CN117050446B - High-performance tetrapropylacetonate fluororubber composition and preparation method thereof - Google Patents
High-performance tetrapropylacetonate fluororubber composition and preparation method thereof Download PDFInfo
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- CN117050446B CN117050446B CN202311209843.8A CN202311209843A CN117050446B CN 117050446 B CN117050446 B CN 117050446B CN 202311209843 A CN202311209843 A CN 202311209843A CN 117050446 B CN117050446 B CN 117050446B
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- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 229920001973 fluoroelastomer Polymers 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 229920001971 elastomer Polymers 0.000 claims abstract description 127
- 239000005060 rubber Substances 0.000 claims abstract description 126
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 55
- -1 tetrapropylacetone Chemical compound 0.000 claims abstract description 52
- 238000002834 transmittance Methods 0.000 claims abstract description 47
- 239000006229 carbon black Substances 0.000 claims abstract description 46
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 42
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims abstract description 33
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 22
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000004073 vulcanization Methods 0.000 claims description 57
- 150000001875 compounds Chemical class 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 17
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 0.000 claims description 12
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 11
- 239000004065 semiconductor Substances 0.000 claims description 10
- 229920006172 Tetrafluoroethylene propylene Polymers 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 241000872198 Serjania polyphylla Species 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 abstract description 13
- 230000007797 corrosion Effects 0.000 abstract description 9
- 238000005260 corrosion Methods 0.000 abstract description 9
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 125000002081 peroxide group Chemical group 0.000 abstract 1
- 235000019241 carbon black Nutrition 0.000 description 40
- 239000000395 magnesium oxide Substances 0.000 description 31
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 31
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 30
- 238000005096 rolling process Methods 0.000 description 27
- 238000012360 testing method Methods 0.000 description 25
- 239000004636 vulcanized rubber Substances 0.000 description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 16
- 238000007906 compression Methods 0.000 description 16
- 230000006835 compression Effects 0.000 description 16
- 230000009965 odorless effect Effects 0.000 description 16
- 235000019506 cigar Nutrition 0.000 description 15
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- 239000002253 acid Substances 0.000 description 14
- 238000007599 discharging Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 14
- 230000000704 physical effect Effects 0.000 description 14
- 238000010074 rubber mixing Methods 0.000 description 14
- 238000007792 addition Methods 0.000 description 13
- 239000012071 phase Substances 0.000 description 13
- 229910052717 sulfur Inorganic materials 0.000 description 13
- 239000011593 sulfur Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- JPEJJWOTBXVQJJ-UHFFFAOYSA-N 4,5-dipropyloct-4-ene Chemical group CCCC(CCC)=C(CCC)CCC JPEJJWOTBXVQJJ-UHFFFAOYSA-N 0.000 description 9
- 239000004642 Polyimide Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229920001721 polyimide Polymers 0.000 description 9
- 238000004132 cross linking Methods 0.000 description 7
- 229910021485 fumed silica Inorganic materials 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
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- 238000007789 sealing Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
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- 150000001412 amines Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
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- 230000006872 improvement Effects 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
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- 230000008569 process Effects 0.000 description 2
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- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000009428 plumbing Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of fluororubber products, in particular to a high-performance tetrapropylacetone fluororubber composition and a preparation method thereof. The tetrapropylacetonate fluororubber composition comprises the following raw materials in parts by weight: 100 parts of tetrapropylacetonate rubber without vinylidene fluoride units; 4-7 parts of triallyl isocyanurate; 1.1-3 parts of vulcanizing agent; 5-25 parts of white carbon black; 0-3 parts of nano MgO; 0-5 parts of polytetrafluoroethylene micropowder; the vulcanizing agent is selected from peroxide, and the temperature of the peroxide with 1-minute half-life period is 165-185 ℃; the solar light transmittance of the tetrapropylacetone rubber composition is more than or equal to 25%, the visible light transmittance is more than or equal to 2.5%, and the color degree L of the tetrapropylacetone rubber composition is more than 60 and delta L is more than 30. The invention ensures that the prepared tetrapropylacetone rubber composition has the comprehensive properties of high light transmittance, high purity, corrosion resistance, high temperature resistance, prolonged service life and the like.
Description
Technical Field
The invention relates to the technical field of fluororubber products, in particular to a high-performance tetrapropylacetone fluororubber composition and a preparation method thereof.
Background
In the field of semiconductors, high requirements on purity, corrosion resistance, high temperature resistance and the like of polymer materials such as plastics, rubber and other parts for semiconductor equipment are met, the aim is to reduce corrosion of corrosive gas/liquid or plasma on the parts as much as possible, prolong the service life of the parts, reduce the generation of particles as much as possible and reduce pollution to the semiconductor equipment as much as possible. In general, plastic parts in contact with semiconductor medical fluids or high purity water often select highly pure corrosion resistant perfluororesin materials for tank liners, piping, plumbing, valves, and the like. The sealing member used in the semiconductor device is also made of high-end perfluororubber, high-performance fluororubber or the like.
The material components of the sealing part are as few as possible under the condition of meeting the sealing performance requirement, because the mechanical properties of the product are improved after certain components are added, and the corrosion resistance, the heat resistance, the plasma resistance, the generation of particles and the like can be reduced.
The tetrafluoroethylene-propylene copolymer (FEPM) is an alternating copolymer of tetrafluoroethylene and propylene, and is characterized by excellent chemical resistance, particularly good resistance to organic acids/bases and inorganic acids/bases, such as organic amines, and good resistance to water vapor and heat. FEMP the copolymer structure is preferably that of a cross-linking point monomer containing bromine or iodine atoms, other monomer units may or may not include ethylene monomer units.
The raw rubber of the tetrapropylacetone rubber has lower hardness, only about 45 Shore A hardness and poorer tensile strength, so that the tetrapropylacetone rubber has practical value only when the properties of hardness, stretching, permanent compression set and the like reach proper values by adding a large amount of other materials or reinforcing materials.
