CN104045868A - Preparation method of nano cerium oxide/natural rubber composite material - Google Patents
Preparation method of nano cerium oxide/natural rubber composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a nano cerium oxide/natural rubber composite material. The method comprises the following steps: (1) by mass parts, dissolving 0.5-1 part of stearic acid in 0.5-5 parts of absolute ethanol, adjusting the pH value to be 3-5, adding 3-6 parts of nano cerium oxide, stirring, performing suction filtration, and drying in vacuum to prepare modified nano cerium oxide; (2) weighing 0.5-6 parts of absolute ethanol and 0.5-3 parts of a silane coupling agent to prepare a compound solution, adding the modified nano cerium oxide into the compound solution, uniformly stirring, standing until a water film appears on the nano cerium oxide plane, and adding 37-43 parts of de-ionized water to prepare a nano cerium oxide suspension solution; and (3) adding the prepared nano cerium oxide suspension solution into 80-100 parts of natural latex, and uniformly stirring to prepare the latex-state nano cerium oxide/natural rubber composite material.
Description
Technical field
The present invention relates to the preparation method of natural rubber based composites, particularly a kind of preparation method of nano-cerium oxide/native rubber composite material.
Background technology
As natural unsaturated macromolecular material, the excellent combination property of natural rubber, as the good film-forming property of natural rubber latex, wet gel strength is high, be easy to sulfuration, the dry glue of natural rubber has the superior performances such as snappiness, high elongation rate and low creep, and from universal performance, there is no at present other material can substitute.The integral level of China's caoutchouc industry still falls behind, particularly aspect Natural Rubber Latex Products, there is " low tensile strength, low tearing toughness and ageing resistance are poor " problem, be difficult to satisfy social needs, prior art is difficult to effectively solve the key technical problem of above Natural Rubber Latex Products industry development.
Cerium oxide is a kind of rare earth material of excellent performance, in recent years, China researchist Fu Hai (pay sea. the applied research [D] of cerium oxide in natural rubber. packet header: School of Materials & Metallurgy of University Of Science and Technology of the Inner Mongol, 2009) using cerium oxide rare earth as loading material of rubber, by the mode of mechanical blending, be about to the dry glue of natural rubber and by strong mechanical shear stress effect, mix on opening rubber mixing machine with cerium oxide rare earth, made cerium oxide/native rubber composite material.Because cerium oxide has stronger surface polarity, poor with the interface adhesion of natural rubber, mechanical blending process is difficult to realize dispersed in natural rubber matrix of cerium oxide rare earth, and strong mechanical shear stress itself will damage the performance of natural rubber, the cerium oxide/native rubber composite material performance therefore making is not good; Meanwhile, this method is higher to mixing operational requirement, operates lack of standardizationly, as every batch of inconsistent grade of mixing time all can cause batch products performance inconsistency large, affects the use of product.
Therefore, also need to provide a kind of preparation method of high performance nano-cerium oxide/native rubber composite material, solve the agglomeration traits of nano oxidized cerium mischmetal in natural rubber matrix, reach good reinforcement and the object of raising ageing resistance.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation method of nano-cerium oxide/native rubber composite material, makes the nano-cerium oxide/native rubber composite material with good mechanical property and ageing resistance.
In order to solve the problems of the technologies described above, the present invention adopts the wet processing of " blend of liquid-liquid ".Specifically, take natural rubber latex as matrix, add appropriate cerium source suspension, stir, make the nano-cerium oxide/native rubber composite material of latex state; Nano-cerium oxide/the native rubber composite material of this latex shape can be further by solidifying, compressing tablet, washing, the standard Chinese rubber conventional machining technique such as dry, obtain the nano-cerium oxide/native rubber composite material of dry gluey state.Concrete steps are as follows:
1) in mass, 0.5～1 part of stearic acid is dissolved in 0.5～5 part of dehydrated alcohol, pH is adjusted to 3～5, then adds 3～6 parts of nano-cerium oxides to stir and makes modified nano cerium oxide by suction filtration, vacuum-drying;
2) in mass, taking 0.5～6 part of dehydrated alcohol and 0.5～3 part of silane coupling agent is made compositional liquor, by step 1) modified nano cerium oxide that makes adds 37～43 parts of deionized water and stirring evenly to make nano-cerium oxide suspension in room temperature lower seal is standing after being placed in compositional liquor and stirring after moisture film appears in nano-cerium oxide plane;
3) by step 2) the nano-cerium oxide suspension that makes adds in 80～100 parts of natural rubber latexes, stirs, and makes the nano-cerium oxide/native rubber composite material of latex shape.
