Fluororesin fluororubber composite material with high fracture work and preparation method thereof

Abstract

The invention provides a fluororesin fluororubber composite material with high fracture work and a preparation method thereof, and the fluororesin fluororubber composite material comprises the following raw materials by weight: 100-120 parts of fluororubber; 20 to 40 parts of fluororesin micro powder; 1-8 parts of a cross-linking agent; and 0.1-6 parts of an assistant cross-linking agent. The fluororesin and fluororubber composite material disclosed by the invention not only can improve the fracture energy, but also can improve the cleanliness, and also can improve the etching gas resistance.

Description

Technical Field

[0001] The invention relates to the technical field of fluororubber composite materials, and in particular to a fluororesin fluororubber composite material with high work of fracture and a preparation method thereof. Background Art

[0002] Fluororubber refers to a synthetic polymer rubber (elastomer) containing fluorine atoms on the carbon atoms of the main chain or side chain. Due to the strong electronegativity of fluorine atoms and the high bond energy of fluorine-carbon bonds, fluororubber has outstanding chemical resistance, weather resistance, heat resistance and other characteristics. Therefore, it is currently widely used as a sealing material in semiconductor process equipment under harsh working conditions.

[0003] Fluororubber generally needs a certain amount of filler for reinforcement. In addition to traditional fillers such as carbon black and white carbon black, fluororesin, as a new type of filler, has also received more and more attention. Commonly used fluororesin has better plasma resistance and cleanliness than traditional fillers, but its reinforcement is generally not as good as traditional fillers.

[0004] In the prior art, the patent application document with the authorization number CN 113681740 B discloses a method for modifying ternary fluororubber with fluororesin, which can improve the processing performance and physical properties of F246 ternary fluororubber by taking advantage of the excellent comprehensive performance of fluororesin powder, good dispersibility, and easy uniform mixing with other materials. The patent application document with the authorization number CN 113943467 B discloses a fluororubber composition, its preparation method and application, and uses fluororesin to reduce the friction coefficient of fluororubber dynamic seals, thereby extending their service life.

[0005] In summary, the fluororubber compositions in the prior art cannot simultaneously have high plasma resistance, high fracture work and fracture toughness. In theory, the higher the fluorine content of the resin, the better the resistance to fluorine-containing etching gas, but most PTFE micropowders are only used as fillers in the rubber formulation system, and there is no good interaction between the crystalline resin and the rubber system, that is, there is no interaction to form chemical or polar physical bonds, so the fracture energy of the entire system will be very low. Summary of the invention

[0006] In view of the above-mentioned shortcomings of the prior art, the object of the present invention is to provide a fluororesin-fluororubber composite material with high fracture work and a preparation method thereof, which can not only improve the fracture energy, but also improve the cleanliness and the etching gas resistance, thereby solving the problems in the prior art.

[0007] In order to achieve the above-mentioned object and other related objects, one aspect of the present invention provides a fluororesin fluororubber composite material, wherein the raw materials of the fluororesin fluororubber composite material include the following components in parts by weight:

[0008]

[0009]

[0010] The fluororesin powder is selected from one or more of tetrafluoroethylene hexafluoropropylene copolymer, polyvinylidene fluoride, polytetrafluoroethylene and fusible polytetrafluoroethylene.

[0011] The second aspect of the present invention provides a method for preparing the fluororesin-fluororubber composite material according to the first aspect of the present invention, the preparation method comprising:

[0012] 1) The fluororubber is plasticized evenly on a double-roll open mill, and then the fluororesin powder, cross-linking agent and auxiliary cross-linking agent are added into the open mill and mixed evenly to obtain a rubber mixture for coating the rolls;

[0013] 2) Cut the rubber mixture on the roll on the left and right sides, adjust the roller distance of the mixing mill to the minimum, make a triangle bag, mix evenly and then produce a sheet to obtain the mixed rubber;

[0014] 3) Set the mixed rubber aside and re-refine it into sheets for later use.

[0015] The third aspect of the present invention provides use of the fluororesin fluororubber composite material as described in the first aspect of the present invention in the fields of semiconductors, photovoltaics, and aerospace.

