CN115847665A - Crushing process for recovering perfluoroether rubber and perfluoroether sealing element prepared by same - Google Patents
Crushing process for recovering perfluoroether rubber and perfluoroether sealing element prepared by same Download PDFInfo
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- CN115847665A CN115847665A CN202211261202.2A CN202211261202A CN115847665A CN 115847665 A CN115847665 A CN 115847665A CN 202211261202 A CN202211261202 A CN 202211261202A CN 115847665 A CN115847665 A CN 115847665A
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Abstract
The invention relates to the technical field of semiconductor materials, in particular to the field of IPC 08L29, and more particularly relates to a crushing process for recovering perfluoroether rubber and a perfluoroether sealing element prepared by the same. The recovered perfluoroether rubber is cut into particles, and the particles of the perfluoroether rubber are put into a liquid nitrogen freezing pulverizer to be pulverized for 20-40min, so that the perfluoroether rubber micro powder is obtained. The invention carries out multistage freezing and crushing on the semiconductor-grade sealing element through a specific crushing process to obtain the perfluoroether rubber micro powder, and the perfluoroether rubber micro powder enters a new formula system through a mixing process again, and the semiconductor-grade perfluoroether sealing element is obtained again through a forming and vulcanizing process.
Description
Technical Field
The invention relates to the technical field of semiconductor materials, in particular to the field of IPC 08L29, and more particularly relates to a crushing process for recovering perfluoroether rubber and a perfluoroether sealing element prepared by the same.
Background
The perfluoroether rubber (FFKM) is a high-performance sealing material, the excellent performance of the perfluoroether rubber enables the perfluoroether rubber to be applied to the whole manufacturing system of semiconductor products, and a perfluoroether sealing ring is one of main consumables required by integrated circuit production. The perfluoro ether rubber is prepared by copolymerizing tetrafluoroethylene and perfluoroalkyl vinyl ether which are used as main monomers with a small amount of cross-linkable third monomer. The perfluoroether rubber macromolecular chain has no carbon-hydrogen bond, and the C-C bond is basically surrounded by F atoms, so that the polymer has remarkable chemical resistance, high and low temperature resistance, high-temperature steam resistance, low release and precipitation performance and plasma resistance.
In semiconductor manufacturing, the reliability of the elastic sealing element is very critical, the replacement of the sealing element is very costly when the production is stopped, the requirements on the cleanliness and the purity of the sealing element are very strict in order to avoid potential risks, and the sealing element must be capable of working for a long time in high-vacuum, aggressive chemical gas and high-temperature environments, so the synthesis technology of the perfluoro-ether rubber is extremely complex and extremely expensive. At present, the synthesis technology is mainly mastered in foreign enterprises such as DuPont, 3M, dajin, AGC, solvay and the like, and the synthesis technology of the perfluoroether rubber in China is still under exploration.
The domestic perfluoroether rubber can not meet the application requirements of semiconductor grade.
In the prior art, patent application document with publication number of CN109111670A discloses a regenerated perfluoroether rubber and a processing technology thereof, wherein environment-friendly plant-based soybean oil oleic acid is selected as a raw material, waste rubber is recycled, and the regenerated perfluoroether rubber is prepared, but the rubber has low elongation at break and is not suitable for being applied to the field of semiconductors.
Patent application document CN114395240A discloses a high-temperature-resistant ultra-pure perfluoroether rubber and a preparation method thereof, wherein the performance of the material is improved by adopting fumed silica, but the cost is high.
Disclosure of Invention
In order to solve the above problems, the present invention provides, in a first aspect, a pulverization process for recovering a perfluoroether rubber, comprising the steps of:
cutting the recovered perfluoroether rubber into particles, and pulverizing the particles of perfluoroether rubber in a liquid nitrogen freezing pulverizer for 20-40min to obtain the perfluoroether rubber micropowder.
Preferably, the length of the granular perfluoroether rubber is 0.3 to 1.0cm.
Preferably, the temperature of the liquid nitrogen freezing pulverizer is-196 to-150 ℃; more preferably, the temperature is-196 to-170 ℃; further, it was-196 ℃.
The crushing process for recovering the perfluoroether rubber in the invention is suitable for all the perfluoroether rubbers on the market.
