CN111019231A - Elastomer composite material and preparation method thereof - Google Patents
Elastomer composite material and preparation method thereof Download PDFInfo
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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Abstract
The invention discloses an elastomer composite material and a preparation method thereof, relates to the technical field of thermoplastic elastomer preparation, and solves the problem that the structure of the thermoplastic elastomer is easy to damage when the thermoplastic elastomer is applied in a high-oil environment due to poor oil resistance. An elastomer composite material comprises the following components in parts by weight: 20-35 parts of polyolefin elastomer; 60-75 parts of polypropylene; 5-15 parts of calcium carbonate; 0.01-2 parts of antioxidant; 0.01-2 parts of ultraviolet absorbent; 0.01-5 parts of a lubricant; 4-8 parts of para-aramid fiber; 2-5 parts of fluorinated polyphosphazene rubber. The elastomer composite material disclosed by the invention has good oil resistance, and when the elastomer composite material is applied to a high-oil environment, the integral structure of the elastomer composite material can keep good stability, is not easy to damage, and has a good application effect.
Description
Technical Field
The invention relates to the technical field of thermoplastic elastomer preparation, in particular to an elastomer composite material and a preparation method thereof.
Background
Thermoplastic elastomers, also known as elastomers or synthetic rubbers, are polymeric materials that exhibit rubber elasticity at ambient temperature and are capable of being plasticized at elevated temperatures, and therefore such polymers have some of the characteristics of both thermoplastic rubbers and thermoplastics.
The invention discloses an environment-friendly thermoplastic elastomer particle in Chinese patent application with publication number CN104250390A, which comprises the following components in parts by weight: 10-20 parts of thermoplastic elastomer, 45-65 parts of active calcium, 10-20 parts of modified polypropylene, 15-25 parts of polyethylene, 10-15 parts of polyolefin elastomer, 0.5-1 part of heat stabilizer, 0.5-1 part of antioxidant, 0.5-1 part of titanium dioxide, 0.5-1 part of stearic acid and 05-1 part of plasticizer. The preparation method comprises the following steps: 1) mixing materials: mixing a thermoplastic elastomer, active calcium, modified polypropylene, polyethylene, a polyolefin elastomer, a heat stabilizer, an antioxidant, titanium dioxide, stearic acid and a plasticizer, feeding the mixture into a high-speed stirrer, and stirring for 20-30 min at a stirring speed of 200 revolutions per minute; 2) melting: feeding the mixed materials into a double-screw extruder for melt extrusion, wherein the screw speed of the screw extruder is 250-300 rpm, the melting time is 10-15min, and the melting temperature is 180-200 ℃; 3) cooling to obtain a finished product: and cooling the extruded material, cutting, and then performing weathering treatment on the material to obtain a finished product.
In the above application documents, modified polypropylene and polyethylene are used as raw materials, which can improve the compatibility of the copolymer during the mixing copolymerization, and play a certain role in improving the strength thereof, isooctyl dithioacetate dimethyl tin is used as a heat stabilizer to improve the overall thermal stability thereof, and meanwhile, an environment-friendly plasticizer is added in the raw materials, which has the effects of environmental protection and no toxicity, but the oil resistance of the thermoplastic elastomer environment-friendly particles is poor, so that when the particles are applied to a high-oil environment, the particles are easy to dissolve, swell, crack, deform or reduce the physical properties, and the overall structure is easy to damage, therefore, a new scheme needs to be provided to solve the above problems.
Disclosure of Invention
Aiming at the problem that the structure of the thermoplastic elastomer is easily damaged when the thermoplastic elastomer is applied to a high-oil environment due to poor oil resistance in the prior art, the invention aims to provide the elastomer composite material, which solves the technical problem, has good oil resistance, can keep good structural stability when being applied to the high-oil environment, and has good application effect.
