A fluorine-containing elastomer composition and its preparation method and application

Abstract

The present invention relates to the technical field of fluorine-containing elastomer compositions, and specifically to a fluorine-containing elastomer composition, a preparation method thereof, and an application thereof. The fluorine-containing elastomer composition is characterized in that, by weight, its preparation raw materials include: 90-110 parts of fluorine-containing elastomer, 20-30 parts of reinforcing agent, 0.5-1.5 parts of cross-linking agent, and 1-2 parts of auxiliary cross-linking agent; the compression permanent deformation of the fluorine-containing elastomer composition during application is less than or equal to 25%. In the present application, when an internal release agent is not added, the problem of sticky mold and dirty mold on the mold during the flat plate vulcanization process can be solved when the fluorine-containing elastomer composition contains fluorinated diene and white carbon black.

Description

Technical Field

[0001] The invention relates to the technical field of fluorine-containing elastomer compositions, and in particular to a fluorine-containing elastomer composition and a preparation method and application thereof. Background Art

[0002] In order to improve the high temperature resistance of the fluorinated elastomer composition during the application process, fluorinated elastomers containing fluorinated dienes in the main chain structure are currently used, or fluorinated dienes are added to the fluorinated elastomer; when the fluorinated elastomer contains fluorinated dienes in the main chain structure, it can be directly cross-linked using a peroxide system cross-linking agent, so there is no need to add an auxiliary cross-linking agent; for fluorinated elastomers that do not contain fluorinated dienes in the main chain structure, the method of adding fluorinated dienes is generally used to improve the high temperature resistance of the fluorinated elastomer composition during the application process; but when the fluorinated elastomer uses white carbon black as a reinforcing material, during the flat plate vulcanization process, problems such as mold sticking and dirty molds will occur on the mold with poor demoulding properties; and when the mold sticks, part of the product will adhere to the mold, resulting in product defects, poor product integrity, and a high scrap rate; and when the mold is dirty, the rubber edge will adhere to the mold and cannot be removed with the product, which increases the time cost of cleaning the mold and reduces production efficiency. Generally, the problem of poor demoulding properties is solved by adding an internal mold release agent to the fluorinated elastomer. However, the internal mold release agent is a small molecule plasticizer. The addition of the internal mold release agent will affect the performance of the fluorinated elastomer products. In particular, when used at high temperatures, the small molecule plasticizer will escape from the product due to the influence of temperature, which will greatly limit the application of fluorinated elastomer products.

[0003] Japanese patent application number JP2006241972 discloses cross-linked fluoroelastomers, compositions thereof and cross-linked rubber molded products. The problem of poor demolding properties is solved by adding fluororesin to fluoroelastomers. However, not all fluoroelastomers are suitable for adding fluororesin. It also needs to be determined based on the actual application of the fluoroelastomer.

[0004] Therefore, providing a fluorine-containing elastomer composition product with good demoulding properties and low compression set during application is a major technical problem that needs to be solved at present. Summary of the invention

[0005] In order to solve the above technical problems, the first aspect of the present invention provides a fluorine-containing elastomer composition, which is prepared by raw materials including, by weight: 90-110 parts of fluorine-containing elastomer, 20-30 parts of reinforcing agent, 0.5-1.5 parts of cross-linking agent, and 1-2 parts of auxiliary cross-linking agent; when the fluorine-containing elastomer composition is used, the compression permanent deformation tested at 204°C and 70h according to the ASTM D395-03 test standard is less than or equal to 25%.

[0006] In one embodiment, the fluorine-containing elastomer composition is prepared from raw materials including, by weight, 100 parts of fluorine-containing elastomer, 20-24 parts of reinforcing agent, 0.5-1.5 parts of cross-linking agent, and 1-2 parts of auxiliary cross-linking agent.

[0007] In one embodiment, the reinforcing agent includes white carbon black, silica microspheres, or a combination of both.

[0008] In one embodiment, the reinforcing agent consists of white carbon black and silica microspheres.

[0009] In one embodiment, the weight ratio of white carbon black to silica microspheres is 1:(1.2-3).

[0010] In one embodiment, the weight ratio of white carbon black to silica microspheres is 1:(1.5-2).

[0011] In one embodiment, the weight ratio of the auxiliary cross-linking agent to the reinforcing agent is 1:(10-24).

[0012] In one embodiment, the co-crosslinking agent comprises a fluorinated diene.

[0013] In a preferred embodiment, the auxiliary cross-linking agent is a fluorinated diene.

[0014] In one embodiment, the fluorinated diene olefin is dodecafluoro-1,9-decadiene.

