CN103224632B - Poly(itaconate/isoprene)bio-based elastomer/layered silicate nanocomposite material preparation method - Google Patents
Poly(itaconate/isoprene)bio-based elastomer/layered silicate nanocomposite material preparation method Download PDFInfo
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- CN103224632B CN103224632B CN201310092996.9A CN201310092996A CN103224632B CN 103224632 B CN103224632 B CN 103224632B CN 201310092996 A CN201310092996 A CN 201310092996A CN 103224632 B CN103224632 B CN 103224632B
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 34
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920001971 elastomer Polymers 0.000 title abstract description 63
- 239000000463 material Substances 0.000 title abstract description 13
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 title abstract description 9
- 239000002114 nanocomposite Substances 0.000 title abstract description 9
- 239000000806 elastomer Substances 0.000 title abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 239000006229 carbon black Substances 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003292 glue Substances 0.000 claims description 73
- 239000000725 suspension Substances 0.000 claims description 62
- 230000036541 health Effects 0.000 claims description 55
- 241000353097 Molva molva Species 0.000 claims description 49
- 238000005189 flocculation Methods 0.000 claims description 26
- 230000016615 flocculation Effects 0.000 claims description 26
- 239000011259 mixed solution Substances 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 22
- 239000004816 latex Substances 0.000 claims description 19
- 229920000126 latex Polymers 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 239000005864 Sulphur Substances 0.000 claims description 11
- 238000004073 vulcanization Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 150000004760 silicates Chemical class 0.000 claims description 5
- 239000000084 colloidal system Substances 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- -1 silicate compound Chemical class 0.000 claims description 2
- 239000005060 rubber Substances 0.000 abstract description 56
- 230000004888 barrier function Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 238000010382 chemical cross-linking Methods 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000012744 reinforcing agent Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 14
- 235000019241 carbon black Nutrition 0.000 description 12
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 10
- 229910052901 montmorillonite Inorganic materials 0.000 description 10
- 235000021355 Stearic acid Nutrition 0.000 description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 9
- 239000008117 stearic acid Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000003643 water by type Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000002156 mixing Methods 0.000 description 5
- 239000000945 filler Substances 0.000 description 4
- 230000002787 reinforcement Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- Processes Of Treating Macromolecular Substances (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a poly(itaconate/isoprene)bio-based elastomer/layered silicate nanocomposite material preparation method. A poly(itaconate/isoprene)bio-based elastomer/layered silicate nanocomposite material is obtained through wet compounding of a poly(itaconate/isoprene)bio-based elastomer and layered silicate, and chemical cross-linking. The layered silicate/poly(itaconate/isoprene)bio-based elastomer nanocomposite material is a novel environmentally-friendly composite material, and the filling of layered silicate can reduce the rubber cost, so the composite material is an airtight green rubber product having a very good prospect. The material prepared in the invention has an environmental protection property and a gas barrier performance, and the gas permeation coefficient of the poly(itaconate/isoprene)bio-based elastomer/layered silicate nanocomposite material is 1.7-10.4*10<-17>m<2>s<-1>Pa<-1>. 20-50 parts by mass of combined reinforcing agents comprising white carbon black (SiO2) or carbon black, and the like can be added to improve the strength of the composite material.
Description
Technical field
The present invention relates to the preparation method of a kind of poly-(itaconic ester/isoprene) bio-based elastomer/laminated silicate nanometer composite material preparation method's, particularly a kind of high gas-obstructing character biological engineering rubber.
Background technology
Rubber industry in occupation of very important status, all needs the extensive application of rubber in national economy in the fields such as military affairs, medical treatment and the people's livelihood.The special molecular structure of rubber has determined that it has snappiness but the characteristic of intensity shortcoming must just can obtain having the rubber item of practical value by the reinforcement of small molecules filler.Carbon black and white carbon black are most widely used strengthening agents in rubber, can significantly improve stress at definite elongation and the anti-damage performance of cross-linked rubber.But along with developing rapidly of rubber industry, their limitation reveals gradually: carbon black depends on petrochemical industry, produces a large amount of dust, contaminate environment in production process; White carbon black production is comparatively complicated, and not as carbon black, density is little and cost is higher with the affinity of colloid.In view of the foregoing, utilize nanometer inorganic filler to strengthen and become a kind of inevitable trend.In inorganic nano-filler, layered silicate becomes the rubber nano strengthening agent of tool application prospect with abundant, the cheap and good reinforcing effect of reserves.