Nano-cerium oxide/the native rubber composite material of this latex shape can be further by solidifying, compressing tablet, washing, the standard Chinese rubber conventional machining technique such as dry, obtain the nano-cerium oxide/native rubber composite material of dry gluey state.
The particle size range of described nano-cerium oxide is 20～40nm, and specific surface area is 50～60m
2/ g.
Described silane coupling agent is two-[3-(triethoxysilicane) propyl group]-tetrasulfide, APTES.
The concentrated natural latex that described natural rubber latex total solids level is 31.3%～60%.
Nano-cerium oxide/the native rubber composite material that adopts the present invention to prepare can adopt conventional vulcanization system, as effective vulcanization system, semi effcient vulcanization system etc., makes prevulcanized latex, by impregnation technology, produces various latex products; Also can carry out mixing sulfuration according to conventional machining technique, produce various dry glue goods.
The present invention joins the nano-cerium oxide through stearic acid surface modification in the compositional liquor that dehydrated alcohol and silane coupling agent make, or the compositional liquor that dehydrated alcohol and silane coupling agent are made is added in the nano-cerium oxide of stearic acid surface modification, room temperature condition lower seal is standing all produces the moisture film that one deck 0.1mm is thick to nano-cerium oxide particle surface, in standing process, on the one hand, the hydrophilic radical containing in compositional liquor and hydrophobic group can be little by little to the stearic acid infiltration of nano-cerium oxide particle surface, also comprise the stearic acid that is penetrated into the nano-cerium oxide particle surface of assembling agglomerating centre, solved the agglomeration traits of nano-cerium oxide, on the other hand, after cerium oxide nano, the small-size effect of self makes it have the effect of oozing of becoming silted up, near its unsaturated link(age) that can be deep into natural rubber molecular chain electronic cloud also and unsaturated link(age) is had an effect, strengthen the interfacial adhesion of itself and natural rubber, thereby reach the effect of good reinforcement, in addition, the special 4f electronic configuration of nano-cerium oxide makes it have superior oxygen function and the quick oxygen of the high temperature room diffusibility stored, can catch the free radical in natural rubber weathering process, make the unsaturated double-bond on natural rubber molecular chain stable, improve the ageing resistance of natural rubber.
Adopt the wet processing of " blend of liquid-liquid ", nano-cerium oxide after soon modification adds in natural rubber latex with the form of suspension, by stirring at low speed, realize dispersed in natural rubber latex of nano-cerium oxide suspension after modification, technological operation is easy, easily control, stirring at low speed only has dissemination simultaneously, do not shear porphyrization, therefore can not damage the performance of product.
Nano-cerium oxide/the native rubber composite material that adopts the present invention to prepare has following unusual effect:
1, mechanical property and the ageing resistance of natural rubber have significantly been promoted.Tensile strength before the nano-cerium oxide/native rubber composite material that adopts the present invention to prepare makes natural rubber vulcanized rubber sheet aging is mentioned to 31.5～33.9MPa by 22.7MPa, and tensile yield is increased to 869～936% by 829%, and tear strength is by 37.1KN.m
-1be increased to 44.6～46.9KN.m
-1; Tensile strength after 100 ℃ of hot air aging 24h is increased to 28.4～31.4MPa by 19.7MPa, and tensile yield is increased to 829～868% by 789%, and tear strength is by 35.0KN.m
-1be increased to 40～43.6KN.m
-1.