[0015] In order to solve the problem of poor demoulding properties such as sticking and dirty molds on the mold during the flat plate vulcanization process of the fluorinated elastomer composition, and to improve the compression performance of the fluorinated elastomer composition during application, the inventors found in the experimental process that the fluorinated elastomer composition includes a fluorinated elastomer, a fluorinated diene, and a reinforcing agent composed of white carbon black and silica microspheres, and the weight ratio of white carbon black to silica microspheres is 1: (1.2-3), especially when the weight ratio of white carbon black to silica microspheres is 1: (1.5-2), and the weight ratio of the co-crosslinking agent to the reinforcing agent is 1: (10-24), the flow of the fluorinated elastomer composition during vulcanization at high temperature can be enhanced. The silica microspheres have a spherical structure and a "rolling ball" effect in the fluorinated elastomer composition, which enhances the fluidity of the fluorinated elastomer composition and is beneficial to improving the demoulding effect. In addition, the fluorinated diene contained in the fluorinated elastomer composition has a double bond at the end, which can be added to the formula as a cross-linking agent, and after being combined with white carbon black and silica microspheres, the compatibility of the reinforcing agent and the fluorinated elastomer composition can be improved, which can play a plasticizing effect, so that the fluorinated elastomer composition has good processability and excellent demoulding effect, while ensuring low compression set of the product prepared from the fluorinated elastomer composition.

[0016] In one embodiment, the auxiliary cross-linking agent may be an unsaturated carboxylate.

[0017] In one embodiment, the unsaturated carboxylate is magnesium dimethacrylate.

[0018] In one embodiment, the auxiliary cross-linking agent may be maleimide.

[0019] In one embodiment, the auxiliary cross-linking agent may be triallyl ester.

[0020] In one embodiment, the triallyl ester is triallyl isocyanurate.

[0021] In one embodiment, the crosslinking agent is a peroxy system crosslinking agent.

[0022] In one embodiment, the peroxy system crosslinking agent is a vulcanizing agent di-250, with a CAS number of 78-63-7.

[0023] A second aspect of the present invention provides a method for preparing a fluorine-containing elastomer composition, comprising the following steps:

[0024] S1. mixing a fluorinated elastomer and a reinforcing agent to obtain a masterbatch;

[0025] S2. Adding a co-crosslinking agent and a crosslinking agent into the masterbatch to obtain a fluorine-containing elastomer composition.

[0026] In one embodiment, the method for preparing the fluorinated elastomer composition comprises the following steps:

[0027] S1. Put the fluorine-containing elastomer into an internal mixer, put the silica microspheres and white carbon black into the internal mixer in sequence, and after mixing evenly, discharge the glue, and press the glue on an open mixer, and leave it for 18 hours to obtain a masterbatch; the discharge glue temperature is 100°C.

[0028] S2. The masterbatch is thinly passed on an open mixing mill, with the left and right cutters cutting 3 times each, the roller speed is 12r / min for the front roller and 14r / min for the rear roller, the roller spacing is adjusted to 0.6mm, the auxiliary cross-linking agent and the cross-linking agent are added in sequence, and the triangle package is made 20 times at a roller spacing of 0.4mm, and the fluorine-containing elastomer composition is obtained by sheeting.

[0029] A third aspect of the present invention provides an application of a fluorine-containing elastomer composition, wherein the fluorine-containing elastomer composition is vulcanized to obtain a fluorine-containing elastomer cross-linked product which is applied in the fields of semiconductor, medical, chemical, aviation, aerospace and petroleum technology.

[0030] In one embodiment, the cross-linked fluorine-containing elastomer product has a compression set of less than or equal to 25% when tested at 204° C. for 70 h according to ASTM D395-03 test standard.

[0031] In one embodiment, a fluorine-containing elastomer composition is placed in a mold, and the mold is placed in a flat vulcanizer for a first stage of compression vulcanization to obtain a sulfur product. After the sulfur product is left for 16 hours, it is placed in an oven for a second stage of vulcanization to obtain a fluorine-containing elastomer cross-linked product.

[0032] In one embodiment, the one-stage compression vulcanization has a vulcanization temperature of 170-185° C., a vulcanization time of 10-20 min, and a vulcanization pressure of 10-15 MPa.

[0033] In one embodiment, the vulcanization temperature of the one-stage compression vulcanization is 180° C., the vulcanization pressure is 11 MPa, and the vulcanization time is 15 min. The one-stage compression vulcanization obtains a sulfur product and is parked for 16 hours for standby use.

[0034] The two-stage vulcanization process is to put the parked single-sulfur product into an oven for secondary vulcanization, the vulcanization temperature is 290° C., the vulcanization time is 16 hours, and the fluorine-containing elastomer cross-linked product is obtained after the two-stage vulcanization.

[0035] Beneficial Effects

[0036] (1) The fluorine-containing elastomer composition provided by the present application has good mold release performance.

[0037] (2) In the present application, the specific content of fluorinated diene, white carbon black and silica microspheres is combined to improve the demoulding performance of the fluorinated elastomer composition during high temperature vulcanization.

[0038] (3) In the present application, by adding a specific amount of fluorinated diene, white carbon black and silica microspheres to the fluorinated elastomer composition for compounding, the product prepared from the fluorinated elastomer composition can have good compression performance.

[0039] (4) The fluorinated elastomer composition provided by the present application has a compression set of less than or equal to 25% during application, and can be used in the fields of semiconductors, medicine, chemicals, aviation, aerospace, petroleum, etc.