[0016] Compared with the prior art, the present invention has the following beneficial effects:

[0017] The present invention provides a fluororesin fluororubber composite material and a preparation method thereof. By adding specific fluororesin micropowder to fluororubber to prepare the composite material, not only the fracture work and mechanical properties of the fluororubber can be improved, but also the fluororubber can maintain a relatively high cleanliness after being subjected to a high plasma working environment, thereby expanding the scope of use of the fluororubber. This can meet the working conditions of semiconductors, photovoltaics, aerospace and other fields that require sealing materials to have high fracture resistance and plasma resistance. Specifically, the Shore A hardness is >56, preferably >60; the tensile strength is >9MPa, preferably greater than 11MPa; the elongation at break is >240%, preferably ≥250%; the 100% modulus is >5MPa, preferably greater than 9MPa; the fracture work is ≥0.35N / m, preferably >0.4MN / m; the plasma mass loss is less than 1.6%, preferably less than 1.5%. DETAILED DESCRIPTION

[0018] Hereinafter, embodiments of a fluororesin-fluororubber composite material having high work of rupture and a method for preparing the same are specifically disclosed.

[0019] "Scope" disclosed in the present application is limited in the form of lower limit and upper limit, and a given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a special range. The scope limited in this way can be including end values ​​or not including end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a scope. For example, if the scope of 60-120 and 80-110 is listed for a specific parameter, it is understood that the scope of 60-110 and 80-120 is also expected. In addition, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3, 4 and 5 are listed, the following scope can be all expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present application, unless otherwise specified, the numerical range "ab" represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations. In addition, when a parameter is expressed as an integer ≥ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0020] Unless otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.

[0021] The present invention optimizes the formula, specifically, by comprehensively selecting a specific type of fluororesin powder and adding it to fluororubber to prepare a composite material, which can not only improve the fracture work and mechanical properties of the fluororubber, but also enable the fluororubber to maintain a relatively high cleanliness after being subjected to a high plasma working environment, thereby expanding the scope of use of the fluororubber. This can meet the requirements of semiconductors, photovoltaics, aerospace and other fields for sealing materials with high fracture resistance and plasma resistance. On this basis, the present invention is completed.

[0022]

Fluororesin and fluororubber composite materials

[0023] One aspect of the present invention provides a fluororesin-fluororubber composite material, the raw materials of which include fluororubber, fluororesin micropowder, a crosslinking agent, and a crosslinking aid.

[0024] The raw materials of the fluororesin-fluororubber composite material provided by the present invention may include 100-120 parts of fluororubber by weight. Optionally, the weight of the fluororubber is 100-110 parts, 110-120 parts, or 100 parts.

[0025] Furthermore, the fluororubber is selected from one or more of fluororubber type 26 (FKM26), fluororubber type 246 (FKM246), fluoroethylene rubber (FKM24), tetrafluoropropylene rubber (FEPM), perfluoroether rubber (FFKM), and fluorinated phosphazene rubber.

[0026] In the fluororesin fluororubber composite material provided by the present invention, the raw materials can include 20-40 parts of fluororesin powder by weight. Optionally, the weight of the fluororesin powder is 20-30 parts, 30-40 parts, 20-35 parts, 35-40 parts. Preferably, it is 30-40 parts, and more preferably, it is 35-40 parts. If the amount is too much, the plasticity is too strong and the elasticity is weakened, and if the amount is too little, the reinforcement is insufficient and the plasma resistance is weak.

[0027] Further, the fluororesin powder is selected from one or more of tetrafluoroethylene hexafluoropropylene copolymer (FEP), polyvinylidene fluoride (PVDF), polytetrafluoroethylene and meltable polytetrafluoroethylene. Optionally, the meltable polytetrafluoroethylene can be EA2000 produced by AGC.