2, realize the object that single filler improves natural rubber mechanical property and ageing resistance simultaneously, reduced cost, expanded the range of application of natural rubber.
Embodiment
The present invention will be described to adopt non-limiting examples below.Should be understood that these embodiment are only not used in the scope of the present invention that limits for the present invention is described.Except as otherwise noted, the umber adopting is below weight part.
Embodiment 1
A. the modification of nano-cerium oxide
Take 0.8 part of stearic acid and be placed in the flask that 5 parts of dehydrated alcohols are housed and dissolve, with second acid for adjusting pH to 4, then add 4 parts of nano-cerium oxides to stir suction filtration after 48h, gained filter cake obtains modified nano cerium oxide through 60 ℃ of vacuum-drying 24h;
B. the preparation of nano-cerium oxide suspension
Take 6 parts of dehydrated alcohols and become compositional liquor with 3 parts of two-[3-(triethoxysilicane) propyl group]-tetrasulfides, after being placed in to compositional liquor and stirring, the modified nano cerium oxide making in step a in nano-cerium oxide plane, all occurs, after moisture film that one deck 0.1mm is thick, adding 37 parts of deionized water and stirring evenly to obtain nano-cerium oxide suspension after the standing 30h of room temperature lower seal;
C. adopt liquid-liquid blending method, the nano-cerium oxide suspension that step b is made adds in 100 parts of natural rubber latexes that are derived from Brazilian para ruber, this natural rubber latex total solids level is 31.3%, stir speed (S.S.) with 300r/min under room temperature stirs 2 hours, make the nano-cerium oxide/native rubber composite material of latex shape, nano-cerium oxide/the native rubber composite material of this latex shape is by solidifying, compressing tablet, washing, the standard Chinese rubber conventional machining technique such as dry, obtain the nano-cerium oxide/native rubber composite material of dry gluey state, concrete operations are: under agitation nano-cerium oxide/the native rubber composite material to the latex shape making adds 0.2 part of zinc oxide, 1 part of sulphur, 0.4 part of zinc diethyldithiocarbamate and 0.05 part of sodium metnylene bis-naphthalene sulfonate, plastic film mulch on sheet glass, 60 ℃ of water-baths are vulcanized 3 hours, dry, make nano-cerium oxide/native rubber composite material sulfuration glued membrane.In addition, directly take and be derived from natural rubber latex (total solids level is 31.3%) plastic film mulch, dry on sheet glass of Brazilian para ruber, prepare blank sample-1.According to GB/T3512-2001, carry out air oven aging test, test conditions: 100 ℃ * 24h.Gained sulfide film mechanical property is in Table 1.
The aging front and back of the nano-cerium oxide/native rubber composite material mechanical property that table 1 makes according to embodiment 1
Embodiment 2
A. the modification of nano-cerium oxide
Take 1 part of stearic acid and be placed in the flask that 4.5 parts of dehydrated alcohols are housed and dissolve, with second acid for adjusting pH to 3, then add 5 parts of nano-cerium oxides to stir suction filtration after 48h, gained filter cake obtains modified nano cerium oxide through 60 ℃ of vacuum-drying 24h;
B. the preparation of nano-cerium oxide suspension
Take 4 parts of dehydrated alcohols and 1.8 parts two-[3-(triethoxysilicane) propyl group]-tetrasulfides make compositional liquor, after the modified nano cerium oxide making in step a is placed in to compositional liquor and stirs, after the standing 33h of room temperature lower seal, in nano-cerium oxide plane, all there is the moisture film that one deck 0.1mm is thick, add 40.2 parts of deionized water and stirring evenly to obtain nano-cerium oxide suspension;
C. adopt liquid-liquid blending method, the nano-cerium oxide suspension that step b is made adds in the concentrated natural latex that 90 parts of centrifugal concentrating total solids levels are 60%, speed with 400r/min under room temperature stirs 3 hours, make the nano-cerium oxide/native rubber composite material of latex shape, then under agitation add 1 part of sulphur, 0.5 part of zinc oxide, 1.0 parts of tetramethyl-thiuram disulfides, on sheet glass, plastic film mulch, 60 ℃ of water-baths are vulcanized 2 hours, dry, make nano-cerium oxide/native rubber composite material sulfuration glued membrane.In addition, the concentrated natural latex that the centrifugal concentrating total solids level of directly take is 60% plastic film mulch, dry on sheet glass, prepares blank sample-2.According to GB/T3512-2001, carry out air oven aging test, test conditions: 100 ℃ * 24h.Gained sulfide film mechanical property is in Table 2.