Some traditional ethylene propylene diene monomer, fluorine silica gel particles, ternary fluorine rubber or other rubbers are added into the tetrapropylacetone rubber, and some fillers and auxiliary agents are also added, so that although the final mechanical property is improved and the permanent compression set is reduced to an acceptable range, the excellent properties of high temperature resistance, chemical resistance, organic amine resistance, high purity and the like of the tetrapropylacetone rubber are correspondingly sacrificed, and the advantage performance of the tetrapropylacetone rubber cannot be exerted.
There are also cases where a large amount of Polytetrafluoroethylene (PTFE) micropowder or other fluororesin micropowder or engineering plastics such as Polyimide (PI) micropowder is added to the tetrapropylacetone rubber to improve the physical properties of the tetrapropylacetone rubber, but when the PTFE micropowder or other fluororesin micropowder is added, the overall hardness and modulus of the tetrapropylacetone rubber are slowly improved, the elasticity of the vulcanized rubber is poor, the permanent compression set at high temperature is greatly increased, and the effect of the final product applied to the sealing field is not ideal. Since the magnitude of compression set is an important indicator for the sealing performance and service life of the formulation, the smaller this number, the better.
There are also patent documents reporting that a large amount of PI fine powder is added to tetrapropylfluororubber, but the compatibility of the tetrapropylfluororubber with PI powder is not good, and the microscopic compatibility cannot be achieved, and considering that the temperature of the tetrapropylfluororubber is about 200 ℃ at the time of secondary vulcanization, the short term of temperature resistance is not higher than 230 ℃, that means that PI fine powder in the structure cannot be melted to form a continuous phase by heating to a high temperature when PI fine powder is added to the tetrapropylfluororubber for mixing, and thus a structure of mutual wrapping is formed between the PI fine powder and the tetrapropylfluororubber, so that the strength of the final vulcanized rubber is mainly provided by a crosslinked network structure formed by vulcanization of the tetrapropylfluororubber. When the addition amount of the PI and other resins reaches more than 5 parts, the rebound resilience of the tetrapropylacetone rubber is greatly reduced, and the tetrapropylacetone rubber is difficult to recover to the original shape even after being stressed instantly, so that when a large amount of PI micro powder is added, the overall performance of the tetrapropylacetone rubber, including compression set, elastic recovery performance and the like, is greatly reduced, and the tetrapropylacetone rubber has compact defects when being used as an elastomer sealing material.
The common fluororubber FKM generally contains vinylidene fluoride, hydrofluoric acid gas is generated in the crosslinking reaction process, and metal is corroded and polluted, so that a proper amount of acid absorbent is added into a vulcanization system to smoothly carry out the vulcanization process, good rheological property and physical property are realized, and the processing requirement is met. Metal oxides such as magnesium oxide (MgO), calcium oxide, calcium hydroxide, and zinc oxide are important acid absorbers in fluororubbers. The inorganic base affects both the rheological and physical properties of the fluororubber compounds, and a combination of MgO and calcium hydroxide generally achieves a good balance of properties. In the formula system of the fluororubber, when the magnesium oxide is used as an acid absorbent, the addition part of the low-activity magnesium oxide is generally 10-15 parts, and the addition part of the high-activity magnesium oxide is generally 3-6 parts.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide a high-performance tetrapropylafluoro rubber composition and a method for preparing the same, which are used for solving the problems of the prior art.
To achieve the above and other related objects, an aspect of the present invention provides a tetrapropylacetone rubber composition, which comprises the following raw materials in parts by weight:
the vulcanizing agent is selected from peroxide, and the temperature of the peroxide with 1-minute half-life period is 165-185 ℃;
The solar light transmittance of the tetrapropylacetone rubber composition is more than or equal to 25%, the visible light transmittance is more than or equal to 2.5%, and the color degree L of the tetrapropylacetone rubber composition is more than 60 and delta L is more than 30.
In some embodiments of the invention, the tetrapropylating fluororubber composition has a solar light transmittance of greater than or equal to 35% and a visible light transmittance of greater than or equal to 3.5%.
In some embodiments of the invention, 60 < L < 80, 30 < ΔL < 50.
In some embodiments of the invention, the tetrafluoroethylene-propylene rubber free of vinylidene fluoride units is selected from the group consisting of Aflas 100,150 series, aflas series model number 600 raw rubber. The peroxide has difunctional groups and has an active oxygen content of greater than 9%.
In some embodiments of the invention, the vulcanizing agent is 1.5 to 2.4 parts by weight.
In some embodiments of the invention, the sulfiding agent is selected from 1, 3-bis (t-butylperoxyisopropyl) benzene and/or 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane.
In some embodiments of the present invention, the white carbon black is selected from fumed white carbon black, which is selected from fumed white carbon black having an acidic surface or fluorocarbon-modified, silane-modified white carbon black.
In some embodiments of the invention, the nano-magnesia has a particle size of 1nm to 100nm.
In some embodiments of the invention, the nano magnesium oxide is 1-3 parts by weight.
In some embodiments of the present invention, the polytetrafluoroethylene micropowder has a particle size of 2 to 5 μm.
In some embodiments of the present invention, when the white carbon black is selected from the group consisting of fumed white carbon blacks having acidic surfaces, the vulcanizing agent is selected from the group consisting of 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane and 1, 3-bis (t-butylperoxy isopropyl) benzene, and the mass ratio of the 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane to the 1, 3-bis (t-butylperoxy isopropyl) benzene is (1:5) - (5:1).
In some embodiments of the present invention, the vulcanizing agent is selected from 1, 3-bis (t-butylperoxyisopropyl) benzene when adding a composition of white carbon black and nano MgO or adding white carbon black having a surface pH greater than 7.
According to a second aspect of the present invention, there is provided a method for producing a tetrafluoro rubber composition according to the first aspect of the present invention, comprising mixing a tetrafluoro rubber containing no vinylidene fluoride unit, polytetrafluoroethylene fine powder, white carbon black and nano MgO, adding a vulcanizing agent and triallyl isocyanurate, and mixing to obtain a mixed rubber, and subjecting the mixed rubber to primary vulcanization and secondary vulcanization to produce a tetrafluoro rubber composition.
