CN112011185B - Method for preparing organic silicon thermoplastic vulcanized rubber by double-premixing dynamic vulcanization process - Google Patents
Method for preparing organic silicon thermoplastic vulcanized rubber by double-premixing dynamic vulcanization process Download PDFInfo
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- CN112011185B CN112011185B CN201910460909.8A CN201910460909A CN112011185B CN 112011185 B CN112011185 B CN 112011185B CN 201910460909 A CN201910460909 A CN 201910460909A CN 112011185 B CN112011185 B CN 112011185B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a method for preparing organic silicon thermoplastic vulcanized rubber by a double-premixing dynamic vulcanization process. The method comprises the following steps: (1) preparation of the rubber-plastic premix: melting and blending silicon rubber, thermoplastic polyurethane, compatibilizer and antioxidant in a double-screw extruder; (2) preparation of premix a: taking one half of the rubber-plastic premix, adding hydrogen-containing silicone oil into the rubber-plastic premix at the temperature of 20-40 ℃, and uniformly mixing; (3) preparation of premix B: taking half of the rubber-plastic premix, adding a platinum catalyst into the rubber-plastic premix at the temperature of 20-40 ℃, and uniformly mixing; (4) dynamic vulcanization: and placing the premixes A and B in a double-screw extruder, and dynamically vulcanizing to obtain the organic silicon thermoplastic vulcanized rubber. The organic silicon thermoplastic vulcanized rubber prepared by the method has excellent mechanical property, good elasticity and thermoplasticity, can be repeatedly processed, and is an environment-friendly elastomer material.
Description
Technical Field
The invention relates to the technical field of high polymer material processing, in particular to a method for preparing organic silicon thermoplastic vulcanized rubber by a double-premixing dynamic vulcanization process.
Background
The thermoplastic vulcanizate (TPV for short) is a blending type thermoplastic elastomer, which is prepared by taking high-content (50 wt% -80 wt%) crosslinked rubber as a disperse phase and low-content (20 wt% -50 wt%) plastic as a continuous phase through a dynamic full vulcanization technology. The dynamic full vulcanization technology means that when thermoplastic resin and rubber are melted and blended, a rubber phase is crosslinked in situ under the action of a crosslinking agent, and is crushed into a large number of micron-sized particles under the action of high-speed mixing and high shearing force, and the micron-sized particles are dispersed in a continuous thermoplastic resin matrix, so that TPV is formed. TPV has both high elasticity of conventional vulcanized rubber and repeatable processability of plastics, and has attracted attention as a novel green and environment-friendly material.
The polysiloxane which is composed of siloxane bonds as a framework is the most numerous, deeply researched and widely applied class in organic silicon compounds and accounts for more than 90 percent of the total dosage. Silicone rubbers most retain their original physical properties over a wide temperature range compared to other hydrocarbon polymers. However, the traditional vulcanized silicone rubber is a thermosetting material, and cannot be recycled, so that a great deal of resource waste is caused. Thermoplastic Polyurethane (TPU) has excellent properties such as high strength, high toughness and wear resistance. Blending is a very common and economical modification means in the polymer field. By blending silicone rubber with different thermoplastic resins, novel materials with superior properties can be obtained.
The silicone rubber can be classified into room-temperature vulcanization type silicone rubber and high-temperature vulcanization type silicone rubber according to the difference in vulcanization temperature. Dynamic vulcanization requires high temperature and high shear conditions, so that the silicone rubber used as the rubber phase must be a high temperature vulcanization system. Common vulcanization systems for high temperature vulcanized silicone rubber are peroxide vulcanization systems and hydrosilylation vulcanization systems. The use of peroxides in the preparation of silicone thermoplastic vulcanizates is limited because they can cause the thermoplastic polyurethane as the thermoplastic matrix to crosslink and lose plasticity. Therefore, in the field of organosilicon thermoplastic vulcanizates, a commonly used vulcanization system is a hydrosilylation vulcanization system.
The cross-linking principle of the hydrosilylation vulcanization system is that silicone oil containing active hydrogen and silicone rubber molecules containing vinyl generate addition reaction under the action of a platinum catalyst to cause cross-linking between silicone rubber macromolecular chains. The biggest problem of the system is that the platinum catalyst has high catalytic activity, so that the crosslinking reaction of the silicone rubber can be catalyzed at room temperature, and the crosslinking reaction of the silicone rubber is difficult to control.