The inventor creatively discovers that the recovered perfluoroether rubber is cut into specified particles, the particles with the particle size less than or equal to 1000 mu m are crushed for 20-40min by a liquid nitrogen freezing and crushing machine, the obtained particles with the particle size less than or equal to 95 percent, and the particles are subsequently applied to the preparation of the cross-linked fluorine-containing elastomer, the contact area between the particles and other raw materials is large, the particles can play a role of a filler and participate in vulcanization cross-linking reaction, so that the hardness and the tensile strength of the finally prepared cross-linked fluorine-containing elastomer can be improved. In some preferred schemes, the recovered perfluoroether rubber can be pulverized into smaller particle size by a liquid nitrogen freezing pulverizer for a plurality of times, but the cost is relatively higher, so that the invention only needs to put the granular perfluoroether rubber into the liquid nitrogen freezing pulverizer for pulverizing once for the consideration of the cost and the performance of the crosslinked fluorine-containing elastomer obtained by the subsequent preparation.
The second aspect of the invention provides the perfluoro ether rubber micro powder prepared by the grinding process for recovering the perfluoro ether rubber.
The third aspect of the invention provides a perfluoroether sealing element prepared from the perfluoroether rubber micropowder, wherein the perfluoroether sealing element is prepared from the following raw materials in parts by weight: 0-60 parts of perfluoroether rubber micro powder (not including 0), 100 parts of raw rubber, 0.2-1.5 parts of vulcanizing agent and 0.2-1.5 parts of cross-linking agent.
Preferably, the Mooney viscosity ML120 ℃ 1+10 of the crude rubber at 100 ℃ is 20-130.
Preferably, the vulcanizing agent comprises one or more of peroxides and amine compounds.
Preferably, the peroxide comprises one or more of dialkyl peroxides, diacyl peroxides, ketal peroxides, peroxyesters.
Preferably, the dialkyl peroxides include one or more of dicumyl peroxide (CAS number: 80-43-3), di (t-butylperoxyisopropyl) benzene (CAS number: 2212-81-9), 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane (CAS number: 78-63-7), 1,1 di (t-butylperoxy) 3,3,5 trimethylcyclohexane (CAS number: 6731-36-8); further preferred is 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane.
Preferably, the diacyl peroxides include bis (2,4-dichlorobenzoyl) peroxide (CAS number: 133-14-2).
Preferably, the ketal peroxide comprises 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane (CAS number: 6731-36-8).
Preferably, the peroxyesters include one or more of tert-butyl peroxybenzoate (CAS number: 614-45-9), tert-amyl peroxybenzoate (CAS number: 4511-39-1), dicetyl peroxydicarbonate (CAS number: 26322-14-5), tert-butylcumyl peroxide (CAS number: 3457-61-2), and tert-butyl peroxyisopropylcarbonate (CAS number: 2372-21-6).
Preferably, the amine compound contains at least two amino groups.
Preferably, the amine compound includes one or more of m-phenylenediamine (CAS No.: 108-45-2), hexamethylenediamine carbamate (CAS No.: 143-06-6), 2,2-bis (3-amino-4 hydroxyphenyl) -hexafluoropropane (CAS No.: 83558-87-6), hexamethylenediamine (CAS No.: 124-09-4), tert-butyl bis (2-aminoethyl) carbamate (CAS No.: 556082-02-1), 2,2 bis [4 (4 aminophenoxy) phenyl ] propane (CAS No.: 13080-86-9), 4,4 'methylenedianiline (CAS No.: 101-77-9), 4,4' -diaminodicyclohexylmethane (CAS No.: 1761-71-3), 2,2 bis (3 amino 4 hydroxyphenyl) hexafluoropropane (CAS No.: 4234 zxft 34-6-4287), isophorone diamine (CAS No.: 2855-5364), and isophorone diamine (CAS No.: 2455-79).
Preferably, the cross-linking agent comprises one or more of an olefin, a halide, a nitrile compound.
Further preferably, the crosslinking agent is triallyl isocyanurate (CAS number: 1025-15-6).
In some preferred schemes, the selection of the cross-linking agent is related to the performance of the fine perfluoroether rubber powder, and the inventor creatively discovers that different fine perfluoroether rubber powder and different cross-linking agents can form different cross-linking systems, so that the perfluoroether sealing element with excellent performance can be prepared.