The aging front and back of the nano-cerium oxide/native rubber composite material mechanical property that table 2 makes according to embodiment 2
Embodiment 3
A. the modification of nano-cerium oxide
Take 0.5 part of stearic acid and be placed in the flask that 0.5 part of dehydrated alcohol is housed and dissolve, with second acid for adjusting pH to 5, then add 3 parts of nano-cerium oxides to stir suction filtration after 48h, gained filter cake obtains modified nano cerium oxide through 60 ℃ of vacuum-drying 24h;
B. the preparation of nano-cerium oxide suspension
Take 3.5 parts of dehydrated alcohols and 1.8 parts of APTESs are made compositional liquor, after the modified nano cerium oxide making in step a is placed in to compositional liquor and stirs, in room temperature lower seal, after standing 40 hours, in nano-cerium oxide plane, all there is the moisture film that one deck 0.1mm is thick, add 41.7 parts of deionized water and stirring evenly to obtain nano-cerium oxide suspension;
C. adopt liquid-liquid blending method, the nano-cerium oxide suspension that step b is made adds in the concentrated natural latex that 80 parts of centrifugal concentrating total solids levels are 60%, speed with 400r/min under room temperature stirs 2 hours, make the nano-cerium oxide/native rubber composite material of latex shape, then under agitation add 1 part of sulphur, 0.5 part of zinc oxide, 1.0 parts of tetramethyl-thiuram disulfides, on sheet glass, plastic film mulch, 60 ℃ of water-baths are vulcanized 2.5 hours, dry, make nano-cerium oxide/native rubber composite material sulfuration glued membrane, gained sulfide film mechanical property is in Table 3.
The aging front and back of the nano-cerium oxide/native rubber composite material mechanical property that table 3 makes according to embodiment 3
| Nano-cerium oxide is outstanding | Tensile strength/MPa | Tensile yield/% | Tear strength/KN.m -1 |
| Supernatant liquid adds umber | Before aging | After aging | Before aging | After aging | Before aging | After aging |
| 3 | 31.8 | 29.0 | 879 | 829 | 44.6 | 41.4 |
Embodiment 4
A. the modification of nano-cerium oxide
Take 1 part of stearic acid and be placed in the flask that 4.5 parts of dehydrated alcohols are housed and dissolve, with second acid for adjusting pH to 4, then add 6 parts of nano-cerium oxides to stir suction filtration after 48h, gained filter cake obtains modified nano cerium oxide through 60 ℃ of vacuum-drying 24h;
B. the preparation of nano-cerium oxide suspension
Take 0.5 part of dehydrated alcohol and 0.5 part two-[3-(triethoxysilicane) propyl group]-tetrasulfide makes compositional liquor, after the modified nano cerium oxide making in step a is placed in to compositional liquor and stirs, after the standing 46h of room temperature lower seal, in nano-cerium oxide plane, all there is the moisture film that one deck 0.1mm is thick, add 43 parts of deionized water and stirring evenly to obtain nano-cerium oxide suspension;
C. adopt liquid-liquid blending method, the nano-cerium oxide suspension that step b is made adds in the concentrated natural latex that 95 parts of centrifugal concentrating total solids levels are 60%, speed with 350r/min under room temperature stirs 2.5 hours, employing formic acid solidifies, compressing tablet, washing, dry, make the nano-cerium oxide/native rubber composite material of dry gluey state, on opening rubber mixing machine, in above-mentioned dry gluey state matrix material, add 6 parts of zinc oxide successively subsequently, 0.5 part of stearic acid, 3.5 parts of sulphur, 0.5 part of 2-benzothiazolyl mercaptan, mixingly at 140 ℃, vulcanize 25 minutes after evenly, make nano-cerium oxide/native rubber composite material sulfide film.Gained sulfide film mechanical property is in Table 4.