In a third aspect the present invention provides the use of a tetrapropylacetone rubber composition according to the first aspect of the invention in the semiconductor field.
Compared with the prior art, the invention has the beneficial effects that:
According to the invention, the use amount of each component is reasonably adjusted by comprehensively selecting the tetrapropylacetone rubber without vinylidene fluoride units, triallyl isocyanurate, the vulcanizing agent, the white carbon black, the nano MgO and the polytetrafluoroethylene micro powder, and the prepared tetrapropylacetone rubber composition has the comprehensive properties of high light transmittance, high purity, corrosion resistance, high temperature resistance, prolonged service life and the like through further adjustment of light transmittance, yan Sedu and half life of peroxide through synergistic effect among the components. More specifically, the inventors of the present invention have unexpectedly found that a small amount of nano magnesium oxide or white carbon black is added to the tetrapropylase rubber containing no vinylidene fluoride polymerization unit, respectively, to have the effects of accelerating vulcanization, accelerating crosslinking and improving mechanical strength, and that the combination of the two has a better effect in accelerating vulcanization and improving the comprehensive properties of the tetrapropylase rubber.
Detailed Description
The semiconductor field has high requirements on the comprehensive performance of the tetrapropylfluororubber products, so that the tetrapropylfluororubber products applied to the semiconductor field have the characteristics of high temperature resistance, high purity, corrosion resistance, prolonged service life and the like. Through a large number of exploring experiments, the inventor does not need to add other types of rubber to achieve the characteristic of low compression deformation by optimizing a formula, and the high purity, heat resistance, corrosion resistance (alkali resistance, organic amine resistance, solvent resistance) and the like of the tetrapropylacetone rubber are basically not affected.
Specifically, the prepared tetrapropofluororubber composition has the comprehensive properties of purity, corrosion resistance, high temperature resistance, service life prolonging and the like by comprehensively selecting the tetrapropofluororubber without vinylidene fluoride units, triallyl isocyanurate, vulcanizing agent, white carbon black, nano MgO and polytetrafluoroethylene micro powder, reasonably adjusting the dosage of each component, and further adjusting the transmittance, yan Sedu and half-life of peroxide through the synergistic effect of each component. More specifically, the inventors of the present invention have unexpectedly found that a small amount of nano magnesium oxide or white carbon black is added to the tetrapropylase rubber containing no vinylidene fluoride polymerization unit, respectively, to have the effects of accelerating vulcanization, accelerating crosslinking and improving mechanical strength, and that the combination of the two has a better effect in accelerating vulcanization and improving the comprehensive properties of the tetrapropylase rubber. On this basis, the present invention has been completed.
The following detailed description specifically discloses embodiments of a high performance tetrapropylacetonate rubber composition and a method for preparing the same.
The "range" disclosed herein is defined in terms of lower and upper limits, with the given range being defined by the selection of a lower and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges that are defined in this way can be inclusive or exclusive of the endpoints, and any combination can be made, i.e., any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3,4 and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present application, unless otherwise indicated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed throughout, and "0-5" is simply a shorthand representation of a combination of these values. When a certain parameter is expressed as an integer of 2 or more, it is disclosed that the parameter is, for example, an integer of 2,3, 4, 5,6, 7, 8, 9, 10, 11, 12 or the like.
All embodiments of the application and alternative embodiments may be combined with each other to form new solutions, unless otherwise specified.
Tetrapropyl fluororubber composition
In one aspect, the invention provides a tetrapropylacetone rubber composition, which comprises the raw materials of the tetrapropylacetone rubber without vinylidene fluoride units, triallyl isocyanurate, a vulcanizing agent, white carbon black, nano MgO and polytetrafluoroethylene micro powder.
The tetrapropylacetonate rubber composition provided by the invention can comprise 100 parts by weight of tetrapropylacetonate rubber without vinylidene fluoride units. The tetrapropylacetonate rubber in the invention does not contain vinylidene fluoride (VDF or VF 2) units, and specific types of the tetrapropylacetonate rubber are raw rubber of the types such as Aflas/150 series, aflas X series and the like of AGC company.
The raw materials of the tetrapropylacetone rubber composition provided by the invention can comprise 4-7 parts by weight of triallyl isocyanurate (TAIC for short). Alternatively, the triallyl isocyanurate may be, for example, 4 to 6.8 parts by weight or 6.8 to 7 parts by weight. Preferably, the triallyl isocyanurate is present in an amount of 4 to 6.8 parts by weight.
The tetrapropylating fluororubber composition provided by the invention can comprise 1.1-3 parts of vulcanizing agent according to parts by weight. Alternatively, the vulcanizing agent may be 1.1 to 1.5 parts by weight, 1.5 to 2.4 parts by weight, 2.4 to 3 parts by weight, or the like, for example. Preferably, the vulcanizing agent is 1.5 to 2.4 parts by weight.
Further, the vulcanizing agent is selected from peroxides, the temperature of the peroxide with a half-life period of 1 minute is 165 ℃ to 185 ℃, and the variety with a difunctional structure and an active oxygen content of more than 9% is preferable, because the vulcanizing temperature of the process such as the mono-sulfur compression molding of the tetrapropylane rubber is generally set in the range of 160 ℃ to 180 ℃, and the vulcanizing time is preferably selected to be 6 to 10 times of the half-life period of the peroxide at the set vulcanizing temperature, and in the range of the processing temperature, if the half-life period of the peroxide is too long, the mono-sulfur vulcanizing time is too long, so that the production efficiency is very low, if the mono-sulfur time is too short, scorching is easy during production, the operation time margin is too small, the process is difficult to control stably, and the fluctuation of the product quality is large.
Further, the vulcanizing agent is selected from 1, 3-bis (tert-butylperoxyisopropyl) benzene (abbreviated as odorless DCP) and/or 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane (abbreviated as TX 101).