Preferably, the preparation process of the perfluoroether seal comprises the following steps: the raw materials are put into an internal mixing chamber for internal mixing according to the parts by weight, and then put into an open mill for roll wrapping and vulcanization to obtain the rubber composition.
Further preferably, the preparation process of the perfluoroether seal comprises the following steps: raising the temperature of an internal mixer to 110-130 ℃, putting raw rubber into an internal mixing chamber for internal mixing for 60-120s, adding the perfluoroether rubber micro powder and the cross-linking agent, slowly adding the raw rubber into the internal mixing chamber in batches, stirring the mixture uniformly, continuing the internal mixing for 60-120s, discharging the rubber at the temperature of below 150 ℃, rolling the mixture on an open mill to obtain sheets, standing and cooling for more than 4 hours; putting the parked and cooled rubber sheets into an open mill, wrapping rollers for 2-3 circles at normal temperature, slowly adding a vulcanizing agent, uniformly mixing the rubber sheets by a left cutter and a right cutter for 8-12 times respectively, adjusting the roller spacing to 0.1-0.2 mm, wrapping the rubber sheets in a triangular bag for 8-12 times, thinly passing the rubber sheets for 8-12 times, adjusting the roller spacing of the open mill to 1-5 mm, discharging the rubber sheets, and standing and cooling for more than 12 hours for later use; and vulcanizing the fluorine-containing elastomer obtained from the sheet under the pressure of 7-15 MPa and at the temperature of 160-180 ℃ for 5-20 min, and cooling to room temperature to obtain the perfluoroether sealing element.
In some preferable schemes, when the raw rubber is 100 parts, the weight part of the perfluoroether rubber micro powder is less than or equal to 60 parts, so that the processability in the preparation process can be ensured while the performance of the prepared perfluoroether sealing element is ensured. The reason for this is probably that the particle size of the required perfluoroether rubber micro powder needs to be strictly controlled in order to prepare the perfluoroether sealing member with excellent performance, but the perfluoroether rubber micro powder with a fine particle size is easy to leak during processing, which increases the difficulty and uncontrollable property of rubber mixing. The applicant creatively discovers that when the raw rubber is 100 parts, the weight part of the perfluoroether rubber micro powder prepared by the specific process is less than or equal to 60 parts, so that the performance of the prepared perfluoroether sealing element can be ensured, the processability in the preparation process can be ensured, and the cost is reduced.
Has the advantages that:
1. according to the invention, the recovered perfluoroether rubber is cut into specified particles, and the particles are crushed for 20-40min by a liquid nitrogen freezing crusher to obtain the perfluoroether rubber micropowder which is applied to the preparation of the perfluoroether sealing element, so that the hardness and tensile strength of the finally prepared crosslinked fluorine-containing elastomer can be improved.
2. According to the invention, different cross-linking agents and vulcanizing agents are selected for mixing and banburying the perfluoro ether rubber micro powder of different systems, so that the compatibility of the system can be increased, and different cross-linking systems are formed in specific crude rubber, thereby preparing the perfluoro ether sealing element with excellent performance.
3. According to the invention, by controlling the weight parts of the crude rubber and the perfluoroether rubber micro powder, the performance of the prepared perfluoroether sealing element can be ensured, and the processability in the preparation process can also be ensured.
4. The invention carries out multistage freezing and crushing on the semiconductor-grade sealing element through a specific crushing process to obtain the perfluoroether rubber micro powder, and the perfluoroether rubber micro powder enters a new formula system through a mixing process again, and the semiconductor-grade perfluoroether sealing element is obtained again through a forming and vulcanizing process.
Detailed Description
Examples
Example 1
Embodiment 1 provides a pulverization process for recovering perfluoroether rubber, comprising the steps of:
cutting the recovered perfluoroether rubber into particles, and putting the particles of the perfluoroether rubber into a liquid nitrogen freezing pulverizer to pulverize for 30min to obtain the perfluoroether rubber micro powder.
The length of the granular perfluoroether rubber is 0.5cm.
The temperature of the liquid nitrogen freezing pulverizer is-196 ℃.
The perfluoroether rubber was purchased from PFR 5910M of solvay.
Example 1 in a second aspect provides a fine powder of perfluoro ether rubber prepared by the above pulverization process for recovering perfluoro ether rubber.