[0028] The fluororesin micropowders all have melting peaks, and the fluororesin micropowders include C, F and other elements, wherein the other elements are one or more of oxygen, sulfur and nitrogen, and the molar ratio of other elements to the total elements is 3-10 thousandths. Optionally, the molar ratio of other elements to the total elements is 3-5 thousandths, 5-10 thousandths, 5-8 thousandths, and 8-10 thousandths. When the proportion of other elements exceeds 10 thousandths, the crystallization of the resin is destroyed, the difficulty of polymerization increases, and the etching resistance of the formed micropowder will decrease. When the proportion of other elements is less than 3%, the formed resin micropowder has a poor effect on improving the fracture energy.

[0029] The molar ratio of the elements is the result obtained by standard XPS elemental analysis, as shown in Table 1 below:

[0030] Table 1

[0031]

[0032] The raw materials of the fluororesin-fluororubber composite material provided by the present invention may include 1-8 parts of a crosslinking agent by weight. Optionally, the crosslinking agent may be 1-3 parts, 3-8 parts, 3-5 parts or 5-8 parts by weight.

[0033] Further, the cross-linking agent is selected from one or more of 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane (such as DBPH), 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane (such as BOAP), and fluoroaralkylphosphonic acid salts. Preferably, the cross-linking agent is 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane.

[0034] The raw materials of the fluororesin and fluororubber composite material provided by the present invention may include 0.1-6 parts by weight of a cross-linking agent. Optionally, the cross-linking agent may be 3-6 parts, 3-4 parts, 4-5 parts or 5-6 parts by weight.

[0035] Further, the auxiliary cross-linking agent is triallyl isocyanurate (TAIC) or trimethallyl isocyanate (TMAIC). Preferably, the auxiliary cross-linking agent is triallyl isocyanurate.

[0036] In the fluororesin-fluororubber composite material provided by the present invention, the Shore A hardness of the fluororesin-fluororubber composite material is >56, preferably >60, such as 60-70, 60-65, etc., and more preferably >65.

[0037] In the fluororesin-fluororubber composite material provided by the present invention, the tensile strength of the fluororesin-fluororubber composite material is >9 MPa, preferably >11 MPa, for example, 11 to 14, and more preferably >13 MPa.

[0038] In the fluororesin-fluororubber composite material provided by the present invention, the elongation at break of the fluororesin-fluororubber composite material is greater than 240%, preferably greater than or equal to 250%, such as 250-270%, and more preferably greater than or equal to 260%.

[0039] In the fluororesin-fluororubber composite material provided by the present invention, the 100% modulus of the fluororesin-fluororubber composite material is >5MPa, preferably >9MPa, such as 9.2-12MPa, and more preferably >11MPa.

[0040] In the fluororesin-fluororubber composite material provided by the present invention, the fracture work of the fluororesin-fluororubber composite material is ≥ 0.35 N / m, preferably > 0.4 MN / m, and more preferably > 0.45 MN / m.

[0041] In the fluororesin-fluororubber composite material provided by the present invention, the plasma mass loss of the fluororesin-fluororubber composite material is lower than 1.6%, preferably lower than 1.5%, such as 1.1-1.4, and more preferably lower than 1.2%.

[0042]

Preparation method of fluororesin and fluororubber composite materials

[0043] The second aspect of the present invention provides a method for preparing the fluororesin-fluororubber composite material according to the first aspect of the present invention, the preparation method comprising:

[0044] 1) The fluororubber is plasticized evenly on a double-roll open mill, and then the fluororesin powder, cross-linking agent and auxiliary cross-linking agent are added into the open mill and mixed evenly to obtain a rubber mixture for coating the rolls;

[0045] 2) Cut the rubber mixture on the roll on the left and right sides, adjust the roller distance of the mixing mill to the minimum, make a triangle bag, mix evenly and then produce a sheet to obtain the mixed rubber;

[0046] 3) Set the mixed rubber aside and re-refine it into sheets for later use.

[0047] In the method for preparing the fluororesin-fluororubber composite material provided by the present invention, in step 2), the left and right sides are cut 3-10 times each.

[0048] In the method for preparing the fluororesin-fluororubber composite material provided by the present invention, in step 2), the triangular packing is performed 10-30 times.

[0049] In the method for preparing the fluororesin-fluororubber composite material provided by the present invention, in step 2), the temperature of the roller of the mixing mill is controlled within 60°C.