In order to achieve the first purpose, the invention provides the following technical scheme:
an elastomer composite material comprises the following components in parts by weight:
20-35 parts of polyolefin elastomer;
60-75 parts of polypropylene;
5-15 parts of calcium carbonate;
0.01-2 parts of antioxidant;
0.01-2 parts of ultraviolet absorbent;
0.01-5 parts of a lubricant;
4-8 parts of para-aramid fiber;
2-5 parts of fluorinated polyphosphazene rubber.
By adopting the technical scheme, the polyolefin elastomer and the polypropylene have good compatibility, and the formed base material has good performances of small density, large bending, high low-temperature impact resistance and easy processing. Calcium carbonate is a good filler, and can effectively improve the rigidity, toughness and bending strength of the elastomer composite material. The para-aramid fiber is a very loose paddle-shaped fiber with good dispersion, can be combined with the polyolefin elastomer in a similar way of combining with the carbon black and the elastomer, not only can play a good toughening and reinforcing role, but also can improve the oil resistance of the elastomer composite material, is not easy to dissolve, swell, crack, deform or reduce the physical property in a high-oil environment, and has good overall stability. The fluorinated polyphosphazene rubber has the advantages that the fluorinated alkoxy is mainly used as a side group structure, a small amount of side group structures containing double bond groups are introduced to provide vulcanization crosslinking points, so that the flame retardant property and the high and low temperature resistance of the elastomer composite material are greatly improved, and the oil corrosion resistance of the elastomer composite material is greatly improved through the fluorinated alkoxy groups introduced by the fluorinated polyphosphazene rubber. When the fluorinated polyphosphazene rubber and the para-aramid fiber act together, good compounding and synergism can be achieved between the fluorinated polyphosphazene rubber and the para-aramid fiber, and the elastomer composite material has good oil resistance and stable structural strength.
More preferably, the components of the elastomer composite material are added with 2-3 parts by weight of graphene oxide.
By adopting the technical scheme, the graphene oxide sheet is a product of graphite powder after chemical oxidation and stripping, has higher specific surface area and rich surface functional groups, mainly comprises hydroxyl and epoxy groups, can improve the overall structural strength of the elastomer composite material, can greatly improve the oil resistance of the elastomer composite material, and simultaneously improves the corrosion resistance of the elastomer composite material due to the unique insulating property of the graphene oxide.
More preferably, 3-5 parts by weight of methyl vinyl silicone rubber is also added into the components of the elastomer composite material.
By adopting the technical scheme, the methyl vinyl silicone rubber is copolymerized by dimethyl siloxane and a small amount of vinyl siloxane, the oil resistance and the high temperature resistance of the whole elastomer composite material can be improved by introducing the methyl vinyl silicone rubber, and the methyl vinyl silicone rubber has good aging resistance, so that the structural stability of the whole elastomer composite material is not easily damaged.
More preferably, 0.2 to 0.5 part by weight of pentafluoropropionic anhydride is further added to the components of the elastomer composite.
By adopting the technical scheme, the addition of the pentafluoropropionic anhydride can improve the oil resistance and the heat resistance of the elastomer composite material, so that the elastomer composite material is not easy to dissolve, swell, crack, deform or reduce the physical properties in a high-oil environment, and the elastomer composite material can maintain good structural stability and has good application effect.
More preferably, the antioxidant is any one of zinc dialkyl dithiophosphate, dialkyl diphenylamine and alkyl vinyl ester.
By adopting the technical scheme, the antioxidant has good compatibility with other component raw materials, has high oxidation resistance, is not volatilized and decomposed at higher processing temperature, can keep the excellent performance of the elastomer composite material, and prolongs the service life.
More preferably, the ultraviolet absorbent is any one of phenyl ortho-hydroxybenzoate, benzotriazole and 2, 4-dihydroxy benzophenone.
By adopting the technical scheme, the ultraviolet absorbent can absorb ultraviolet parts in sunlight and a fluorescent light source, has good compatibility with raw materials of all components and small volatility, has good and obvious synergistic effect when being used together with an antioxidant, and greatly improves the ageing resistance of the elastomer composite material.