Chinese patent CN102153853 and US6759487B2 both adopt similar process to prepare silicone rubber/polyurethane thermoplastic elastomer, and TPU, silicone rubber, compatilizer, hydrogen-containing silicone oil and filler are melted and blended at high temperature, and platinum catalyst is added for dynamic vulcanization. Because the activity of the platinum catalyst is higher, the rubber phase is crosslinked quickly after the catalyst is added, the catalyst is difficult to break and disperse uniformly in a TPU matrix, and the mechanical property of the material is poorer.
Disclosure of Invention
Aiming at the problem that in the dynamic vulcanization process of the organic silicon thermoplastic vulcanized rubber, a silicon-hydrogen vulcanization system is adopted, and the rubber phase and the plastic phase are mixed for a short time before crosslinking and are difficult to be fully and uniformly mixed; the invention provides a method for preparing organic silicon thermoplastic vulcanized rubber by dynamic vulcanization of double premixes, which is characterized in that different components of a hydrosilylation vulcanization system are respectively added into a rubber-plastic premix to prepare A, B two premixes, and then the dynamic vulcanization is carried out.
The invention aims to provide a method for preparing organic silicon thermoplastic vulcanized rubber by a double-premixing dynamic vulcanization process.
The method comprises the following steps:
(1) preparation of the rubber-plastic premix: melting and blending silicon rubber, thermoplastic polyurethane, compatibilizer and antioxidant;
(2) preparation of premix a: taking one half of the rubber-plastic premix, adding hydrogen-containing silicone oil into the rubber-plastic premix at the temperature of 20-40 ℃, and uniformly mixing;
(3) preparation of premix B: taking half of the rubber-plastic premix, adding a platinum catalyst into the rubber-plastic premix at the temperature of 20-40 ℃, and uniformly mixing;
(4) dynamic vulcanization: and placing the premixes A and B in a double-screw extruder, and dynamically vulcanizing to obtain the organic silicon thermoplastic vulcanized rubber.
The components are calculated according to the parts by weight,
the preferable dosage range of the thermoplastic polyurethane is 25-100 parts by weight, and in the range, the content of the plastic matrix is higher, the crosslinked rubber phase is easier to disperse, and the mechanical property of the material is better.
The preferred dosage of the hydrogen-containing silicone oil is 2-4 parts by weight; the amount of the platinum catalyst is preferably 0.4 to 0.8 part by weight;
the amount of the hydrogen-containing silicone oil and the platinum catalyst can affect the crosslinking degree and the crosslinking speed of the silicone rubber in the dynamic vulcanization process.
In the step (4), the temperature of the screw is 180-210 ℃, and the rotating speed is 300-700 rpm.
The silicone rubber is one or a combination of methyl vinyl silicone rubber, methyl vinyl phenyl silicone rubber and methyl vinyl trifluoropropyl silicone rubber.
The thermoplastic polyurethane is one or a combination of polyether polyurethane and polyester polyurethane.
The platinum catalyst is a liquid platinum catalyst commonly adopted in the field, and is a liquid platinum complex; can be isopropanol complex of chloroplatinic acid, platinum catalyst coordinated by tetrahydrofuran, platinum catalyst coordinated by methyl vinyl siloxane;
the compatibilizer is one or a combination of commercial ethylene-methyl acrylate copolymer (EMA) and ethylene-methyl acrylate-glycidyl methacrylate random terpolymer (EMA-g-GMA).
The antioxidant in the present invention is a conventional antioxidant in the art, and is preferably 1010.
The purpose of adding the compatibilizer is to further improve the compatibility of the silicone rubber and the thermoplastic resin and further improve the performance of the material; the antioxidant is added to reduce the degradation reaction of the thermoplastic resin at high temperature and improve the material performance.
The invention can also add other conventional auxiliary agents according to the actual situation: such as: conventional plasticizers, such as dioctyl phthalate (DOP), Butyl Benzyl Phthalate (BBP), etc., may be added to the TPU prior to the preparation of the rubber-plastic premix. The amounts are also conventional.
The specific technical scheme of the invention is as follows: blending hydrogen-containing silicone oil and a platinum catalyst in a hydrosilylation vulcanization system with the rubber-plastic premix respectively to prepare two premixes. And then dynamically vulcanizing the two premixes under the conditions of high temperature and high shear to prepare the organic silicon thermoplastic vulcanized rubber.
The operation steps for preparing the silicone thermoplastic vulcanizate are as follows:
(1) preparation of the rubber-plastic premix: melting and blending silicon rubber, thermoplastic polyurethane, compatibilizer and antioxidant;
(2) preparation of premix a: taking one half of the rubber-plastic premix, adding hydrogen-containing silicone oil into the rubber-plastic premix at the temperature of 20-40 ℃, and uniformly mixing;
(3) preparation of premix B: taking half of the rubber-plastic premix, adding a platinum catalyst into the rubber-plastic premix at the temperature of 20-40 ℃, and uniformly mixing;
(4) dynamic vulcanization: and placing the premixes A and B in a double-screw extruder, and dynamically vulcanizing to obtain the organic silicon thermoplastic vulcanized rubber.