Poly-(itaconic ester/isoprene) bio-based elastomerics, is called for short health penta glue, is a kind of novel, environmentally friendly bio-based elastomerics.The relevant polymerization process of health penta glue and performance have been published in patent " method of itaconate/isoprene copolymer type bio-based engineering elastomer rubber is prepared in a kind of low temperature letex polymerization " (patent No.: 201110440385.X).Health penta glue and same eco-friendly layered silicate are prepared to a kind of nano composite material of high gas-obstructing character by complex method couplings such as latex coprecipitations, at home and abroad all without report.
Summary of the invention
A kind of health penta glue/laminated nm-silicate composite material of the present invention, for a kind of health penta glue that derives from renewable biomass resource and layered silicate form through chemically crosslinked after compound again.
Concrete preparation condition and step are as follows:
A: the preparation of layered silicate aqeous suspension
By layered silicate and deionized water in mass ratio 2 ~ 5:100 mix, be stirred to evenly, standing to no longer sedimentation of suspension, after removing impurity, obtain stable layered silicate aqeous suspension, get suspension sample in watch-glass to just paving, dry watch-glass, calculate silicate solid content s.The method of calculation of solid content can be calculated by following formula:
s=(?m
1-?m
0)/?(?m
2-?m
0)
Wherein, m
0for empty watch-glass quality, m
1for drying the quality of rear surface ware and silicate, m
2quality for watch-glass and suspension.
Described layered silicate is polynite, rectorite leng etc.
B: health penta glue and layered silicate compound
By above-mentioned layered silicate and health penta glue in mass ratio 10 ~ 80:100 mix, wherein the quality of silicate is determined by suspension solid content, the solid content that health penta colloid amount is pressed latex calculates.
Mixed solution stirs 20 ~ 30min, adds flocculation agent flocculation.
The sample that flocculation is obtained is dried moisture in 40 ~ 60 ℃ of air dry ovens, then dries to constant weight in 40 ~ 60 ℃ of vacuum drying ovens, obtains the flocculent gel of health penta glue/laminated nm-silicate composite material.
It is the diluted acid of 1-2 or the calcium chloride water that pH is 5-6 that flocculation agent used can be selected pH.
C: chemically crosslinked process
Get flocculent gel 100 mass parts of above-mentioned health penta glue/layered silicate matrix material and 0.5～2.5 part of sulphur, 0.5～2 part of captax, the accelerant CZ of 0.5～2 part by mill or Banbury mixer blend, at 130～160 ℃ of molded vulcanizations, make health penta glue/phyllosilicate nano compounded rubber.
For improving intensity, also can add the white carbon black (SiO of 20～50 mass parts
2) or the associating such as carbon black toughener.
The white carbon black of usining during toughener, can add 1～5 mass parts coupling agent to improve composite effect as associating.
Material prepared by the present invention has environment friendly and gas barrier property, and the gas transmission coefficient of described health penta glue/laminated nm-silicate composite material is 1.7～10.4 * 10
-17m
2s
-1pa
-1.
Accompanying drawing explanation
Fig. 1 is the 20phr(per hundred rubber of the embodiment of the present invention one preparation, i.e. weight part in 100 parts of rubber, phr is rubber materials universal word) 100000 times of enlarged photographs of reinforcement health penta glue transmission electron microscope.Can find out, filler has good dispersion effect in health penta glue, is monolithic layer state.
Fig. 2 is the XRD result of 60phr rectorite leng reinforcement health penta glue of the embodiment of the present invention three preparations.Can find out, glue sample is very weak at the rectorite leng characteristic peak position at 2.4nm place, illustrates that fillers dispersed is good.
Fig. 3 is the cross-linked rubber photo of 60phr reinforcement health penta glue of the embodiment of the present invention three preparations.