[0040] (5) In the present application, the problem of mold sticking and mold dirtiness on the mold during the flat plate vulcanization process can be solved when the fluorinated elastomer composition contains fluorinated diene and white carbon black without adding an internal mold release agent. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 This is a diagram showing the scorched state of the compound rubber formed by adding the co-crosslinking agent and the crosslinking agent to the masterbatch.

[0042] Figure 2 This is a state diagram of a mold cavity without a sticky mold or a dirty mold when the fluorine-containing elastomer composition provided in Example 1, Example 2, Example 3, and Example 4 is vulcanized.

[0043] Figure 3 This is a state diagram of a mold cavity without a sticky mold and with a dirty mold when the fluorine-containing elastomer composition provided in Example 8 and Example 9 is vulcanized.

[0044] Figure 4 This is a state diagram of a mold cavity having a sticky mold and a dirty mold when the fluorine-containing elastomer composition provided in Example 5 and Example 6 is vulcanized. DETAILED DESCRIPTION

[0045] The purchase sources and models of the raw materials used in the following examples are shown in Table 1:

[0046] Table 1

[0047]

[0048] Example 1

[0049] The first aspect of the present embodiment provides a fluorine-containing elastomer composition, wherein the raw materials for preparing the fluorine-containing elastomer include, by weight: 100 parts of fluorine-containing elastomer, 20 parts of reinforcing agent, 2 parts of auxiliary cross-linking agent, and 0.8 parts of cross-linking agent.

[0050] The reinforcing agent consists of white carbon black and silicon dioxide microspheres.

[0051] In parts by weight, the reinforcing agent includes 8 parts of white carbon black and 12 parts of silica microspheres.

[0052] The auxiliary cross-linking agent is a fluorinated diene.

[0053] The cross-linking agent is a vulcanizing agent dichlorobenzene.

[0054] A second aspect of the present embodiment provides a method for preparing a fluorinated elastomer composition, comprising the following steps:

[0055] S1. Put the fluorine-containing elastomer into an internal mixer, put the silica microspheres and white carbon black into the internal mixer in sequence, and after mixing evenly, discharge the glue, and press the glue on an open mixer, and leave it for 18 hours to obtain a masterbatch; the discharge glue temperature is 100°C.

[0056] S2. The masterbatch is thinly passed on an open mixing mill, with the left and right cutters cutting 3 times each, the roller speed is 12r / min for the front roller and 14r / min for the rear roller, the roller spacing is adjusted to 0.6mm, the auxiliary cross-linking agent and the cross-linking agent are added in sequence, and the triangle package is made 20 times at a roller spacing of 0.4mm, and the fluorine-containing elastomer composition is obtained by sheeting.

[0057] A third aspect of this embodiment provides an application of a fluorine-containing elastomer composition, wherein the fluorine-containing elastomer composition is vulcanized to obtain a fluorine-containing elastomer cross-linked product which is applied in the fields of semiconductor, medical, chemical, aviation, aerospace and petroleum technology.

[0058] The method for vulcanizing the fluorine-containing elastomer composition is as follows: putting the fluorine-containing elastomer composition into a mold, placing the mold in a flat vulcanizer for a first-stage molding vulcanization to obtain a sulfur product, and after the sulfur product is parked for 16 hours, placing it in an oven for a second-stage vulcanization to prepare a fluorine-containing elastomer cross-linked product.

[0059] The vulcanization temperature of the one-stage compression vulcanization is 180° C., the vulcanization pressure is 11 MPa, and the vulcanization time is 15 min. The one-stage compression vulcanization obtains a sulfur product and is parked for 16 hours to be used.

[0060] The two-stage vulcanization process is to put the parked single-sulfur product into an oven for secondary vulcanization, the vulcanization temperature is 290° C., the vulcanization time is 16 hours, and the fluorine-containing elastomer cross-linked product is obtained after the two-stage vulcanization.

[0061] Example 2

[0062] The first aspect of the present embodiment provides a fluorine-containing elastomer composition, wherein the raw materials for preparing the fluorine-containing elastomer include, by weight: 100 parts of fluorine-containing elastomer, 22 parts of reinforcing agent, 2 parts of auxiliary cross-linking agent, and 0.8 parts of cross-linking agent.

[0063] The reinforcing agent consists of white carbon black and silicon dioxide microspheres.

[0064] In parts by weight, the reinforcing agent includes 8 parts of white carbon black and 14 parts of silica microspheres.

[0065] The auxiliary cross-linking agent is a fluorinated diene.

[0066] The cross-linking agent is a vulcanizing agent dichlorobenzene.

[0067] A second aspect of the present embodiment provides a method for preparing a fluorinated elastomer composition, comprising the following steps:

[0068] S1. Put the fluorine-containing elastomer into an internal mixer, put the silica microspheres and white carbon black into the internal mixer in sequence, and after mixing evenly, discharge the glue, and press the glue on an open mixer, and leave it for 18 hours to obtain a masterbatch; the discharge glue temperature is 100°C.

[0069] S2. The masterbatch is thinly passed on an open mixing mill, with the left and right cutters cutting 3 times each, the roller speed is 12r / min for the front roller and 14r / min for the rear roller, the roller spacing is adjusted to 0.6mm, the auxiliary cross-linking agent and the cross-linking agent are added in sequence, and the triangle package is made 20 times at a roller spacing of 0.4mm, and the fluorine-containing elastomer composition is obtained by sheeting.