[0050] In the method for preparing the fluororesin-fluororubber composite material provided by the present invention, in step 3), the mixed rubber is left to stand for more than 16 hours.

[0051] In the preparation method of the fluororesin-fluororubber composite material provided by the present invention, in step 3), the process is re-refined for 10 minutes to produce a sheet for standby use.

[0052]

application

[0053] The third aspect of the present invention provides use of the fluororesin fluororubber composite material as described in the first aspect of the present invention in the fields of semiconductors, photovoltaics, and aerospace.

[0054] The beneficial effects of the present invention are further illustrated below in conjunction with embodiments.

[0055] In order to make the invention purpose, technical scheme and beneficial technical effect of the present invention clearer, the present invention is further described in detail below in conjunction with examples. However, it should be understood that the examples of the present invention are only for explaining the present invention, not for limiting the present invention, and the examples of the present invention are not limited to the examples given in the specification. The specific experimental conditions or operating conditions not specified in the examples are made under conventional conditions, or are made under the conditions recommended by the material supplier.

[0056] In addition, it should be understood that one or more method steps mentioned in the present invention do not exclude the existence of other method steps before or after the combination step or the insertion of other method steps between these explicitly mentioned steps, unless otherwise specified; it should also be understood that the combination connection relationship between one or more devices / apparatuses mentioned in the present invention does not exclude the existence of other devices / apparatuses before or after the combination device / apparatus or the insertion of other devices / apparatuses between these explicitly mentioned two devices / apparatuses, unless otherwise specified. Moreover, unless otherwise specified, the numbering of each method step is only a convenient tool for identifying each method step, and is not intended to limit the order of arrangement of each method step or the scope of the present invention. Changes or adjustments in their relative relationships should also be regarded as the scope of the present invention without substantially changing the technical content.

[0057] In the following examples, the reagents, materials and instruments used are all commercially available unless otherwise specified.

[0058] The molar ratios of the elements were obtained by standard XPS elemental analysis.

[0059] The fluororubber was purchased from AGC, model 600X.

[0060] Fluororesin powder 1 was purchased from AGC, model EA2000. The content of other elements was 8.1 parts per thousand.

[0061] Fluororesin powder 2 was purchased from Solvay, model F5AR. The content of other elements was 0.5 ppm.

[0062] Fluororesin powder 3 was purchased from Zhejiang Ge Rui, model GR-C547. The content of other elements was 0.2 ppm.

[0063] The crosslinking agent is 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane.

[0064] The auxiliary cross-linking agent is triallyl isocyanurate.

[0065] The test methods or standards involved are as follows

[0066] 1.Shore A hardness: GB / T 531.1;

[0067] 2. Tensile strength: GB / T 528;

[0068] 3. Elongation at break: GB / T 528;

[0069] 4.100% modulus: GB / T 528;

[0070] 5. Work of fracture: integral of the stress-strain curve obtained from the tensile test according to GB / T 528;

[0071] 6. Plasma mass loss: ICP etching, room temperature, 10Pa, 60min, CF4.

[0072] Example 1

[0073] The preparation method of the fluororesin fluororubber composite material comprises the following steps:

[0074] (1) 100 parts of fluororubber were plasticized and rolled evenly on a two-roll mill, and then 20 parts of fluororesin powder, 3 parts of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and 3 parts of triallyl isocyanurate were gradually added to the mill and mixed evenly;

[0075] (2) Cut the rubber mixture on the roll 10 times on each side, adjust the roll distance of the mixing mill to the minimum, make triangle packs 30 times, control the temperature of the mixing mill roll within 60°C, mix evenly and then produce sheets;

[0076] (3) Leave the mixed rubber for 16 hours, re-mix for 10 minutes and make sheets for later use.