Embodiment
Health penta glue adopting in the embodiment of the present invention, is laboratory synthetics, and existing mature technology, can be prepared by commercially available biological process methylene-succinic acid, primary isoamyl alcohol and isoprene.Layered silicate rectorite leng used and polynite are commercially available prod.The rubber performance of the embodiment of the present invention 1～6 and comparative example 1 preparation is listed in table 1.
Case study on implementation one
40 grams of rectorite lengs are mixed with 1960 grams of deionized waters, the rectorite leng aqeous suspension that configuration quality mark is 2%, suspension is placed on homogenizer, and 800 revs/min of rotating speeds at the uniform velocity stir 6 hours.Stir and finish, standing solution 20 hours.After standing completing, getting quality is 48.56g(m
0) watch-glass, measure a small amount of suspension in watch-glass, take the watch-glass quality 49.90g(m containing suspension
2) put into quick moisture evaporimeter evaporate to dryness, obtain drying the quality 48.58g(m of rear surface ware and silicate
1) according to formula (1), calculate the solid content 1.49% of rectorite leng suspension.According to suspension/latex mixed solution of solid content preparation 20phr rectorite leng.Again mixed solution rotating speed with 480 revs/min on homogenizer is stirred 20 minutes.Configuration is 5 with the isopyknic pH of suspension, with the isopyknic calcium chloride solution of suspension, rectorite leng/latex mixed solution is slowly added and is stirred, after standing 1 hour by flocculation with deionized water wash to neutrality.The glue sample that flocculation is obtained dries 8h in 60 ℃ of convection oven, removes moisture, obtains health penta glue/montmorillonite Composite flocculent gel.Glue sample is dried to constant weight in 40 ℃ of vacuum drying ovens.
100 grams of compound rubbers of above-mentioned health penta glue/rectorite leng are mixed and obtain rubber unvulcanizate in two roller mills with 1.5 grams of sulphur, 1.5 grams of short M, 3 grams of short CZ, 0.38 gram of ZnO, 0.75 gram of stearic acid, and rubber unvulcanizate molded vulcanization at 150 ℃ is prepared into health penta glue/rectorite leng rubber industry.
Case study on implementation two
40 grams of rectorite lengs are mixed with 1960 grams of deionized waters, the rectorite leng aqeous suspension that configuration quality mark is 2%, suspension is placed on homogenizer, and 800 revs/min of rotating speeds at the uniform velocity stir 6 hours.Stir and finish, standing solution 24 hours.After standing completing, take a morsel suspension in watch-glass, put into quick moisture evaporimeter evaporate to dryness, calculate the solid content of rectorite leng suspension.According to suspension/latex mixed solution of solid content preparation 50phr rectorite leng.Again mixed solution rotating speed with 480 revs/min on homogenizer is stirred 20 minutes.Configuration is 6 with the isopyknic pH of suspension, with the isopyknic calcium chloride solution of suspension, rectorite leng/latex mixed solution is slowly added and is stirred, after standing 1 hour by deionized water wash for flocculation to nearly neutrality.The glue sample that flocculation is obtained dries 9h in 60 ℃ of convection oven, removes moisture, obtains health penta glue/montmorillonite Composite flocculent gel.Glue sample is dried to constant weight in 50 ℃ of vacuum drying ovens.
100 grams of compound rubbers of above-mentioned health penta glue/rectorite leng are mixed and obtain rubber unvulcanizate in two roller mills with 1 gram of sulphur, 1 gram of short M, 2 grams of short CZ, 0.25 gram of ZnO, 0.5 gram of stearic acid, and rubber unvulcanizate molded vulcanization at 150 ℃ is prepared into health penta glue/rectorite leng rubber industry.