[0070] A third aspect of this embodiment provides an application of a fluorine-containing elastomer composition, wherein the fluorine-containing elastomer composition is vulcanized to obtain a fluorine-containing elastomer cross-linked product which is applied in the fields of semiconductor, medical, chemical, aviation, aerospace and petroleum technology.

[0071] The method for vulcanizing the fluorine-containing elastomer composition is as follows: putting the fluorine-containing elastomer composition into a mold, placing the mold in a flat vulcanizer for a first-stage molding vulcanization to obtain a sulfur product, and after the sulfur product is parked for 16 hours, placing it in an oven for a second-stage vulcanization to prepare a fluorine-containing elastomer cross-linked product.

[0072] The vulcanization temperature of the one-stage compression vulcanization is 180° C., the vulcanization pressure is 11 MPa, and the vulcanization time is 15 min. The one-stage compression vulcanization obtains a sulfur product and is parked for 16 hours to be used.

[0073] The two-stage vulcanization process is to put the parked single-sulfur product into an oven for secondary vulcanization, the vulcanization temperature is 290° C., the vulcanization time is 16 hours, and the fluorine-containing elastomer cross-linked product is obtained after the two-stage vulcanization.

[0074] Example 3

[0075] The first aspect of the present embodiment provides a fluorine-containing elastomer composition, wherein the raw materials for preparing the fluorine-containing elastomer include, by weight: 100 parts of fluorine-containing elastomer, 24 parts of reinforcing agent, 2 parts of auxiliary cross-linking agent, and 0.8 parts of cross-linking agent.

[0076] The reinforcing agent consists of white carbon black and silicon dioxide microspheres.

[0077] In parts by weight, the reinforcing agent includes 8 parts of white carbon black and 16 parts of silica microspheres.

[0078] The auxiliary cross-linking agent is a fluorinated diene.

[0079] The cross-linking agent is a vulcanizing agent dichlorobenzene.

[0080] A second aspect of the present embodiment provides a method for preparing a fluorinated elastomer composition, comprising the following steps:

[0081] S1. Put the fluorine-containing elastomer into an internal mixer, put the silica microspheres and white carbon black into the internal mixer in sequence, and after mixing evenly, discharge the glue, and press the glue on an open mixer, and leave it for 18 hours to obtain a masterbatch; the discharge glue temperature is 100°C.

[0082] S2. The masterbatch is thinly passed on an open mixing mill, with the left and right cutters cutting 3 times each, the roller speed is 12r / min for the front roller and 14r / min for the rear roller, the roller spacing is adjusted to 0.6mm, the auxiliary cross-linking agent and the cross-linking agent are added in sequence, and the triangle package is made 20 times at a roller spacing of 0.4mm, and the fluorine-containing elastomer composition is obtained by sheeting.

[0083] A third aspect of this embodiment provides an application of a fluorine-containing elastomer composition, wherein the fluorine-containing elastomer composition is vulcanized to obtain a fluorine-containing elastomer cross-linked product which is applied in the fields of semiconductor, medical, chemical, aviation, aerospace and petroleum technology.

[0084] The method for vulcanizing the fluorine-containing elastomer composition is as follows: putting the fluorine-containing elastomer composition into a mold, placing the mold in a flat vulcanizer for a first-stage molding vulcanization to obtain a sulfur product, and after the sulfur product is parked for 16 hours, placing it in an oven for a second-stage vulcanization to prepare a fluorine-containing elastomer cross-linked product.

[0085] The vulcanization temperature of the one-stage compression vulcanization is 180° C., the vulcanization pressure is 11 MPa, and the vulcanization time is 15 min. The one-stage compression vulcanization obtains a sulfur product and is parked for 16 hours to be used.

[0086] The two-stage vulcanization process is to put the parked single-sulfur product into an oven for secondary vulcanization, the vulcanization temperature is 290° C., the vulcanization time is 16 hours, and the fluorine-containing elastomer cross-linked product is obtained after the two-stage vulcanization.

[0087] Example 4

[0088] The first aspect of the present embodiment provides a fluorine-containing elastomer composition, wherein the raw materials for preparing the fluorine-containing elastomer include, by weight: 100 parts of fluorine-containing elastomer, 24 parts of reinforcing agent, 1 part of auxiliary cross-linking agent, and 0.8 parts of cross-linking agent.

[0089] The reinforcing agent consists of white carbon black and silicon dioxide microspheres.

[0090] In parts by weight, the reinforcing agent includes 8 parts of white carbon black and 16 parts of silica microspheres.

[0091] The auxiliary cross-linking agent is a fluorinated diene.

[0092] The cross-linking agent is a vulcanizing agent dichlorobenzene.

[0093] A second aspect of the present embodiment provides a method for preparing a fluorinated elastomer composition, comprising the following steps:

[0094] S1. Put the fluorine-containing elastomer into an internal mixer, put the silica microspheres and white carbon black into the internal mixer in sequence, and after mixing evenly, discharge the glue, and press the glue on an open mixer, and leave it for 18 hours to obtain a masterbatch; the discharge glue temperature is 100°C.