[0077] Example 2

[0078] The preparation method of the fluororesin fluororubber composite material comprises the following steps:

[0079] (1) 100 parts of fluororubber were plasticized and rolled evenly on a two-roll mill, and then 30 parts of fluororesin powder, 3 parts of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and 3 parts of triallyl isocyanurate were gradually added into the mill and mixed evenly;

[0080] (2) Cut the rubber mixture on the roll 10 times on each side, adjust the roll distance of the mixing mill to the minimum, make triangle packs 30 times, control the temperature of the mixing mill roll within 60°C, mix evenly and then produce sheets;

[0081] (3) Leave the mixed rubber for 16 hours, re-mix for 10 minutes and make sheets for later use.

[0082] Example 3

[0083] The preparation method of the fluororesin fluororubber composite material comprises the following steps:

[0084] (1) 100 parts of fluororubber were plasticized and rolled evenly on a two-roll mill, and then 40 parts of fluororesin powder, 3 parts of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and 3 parts of triallyl isocyanurate were gradually added into the mill and mixed evenly;

[0085] (2) Cut the rubber mixture on the roll 10 times on each side, adjust the roll distance of the mixing mill to the minimum, make triangle packs 30 times, control the temperature of the mixing mill roll within 60°C, mix evenly and then produce sheets;

[0086] (3) Leave the mixed rubber for 16 hours, re-mix for 10 minutes and make sheets for later use.

[0087] Comparative Example 1

[0088] The preparation method of the fluororesin fluororubber composite material comprises the following steps:

[0089] (1) 100 parts of fluororubber were plasticized evenly on a two-roll mill and rolled, and then 3 parts of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane and 3 parts of triallyl isocyanurate were gradually added into the mill and mixed evenly;

[0090] (2) Cut the rubber mixture on the roll 10 times on each side, adjust the roll distance of the mixing mill to the minimum, make triangle packs 30 times, control the temperature of the mixing mill roll within 60°C, mix evenly and then produce sheets;

[0091] (3) Leave the mixed rubber for 16 hours, re-mix for 10 minutes and make sheets for later use.

[0092] Comparative Example 2

[0093] The preparation method of the fluororesin fluororubber composite material comprises the following steps:

[0094] (1) 100 parts of fluororubber were plasticized and rolled evenly on a two-roll mill, and then 20 parts of fluororesin micropowder, 2 parts of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and 3 parts of triallyl isocyanurate were gradually added into the mill and mixed evenly;

[0095] (2) Cut the rubber mixture on the roll 10 times on each side, adjust the roll distance of the mixing mill to the minimum, make triangle packs 30 times, control the temperature of the mixing mill roll within 60°C, mix evenly and then produce sheets;

[0096] (3) Leave the mixed rubber for 16 hours, re-mix for 10 minutes and make sheets for later use.

[0097] Comparative Example 3

[0098] The preparation method of the fluororesin fluororubber composite material comprises the following steps:

[0099] (1) 100 parts of fluororubber were plasticized and rolled evenly on a two-roll mill, and then 20 parts of fluororesin powder, 3 parts of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and 3 parts of triallyl isocyanurate were gradually added into the mill and mixed evenly;

[0100] (2) Cut the rubber mixture on the roll 10 times on each side, adjust the roll distance of the mixing mill to the minimum, make triangle packs 30 times, control the temperature of the mixing mill roll within 60°C, mix evenly and then produce sheets;

[0101] (3) Leave the mixed rubber for 16 hours, re-mix for 10 minutes and make sheets for later use.

[0102] Comparative Example 4

[0103] The preparation method of the fluororesin fluororubber composite material comprises the following steps:

[0104] (1) 100 parts of fluororubber were plasticized evenly on a two-roll mill and rolled, and then 20 parts of white carbon black R972, 3 parts of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and 3 parts of triallyl isocyanurate were gradually added to the mill and mixed evenly;

[0105] (2) Cut the rubber mixture on the roll 10 times on each side, adjust the roll distance of the mixing mill to the minimum, make triangle packs 30 times, control the temperature of the mixing mill roll within 60°C, mix evenly and then produce sheets;

[0106] (3) Leave the mixed rubber for 16 hours, re-mix for 10 minutes and make sheets for later use.