Case study on implementation three
40 grams of rectorite lengs are mixed with 1960 grams of deionized waters, the rectorite leng aqeous suspension that configuration quality mark is 2%, suspension is placed on homogenizer, and 800 revs/min of rotating speeds at the uniform velocity stir 7 hours.Stir and finish, standing solution 20 hours.After standing completing, take a morsel suspension in watch-glass, put into quick moisture evaporimeter evaporate to dryness, calculate the solid content of rectorite leng suspension.According to suspension/latex mixed solution of solid content preparation 60phr rectorite leng.Again mixed solution rotating speed with 480 revs/min on homogenizer is stirred 30 minutes.Configuration is 1 with the isopyknic pH of suspension, with the isopyknic hydrochloric acid soln of suspension, rectorite leng/latex mixed solution is slowly added and is stirred, after standing 1 hour by deionized water wash for flocculation to nearly neutrality.The glue sample that flocculation is obtained dries 8h in 50 ℃ of convection oven, removes moisture, obtains health penta glue/montmorillonite Composite flocculent gel.Glue sample is dried to constant weight in 40 ℃ of vacuum drying ovens.
100 grams of compound rubbers of above-mentioned health penta glue/rectorite leng are mixed and obtain rubber unvulcanizate in two roller mills with 1 gram of sulphur, 2 grams of short M, 1 gram of short CZ, 0.25 gram of ZnO, 0.5 gram of stearic acid, and rubber unvulcanizate molded vulcanization at 150 ℃ is prepared into health penta glue/rectorite leng rubber industry.
Case study on implementation four
40 grams of rectorite lengs are mixed with 1960 grams of deionized waters, the rectorite leng aqeous suspension that configuration quality mark is 2%, suspension is placed on homogenizer, and 800 revs/min of rotating speeds, at the uniform velocity stir more than 6 hours.Stir and finish, standing solution 22 hours.After standing completing, take a morsel suspension in watch-glass, put into quick moisture evaporimeter evaporate to dryness, calculate the solid content of rectorite leng suspension.According to suspension/latex mixed solution of solid content preparation 80phr rectorite leng.Again mixed solution rotating speed with 480 revs/min on homogenizer is stirred 30 minutes.Configuration pH is 2, with the isopyknic sulphuric acid soln of suspension, rectorite leng/latex mixed solution is slowly added and is stirred, after standing 1 hour by deionized water wash for flocculation to nearly neutrality.The glue sample that flocculation is obtained dries 7h in 60 ℃ of convection oven, removes moisture, obtains health penta glue/montmorillonite Composite flocculent gel.Glue sample is dried to constant weight in 60 ℃ of vacuum drying ovens.
By 100 grams of compound rubbers of above-mentioned health penta glue/rectorite leng, by mixing and obtain rubber unvulcanizate in two roller mills with 1 gram of sulphur, 2 grams of short M, 1 gram of short CZ, 0.25 gram of ZnO, 0.5 gram of stearic acid, rubber unvulcanizate molded vulcanization at 150 ℃ is prepared into health penta glue/rectorite leng rubber industry.
Case study on implementation five
100 grams of polynites are mixed with 1900 grams of deionized waters, the polynite aqeous suspension that configuration quality mark is 5%, suspension is placed on homogenizer, and 800 revs/min of rotating speeds at the uniform velocity stir 8 hours.Stir and finish, standing solution 20 hours.After standing completing, take a morsel suspension in watch-glass, put into quick moisture evaporimeter evaporate to dryness, calculate the solid content of montmorillonite suspension liquid.According to suspension/latex mixed solution of solid content preparation 20phr polynite.Again mixed solution rotating speed with 480 revs/min on homogenizer is stirred 20 minutes.Configuration pH is 5, with the isopyknic calcium chloride solution of suspension, polynite/latex mixed solution is slowly added and is stirred, after standing 1 hour by deionized water wash for flocculation to nearly neutrality.The glue sample that flocculation is obtained dries 9h in 50 ℃ of convection oven, removes moisture, obtains health penta glue/montmorillonite Composite flocculent gel.Glue sample is dried to constant weight in 60 ℃ of vacuum drying ovens.
By 100 grams of above-mentioned health penta glue/montmorillonite Composite rubbers, by mixing and obtain rubber unvulcanizate in two roller mills with 1 gram of sulphur, 1 gram of short M, 2 grams of short CZ, 0.25 gram of ZnO, 0.5 gram of stearic acid, rubber unvulcanizate molded vulcanization at 150 ℃ is prepared into health penta glue/polynite rubber industry.