[0095] S2. The masterbatch is thinly passed on an open mixing mill, with the left and right cutters cutting 3 times each, the roller speed is 12r / min for the front roller and 14r / min for the rear roller, the roller spacing is adjusted to 0.6mm, the auxiliary cross-linking agent and the cross-linking agent are added in sequence, and the triangle package is made 20 times at a roller spacing of 0.4mm, and the fluorine-containing elastomer composition is obtained by sheeting.

[0096] A third aspect of this embodiment provides an application of a fluorine-containing elastomer composition, wherein the fluorine-containing elastomer composition is vulcanized to obtain a fluorine-containing elastomer cross-linked product which is applied in the fields of semiconductor, medical, chemical, aviation, aerospace and petroleum technology.

[0097] The method for vulcanizing the fluorine-containing elastomer composition is as follows: putting the fluorine-containing elastomer composition into a mold, placing the mold in a flat vulcanizer for a first-stage molding vulcanization to obtain a sulfur product, and after the sulfur product is parked for 16 hours, placing it in an oven for a second-stage vulcanization to prepare a fluorine-containing elastomer cross-linked product.

[0098] The vulcanization temperature of the one-stage compression vulcanization is 180° C., the vulcanization pressure is 11 MPa, and the vulcanization time is 15 min. The one-stage compression vulcanization obtains a sulfur product and is parked for 16 hours to be used.

[0099] The two-stage vulcanization process is to put the parked single-sulfur product into an oven for secondary vulcanization, the vulcanization temperature is 290° C., the vulcanization time is 16 hours, and the fluorine-containing elastomer cross-linked product is obtained after the two-stage vulcanization.

[0100] Example 5

[0101] The first aspect of the present embodiment provides a fluorine-containing elastomer composition, wherein the raw materials for preparing the fluorine-containing elastomer include, by weight: 100 parts of fluorine-containing elastomer, 20 parts of reinforcing agent, 2 parts of auxiliary cross-linking agent, and 0.8 parts of cross-linking agent.

[0102] The reinforcing agent consists of white carbon black and silicon dioxide microspheres.

[0103] In parts by weight, the reinforcing agent includes 8 parts of white carbon black and 12 parts of silica microspheres.

[0104] The auxiliary cross-linking agent is an unsaturated carboxylate.

[0105] The cross-linking agent is a vulcanizing agent dichlorobenzene.

[0106] A second aspect of the present embodiment provides a method for preparing a fluorinated elastomer composition, comprising the following steps:

[0107] S1. Put the fluorine-containing elastomer into an internal mixer, put the silica microspheres and white carbon black into the internal mixer in sequence, and after mixing evenly, discharge the glue, and press the glue on an open mixer, and leave it for 18 hours to obtain a masterbatch; the discharge glue temperature is 100°C.

[0108] S2. The masterbatch is thinly passed on an open mixing mill, with the left and right cutters cutting 3 times each, the roller speed is 12r / min for the front roller and 14r / min for the rear roller, the roller spacing is adjusted to 0.6mm, the auxiliary cross-linking agent and the cross-linking agent are added in sequence, and the triangle package is made 20 times at a roller spacing of 0.4mm, and the fluorine-containing elastomer composition is obtained by sheeting.

[0109] A third aspect of this embodiment provides an application of a fluorine-containing elastomer composition, wherein the fluorine-containing elastomer composition is vulcanized to obtain a fluorine-containing elastomer cross-linked product which is applied in the fields of semiconductor, medical, chemical, aviation, aerospace and petroleum technology.

[0110] The method for vulcanizing the fluorine-containing elastomer composition is as follows: putting the fluorine-containing elastomer composition into a mold, placing the mold in a flat vulcanizer for a first-stage molding vulcanization to obtain a sulfur product, and after the sulfur product is parked for 16 hours, placing it in an oven for a second-stage vulcanization to prepare a fluorine-containing elastomer cross-linked product.

[0111] The vulcanization temperature of the one-stage compression vulcanization is 180° C., the vulcanization pressure is 11 MPa, and the vulcanization time is 15 min. The one-stage compression vulcanization obtains a sulfur product and is parked for 16 hours to be used.

[0112] The two-stage vulcanization process is to put the parked single-sulfur product into an oven for secondary vulcanization, the vulcanization temperature is 290° C., the vulcanization time is 16 hours, and the fluorine-containing elastomer cross-linked product is obtained after the two-stage vulcanization.

[0113] Example 6

[0114] The first aspect of the present embodiment provides a fluorine-containing elastomer composition, wherein the raw materials for preparing the fluorine-containing elastomer include, by weight: 100 parts of fluorine-containing elastomer, 20 parts of reinforcing agent, 2 parts of auxiliary cross-linking agent, and 0.8 parts of cross-linking agent.

[0115] The reinforcing agent consists of white carbon black and silicon dioxide microspheres.

[0116] In parts by weight, the reinforcing agent includes 8 parts of white carbon black and 12 parts of silica microspheres.

[0117] The auxiliary cross-linking agent is maleimide.