More preferably, the lubricant is any one of erucamide, stearic acid, polyethylene wax and calcium stearate.
By adopting the technical scheme, the erucamide, the stearic acid, the polyethylene wax and the calcium stearate are good lubricants, and the effects of cohesive force among polymer molecules can be obviously reduced in the elastomer composite material, so that the internal friction heat generation and the melt fluidity of the elastomer composite material are improved, and the integral quality of the elastomer composite material is improved.
The second purpose of the invention is to provide a preparation method of the elastomer composite material, and the elastomer composite material prepared by the method has good oil resistance, can keep good structural stability when being applied to a high-oil environment, and has good application effect.
In order to achieve the second purpose, the invention provides the following technical scheme, which comprises the following steps:
step one, preparing materials: preparing various raw materials according to corresponding parts by weight;
step two, mixing materials: mixing and stirring polyolefin elastomer, polypropylene, calcium carbonate, an antioxidant, an ultraviolet absorbent, a lubricant, para-aramid fiber and fluorinated polyphosphazene rubber in corresponding parts by weight for 10-15min at a stirring speed of 200-500rpm to obtain a mixed material;
step three, melt extrusion: and (3) putting the raw materials into a double-screw extruder for extrusion granulation, wherein the rotating speed of the screw extruder is 600rpm plus 300-.
In summary, compared with the prior art, the invention has the following beneficial effects:
(1) the para-aramid fiber and the fluorinated polyphosphazene rubber are used, so that the toughening and reinforcing effects are good, the oil resistance of the elastomer composite material can be improved, and the good compounding and synergistic effects can be achieved among the para-aramid fiber and the fluorinated polyphosphazene rubber, so that the elastomer composite material has good oil resistance, stable structural strength and good overall stability;
(2) due to the addition of the graphene oxide, the methyl vinyl silicone rubber and the pentafluoropropionic anhydride, the elastomer composite material is not easy to dissolve, swell, crack, deform or reduce physical properties in a high-oil environment, the overall structural strength and oil resistance are greatly improved, good structural stability can be maintained, and a good application effect is achieved.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and examples.
Example 1: an elastomer composite material, the components and the corresponding parts by weight thereof are shown in table 1, and is prepared by the following steps:
step one, preparing materials: preparing various raw materials according to corresponding parts by weight;
step two, mixing materials: mixing and stirring polyolefin elastomer, polypropylene, calcium carbonate, zinc dialkyl dithiophosphate, phenyl o-hydroxybenzoate, erucamide, para-aramid fiber and fluorinated polyphosphazene rubber in corresponding parts by weight for 12.5min at the stirring speed of 350rpm to obtain a mixed material;
step three, melt extrusion: and putting the raw materials into a double-screw extruder for extrusion granulation, wherein the rotating speed of the screw extruder is 450rpm, the processing temperature is 205 ℃, the melting time is 12.5min, and cooling is carried out after the extrusion granulation, so that the elastomer composite material is obtained.
Note: the para-aramid fiber in step two above was obtained from Shanghai Jinman plastics, Inc. under the designation WAL 34I.
Example 2: an elastomer composite material is different from the elastomer composite material in the embodiment 1, and specifically comprises the following steps: step one, preparing materials: preparing various raw materials according to corresponding parts by weight;
step two, mixing materials: mixing and stirring polyolefin elastomer, polypropylene, calcium carbonate, zinc dialkyl dithiophosphate, phenyl o-hydroxybenzoate, erucamide, para-aramid fiber and fluorinated polyphosphazene rubber in corresponding parts by weight for 10min at a stirring speed of 500rpm to obtain a mixed material;
step three, melt extrusion: and (3) putting the raw materials into a double-screw extruder for extrusion granulation, wherein the rotating speed of the screw extruder is 300rpm, the processing temperature is 180 ℃, the melting time is 15min, and cooling is carried out after extrusion granulation to obtain the elastomer composite material.
