 minutes, sealing, backflow 4h is up to reacting completely suction filtration, cyclic washing in blanket of nitrogen, 110 ℃ of vacuum drying obtain hyperbranched modified nano powder HAPE-Al
2O
3
Embodiment 3
With SiC is initial raw material, connect ethylenediamine after acidified, the acidylate after, in the presence of BFEE, cause the epoxy prapanol polymerization, then obtain the SiC of the synthetic grafted by super branched polymer of original position.
Step (a): in the single neck round-bottomed flask of the 100ml that the magnetic agitation rotor is housed, add the SiC40ml 60%HNO of 4g drying
3, being heated to 120 ℃ behind the ultrasonic 30min, the reaction 24h down that stirs and reflux with the microporous teflon membran suction filtration, to neutral, obtains acidifying SiC 3.5g with the deionized water cyclic washing behind 80 ℃ of vacuum drying 24h;
Step (b): in the single neck round-bottomed flask of the 100ml of the rotor that magnetic agitation is housed, add step (a) gained acidifying SiC 3.5g and thionyl chloride 15g, ultrasonic 30min, be heated to 60 ℃, reaction 24h down stirs and refluxes, suction filtration and cyclic washing are removed thionyl chloride, obtain the SiC 3.0g of acidylate;
Step (c): in the single neck round-bottomed flask of the 100ml of the rotor that magnetic agitation is housed, add step (b) gained acidylate SiC 3.0g and ethylenediamine 40g, sealing is taken out argon gas three times, ultrasonic 30min repeatedly, be heated to 80 ℃, the reaction 24h, suction filtration is removed reactant and accessory substance, spend deionised water repeatedly after, 110 ℃ of vacuum drying obtain the surface and have amino SiC 2.8g;
Step (d): in the single neck round-bottomed flask of the 100ml of the rotor that magnetic agitation is housed, add step (c) gained surface and have amino SiC 2.8g and alpha-brominated propionyl bromide 2.8g, DMF 50ml, sealing is taken out argon gas three times repeatedly, ultrasonic 30min, react 1-24h under the room temperature, suction filtration is removed reactant and accessory substance, spend deionised water repeatedly after, 110 ℃ of vacuum drying, obtain the surface have initiating group SiC;
Step (e): in the single neck round-bottomed flask of the 100ml of the rotor that magnetic agitation is housed, adding step (d) gained surface has the SiC 2.0g of initiating group, and sealing is taken out argon gas three times repeatedly, add catalyst BFEE 0.1g and DMF 20ml, behind the ultrasonic 30min, drip epoxy prapanol 50g, under ice-water bath, react 24h, suction filtration is removed reactant and accessory substance, after spending deionised water repeatedly, 110 ℃ of vacuum drying obtain the HBP-SiC of in-situ polymerization grafted by super branched polymer;
Comparative Examples 1
Experimental basis prescription rubber performance
Table 1 sizing recipe ingredient (weight portion)
According to standard GB-528-83, the GB/T10707 standard is carried out the physics stretching and abrasion resistance is made sample, and experimental result is listed in table 3
Comparative Examples 2
Test of the influence of unmodified nano aluminium oxide to properties of rubber
Table 2 sizing compound formula component (weight portion)
It is consistent with basic components in the Comparative Examples 1 to fill a prescription, other adds 5 parts unmodified nano aluminium oxide, technological process does not change yet, after fully mixing, obtain rubber, again through sulfidization molding, according to standard GB-528-83, the GB/T10707 standard is carried out the physics stretching and abrasion resistance is made sample, and experimental result is listed in table 3.
Comparative Examples 3
Test KH550 modified Nano aluminium oxide is to the influence of properties of rubber
It is consistent with basic components in the Comparative Examples 1 to fill a prescription, and other adds 5 parts KH550 modified Nano aluminium oxide KH550-Al
2O
3, technological process does not change yet, and obtains rubber after fully mixing, and again through sulfidization molding, according to standard GB-528-83, the GB/T10707 standard is carried out the physics stretching and abrasion resistance is made sample, and experimental result is listed in table 3.
Embodiment 4
The test hyperbranched graft modification nano aluminium oxide HBP-Al of direct grafting (graft to) method modification among the embodiment 1
2O
3Influence to properties of rubber
The technology of present embodiment is all identical with above-mentioned comparative example 1-3, and different is that this example is mainly tested HBP-Al
2O
3Influence to properties of rubber.After pressing table 1 and adding successively, make sample according to national standard, test result is as shown in table 3 below.
Embodiment 5
The hyperbranched graft modification nano aluminium oxide HAPE-Al of (graft from) method modification is synthesized in test with original position among the embodiment 2
2O
3Influence to properties of rubber.
The technology of present embodiment is all identical with above-mentioned comparative example 1-3, and different is that this example is mainly tested HAPE-Al
2O
3Influence to properties of rubber.After pressing table 1 and adding successively, make sample according to national standard, test result is as shown in table 3 below.
Embodiment 6
Test is synthesized the influence of the hyperbranched graft modification nano aluminium oxide HBP-SiC of (graft from) method modification to properties of rubber with original position among the embodiment 3.The technology of present embodiment is all identical with above-mentioned comparative example 1-3, and different is that this example is mainly tested the influence of HBP-SiC to properties of rubber.After pressing table 1 and adding successively, make sample according to national standard, test result is as shown in table 3 below.