[0118] The cross-linking agent is a vulcanizing agent dichlorobenzene.

[0119] A second aspect of the present embodiment provides a method for preparing a fluorinated elastomer composition, comprising the following steps:

[0120] S1. Put the fluorine-containing elastomer into an internal mixer, put the silica microspheres and white carbon black into the internal mixer in sequence, and after mixing evenly, discharge the glue, and press the glue on an open mixer, and leave it for 18 hours to obtain a masterbatch; the discharge glue temperature is 100°C.

[0121] S2. The masterbatch is thinly passed on an open mixing mill, with the left and right cutters cutting 3 times each, the roller speed is 12r / min for the front roller and 14r / min for the rear roller, the roller spacing is adjusted to 0.6mm, the auxiliary cross-linking agent and the cross-linking agent are added in sequence, and the triangle package is made 20 times at a roller spacing of 0.4mm, and the fluorine-containing elastomer composition is obtained by sheeting.

[0122] A third aspect of this embodiment provides an application of a fluorine-containing elastomer composition, wherein the fluorine-containing elastomer composition is vulcanized to obtain a fluorine-containing elastomer cross-linked product which is applied in the fields of semiconductor, medical, chemical, aviation, aerospace and petroleum technology.

[0123] The method for vulcanizing the fluorine-containing elastomer composition is as follows: putting the fluorine-containing elastomer composition into a mold, placing the mold in a flat vulcanizer for a first-stage molding vulcanization to obtain a sulfur product, and after the sulfur product is parked for 16 hours, placing it in an oven for a second-stage vulcanization to prepare a fluorine-containing elastomer cross-linked product.

[0124] The vulcanization temperature of the one-stage compression vulcanization is 180° C., the vulcanization pressure is 11 MPa, and the vulcanization time is 15 min. The one-stage compression vulcanization obtains a sulfur product and is parked for 16 hours to be used.

[0125] The two-stage vulcanization process is to put the parked single-sulfur product into an oven for secondary vulcanization, the vulcanization temperature is 290° C., the vulcanization time is 16 hours, and the fluorine-containing elastomer cross-linked product is obtained after the two-stage vulcanization.

[0126] Example 7

[0127] The first aspect of the present embodiment provides a fluorine-containing elastomer composition, wherein the raw materials for preparing the fluorine-containing elastomer include, by weight: 100 parts of fluorine-containing elastomer, 20 parts of reinforcing agent, 2 parts of auxiliary cross-linking agent, and 0.8 parts of cross-linking agent.

[0128] The reinforcing agent consists of white carbon black and silicon dioxide microspheres.

[0129] In parts by weight, the reinforcing agent includes 8 parts of white carbon black and 12 parts of silica microspheres.

[0130] The auxiliary cross-linking agent is triallyl ester.

[0131] The cross-linking agent is a vulcanizing agent dichlorobenzene.

[0132] A second aspect of the present embodiment provides a method for preparing a fluorinated elastomer composition, comprising the following steps:

[0133] S1. Put the fluorine-containing elastomer into an internal mixer, put the silica microspheres and white carbon black into the internal mixer in sequence, and after mixing evenly, discharge the glue, and press the glue on an open mixer, and leave it for 18 hours to obtain a masterbatch; the discharge glue temperature is 100°C.

[0134] S2. The masterbatch is thinly passed on an open mixing mill, with the left and right cutters cutting 3 times each, the roller speed is 12r / min for the front roller and 14r / min for the rear roller, the roller spacing is adjusted to 0.6mm, the auxiliary cross-linking agent and the cross-linking agent are added in sequence, and the triangle package is made 20 times at a roller spacing of 0.4mm, and the fluorine-containing elastomer composition is obtained by sheeting.

[0135] Example 8

[0136] The first aspect of the present embodiment provides a fluorine-containing elastomer composition, wherein the raw materials for preparing the fluorine-containing elastomer include, by weight: 100 parts of fluorine-containing elastomer, 24 parts of reinforcing agent, 0.5 parts of auxiliary cross-linking agent, and 0.8 parts of cross-linking agent.

[0137] The reinforcing agent consists of white carbon black and silicon dioxide microspheres.

[0138] In parts by weight, the reinforcing agent includes 8 parts of white carbon black and 16 parts of silica microspheres.

[0139] The auxiliary cross-linking agent is a fluorinated diene.

[0140] The cross-linking agent is a vulcanizing agent dichlorobenzene.

[0141] A second aspect of the present embodiment provides a method for preparing a fluorinated elastomer composition, comprising the following steps:

[0142] S1. Put the fluorine-containing elastomer into an internal mixer, put the silica microspheres and white carbon black into the internal mixer in sequence, and after mixing evenly, discharge the glue, and press the glue on an open mixer, and leave it for 18 hours to obtain a masterbatch; the discharge glue temperature is 100°C.

[0143] S2. The masterbatch is thinly passed on an open mixing mill, with the left and right cutters cutting 3 times each, the roller speed is 12r / min for the front roller and 14r / min for the rear roller, the roller spacing is adjusted to 0.6mm, the auxiliary cross-linking agent and the cross-linking agent are added in sequence, and the triangle package is made 20 times at a roller spacing of 0.4mm, and the fluorine-containing elastomer composition is obtained by sheeting.