Example 3: an elastomer composite material is different from the elastomer composite material in the embodiment 1, and specifically comprises the following steps: step one, preparing materials: preparing various raw materials according to corresponding parts by weight;
step two, mixing materials: mixing and stirring polyolefin elastomer, polypropylene, calcium carbonate, zinc dialkyl dithiophosphate, phenyl o-hydroxybenzoate, erucamide, para-aramid fiber and fluorinated polyphosphazene rubber in corresponding parts by weight for 15min at a stirring speed of 200rpm to obtain a mixed material;
step three, melt extrusion: and (3) putting the raw materials into a double-screw extruder for extrusion granulation, wherein the rotating speed of the screw extruder is 600rpm, the processing temperature is 230 ℃, the melting time is 10min, and cooling is carried out after extrusion granulation to obtain the elastomer composite material.
Examples 4 to 5: an elastomer composite differing from example 1 in that the components and their respective parts by weight are shown in table 1.
TABLE 1 Components and parts by weight of examples 1-5
Example 6: an elastomer composite differing from example 1 in that the zinc dialkyldithiophosphate in step two was replaced with an equal mass of dialkyldiphenylamine.
Example 7: an elastomer composite differing from example 1 in that the zinc dialkyldithiophosphate in step two was replaced with an alkyl vinyl ester of equal mass.
Example 8: an elastomer composite material was different from that of example 1 in that phenyl ortho-hydroxybenzoate in the second step was replaced with benzotriazole of equal mass.
Example 9: an elastomer composite was different from example 1 in that phenyl ortho-hydroxybenzoate in the second step was replaced with an equal mass of 2, 4-dihydroxybenzophenone.
Example 10: an elastomer composite differing from example 1 in that erucamide in step two was replaced with equal mass of stearic acid.
Example 11: an elastomer composite, different from example 1 in that erucamide in step two was replaced with equal mass of polyethylene wax.
Example 12: an elastomer composite differing from example 1 in that erucamide in step two was replaced with equal mass of calcium stearate.
Example 13: an elastomer composite material is different from the elastomer composite material in the embodiment 1 in that the step two is specifically set as follows: mixing and stirring polyolefin elastomer, polypropylene, calcium carbonate, zinc dialkyl dithiophosphate, phenyl o-hydroxybenzoate, erucamide, para-aramid fiber, fluorinated polyphosphazene rubber and 2.5 parts of graphene oxide in corresponding parts by weight for 12.5min at the stirring speed of 350rpm to obtain a mixed material.
Example 14: an elastomer composite material is different from the elastomer composite material in the embodiment 1 in that the step two is specifically set as follows: mixing and stirring polyolefin elastomer, polypropylene, calcium carbonate, zinc dialkyl dithiophosphate, phenyl o-hydroxybenzoate, erucamide, para-aramid fiber, fluorinated polyphosphazene rubber and 2 parts of graphene oxide in corresponding parts by weight for 12.5min at the stirring speed of 350rpm to obtain a mixed material.
Example 15: an elastomer composite material is different from the elastomer composite material in the embodiment 1 in that the step two is specifically set as follows: mixing and stirring polyolefin elastomer, polypropylene, calcium carbonate, zinc dialkyl dithiophosphate, phenyl o-hydroxybenzoate, erucamide, para-aramid fiber, fluorinated polyphosphazene rubber and 3 parts of graphene oxide in corresponding parts by weight for 12.5min at the stirring speed of 350rpm to obtain a mixed material.
Example 16: an elastomer composite material is different from the elastomer composite material in the embodiment 1 in that the step two is specifically set as follows: mixing and stirring polyolefin elastomer, polypropylene, calcium carbonate, zinc dialkyl dithiophosphate, phenyl o-hydroxybenzoate, erucamide, para-aramid fiber, fluorinated polyphosphazene rubber and 4 parts of methyl vinyl silicone rubber in corresponding parts by weight for 12.5min at the stirring speed of 350rpm to obtain a mixed material.