Further, in view of the fact that in the high transmittance formulation of tetrapropylating fluororubber, only odorless DCP vulcanizing agent is added, when MDR is used for testing the mixture, the T90 time at 168 ℃ is longer, some formulations are even more than 10 minutes, after acidic fumed silica is added, T90 is reduced, but still higher, the production efficiency is not beneficial to improvement, the yield of the product is also reduced, the invention is preferably the compounding of 1, 3-bis (tert-butylperoxyisopropyl) benzene and 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, wherein the mass ratio of 1, 3-bis (tert-butylperoxyisopropyl) benzene and 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane is (1:5) - (5:1), and the compounding of vulcanizing agent can effectively reduce the T90 time when the vulcanized rubber is vulcanized, meanwhile, the light transmittance of the product is not influenced, and the physical property of the vulcanized rubber is generally improved. Optionally, the mass ratio of 1, 3-bis (tert-butylperoxyisopropyl) benzene to 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane may be (1:3) - (5:1), (3:5) - (5:1), (1:5) - (5:3), or (1:5) - (3:1).
The tetrapropylacetonate fluororubber composition provided by the invention can comprise 5-25 parts of white carbon black by weight. Alternatively, the weight part of the white carbon black may be, for example, 5 to 10 parts, 10 to 15 parts, 15 to 20 parts, 20 to 25 parts, or the like.
Further, the white carbon black is selected from fumed silica, and the fumed silica is selected from fumed silica with acidic surface (surface pH value is less than 7) or fumed silica with alkaline surface after modification treatment.
The applicant needs to emphasize that: the vulcanizing agent and the white carbon black are not arranged conventionally, but a large number of experiments show that the light transmittance and other physical properties can be simultaneously met by the vulcanizing agent and the white carbon black in the range of the application. The reason is that too little vulcanizing agent is easy to cause insufficient crosslinking degree of vulcanized rubber, the yield of the product is low, the final physical properties, especially tensile strength or permanent compression set at high temperature are low, and too much vulcanizing agent is easy to cause unnecessary material waste, excessive micromolecular substances in the production process are released, the transmittance of the product is reduced, and the performances of certain physical properties, such as elongation at break and the like, are reduced. The addition amount of the white carbon black is too small, so that the hardness and physical properties such as tensile strength of the vulcanized rubber are still in a relatively low level, the requirements of a plurality of application scenes are not met, the addition amount of the white carbon black is too large, the hardness of the vulcanized rubber is too large, certain physical properties such as permanent compression deformation can be greatly increased, the white carbon black is easy to agglomerate, the transmittance of the vulcanized rubber is greatly reduced, and the like.
The tetrapropylacetonate fluororubber composition provided by the invention can comprise 0-3 parts of nano MgO according to parts by weight. Optionally, the weight portion of the nano MgO is 0 to 1 portion, 1 to 3 portions, 1 to 2 portions or 2 to 3 portions, etc. Preferably, the weight part of the nano MgO is 1-3 parts. The nano magnesium oxide is not an acid absorber in the invention.
Further, the particle size of the nano magnesium oxide is 1 nm-100 nm. Optionally, the particle size of the nano magnesium oxide can be1 nm-30 nm, 30 nm-50 nm, 50 nm-80 nm or 80 nm-100 nm, etc. Within the particle size range, the silica gel has the advantages of high specific surface area, more lattice defects, high reaction activity, high adsorptivity, easy dispersibility in a tetrapropylacetone rubber matrix, excellent compatibility with white carbon black particles of more than 100nm, and low reaction activity and difficult dispersion, and has the defects of fewer lattice defects. Less than 1nm, has the defects of difficult acquisition, high cost and poor product stability.
If only the gas-phase white carbon black with the acidic surface is added, the peroxide vulcanizing agent is preferably the compound combination of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane (TX 101 for short) and 1, 3-bis (tert-butylperoxyisopropyl) benzene (odorless DCP), the mass ratio of the two is (1:5) - (5:1), and the vulcanized rubber product with high light transmittance (the sunlight transmittance is more than or equal to 35 percent, the visible light transmittance is more than or equal to 5 percent) and better physical property is obtained in the range of the proportion. The light transmittance refers to the light transmittance measured by sunlight with the wavelength of 300-2500nm and visible light with the wavelength of 380-780nm (the standard of sunlight and visible light refers to ISO 9050-2003) and the vulcanized rubber of the tetrapropylarene with the components is used for preparing a sample wafer with the thickness of 4 mm.
If the composition of the gas-phase white carbon black with the surface being acidic and the nano MgO or the alkaline white carbon black with the surface pH value being more than 7 is added, the combination of 1, 3-bis (tert-butylperoxyisopropyl) benzene (abbreviated as odorless DCP) and triallyl isocyanurate (abbreviated as TAIC) is more preferable, at the moment, various physical properties of the vulcanized rubber are better, and the color of the vulcanized rubber is lighter or the transmittance of the vulcanized rubber is higher. The color degree is expressed by a Lab value measured by a color difference meter, and the light color is that the L value is more than 60 and the DeltaL value is more than 30 (L=28.92, a=0.36 and b=1.34 relative to the standard sample, namely the anti-reflection coated glass). The higher transmittance means that the sunlight transmittance is more than or equal to 25 percent and the visible light transmittance is more than or equal to 2.5 percent.
The tetrapropylating fluororubber composition provided by the invention can comprise 0-5 parts of polytetrafluoroethylene micro powder according to parts by weight. Alternatively, the polytetrafluoroethylene fine powder may be, for example, 0 to 3 parts, 3 to 5 parts, 0 to 1 part, 1 to 2 parts, 2 to 3 parts, or the like by weight. The addition of PTFE micropowder can improve the wear resistance and the adhesive property of the tetrapropylacetone vulcanized rubber, and slightly improve the hardness, the tensile property, the 100% stretching modulus and the like, but the addition amount is not more than 5 parts, preferably about 3 parts, and the addition amount of more than 5 parts has very obvious adverse effects on the compression deformation and the rebound resilience performance of the final product.