[0144] A third aspect of this embodiment provides an application of a fluorine-containing elastomer composition, wherein the fluorine-containing elastomer composition is vulcanized to obtain a fluorine-containing elastomer cross-linked product which is applied in the fields of semiconductor, medical, chemical, aviation, aerospace and petroleum technology.

[0145] The method for vulcanizing the fluorine-containing elastomer composition is as follows: putting the fluorine-containing elastomer composition into a mold, placing the mold in a flat vulcanizer for a first-stage molding vulcanization to obtain a sulfur product, and after the sulfur product is parked for 16 hours, placing it in an oven for a second-stage vulcanization to prepare a fluorine-containing elastomer cross-linked product.

[0146] The vulcanization temperature of the one-stage compression vulcanization is 180° C., the vulcanization pressure is 11 MPa, and the vulcanization time is 15 min. The one-stage compression vulcanization obtains a sulfur product and is parked for 16 hours to be used.

[0147] The two-stage vulcanization process is to put the parked single-sulfur product into an oven for secondary vulcanization, the vulcanization temperature is 290° C., the vulcanization time is 16 hours, and the fluorine-containing elastomer cross-linked product is obtained after the two-stage vulcanization.

[0148] Example 9

[0149] The first aspect of the present embodiment provides a fluorine-containing elastomer composition, wherein the raw materials for preparing the fluorine-containing elastomer include, by weight: 100 parts of fluorine-containing elastomer, 16 parts of reinforcing agent, 2 parts of auxiliary cross-linking agent, and 0.8 parts of cross-linking agent.

[0150] The reinforcing agent consists of white carbon black and silicon dioxide microspheres.

[0151] In parts by weight, the reinforcing agent includes 8 parts of white carbon black and 8 parts of silica microspheres.

[0152] The auxiliary cross-linking agent is a fluorinated diene.

[0153] The cross-linking agent is a vulcanizing agent dichlorobenzene.

[0154] A second aspect of the present embodiment provides a method for preparing a fluorinated elastomer composition, comprising the following steps:

[0155] S1. Put the fluorine-containing elastomer into an internal mixer, put the silica microspheres and white carbon black into the internal mixer in sequence, and after mixing evenly, discharge the glue, and press the glue on an open mixer, and leave it for 18 hours to obtain a masterbatch; the discharge glue temperature is 100°C.

[0156] S2. The masterbatch is thinly passed on an open mixing mill, with the left and right cutters cutting 3 times each, the roller speed is 12r / min for the front roller and 14r / min for the rear roller, the roller spacing is adjusted to 0.6mm, the auxiliary cross-linking agent and the cross-linking agent are added in sequence, and the triangle package is made 20 times at a roller spacing of 0.4mm, and the fluorine-containing elastomer composition is obtained by sheeting.

[0157] A third aspect of this embodiment provides an application of a fluorine-containing elastomer composition, wherein the fluorine-containing elastomer composition is vulcanized to obtain a fluorine-containing elastomer cross-linked product which is applied in the fields of semiconductor, medical, chemical, aviation, aerospace and petroleum technology.

[0158] The method for vulcanizing the fluorine-containing elastomer composition is as follows: putting the fluorine-containing elastomer composition into a mold, placing the mold in a flat vulcanizer for a first-stage molding vulcanization to obtain a sulfur product, and after the sulfur product is parked for 16 hours, placing it in an oven for a second-stage vulcanization to prepare a fluorine-containing elastomer cross-linked product.

[0159] The vulcanization temperature of the one-stage compression vulcanization is 180° C., the vulcanization pressure is 11 MPa, and the vulcanization time is 15 min. The one-stage compression vulcanization obtains a sulfur product and is parked for 16 hours to be used.

[0160] The two-stage vulcanization process is to put the parked single-sulfur product into an oven for secondary vulcanization, the vulcanization temperature is 290° C., the vulcanization time is 16 hours, and the fluorine-containing elastomer cross-linked product is obtained after the two-stage vulcanization.

[0161] The fluorine-containing elastomer composition provided in the above embodiment can be put into a mold to prepare an O-ring.

[0162] Performance Testing

[0163] 1. Scorch test

[0164] According to the preparation method of the fluorine-containing elastomer composition provided in Examples 1-9, a crosslinking aid and a crosslinking agent are added to the masterbatch, and the state of the mixed rubber and the temperature of the film are observed during the mixing process on the open mill to observe whether the problem of early vulcanization leading to a scorched state will occur. If the film surface is not smooth and the film temperature is greater than 80°C, the evaluation result is "yes", and a scorched state has occurred; if the film surface is smooth and the film temperature is less than 80°C, the evaluation result is "no", and no scorched state has occurred; the test results are shown in Table 2. The scorched state of the mixed rubber formed by adding the crosslinking aid and the crosslinking agent to the masterbatch is shown in Table 2. Figure 1 .