Example 17: an elastomer composite material is different from the elastomer composite material in the embodiment 1 in that the step two is specifically set as follows: mixing and stirring polyolefin elastomer, polypropylene, calcium carbonate, zinc dialkyl dithiophosphate, phenyl o-hydroxybenzoate, erucamide, para-aramid fiber, fluorinated polyphosphazene rubber and 3 parts of methyl vinyl silicone rubber in corresponding parts by weight for 12.5min at the stirring speed of 350rpm to obtain a mixed material.
Example 18: an elastomer composite material is different from the elastomer composite material in the embodiment 1 in that the step two is specifically set as follows: mixing and stirring polyolefin elastomer, polypropylene, calcium carbonate, zinc dialkyl dithiophosphate, phenyl o-hydroxybenzoate, erucamide, para-aramid fiber, fluorinated polyphosphazene rubber and 5 parts of methyl vinyl silicone rubber in corresponding parts by weight for 12.5min at the stirring speed of 350rpm to obtain a mixed material.
Example 19: an elastomer composite material is different from the elastomer composite material in the embodiment 1 in that the step two is specifically set as follows: mixing and stirring polyolefin elastomer, polypropylene, calcium carbonate, zinc dialkyl dithiophosphate, phenyl o-hydroxybenzoate, erucamide, para-aramid fiber, fluorinated polyphosphazene rubber and 0.35 part of pentafluoropropionic anhydride in corresponding parts by weight for 12.5min at the stirring speed of 350rpm to obtain a mixed material.
Example 20: an elastomer composite material is different from the elastomer composite material in the embodiment 1 in that the step two is specifically set as follows: mixing and stirring polyolefin elastomer, polypropylene, calcium carbonate, zinc dialkyl dithiophosphate, phenyl o-hydroxybenzoate, erucamide, para-aramid fiber, fluorinated polyphosphazene rubber and 0.2 part of pentafluoropropionic anhydride in corresponding parts by weight for 12.5min at the stirring speed of 350rpm to obtain a mixed material.
Example 21: an elastomer composite material is different from the elastomer composite material in the embodiment 1 in that the step two is specifically set as follows: mixing and stirring polyolefin elastomer, polypropylene, calcium carbonate, zinc dialkyl dithiophosphate, phenyl o-hydroxybenzoate, erucamide, para-aramid fiber, fluorinated polyphosphazene rubber and 0.5 part of pentafluoropropionic anhydride in corresponding parts by weight for 12.5min at the stirring speed of 350rpm to obtain a mixed material.
Comparative example 1: an elastomer composite material is different from the elastomer composite material in the embodiment 1 in that the step two is specifically set as follows: and (2) mixing and stirring the polyolefin elastomer, the polypropylene, the calcium carbonate, the zinc dialkyl dithiophosphate, the phenyl o-hydroxybenzoate, the erucamide and the fluorinated polyphosphazene rubber in corresponding parts by weight for 12.5min at the stirring speed of 350rpm to obtain a mixed material.
Comparative example 2: an elastomer composite material is different from the elastomer composite material in the embodiment 1 in that the step two is specifically set as follows: mixing and stirring the polyolefin elastomer, the polypropylene, the calcium carbonate, the zinc dialkyl dithiophosphate, the phenyl o-hydroxybenzoate, the erucamide and the para-aramid fiber in corresponding parts by weight for 12.5min at the stirring speed of 350rpm to obtain a mixed material.
Comparative example 3: an elastomer composite material is different from the elastomer composite material in the embodiment 1 in that the step two is specifically set as follows: and (3) mixing and stirring the polyolefin elastomer, the polypropylene, the calcium carbonate, the zinc dialkyl dithiophosphate, the phenyl o-hydroxybenzoate and the erucamide in corresponding parts by weight for 12.5min at a stirring speed of 350rpm to obtain a mixed material.