The invention has the advantages that: (1) before dynamic vulcanization, the silicon rubber and the polyurethane are fully pre-dispersed, and the silicon rubber and the polyurethane are uniformly mixed; (2) adding a cross-linking agent (hydrogen-containing silicone oil) and a platinum catalyst into the premix at the temperature of 20-40 ℃, wherein because the polyurethane contains a crystalline state at the temperature of 20-40 ℃, the components of a vulcanization system are difficult to enter, and most of the cross-linking agent and the catalyst only enter a rubber phase to act on the rubber phase; (3) only after the components of pre-mixture A, B are thoroughly and uniformly mixed will the silicone rubber begin to crosslink, and the rate of crosslinking of the silicone rubber is easily controlled. Because the hydrogen-containing silicone oil can only generate a cross-linking reaction with the vinyl-containing silicone rubber under the action of the platinum catalyst. At the beginning of the dynamic vulcanization mixing process, since the platinum catalyst and the hydrogen-containing silicone oil are respectively wrapped by the premix A and the premix B, the cross-linking reaction of the silicone rubber cannot occur, and only after the mixture is mixed for a period of time, the premix A, B is fully contacted, and the silicone rubber can undergo the cross-linking reaction.
The organic silicon thermoplastic vulcanized rubber prepared in the way has excellent mechanical property, good elasticity and thermoplasticity, can be repeatedly processed, and is an environment-friendly elastomer material.
Detailed Description
The present invention will be further described with reference to the following examples.
The starting materials used in the examples are all commercially available.
The platinum catalyst is a commercial methyl vinyl siloxane coordinated platinum catalyst, and the concentration of the platinum catalyst is 1000 ppm; the antioxidant is antioxidant 1010. The content of active hydrogen in the hydrogen-containing silicone oil is 0.8 wt%;
tensile strength, elongation at break and Shore A hardness in the examples were determined according to the following standards GB/T528-2009, GB/T528-2009 and GB/T531.1-2008, respectively.
The raw material compositions and the parts by mass of each example and comparative example are shown in table 1:
TABLE 1
| Silicone rubber | Polyurethane | Hydrogen-containing silicone oil | Platinum catalyst | Antioxidant agent | Compatibilizer | |
| Example 1 | 100 | 150 | 3 | 0.4 | 0.50 | 5 |
| Comparative example 1 | 100 | 150 | 3 | 0.4 | 0.50 | 5 |
| Example 2 | 100 | 60 | 2 | 0.6 | 2 | 10 |
| Comparative example 2 | 100 | 60 | 2 | 0.6 | 2 | 10 |
| Example 3 | 100 | 50 | 4 | 0.8 | 1 | 1 |
| Example 4 | 100 | 10 | 3 | 0.5 | 1.5 | 8 |
Description of the drawings:
1. examples 1, 3 the silicone rubber was methyl vinyl silicone rubber; examples 2 and 4 were methyl vinyl phenyl silicone rubber and methyl vinyl trifluoropropyl silicone rubber, respectively.
2. The polyurethanes used in examples 1 and 3 were polyether polyurethanes; the polyurethanes used in examples 2 and 4 were polyester polyurethanes.
3. The compatibilizer used in example 1.2 was EMA; the compatibilizer used in examples 3 and 4 was EMA-g-GMA.
3. The comparative examples have the same formulation as the corresponding examples.
Example 1
The operation steps are as follows:
preparation of the rubber-plastic premix: melting and blending silicon rubber, thermoplastic polyurethane, compatibilizer and antioxidant;
preparation of premix a: taking half of the rubber-plastic premix, adding hydrogen-containing silicone oil at 20 ℃ and mixing uniformly;
preparation of premix B: taking half of the rubber-plastic premix, adding a platinum catalyst into the rubber-plastic premix at the temperature of 20 ℃, and uniformly mixing;
dynamic vulcanization: and (3) placing the premixes A and B in a double-screw extruder, setting the temperature of the double-screw extruder to be 180 ℃ and the rotating speed to be 300rpm, and dynamically vulcanizing to obtain the organic silicon thermoplastic vulcanized rubber. The material properties are shown in Table 2.
Comparative example 1
The operation steps are as follows:
the silicone rubber, polyurethane, hydrogen-containing silicone oil, an antioxidant and a compatibilizer are melted and blended in a double-screw extruder under the conditions of 180 ℃ and 300rpm, and then a platinum catalyst is added for dynamic vulcanization to prepare the organic silicon thermoplastic vulcanized rubber. The material properties are shown in Table 2.