[0107] Comparative Example 5

[0108] The preparation method of the fluororesin fluororubber composite material comprises the following steps:

[0109] (1) 100 parts of fluororubber were plasticized evenly on a two-roll mill and rolled, and then 20 parts of carbon black N990, 3 parts of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and 3 parts of triallyl isocyanurate were gradually added to the mill and mixed evenly;

[0110] (2) Cut the rubber mixture on the roll 10 times on each side, adjust the roll distance of the mixing mill to the minimum, make triangle packs 30 times, control the temperature of the mixing mill roll within 60°C, mix evenly and then produce sheets;

[0111] (3) Leave the mixed rubber for 16 hours, re-mix for 10 minutes and make sheets for later use.

[0112] Comparative Example 6

[0113] The preparation method of the fluororesin fluororubber composite material comprises the following steps:

[0114] (1) 100 parts of fluororubber were plasticized evenly on a two-roll mill and rolled, and then 10 parts of fluororesin powder 1, 3 parts of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and 3 parts of triallyl isocyanurate were gradually added into the mill and mixed evenly;

[0115] (2) Cut the rubber mixture on the roll 10 times on each side, adjust the roll distance of the mixing mill to the minimum, make triangle packs 30 times, control the temperature of the mixing mill roll within 60°C, mix evenly and then produce sheets;

[0116] (3) Leave the mixed rubber for 16 hours, re-mix for 10 minutes and make sheets for later use.

[0117] Comparative Example 7

[0118] The preparation method of the fluororesin fluororubber composite material comprises the following steps:

[0119] (1) 100 parts of fluororubber were plasticized and rolled evenly on a two-roll mill, and then 50 parts of fluororesin powder, 3 parts of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and 3 parts of triallyl isocyanurate were gradually added into the mill and mixed evenly;

[0120] (2) Cut the rubber mixture on the roll 10 times on each side, adjust the roll distance of the mixing mill to the minimum, make triangle packs 30 times, control the temperature of the mixing mill roll within 60°C, mix evenly and then produce sheets;

[0121] (3) Leave the mixed rubber for 16 hours, re-mix for 10 minutes and make sheets for later use.

[0122] The raw materials and dosage of each embodiment and comparative example are shown in Table 2

[0123] Table 2

[0124]

[0125]

[0126] The performance test results are detailed in Table 3.

[0127] Table 3

[0128]

[0129] Combining Table 2 and Table 3, it can be seen from the analysis of Examples 1 to 3 and Comparative Examples 6 and 7 that with the increase in the amount of fluororesin micropowder, the Shore A hardness, tensile strength, 100% modulus, and fracture work all increase, and the plasma mass loss decreases. In Comparative Example 7, when it exceeds 40 parts, the material formability deteriorates, the fracture work decreases, and the elongation at break deteriorates.

[0130] Combining Table 2 and Table 3, it can be seen from the comparison between Example 1 and Comparative Example 1 that, other things remain unchanged, Comparative Example 1 only removes the fluororesin powder of the present invention, and the Shore A hardness, tensile strength, 100% modulus, and especially the fracture work are significantly reduced. In addition, the plasma mass loss is significantly increased.

[0131] Combining Table 2 and Table 3, it can be seen from the comparison between Example 1 and Comparative Examples 2 and 3 that, when the fluororesin powder of the present invention is replaced with other fluororesin powders, the Shore A hardness, tensile strength, 100% modulus, and fracture work are all reduced, and the plasma mass loss is increased.

[0132] Combining Table 2 and Table 3, it can be seen from the comparison between Example 1 and Comparative Example 4 that, when the fluororesin powder of the present invention is replaced with white carbon black R972 while other factors remain unchanged, the fracture work increases and the plasma mass loss increases significantly.

[0133] Combining Table 2 and Table 3, from the comparison between Example 1 and Comparative Example 5, it can be seen that, with other things unchanged, only after the fluororesin powder of the present invention is replaced with carbon black N990, the Shore A hardness, tensile strength, 100% modulus, and fracture work all decrease, especially the fracture work decreases significantly, and the plasma mass loss increases significantly.