The grain size of the polytetrafluoroethylene micropowder is 2-5 mu m. Alternatively, the particle diameter of the polytetrafluoroethylene fine powder may be, for example, 2 to 3 μm or 3 to 5 μm. In the particle size range, the particle size has the advantages of easy dispersion, effective increase of lubricity and wear resistance, moderate improvement of transmittance of vulcanized rubber, larger particles than 5 mu m, difficult uniform dispersion, adverse effect on transmittance of vulcanized rubber, high price below 2 mu m, difficult acquisition and certain environmental protection risk.
In a specific embodiment of the invention, the raw materials of the tetrapropylacetone rubber composition comprise the following components in parts by weight:
Good light transmittance means that the transmittance of sunlight is more than 35% or the transmittance of visible light is more than 5%; the light transmittance is preferably such that the transmittance of sunlight is more than 25% and the transmittance of visible light is more than 2.5%, yan Sedu means that the L value of Lab values measured by a color difference meter is more than 60 or the DeltaL value relative to a standard sample is more than 30, and the values are light. (sunlight and visible light standards refer to ISO 9050-2003, standard sample is anti-reflective coated glass, l=28.92, a=0.36, b= -1.34)
Optionally, the solar light transmittance of the tetrapropylating fluororubber composition is more than or equal to 35% and less than or equal to 50%. The visible light transmittance is more than or equal to 3.5 percent and less than or equal to 15 percent;
the vulcanizing agent is selected from peroxides having a1 minute half-life temperature of 165 ℃ to 185 ℃.
Preparation method of tetrapropylfluororubber composition
According to a second aspect of the present invention, there is provided a method for producing a tetrafluoro rubber composition according to the first aspect of the present invention, comprising mixing a tetrafluoro rubber containing no vinylidene fluoride unit, polytetrafluoroethylene fine powder, white carbon black and nano MgO, adding a vulcanizing agent and triallyl isocyanurate, and mixing to obtain a mixed rubber, and subjecting the mixed rubber to primary vulcanization and secondary vulcanization to produce a tetrafluoro rubber composition.
Specifically, the preparation method of the tetrapropylacetonate rubber composition comprises the following steps:
1) Mixing 100 parts of tetrapropofluor rubber without vinylidene fluoride units with a certain part of polytetrafluoroethylene micropowder, white carbon black and nano MgO in an internal mixer at a medium temperature;
2) Opening an open mill, adjusting proper intervals between rollers according to different rubber mixing amounts, and sequentially adding a vulcanizing agent and triallyl isocyanurate;
3) Finally, regulating the roll gap of the open mill to the minimum value, rolling cigar rolls and triangular bags, increasing the roll gap, and discharging sheets for later use;
4) And (3) after the rubber compound is stored, performing primary vulcanization, namely, performing compression molding to form an O ring of AS568-214, opening a vulcanizing machine, vulcanizing the rubber compound at a certain pressure and temperature, and reasonably setting specific vulcanization temperature and time according to data obtained by an MDR vulcanization curve.
5) Finally, the sulfur tetrapropylfluoride O-ring is placed in an oven for further vulcanization, and then is taken out for physical and mechanical property testing.
In the step 1) of the present invention, the amounts of the tetrafluoro rubber, polytetrafluoroethylene micropowder, white carbon black, nano MgO, vulcanizing agent and triallyl isocyanurate which do not contain vinylidene fluoride units are the same as those used in the formulation of the tetrafluoro rubber composition according to the first aspect of the present invention.
In step 1) of the present invention, the medium temperature is about 80 to 100 DEG C
In the step 2) of the present invention, the mixing time is preferably controlled to 15 to 25 minutes.
In the step 3), the roll gap of the open mill is regulated to the minimum value, and the minimum value is 0.1-0.3 mm.
In step 3) of the invention, the cigar rolls are wrapped, for example, 15 to 25 times, with triangular wrapping, for example, under 15 to 25 times.
In step 4) of the present invention, the storage time may be, for example, 18 to 30 hours.
In step 4) of the invention, the rubber compound is vulcanized for 5 to 10 minutes at 160 to 180 ℃ under the pressure of 4 to 8 MPa.
In step 5) of the present invention, the disulfide vulcanization time is 4 to 8 hours.
Application of
In a third aspect the present invention provides the use of a tetrapropylacetone rubber composition according to the first aspect of the invention in the semiconductor field.
The advantageous effects of the present invention are further illustrated below with reference to examples.
In order to make the objects, technical solutions and advantageous technical effects of the present invention more clear, the present invention is described in further detail below with reference to examples. It should be understood that the examples of the present invention are for the purpose of illustration only and are not intended to be limiting, and that the examples of the present invention are not limited to the examples given in the specification. The specific experimental or operating conditions were not noted in the examples and were made under conventional conditions or under conditions recommended by the material suppliers.
Furthermore, it is to be understood that the reference to one or more method steps in this disclosure does not exclude the presence of other method steps before or after the combination step or the insertion of other method steps between these explicitly mentioned steps, unless otherwise indicated; it should also be understood that the combined connection between one or more devices/means mentioned in the present invention does not exclude that other devices/means may also be present before and after the combined device/means or that other devices/means may also be interposed between these two explicitly mentioned devices/means, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the method steps is merely a convenient tool for identifying the method steps and is not intended to limit the order of arrangement of the method steps or to limit the scope of the invention in which the invention may be practiced, as such changes or modifications in their relative relationships may be regarded as within the scope of the invention without substantial modification to the technical matter.
In the examples described below, reagents, materials and apparatus used are commercially available unless otherwise specified.
MDR data in the examples are expressed in terms of M H-ML, T90 and cross-linking index CRI in the MDR test of a 2000 Rubber Processing Analyzer (RPA), cri=100/(T 90-TS1). Wherein the MDR test is carried out at 170 ℃ for 30min.
The test methods or criteria involved are as follows.