The third aspect of the embodiment 1 provides a perfluoro ether seal member prepared from the perfluoro ether rubber micropowder, wherein the perfluoro ether seal member is prepared from the following raw materials in parts by weight: 20 parts of perfluoroether rubber micro powder, 100 parts of crude rubber, 0.7 part of vulcanizing agent and 0.7 part of cross-linking agent.
The Mooney viscosity ML120 ℃ of 1+10 of the crude rubber is 80.
The crude rubber was purchased from 3M PFE 81T, manufactured by 3M company.
The vulcanizing agent is 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane.
The crosslinking agent is triallyl isocyanurate.
The preparation process of the perfluoroether sealing element comprises the following steps: raising the temperature of an internal mixer to 120 ℃, putting raw rubber into an internal mixing chamber for internal mixing for 100s, adding the perfluoroether rubber micro powder and the cross-linking agent, equally dividing into two parts, respectively and slowly adding the two parts into the internal mixing chamber, stirring uniformly, continuing the internal mixing for 100s, discharging the rubber at the temperature of 100 ℃, rolling out pieces on an open mill, standing and cooling for 8h; putting the parked and cooled rubber sheets into an open mill, wrapping rollers for 3 circles at normal temperature, slowly adding a vulcanizing agent, respectively wrapping left and right cutters for 10 times to uniformly mix the rubber sheets, adjusting the roller spacing to 0.1mm, wrapping a triangular bag for 10 times, thinly passing for 10 times, adjusting the roller spacing of the open mill to 3mm, discharging the rubber sheets, and parking and cooling for 15 hours for later use; and vulcanizing the obtained fluorine-containing elastomer under the pressure of 10MPa and at the temperature of 170 ℃ for 15min, and cooling to 25 ℃ to obtain the perfluoroether sealing element.
Example 2
Embodiment 2 provides a pulverization process for recovering perfluoroether rubber, and the specific implementation manner is the same as that in embodiment 1, except that:
in the preparation raw material of the perfluoroether sealing element, 40 parts of perfluoroether rubber micro powder.
Example 3
Embodiment 3 provides a pulverization process for recovering perfluoroether rubber, and the specific implementation manner is the same as that in embodiment 1, except that:
50 parts of perfluoroether rubber micro powder in the raw materials for preparing the perfluoroether sealing element.
Example 4
Embodiment 4 provides a pulverization process for recovering perfluoroether rubber, and the specific implementation manner is the same as that in embodiment 1, except that:
60 parts of perfluoroether rubber micro powder in the raw materials for preparing the perfluoroether sealing element.
Example 5
Embodiment 5 provides a pulverization process for recovering perfluoroether rubber, and the specific implementation manner is the same as that in embodiment 1, except that:
in the preparation raw materials of the perfluoroether sealing element, 0 part of perfluoroether rubber micropowder is used.
Comparative example 1
Comparative example 1 provides a pulverization process for recovering perfluoroether rubber, and the specific embodiment is the same as example 1, except that:
in the preparation raw material of the perfluoroether sealing element, 70 parts of perfluoroether rubber micro powder.
Comparative example 2
Comparative example 2 provides a pulverization process for recovering perfluoroether rubber, and the specific embodiment is the same as example 3, except that:
replacing the perfluoroether rubber micro powder with common polymer micro powder.
The common polymer micro powder is polyether ether ketone (PEEK) and is purchased from a medium-sized polymer 330UPF, and the particle size is 330 microns.
Performance test method
1. Hardness of
For the perfluoroether seals prepared in examples 1-5 and comparative examples 1-2, the first part of the GB/T531.1-2008 vulcanizate or thermoplastic rubber press-in hardness test method was used: the Shore A hardness was measured by the Shore Durometer method and the results are shown in Table 1.
2. 100% modulus
The 100% modulus of the perfluoroether seals prepared in examples 1-5 and comparative examples 1-2 was measured using ASTM D1414-94 and the results are shown in Table 1.
3. Glass transition temperature
The perfluoroether seals prepared in examples 1-5 and comparative examples 1-2 were measured for glass transition temperature by Differential Scanning Calorimetry (DSC) measurement of GB/T29611-2013 raw rubber glass transition temperature, and the results are shown in Table 1.
4. Elongation at break
The perfluoroether sealants prepared in examples 1 to 5 and comparative examples 1 to 2 were measured for elongation at break using ASTM D1414-94, and the results are shown in Table 1.