Performance testing
Test samples: the elastomer composites obtained in examples 1 to 21 were used as test samples 1 to 22, and the elastomer composites obtained in comparative examples 1 to 3 were used as control samples 1 to 3.
The test method comprises the following steps: the test samples 1-21 and the control samples 1-3 are subjected to an oil resistance test according to the standard GB/T, then the test samples 1-21 and the control samples 1-3 after being soaked for 12 hours are taken out, and then the hardness and the tensile strength are respectively measured according to the standard GB/T1690-.
And (3) test results: the test results of the test samples 1 to 21 and the control samples 1 to 3 are shown in Table 2. As can be seen from table 2, by comparing the test results of the test samples 1 to 5 with the test results of the control samples 1 to 3, the oil resistance of the elastomer composite can be improved and the elastomer composite can maintain good and stable hardness and tensile strength by using the para-aramid fiber or the fluorinated polyphosphazene rubber, and when the para-aramid fiber and the fluorinated polyphosphazene rubber are used together, a good compounding synergistic effect can be achieved, and the improvement effect is better. The comparison of the test results of test samples 6-12 and test sample 1 shows that the antioxidant, ultraviolet absorber and lubricant disclosed by the invention are all suitable for preparing elastomer composite materials, and the obtained elastomer composite materials have good and stable quality. The test results of the test samples 13-15, the test samples 16-18, the test samples 19-21 and the test sample 1 are compared respectively, and the oil resistance of the elastomer composite material can be improved and the good and stable hardness and tensile strength can be kept by adding the graphene oxide, the methyl vinyl silicone rubber and the pentafluoropropionic anhydride.
TABLE 2 test results of test samples 1 to 21 and control samples 1 to 3
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (8)
1. The elastomer composite material is characterized by comprising the following components in parts by weight:
20-35 parts of polyolefin elastomer;
60-75 parts of polypropylene;
5-15 parts of calcium carbonate;
0.01-2 parts of antioxidant;
0.01-2 parts of ultraviolet absorbent;
0.01-5 parts of a lubricant;
4-8 parts of para-aramid fiber;
2-5 parts of fluorinated polyphosphazene rubber.
2. The elastomer composite of claim 1, wherein 2-3 parts by weight of graphene oxide is further added to the components of the elastomer composite.
3. The elastomer composite of claim 1, wherein 3 to 5 parts by weight of methyl vinyl silicone rubber is further added to the components of the elastomer composite.
4. The elastomer composite of claim 1, wherein 0.2 to 0.5 parts by weight of pentafluoropropionic anhydride is further added to the components of the elastomer composite.
5. The elastomer composite of claim 1, wherein the antioxidant is selected from the group consisting of zinc dialkyldithiophosphate, dialkyldiphenylamine and alkylvinylester.
6. The elastomer composite of claim 1, wherein the ultraviolet absorber is selected from any one of phenyl ortho-hydroxybenzoate, benzotriazole, and 2, 4-dihydroxybenzophenone.
7. The elastomer composite of claim 1, wherein the lubricant is any one of erucamide, stearic acid, polyethylene wax, and calcium stearate.
8. A method of preparing the elastomer composite of claim 1, comprising the steps of:
step one, preparing materials: preparing various raw materials according to corresponding parts by weight;
step two, mixing materials: mixing and stirring polyolefin elastomer, polypropylene, calcium carbonate, an antioxidant, an ultraviolet absorbent, a lubricant, para-aramid fiber and fluorinated polyphosphazene rubber in corresponding parts by weight for 10-15min at a stirring speed of 200-500rpm to obtain a mixed material;
step three, melt extrusion: and (3) putting the raw materials into a double-screw extruder for extrusion granulation, wherein the rotating speed of the screw extruder is 600rpm plus 300-.
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