1. ASTM D2240-05 rubber hardness test method;
Sample size: o-ring samples of AS 568-214.
2. ASTM D412-06 vulcanized rubber and thermoplastic elastomer tensile test method tensile strength and tensile modulus, samples were measured AS O-ring samples of size AS 568-214.
3. ASTM D395-03 rubber Standard test Method-permanent compression set, permanent compression set at constant Strain of Method B, 25% Strain, 70 hours @204 ℃, sample was an O-ring sample of AS 568-214. It should be noted that the compression set values measured using the cylindrical test specimens are often much smaller than the values measured for the O-rings of AS568-214, i.e., the values for the compression set for the O-ring test are greater, so that all formulations require data obtained under the same test conditions and under the same size of sample conditions for comparison.
4. Transmittance test:
ISO 9050-2003, determination of building glass-light transmittance, solar direct transmittance, total solar transmittance and ultraviolet transmittance and related gloss coefficients. The sample is a sample wafer with the thickness of 4mm prepared by using vulcanized rubber of tetrapropylacetone rubber with different components, and the light permeability is measured by using sunlight with the wavelength of 300-2500nm and visible light with the wavelength of 380-780nm (standard reference ISO 9050-2003).
GB/T30983-2014, and a method for testing optical performance of glass for photovoltaic.
5. Chromaticity test:
GB/T11942-2022, color building material chromaticity measurement method. The vulcanized rubber sample of the tetrapropylane fluororubber with the thickness of 4mm is subjected to chromaticity test by a colorimeter, the result is expressed by Lab value, and the standard sample is anti-reflection coated glass, wherein L=28.92, a=0.36 and b= -1.34.
Example 1
A method for preparing a tetrapropylethylene composition comprising the steps of:
1) Mixing 100 parts of tetrapropylfluororubber raw rubber without vinylidene fluoride units with 15 parts of acid gas phase white carbon black R972 at a medium temperature (about 100 ℃) in an internal mixer, wherein the mixing time is preferably controlled within 20 minutes;
2) Opening an open mill, and adjusting proper intervals between rollers according to different rubber mixing amounts, and sequentially adding 1.5 parts of vulcanizing agent TX101 and 4.8 parts of triallyl isocyanurate;
3) Regulating the roll gap of an open mill to the minimum value, rolling a cigar roll 20, rolling a triangular bag 20 times, then increasing the roll gap, and discharging sheets for standby;
4) The rubber compound is stored for 24 hours and then vulcanized for the first time, namely, the rubber compound is molded into the O-ring of AS 568-214. Starting a vulcanizing machine, vulcanizing the mixed rubber for 30min at 160-180 ℃ under the pressure of 5MPa, and reasonably setting specific vulcanization temperature and time according to data obtained by an MDR vulcanization curve;
5) Finally, the sulfur tetrapropylfluoride O-ring is placed in a baking oven at 200 ℃ for further vulcanization for 4-8 hours, and then is taken out for physical and mechanical property testing.
Example 2
A method for preparing a tetrapropylethylene composition comprising the steps of:
1) Mixing 100 parts of tetrapropylfluororubber raw rubber without vinylidene fluoride units with 15 parts of acid gas-phase white carbon black R972 in an internal mixer at a medium temperature (about 100 ℃), wherein the mixing time is preferably controlled within 20 minutes;
2) Opening an open mill, adjusting proper intervals between rollers according to different rubber mixing amounts, and sequentially adding 1.5 parts of a vulcanizing agent odorless DCP and 4.8 parts of triallyl isocyanurate;
3) Regulating the roll gap of an open mill to the minimum value, rolling a cigar roll 20, rolling a triangular bag 20 times, then increasing the roll gap, and discharging sheets for standby;
4) The rubber compound is stored for 24 hours and then vulcanized for the first time, namely, the rubber compound is molded into the O-ring of AS 568-214. Starting a vulcanizing machine, vulcanizing the mixed rubber for 30min at 160-180 ℃ under the pressure of 5MPa, and reasonably setting specific vulcanization temperature and time according to data obtained by an MDR vulcanization curve;
5) Finally, the sulfur tetrapropylfluoride O-ring is placed in a baking oven at 200 ℃ for further vulcanization for 4-8 hours, and then is taken out for physical and mechanical property testing.
Example 3
A method for preparing a tetrapropylethylene composition comprising the steps of:
1) Mixing 100 parts of tetrapropylfluororubber raw rubber without vinylidene fluoride units with 15 parts of acid gas-phase white carbon black R972 in an internal mixer at a medium temperature (about 100 ℃), wherein the mixing time is preferably controlled within 20 minutes;
2) Opening an open mill, adjusting proper intervals between rollers according to different rubber mixing amounts, sequentially adding 0.5 part of a vulcanizing agent odorless DCP and 2.4 parts of triallyl isocyanurate, and then adding 1.0 part of TX101 and 2.4 parts of triallyl isocyanurate;
3) Regulating the roll gap of an open mill to the minimum value, rolling a cigar roll 20, rolling a triangular bag 20 times, then increasing the roll gap, and discharging sheets for standby;
4) The rubber compound is stored for 24 hours and then vulcanized for the first time, namely, the rubber compound is molded into the O-ring of AS 568-214. Starting a vulcanizing machine, vulcanizing the mixed rubber for 30min at 160-180 ℃ under the pressure of 5MPa, and reasonably setting specific vulcanization temperature and time according to data obtained by an MDR vulcanization curve;
5) Finally, the sulfur tetrapropylfluoride O-ring is placed in a baking oven at 200 ℃ for further vulcanization for 4-8 hours, and then is taken out for physical and mechanical property testing.