5. Compression set
The perfluoroether seals prepared in examples 1-5 and comparative examples 1-2 were tested at 204 ℃ for 22 hours using test method D395 in ASTM D1414-94, and the results are shown in Table 1.
6. Workability
For the perfluoroether seals prepared in examples 1 to 5 and comparative examples 1 to 2, it was observed whether powder leakage and uneven stirring occurred during the process of preparing the perfluoroether seals, and if not, the processability was acceptable, and the results are shown in table 1.
The cost is reduced along with the addition of the perfluoroether rubber micropowder.
TABLE 1
Claims (10)
1. A crushing process for recovering perfluoroether rubber is characterized by comprising the following process steps: cutting the recovered perfluoroether rubber into particles, and putting the particles of the perfluoroether rubber into a liquid nitrogen freezing pulverizer to pulverize for 20-40min to obtain the perfluoroether rubber micro powder.
2. The pulverizing process for recovering perfluoroether rubber according to claim 1, wherein said granular perfluoroether rubber has a length of 0.3 to 1.0cm.
3. The pulverization process for recovering perfluoroether rubber according to claim 2, wherein the temperature of said liquid nitrogen freezing pulverizer is from-196 to-150 ℃.
4. A fine powder of perfluoro ether rubber produced by the pulverization process for recovering perfluoro ether rubber according to any one of claims 1 to 3.
5. The perfluoroether sealing element prepared from the perfluoroether rubber micropowder according to claim 4 is characterized by comprising the following raw materials in parts by weight: 0-60 parts of perfluoroether rubber micro powder (not including 0), 100 parts of raw rubber, 0.2-1.5 parts of vulcanizing agent and 0.2-1.5 parts of cross-linking agent.
6. The perfluoroether seal according to claim 5, wherein said crude rubber has a Mooney viscosity ML120 ℃ 1+10 at 100 ℃ of 20-130.
7. The perfluoroether seal according to claim 6, wherein said vulcanizing agent comprises one or more of a peroxide, an amine compound.
8. The perfluoroether seal according to claim 7, wherein said cross-linking agent comprises one or more of an olefin, a halide, a nitrile.
9. The perfluoroether seal according to claim 7, wherein said peroxide comprises one or more of dialkyl peroxides, diacyl peroxides, ketal peroxides, peroxyesters.
10. A process for preparing a perfluoroether seal according to any one of claims 5 to 9, comprising the steps of:
the raw materials are put into an internal mixing chamber according to the weight part for internal mixing, then put into an open mill for roll wrapping and vulcanization to obtain the product.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1333116A (en) * | 2000-07-12 | 2002-01-30 | 珠海经济特区精业机电技术研究所 | Technology for producing fine rubber powder by method of liquefied nitrogen internal circulation type recovering cold energy |
| CN105218985A (en) * | 2015-10-28 | 2016-01-06 | 湖北派克密封件有限公司 | Viton of a kind of high temperature high voltage resistant hydrofluoric acid resistant and preparation method thereof |
| CN106584705A (en) * | 2016-11-17 | 2017-04-26 | 冯艳丽 | Fluorinated silicone rubber reclamation method |
| CN107213970A (en) * | 2017-07-27 | 2017-09-29 | 洛阳和梦科技有限公司 | Ultra-fine rubber powder producing method |
-
2022
- 2022-10-14 CN CN202211261202.2A patent/CN115847665A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1333116A (en) * | 2000-07-12 | 2002-01-30 | 珠海经济特区精业机电技术研究所 | Technology for producing fine rubber powder by method of liquefied nitrogen internal circulation type recovering cold energy |
| CN105218985A (en) * | 2015-10-28 | 2016-01-06 | 湖北派克密封件有限公司 | Viton of a kind of high temperature high voltage resistant hydrofluoric acid resistant and preparation method thereof |
| CN106584705A (en) * | 2016-11-17 | 2017-04-26 | 冯艳丽 | Fluorinated silicone rubber reclamation method |
| CN107213970A (en) * | 2017-07-27 | 2017-09-29 | 洛阳和梦科技有限公司 | Ultra-fine rubber powder producing method |
Non-Patent Citations (1)
| Title |
|---|
| 刘毓燕，谢忠麟: "《橡胶制品维修技术》", 解放军出版社, pages: 25 - 26 * |
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