[0134] In summary, the present invention uses a screened fluororesin powder and blends it into fluororubber, which significantly improves the mechanical properties of fluororubber compared to other fillers. The fluororesin / fluororubber composite material prepared by the present invention has better plasma resistance and high cleanliness, and is very suitable for semiconductor, photovoltaic, aerospace and other industries with high cleanliness and plasma resistance requirements.

[0135] In summary, the present invention effectively overcomes various shortcomings of the prior art and has high industrial utilization value.

[0136] The above is only a preferred embodiment of the present invention, and is not any formal or substantial limitation of the present invention. It should be pointed out that ordinary technicians in this technical field can make several improvements and supplements without departing from the method of the present invention, and these improvements and supplements should also be regarded as the protection scope of the present invention. Any technician familiar with this profession, without departing from the spirit and scope of the present invention, can make some changes, modifications and evolutions of the technical content disclosed above, which are equivalent embodiments of the present invention; at the same time, any changes, modifications and evolutions of any equivalent changes made to the above embodiments based on the essential technology of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A fluororesin-fluororubber composite material, characterized in that: The raw materials of the fluororesin and fluororubber composite material include the following components by weight: The fluororesin powder is selected from one or more of tetrafluoroethylene hexafluoropropylene copolymer, polyvinylidene fluoride, polytetrafluoroethylene and fusible polytetrafluoroethylene.

2. The fluororesin-fluororubber composite material according to claim 1, characterized in that: The fluororubber is selected from one or more of type 26 fluororubber, type 246 fluororubber, perfluoroelastomer, tetrapropylene fluororubber, perfluoroelastomer, and fluorinated phosphazene rubber.

3. The fluororesin-fluororubber composite material according to claim 1, characterized in that: The fluororesin powders all have melting peaks, and the fluororesin powders include C, F and other elements, wherein the other elements are one or more of oxygen, sulfur and nitrogen, and the molar ratio of the other elements to the total elements is 3 to 10 thousandths; And / or, the particle size of the fluororesin powder is 1 μm-500 μm; And / or, the weight portion of the fluororesin fine powder is 30-40 parts.

4. The fluororesin-fluororubber composite material according to claim 3, characterized in that: The weight portion of the fluororesin powder is 35-40 parts.

5. The fluororesin-fluororubber composite material according to claim 1, characterized in that: The cross-linking agent is selected from one or more of 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane, and fluoroaralkylphosphonic acid salts; And / or, the auxiliary cross-linking agent is triallyl isocyanurate or trimethallyl isocyanate.

6. The fluororesin-fluororubber composite material according to claim 5, characterized in that: The cross-linking agent is 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane; And / or, the auxiliary cross-linking agent is triallyl isocyanurate.

7. The fluororesin-fluororubber composite material according to claim 1, characterized in that: The fluororesin fluororubber composite material includes any one or more of the following features: A1) Shore A hardness>56; A2) tensile strength>9MPa; A3) Elongation at break>240%; A4) 100% modulus> 5MPa; A5) Fracture work ≥ 0.35 N / m; A6) Plasma mass loss is less than 1.6%.

8. The method for preparing a fluororesin-fluororubber composite material according to any one of claims 1 to 7, characterized in that: The preparation method comprises: 1) The fluororubber is plasticized evenly on a double-roll open mill, and then the fluororesin powder, cross-linking agent and auxiliary cross-linking agent are added into the open mill and mixed evenly to obtain a rubber mixture for coating the rolls; 2) Cut the rubber mixture on the roll on the left and right sides, adjust the roller distance of the mixing mill to the minimum, make a triangle bag, mix evenly and then produce a sheet to obtain the mixed rubber; 3) Set the mixed rubber aside and re-refine it into sheets for later use.

9. The method for preparing a fluororesin and fluororubber composite material according to claim 8, characterized in that: In step 2), make 3-10 cuts on each side; And / or, in step 2), triangular packing is performed 10-30 times; And / or, in step 2), the temperature of the mixing mill drum is controlled within 60°C; And / or, in step 3), the rubber mix is ​​left to stand for more than 16 hours.

10. Use of the fluororesin / fluororubber composite material according to any one of claims 1 to 8 in the fields of semiconductors, photovoltaics, and aerospace.

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