[0165] 2. Demolding test

[0166] The fluorinated elastomer compositions that were not scorched in Examples 1-9 were vulcanized to prepare O-rings, and it was observed whether sticky mold or dirty mold appeared in the vulcanization mold cavity after the fluorinated elastomer compositions were vulcanized; when there was no sticky mold or dirty mold in the mold cavity, it was evaluated as A, and its state was shown as Figure 2 ; When the mold cavity has no sticky mold and dirty mold phenomenon, it is evaluated as B. Figure 3 ; When the mold cavity has sticky mold or dirty mold phenomenon, it is evaluated as C. Figure 4 .

[0167] 3. Tensile properties

[0168] Test method: According to GB / T 528-2009 Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber, the tensile strength and elongation at break of the fluorine-containing elastomer composition after vulcanization without scorching in Examples 1-9 were tested. The test results are shown in Table 2.

[0169] 4. Compression set test

[0170] Test method: The compression set properties of the fluorinated elastomer compositions of Examples 1-9 that did not show scorch after vulcanization were tested according to ASTM D395-03 Standard test methods for rubber property-Compression Set; Sample size: AS568-214 O-ring; Test conditions: 204°C, 70h; Test results are shown in Table 2.

[0171] Table 2

[0172]

[0173] It can be seen from the test results in Table 2 that the fluorine-containing elastomer composition includes a fluorine-containing elastomer, a fluorinated diene, and a reinforcing agent composed of white carbon black and silica microspheres, and the weight ratio of white carbon black to silica microspheres is 1: (1.2-3), especially when the weight ratio of white carbon black to silica microspheres is 1: (1.5-2), and the weight ratio of the co-crosslinking agent to the reinforcing agent is 1: (10-24), the fluidity of the fluorine-containing elastomer composition during vulcanization at high temperature can be enhanced, and a good demoulding effect is achieved, while ensuring low compression set of the product prepared from the fluorine-containing elastomer composition. It can be seen from Example 5 that when unsaturated carboxylates are added to the fluorinated elastomer composition, not only is the demoulding effect poor when vulcanization is carried out at high temperature, but also the compression performance of the obtained vulcanized product is deteriorated, and the compression permanent deformation is greatly increased, which cannot meet the use requirements; it can be seen from Example 6 that when maleimide is added to the fluorinated elastomer composition, although the compression performance of the obtained vulcanized product is greatly improved, the demoulding effect of the fluorinated elastomer composition when vulcanization is carried out at high temperature is still poor; it can be seen from Example 7 that when triallyl is added to the fluorinated elastomer composition, the demoulding effect of the fluorinated elastomer composition when vulcanization is carried out at high temperature is poor. The base ester was scorched during the vulcanization process, resulting in premature vulcanization and failure to obtain a molded product. It can be seen from Example 8 that although a fluorinated diene was added to the fluorinated elastomer composition, when the weight portion of the fluorinated diene was 0.5 parts, the compression set of the vulcanized product obtained and the demolding property of the fluorinated elastomer composition when vulcanized at a high temperature did not meet the requirements. It can be seen from Example 9 that when the amount of silica microspheres in the fluorinated elastomer composition is reduced, the fluidity of the mixed rubber formed by the fluorinated elastomer composition will deteriorate and the demolding property will decrease.

Claims

1. A fluorine-containing elastomer composition, characterized in that The raw materials for its preparation include, by weight: 90-110 parts of fluorine-containing elastomer, 20-30 parts of reinforcing agent, 0.5-1.5 parts of cross-linking agent, and 1-2 parts of auxiliary cross-linking agent; when the fluorine-containing elastomer composition is used, the compression permanent deformation tested at 204°C and 70h according to the ASTM D395-03 test standard is less than or equal to 25%; The reinforcing agent consists of white carbon black and silicon dioxide microspheres; The weight ratio of white carbon black to silica microspheres is 1:(1.2-3); The auxiliary cross-linking agent is a fluorinated diene.

2. The fluorinated elastomer composition according to claim 1, characterized in that The weight ratio of the white carbon black to the silica microspheres is 1:(1.5-2).

3. The fluorinated elastomer composition according to claim 1, characterized in that The weight ratio of the auxiliary cross-linking agent to the reinforcing agent is 1:(10-24).

4. The fluorinated elastomer composition according to claim 1, characterized in that The crosslinking agent is a peroxide system crosslinking agent.

5. A method for preparing a fluorinated elastomer composition according to any one of claims 1 to 4, characterized in that: The following steps are involved: S1. mixing a fluorinated elastomer and a reinforcing agent to obtain a masterbatch; S2. Adding a co-crosslinking agent and a crosslinking agent into the masterbatch to obtain a fluorine-containing elastomer composition.

6. Use of the fluorinated elastomer composition according to any one of claims 1 to 4, characterized in that: The fluorine-containing elastomer composition is vulcanized to obtain a fluorine-containing elastomer cross-linked product which is used in the fields of semiconductor, medical treatment, chemical industry, aviation, aerospace and petroleum technology.

7. Use of the fluorinated elastomer composition according to claim 6, characterized in that: The fluorine-containing elastomer cross-linked product has a compression permanent deformation of less than or equal to 25% when tested at 204° C. for 70 hours according to the ASTM D395-03 test standard.

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