Example 4
A method for preparing a tetrapropylethylene composition comprising the steps of:
1) Mixing 100 parts of tetrapropylfluororubber raw rubber without vinylidene fluoride units with 15 parts of acid gas-phase white carbon black R972 and 1 part of nano MgO (particle size is 60 nm) in an internal mixer at a medium temperature (about 100 ℃), wherein the mixing time is preferably controlled within 20 minutes;
2) Opening an open mill, adjusting proper intervals between rollers according to different rubber mixing amounts, and sequentially adding 1.5 parts of a vulcanizing agent odorless DCP and 4.8 parts of triallyl isocyanurate;
3) Regulating the roll gap of an open mill to the minimum value, rolling a cigar roll 20, rolling a triangular bag 20 times, then increasing the roll gap, and discharging sheets for standby;
4) The rubber compound is stored for 24 hours and then vulcanized for the first time, namely, the rubber compound is molded into the O-ring of AS 568-214. Starting a vulcanizing machine, vulcanizing the mixed rubber for 30min at 160-180 ℃ under the pressure of 5MPa, and reasonably setting specific vulcanization temperature and time according to data obtained by an MDR vulcanization curve;
5) Finally, the sulfur tetrapropylfluoride O-ring is placed in a baking oven at 200 ℃ for further vulcanization for 4-8 hours, and then is taken out for physical and mechanical property testing.
Example 5
A method for preparing a tetrapropylethylene composition comprising the steps of:
1) Mixing 100 parts of tetrapropylfluororubber raw rubber without vinylidene fluoride units with 15 parts of acid gas-phase white carbon black R805 in an internal mixer at a medium temperature (about 100 ℃) for a mixing time of preferably within 20 minutes;
2) Opening an open mill, and adjusting proper intervals between rollers according to different rubber mixing amounts, and sequentially adding 0.3 part/2.4 parts of odorless DCP/TAIC and 1.2 parts/2.4 parts of TX101/TAIC;
3) Regulating the roll gap of an open mill to the minimum value, rolling a cigar roll 20, rolling a triangular bag 20 times, then increasing the roll gap, and discharging sheets for standby;
4) The rubber compound is stored for 24 hours and then vulcanized for the first time, namely, the rubber compound is molded into the O-ring of AS 568-214. Starting a vulcanizing machine, vulcanizing the mixed rubber for 30min at 160-180 ℃ under the pressure of 5MPa, and reasonably setting specific vulcanization temperature and time according to data obtained by an MDR vulcanization curve;
5) Finally, the sulfur tetrapropylfluoride O-ring is placed in a baking oven at 200 ℃ for further vulcanization for 4-8 hours, and then is taken out for physical and mechanical property testing.
Example 6
A method for preparing a tetrapropylethylene composition comprising the steps of:
1) Mixing 100 parts of tetrapropylfluororubber raw rubber without vinylidene fluoride units with 5 parts of acid fumed silica R972 in an internal mixer at a medium temperature (about 100 ℃), wherein the mixing time is preferably controlled within 20 minutes;
2) Opening an open mill, and adjusting proper intervals between rollers according to different rubber mixing amounts, and sequentially adding 0.5 part/2.4 parts of odorless DCP/TAIC and 1.0 part/2.4 parts of TX101/TAIC;
3) Regulating the roll gap of an open mill to the minimum value, rolling a cigar roll 20, rolling a triangular bag 20 times, then increasing the roll gap, and discharging sheets for standby;
4) The rubber compound is stored for 24 hours and then vulcanized for the first time, namely, the rubber compound is molded into the O-ring of AS 568-214. Starting a vulcanizing machine, vulcanizing the mixed rubber for 30min at 160-180 ℃ under the pressure of 5MPa, and reasonably setting specific vulcanization temperature and time according to data obtained by an MDR vulcanization curve;
5) Finally, the sulfur tetrapropylfluoride O-ring is placed in a baking oven at 200 ℃ for further vulcanization for 4-8 hours, and then is taken out for physical and mechanical property testing.
Example 7
A method for preparing a tetrapropylethylene composition comprising the steps of:
1) Mixing 100 parts of tetrapropylfluororubber raw rubber without vinylidene fluoride units with 15 parts of alkali gas-phase white carbon black R504 at a medium temperature (about 100 ℃) in an internal mixer, wherein the mixing time is preferably controlled within 20 minutes;
2) Opening an open mill, adjusting proper intervals between rollers according to different rubber mixing amounts, and sequentially adding 1.5 parts of a vulcanizing agent odorless DCP and 4.8 parts of triallyl isocyanurate;
3) Regulating the roll gap of an open mill to the minimum value, rolling a cigar roll 20, rolling a triangular bag 20 times, then increasing the roll gap, and discharging sheets for standby;
4) The rubber compound is stored for 24 hours and then vulcanized for the first time, namely, the rubber compound is molded into the O-ring of AS 568-214. Starting a vulcanizing machine, vulcanizing the mixed rubber for 30min at 160-180 ℃ under the pressure of 5MPa, and reasonably setting specific vulcanization temperature and time according to data obtained by an MDR vulcanization curve;
5) Finally, the sulfur tetrapropylfluoride O-ring is placed in a baking oven at 200 ℃ for further vulcanization for 4-8 hours, and then is taken out for physical and mechanical property testing.
Example 8
A method for preparing a tetrapropylethylene composition comprising the steps of:
1) Mixing 100 parts of tetrapropylarene raw rubber without vinylidene fluoride units with 15 parts of acid gas phase white carbon black R972 and 3 parts of Polytetrafluoroethylene (PTFE) micropowder in an internal mixer at a medium temperature (about 100 ℃) for a mixing time of preferably within 20 minutes;
2) Opening an open mill, adjusting proper intervals between rollers according to different rubber mixing amounts, and sequentially adding 1.5 parts of a vulcanizing agent odorless DCP and 4.8 parts of triallyl isocyanurate;
3) Regulating the roll gap of an open mill to the minimum value, rolling a cigar roll 20, rolling a triangular bag 20 times, then increasing the roll gap, and discharging sheets for standby;
4) The rubber compound is stored for 24 hours and then vulcanized for the first time, namely, the rubber compound is molded into the O-ring of AS 568-214. Starting a vulcanizing machine, vulcanizing the mixed rubber for 30min at 160-180 ℃ under the pressure of 5MPa, and reasonably setting specific vulcanization temperature and time according to data obtained by an MDR vulcanization curve;
5) Finally, the sulfur tetrapropylfluoride O-ring is placed in a baking oven at 200 ℃ for further vulcanization for 4-8 hours, and then is taken out for physical and mechanical property testing.