The aging front and back of the nano-cerium oxide/native rubber composite material mechanical property that table 4 makes according to embodiment 4
Embodiment 5
A. the modification of nano-cerium oxide
Take 1 part of stearic acid and be placed in the flask that 5 parts of dehydrated alcohols are housed and dissolve, with second acid for adjusting pH to 4, then add 4.5 parts of nano-cerium oxides to stir suction filtration after 48h, gained filter cake obtains modified nano cerium oxide through 60 ℃ of vacuum-drying 24h;
B. the preparation of nano-cerium oxide suspension
Take 5.5 parts of dehydrated alcohols and 2 parts two-[3-(triethoxysilicane) propyl group]-tetrasulfides make compositional liquor, after the modified nano cerium oxide making in step a is placed in to compositional liquor and stirs, after the standing 48h of room temperature lower seal, in nano-cerium oxide plane, all there is the moisture film that one deck 0.1mm is thick, add 38 parts of deionized water and stirring evenly to obtain nano-cerium oxide suspension;
C. adopt liquid-liquid blending method, the nano-cerium oxide suspension that step b is made adds in the concentrated natural latex that 100 parts of centrifugal concentrating total solids levels are 60%, stir speed (S.S.) with 500r/min under room temperature stirs 1.5 hours, make the nano-cerium oxide/native rubber composite material of latex shape, then under agitation add 0.2 part of zinc oxide, 1 part of sulphur, 0.4 part of zinc diethyldithiocarbamate and 0.05 part of sodium metnylene bis-naphthalene sulfonate, make the prevulcanized nano-cerium oxide/native rubber composite material of latex shape, the prevulcanized matrix material of this latex shape is produced glued membrane by impregnation technology, the latex products such as sebific duct.
Claims (4)
1. a preparation method for nano-cerium oxide/native rubber composite material, is characterized in that comprising the following steps:
1) in mass, 0.5～1 part of stearic acid is dissolved in 0.5～5 part of dehydrated alcohol, pH is adjusted to 3～5, then adds 3～6 parts of nano-cerium oxides to stir and makes modified nano cerium oxide by suction filtration, vacuum-drying;
2) in mass, taking 0.5～6 part of dehydrated alcohol and 0.5～3 part of silane coupling agent is made compositional liquor, by step 1) modified nano cerium oxide that makes adds 37～43 parts of deionized water and stirring evenly to make nano-cerium oxide suspension in room temperature lower seal is standing after being placed in compositional liquor and stirring after moisture film appears in nano-cerium oxide plane;
3) by step 2) the nano-cerium oxide suspension that makes adds in 80～100 parts of natural rubber latexes, stirs, and makes the nano-cerium oxide/native rubber composite material of latex state.
2. the preparation method of a kind of nano-cerium oxide/native rubber composite material according to claim 1, the particle size range that it is characterized in that described nano-cerium oxide is 20～40nm, specific surface area is 50～60m
2/ g.
3. the preparation method of a kind of nano-cerium oxide/native rubber composite material according to claim 1, is characterized in that described silane coupling agent is for two-[3-(triethoxysilicane) propyl group]-tetrasulfide or APTES.
4. the preparation method of a kind of nano-cerium oxide/native rubber composite material according to claim 1, is characterized in that the concentrated natural latex that described natural rubber latex total solids level is 31.3%～60%.
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| CN110295414A (en) * | 2019-06-25 | 2019-10-01 | 海南经纬乳胶丝有限责任公司 | A kind of environment-friendly and energy-efficient rubber latex thread product and preparation method thereof |
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| CN113292915A (en) * | 2021-05-18 | 2021-08-24 | 上海东恒化工有限公司 | Novel nanoparticle-based composite demoulding coating |
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