Filling-modified rubber mechanical property of the different grafted by super branched polymer inorganic nanometer powder of table 3 equivalent and anti-wear performance
Data result contrast from table 3, learn in the above-mentioned example: sizing material shows excellent enhancing cooperative effect and interface co-operative effect, and hot strength and elongation at break have had largely and have improved, and anti-wear performance has also had and has significantly improved.
Claims (7)
1. the method for a grafted by super branched polymer inorganic nanometer powder enhancement engineering tire tread glue performance is characterized in that this method has following technical process and step:
A. in flask, add in following ratio, in every 100ml absolute ethyl alcohol, add 1-10g inorganic nanometer powder and 1-5ml gamma-amino propyl-triethoxysilicane oxygen alkane, perhaps γ-sulfydryl propyl-triethoxysilicane oxygen alkane, perhaps γ-glycidyl ether oxygen propyl trimethoxy siloxanes, ultrasonic 30 minutes, stirring and refluxing 2-4h is up to whole suspensions, cyclic washing obtains the inorganic nanometer powder of organic process behind the suction filtration, 110 ℃ of vacuum drying 10-24h;
B. directly grafting: in flask, add step (a) gained and have amino, sulfydryl, hydroxyl, the inorganic nanometer powder of epoxy radicals or do not pass through organically-modified inorganic nanometer powder 1-10 weight portion, solvent 20-100 weight portion, with contain terminal hydroxy group, end carboxyl, the dissaving polymer 1-50 weight portion of the amino or end epoxy radicals of end, sealing, take out nitrogen repeatedly three times, ultrasonic processing 30-1000min reacts 1-24h down at 10-180 ℃, suction filtration, cyclic washing, 10-180 ℃ of vacuum drying obtains the inorganic nanometer powder of hyperbranched modification;
C. step (b) is taked situ-formed graft: to have amino in the step (a), sulfydryl, hydroxyl, the inorganic nanometer powder of epoxy radicals is 1 weight portion for nuclear, consumption, with the AB2 that can react with it is that monomer, consumption are the 0.1-50 weight portion, with other lewis acids such as p-methyl benzenesulfonic acid or BFEEs is that catalyst, consumption are the 0.1-10 weight portion, add the 1-50 parts by weight solvent, 0-180 ℃ is reacted 1min-500h down under argon gas or nitrogen protection, up to reacting completely, filter, drying obtains modified powder; Perhaps will react with 1-50 weight portion polyalcohol or polyamine after the 1-10 weight portion inorganic nanometer powder acidylate; react with 1-50 weight portion alpha-halogen carboxylic acid halides then; obtain the inorganic nanometer powder that the surface has initator functional group; be nuclear with it then; add the double bond containing monomer of 0.1-50 weight portion; the solvent that adds 0.1-5 weight portion catalyst or 0.1-5 weight portion part and 1-50 weight portion; 0-180 ℃ is reacted 1min-500h down under argon gas or nitrogen protection; after being significantly increased, viscosity stops reaction; in methyl alcohol, precipitate; the gained precipitation heavily is dissolved in solvent; suction filtration; washing, 20-180 ℃ of vacuum drying obtains the macromolecular grafted inorganic nanometer powder of in-situ polymerization.
D. in 100 weight portion sizing materials, add the grafted by super branched polymer inorganic nanometer powder of 0.5-20 weight portion, after fully mixing, obtain rubber, behind sulfidization molding, make the engineering tire tread rubber that the grafted by super branched polymer inorganic nanometer powder strengthens.
2. method according to claim 1, it is characterized in that used inorganic nanometer powder for wherein any or several: nanometer Al
2O
3, nanometer SiO
2, nano-TiO
2, nano SiC, nanometer BaSO
4, nanometer BN, nano-MgO, nanometer CaCO
3Deng.
3. method according to claim 1 is characterized in that dissaving polymer used in the step (b) is for containing terminal hydroxy group, end carboxyl or the amino hyperbranched polyether of end, polyester, polyesteramine, polyamide, polyurethane, polysulfones amine, polyureas-ammonia ester.
4. method according to claim 1, it is characterized in that solvent used among step (b), (c) is oxolane, dimethyl sulfoxide (DMSO), N, dinethylformamide, N, N-dimethylacetylamide, chloroform, carrene, ethyl acetate, acetone, toluene, dimethylbenzene etc.
5. method according to claim 1 is characterized in that used AB in the step (c)
2The type monomer is 2, two (hydroxymethyl) propionic acid of 2-, the monobasic ester of trimellitic anhydride, trimesic acid or monobasic acid amides, dihydroxy-benzoic acid, dihydroxy-benzoic acid ester, hydroxy benzenes diacid and derivative thereof, as 5-phenoxy group isophthalic acid, a dihydroxy benzene halide, dihydroxy amine etc.
6. method according to claim 1, it is characterized in that containing double bond monomer in the step (c) comprises methyl acrylate, hydroxy-ethyl acrylate, acrylic acid ammonia ethyl ester, methacrylic acid hydroxy butyl ester and derivative thereof, styrene, methyl styrene and derivative thereof, Methacrylamide, ethyl acrylamide and derivative thereof etc.
7. method according to claim 1 is characterized in that catalyst used in the step (c) is cuprous salt, ferrous salt, inferior lead salt etc.; Part is tetramethylethylenediamine, pentamethyl-diethyl tetramine, hexamethyl-triethyl group tetramine, ethanedioic acid, malonic acid, succinic acid, phthalic acid etc.
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