Case study on implementation six
100 grams of polynites are mixed with 1900 grams of deionized waters, the polynite aqeous suspension that configuration quality mark is 5%, suspension is placed on homogenizer, and 800 revs/min of rotating speeds at the uniform velocity stir 7 hours.Stir and finish, standing solution is more than 24 hours.After standing completing, take a morsel suspension in watch-glass, put into quick moisture evaporimeter evaporate to dryness, calculate the solid content of montmorillonite suspension liquid.According to suspension/latex mixed solution of solid content preparation 40phr polynite.Again mixed solution rotating speed with 480 revs/min on homogenizer is stirred 20 minutes.Configuration pH is 6, with the isopyknic calcium chloride solution of suspension, polynite/latex mixed solution is slowly added and is stirred, after standing 1 hour by deionized water wash for flocculation to nearly neutrality.The glue sample that flocculation is obtained dries 9h in 50 ℃ of convection oven, removes moisture, obtains health penta glue/montmorillonite Composite flocculent gel.Glue sample is dried to constant weight in 60 ℃ of vacuum drying ovens.
By 100 grams of above-mentioned health penta glue/montmorillonite Composite rubbers, by mixing and obtain rubber unvulcanizate in two roller mills with 1 gram of sulphur, 1 gram of short M, 2 grams of short CZ, 0.25 gram of ZnO, 0.25 gram of stearic acid, rubber unvulcanizate molded vulcanization at 150 ℃ is prepared into health penta glue/polynite rubber industry.
Case study on implementation seven
40 grams of rectorite lengs are mixed with 1960 grams of deionized waters, the rectorite leng aqeous suspension that configuration quality mark is 2%, suspension is placed on homogenizer, and 800 revs/min of rotating speeds at the uniform velocity stir 7 hours.Stir and finish, standing solution is more than 22 hours.After standing completing, take a morsel suspension in watch-glass, put into quick moisture evaporimeter evaporate to dryness, calculate the solid content of rectorite leng suspension.According to suspension/latex mixed solution of solid content preparation 40phr rectorite leng.Again mixed solution rotating speed with 480 revs/min on homogenizer is stirred 20 minutes.Configuration pH is 6, with the isopyknic calcium chloride solution of suspension, rectorite leng/latex mixed solution is slowly added and is stirred, after standing 1 hour by deionized water wash for flocculation to nearly neutrality.The glue sample that flocculation is obtained dries 7h in 50 ℃ of convection oven, removes moisture, obtains health penta glue/rectorite leng composite flocculation glue.Glue sample is dried to constant weight in 60 ℃ of vacuum drying ovens.
By 100 grams of compound rubbers of above-mentioned health penta glue/rectorite leng, by mixing and obtain rubber unvulcanizate in two roller mills with 40phrN330 carbon black, 1 gram of sulphur, 1 gram of short M, 2 grams of short CZ, 0.25 gram of ZnO, 0.25 gram of stearic acid, rubber unvulcanizate molded vulcanization at 150 ℃ is prepared into health penta glue/rectorite leng/carbon black rubber industry.
Case study on implementation eight
40 grams of rectorite lengs are mixed with 1960 grams of deionized waters, the rectorite leng aqeous suspension that configuration quality mark is 2%, suspension is placed on homogenizer, and 800 revs/min of rotating speeds at the uniform velocity stir 7 hours.Stir and finish, standing solution is more than 22 hours.After standing completing, take a morsel suspension in watch-glass, put into quick moisture evaporimeter evaporate to dryness, calculate the solid content of rectorite leng suspension.According to suspension/latex mixed solution of solid content preparation 40phr rectorite leng.Again mixed solution rotating speed with 480 revs/min on homogenizer is stirred 20 minutes.Configuration pH is 6, with the isopyknic calcium chloride solution of suspension, rectorite leng/latex mixed solution is slowly added and is stirred, after standing 1 hour by deionized water wash for flocculation to nearly neutrality.The glue sample that flocculation is obtained dries 7h in 60 ℃ of convection oven, removes moisture, obtains health penta glue/rectorite leng composite flocculation glue.Glue sample is dried to constant weight in 50 ℃ of vacuum drying ovens.