Example 2
The rubber-plastic premix and premix A, B were prepared as in example 1. Except that the temperatures for preparing premix A and premix B were 30 ℃;
dynamic vulcanization: and (3) placing the pre-mixture A, B into a double-screw extruder, setting the temperature of the double-screw extruder to be 210 ℃ and the rotating speed to be 700rpm, and dynamically vulcanizing to obtain the organic silicon thermoplastic vulcanized rubber. The material properties are shown in Table 2.
Comparative example 2
The operation steps are as follows:
the silicone rubber, the polyester polyurethane, the hydrogen-containing silicone oil, the antioxidant and the compatibilizer are melted and blended in a double-screw extruder at the temperature of 210 ℃ and the rpm of 700, and then a platinum catalyst is added for dynamic vulcanization to prepare the organic silicon thermoplastic vulcanized rubber. The material properties are shown in Table 2.
Example 3
The operation steps are as follows:
the rubber-plastic premix and premix A, B were prepared as in example 1. Except that the temperatures for preparing premix A and premix B were 40 ℃;
dynamic vulcanization: and (3) placing the pre-mixture A, B and the compatibilizer into a double-screw extruder, setting the temperature of the double-screw extruder to be 190 ℃ and the rotating speed to be 400rpm, and dynamically vulcanizing to obtain the organic silicon thermoplastic vulcanized rubber. The material properties are shown in Table 2.
Example 4
The operation steps are as follows:
the rubber-plastic premix and premix A, B were prepared as in example 1. Except that the temperatures for preparing premix A and premix B were 30 ℃;
dynamic vulcanization: and (3) placing the pre-mixture A, B and the compatibilizer into a double-screw extruder, setting the temperature of the double-screw extruder to be 200 ℃ and the rotating speed to be 600rpm, and dynamically vulcanizing to obtain the organic silicon thermoplastic vulcanized rubber. The material properties are shown in Table 2.
TABLE 2
As can be seen from the data in table 2, the mechanical properties of the materials are greatly improved by using the processes of examples 1 and 2 of the present invention, compared with those of comparative examples 1 and 2. The tensile strength is respectively improved by 98 percent and 88 percent, and the elongation at break is respectively improved by 59 percent and 83 percent. In addition, the hardness of the silicone thermoplastic vulcanizate prepared by the method of the invention is also improved, and the tensile permanent deformation is obviously reduced.
Claims (6)
1. A method for preparing organosilicon thermoplastic vulcanized rubber by a double-premixing dynamic vulcanization process, which is characterized by comprising the following steps:
(1) preparation of the rubber-plastic premix: melting and blending silicon rubber, thermoplastic polyurethane, compatibilizer and antioxidant;
(2) preparation of premix a: taking one half of the rubber-plastic premix, adding hydrogen-containing silicone oil into the rubber-plastic premix at the temperature of 20-40 ℃, and uniformly mixing;
(3) preparation of premix B: taking the other half of the rubber-plastic premix, adding a platinum catalyst into the rubber-plastic premix at the temperature of 20-40 ℃, and uniformly mixing;
(4) dynamic vulcanization: placing the premixes A and B in a double-screw extruder, and dynamically vulcanizing to obtain the organic silicon thermoplastic vulcanized rubber;
the components are calculated according to the parts by weight,
the silicone rubber is one or a combination of methyl vinyl silicone rubber, methyl vinyl phenyl silicone rubber and methyl vinyl trifluoropropyl silicone rubber;
the compatibilizer is one or a combination of ethylene-methyl acrylate copolymer and ethylene-methyl acrylate-glycidyl methacrylate random terpolymer.
2. The method of preparing a silicone thermoplastic vulcanizate of claim 1, wherein:
100 parts of silicon rubber;
25-100 parts by weight of thermoplastic polyurethane.
3. The method of preparing a silicone thermoplastic vulcanizate of claim 1, wherein:
100 parts of silicon rubber;
0.4 to 0.8 part by weight of a platinum catalyst.
4. The method of preparing a silicone thermoplastic vulcanizate of claim 1, wherein:
100 parts of silicon rubber;
2-4 parts of hydrogen-containing silicone oil.
5. The method of preparing a silicone thermoplastic vulcanizate of claim 1, wherein: the polyurethane is one or a combination of polyether polyurethane and polyester polyurethane.
6. The method of preparing a silicone thermoplastic vulcanizate of claim 1, wherein: and (4) controlling the screw temperature to be 180-210 ℃ and the rotating speed to be 300-700 rpm.
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