By 100 grams of compound rubbers of above-mentioned health penta glue/rectorite leng, by mixing and obtain rubber unvulcanizate in two roller mills with 40phr thermal silica, 4phrSi69,1 gram of sulphur, 1 gram of short M, 2 grams of short CZ, 0.25 gram of ZnO, 0.25 gram of stearic acid, rubber unvulcanizate molded vulcanization at 150 ℃ is prepared into health penta glue/rectorite leng/white carbon black rubber industry.
Comparative example 1
The pure glue of 100 grams of health, penta glue is mixed and obtains rubber unvulcanizate in two roller mills with 1 gram of sulphur, 1 gram of short M, 2 grams of short CZ, 0.25 gram of ZnO, 0.5 gram of stearic acid, and rubber unvulcanizate molded vulcanization at 150 ℃ is prepared into health penta glue plastic.
The performance test results of the elastomeric material of preparing in table 1 the invention process case and comparative example
(note: in table, data all adopt conventional national standard testing method to obtain)
From the correlation data of table 1, can find out, layered silicate/health penta glue nano composite material of preparing in the present invention can effectively be improved the gas barrier property of health penta glue, and can strengthen to a certain extent the mechanical propertys such as tensile strength of health penta glue, and have environmental protection, advantage that cost is low with respect to traditional loading material of rubber such as white carbon blacks.Preliminary study shows, layered silicate can also effectively improve the thermotolerance of health penta glue.Therefore, layered silicate/health penta glue nano composite material is expected to be applied on the goods such as gasket, sealing-ring, oil resistant automotive sealant, string rubber, sebific duct.In addition, the main raw material of health penta glue is tunning, be a kind of biological material, and layered silicate also derives from nature but not petrochemical industry resource.Therefore, layered silicate/health penta glue nano composite material is a kind of novel environmentally friendly matrix material, fills the cost that layered silicate can also reduce rubber, is the green rubber item of a kind of very promising airproof.
Claims (2)
1. gather the elastomer/laminated silicate nanometer composite material preparation method of (itaconic ester/isoprene) bio-based, it is characterized in that step is as follows:
A: the preparation of layered silicate aqeous suspension
By layered silicate and deionized water in mass ratio 2 ~ 5:100 mix, be stirred to evenly, standing to no longer sedimentation of suspension, obtain stable layered silicate aqeous suspension after removing impurity; Described layered silicate is polynite or rectorite leng;
B: health penta glue and layered silicate compound
By above-mentioned layered silicate and health penta glue in mass ratio 10 ~ 80:100 mix, wherein the quality of silicate is determined by suspension solid content, the solid content that health penta colloid amount is pressed latex calculates;
Mixed solution stirs 20 ~ 30min, adds flocculation agent flocculation; Flocculation agent used is that pH is the diluted acid of 1-2 or the calcium chloride water that pH is 5-6;
The sample that flocculation is obtained is dried moisture in 40 ~ 60 ℃ of air dry ovens, then dries to constant weight in 40 ~ 60 ℃ of vacuum drying ovens, obtains the flocculent gel of health penta glue/laminated nm-silicate composite material;
C: chemically crosslinked process
Get flocculent gel 100 mass parts of above-mentioned health penta glue/layered silicate matrix material and 0.5～2.5 part of sulphur, 0.5～2 part of captax, the accelerant CZ of 0.5～2 part by mill or Banbury mixer blend, at 130～160 ℃ of molded vulcanizations, make the elastomer/laminated silicate nanometer composite material of poly-(itaconic ester/isoprene) bio-based.
2. a kind of poly-elastomer/laminated silicate nanometer composite material preparation method of (itaconic ester/isoprene) bio-based according to claim 1, is characterized in that:
In step C, also can add white carbon black or the carbon black of 20～50 mass parts.
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| CN104725756B (en) * | 2014-09-06 | 2017-01-25 | 北京化工大学 | Itaconate/isoprene copolymer type biology base elastomer tread rubber and preparation method thereof |
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