Example 9
A method for preparing a tetrapropylethylene composition comprising the steps of:
1) Mixing 100 parts of tetrapropylfluororubber raw rubber without vinylidene fluoride units with 15 parts of alkali gas-phase white carbon black R504 at a medium temperature (about 100 ℃) in an internal mixer, wherein the mixing time is preferably controlled within 20 minutes;
2) Opening an open mill, and adjusting proper intervals between rollers according to different rubber mixing amounts, and sequentially adding 1.5 parts of vulcanizing agent TX101 and 4.8 parts of triallyl isocyanurate;
3) Regulating the roll gap of an open mill to the minimum value, rolling a cigar roll 20, rolling a triangular bag 20 times, then increasing the roll gap, and discharging sheets for standby;
4) The rubber compound is stored for 24 hours and then vulcanized for the first time, namely, the rubber compound is molded into the O-ring of AS 568-214. Starting a vulcanizing machine, vulcanizing the mixed rubber for 30min at 160-180 ℃ under the pressure of 5MPa, and reasonably setting specific vulcanization temperature and time according to data obtained by an MDR vulcanization curve;
5) Finally, the sulfur tetrapropylfluoride O-ring is placed in a baking oven at 200 ℃ for further vulcanization for 4-8 hours, and then is taken out for physical and mechanical property testing.
Comparative example 1
1) Opening an open mill, adjusting proper intervals between rollers according to different rubber mixing amounts, and sequentially adding 0.5/1.5 part of odorless DCP/TAIC and 0.5/1.5 part of TX101/TAIC;
2) Regulating the roll gap of an open mill to the minimum value, rolling a cigar roll 20, rolling a triangular bag 20 times, then increasing the roll gap, and discharging sheets for standby;
3) The rubber compound is stored for 24 hours and then vulcanized for the first time, namely, the rubber compound is molded into the O-ring of AS 568-214. Starting a vulcanizing machine, vulcanizing the mixed rubber for 30 minutes at 160-180 ℃ under the pressure of 15MPa, and reasonably setting specific vulcanization temperature and time according to data obtained by an MDR vulcanization curve;
4) Finally, the sulfur tetrapropylfluoride O-ring is placed in a baking oven at 200 ℃ for further vulcanization for 4-8 hours, and then is taken out for physical and mechanical property testing.
Comparative example 2
1) Mixing 100 parts of raw tetrapropylafluoro rubber with 15 parts of acid gas phase white carbon black R972 and 1 part of nano MgO with the average grain diameter of 200nm in an internal mixer at a medium temperature (about 100 ℃), wherein the mixing time is controlled within 20 minutes;
2) Opening an open mill, adjusting proper intervals between rollers according to different rubber mixing amounts, and sequentially adding 1.5 parts of a vulcanizing agent odorless DCP and 4.8 parts of triallyl isocyanurate;
3) Regulating the roll gap of an open mill to the minimum value, rolling a cigar roll 20, rolling a triangular bag 20 times, then increasing the roll gap, and discharging sheets for standby;
4) The rubber compound is stored for 24 hours and then vulcanized for the first time, namely, the rubber compound is molded into the O-ring of AS 568-214. Starting a vulcanizing machine, vulcanizing the mixed rubber for 30 minutes at 160-180 ℃ under the pressure of 15MPa, and reasonably setting specific vulcanization temperature and time according to data obtained by an MDR vulcanization curve;
5) Finally, the sulfur tetrapropylfluoride O-ring is placed in a baking oven at 200 ℃ for further vulcanization for 4-8 hours, and then is taken out for physical and mechanical property testing.
Comparative example 3
1) Mixing 100 parts of raw tetrafluoro rubber with 1 part of nano ZnO (average particle size of 20 nm) in an internal mixer at a medium temperature (about 100 ℃), wherein the mixing time is preferably controlled within 20 minutes;
2) Opening an open mill, adjusting proper intervals between rollers according to different rubber mixing amounts, and sequentially adding 1.5 parts of a vulcanizing agent odorless DCP and 4.8 parts of triallyl isocyanurate;
3) Regulating the roll gap of an open mill to the minimum value, rolling a cigar roll 20, rolling a triangular bag 20 times, then increasing the roll gap, and discharging sheets for standby;
4) The rubber compound is stored for 24 hours and then vulcanized for the first time, namely, the rubber compound is molded into the O-ring of AS 568-214. Starting a vulcanizing machine, vulcanizing the mixed rubber for 30 minutes at 160-180 ℃ under the pressure of 15MPa, and reasonably setting specific vulcanization temperature and time according to data obtained by an MDR vulcanization curve;
5) Finally, the sulfur tetrapropylfluoride O-ring is placed in a baking oven at 200 ℃ for further vulcanization for 4-8 hours, and then is taken out for physical and mechanical property testing.
Comparative example 4
1) Mixing 100 parts of raw tetrafluoro rubber with 5 parts of nano MgO (particle size of 60 nm) in an internal mixer at a medium temperature (about 100 ℃), wherein the mixing time is preferably controlled within 20 minutes;
2) Opening an open mill, adjusting proper intervals between rollers according to different rubber mixing amounts, and sequentially adding 1.5 parts of a vulcanizing agent odorless DCP and 4.8 parts of triallyl isocyanurate;
3) Regulating the roll gap of an open mill to the minimum value, rolling a cigar roll 20, rolling a triangular bag 20 times, then increasing the roll gap, and discharging sheets for standby;
4) The rubber compound is stored for 24 hours and then vulcanized for the first time, namely, the rubber compound is molded into the O-ring of AS 568-214. Starting a vulcanizing machine, vulcanizing the mixed rubber for 30 minutes at 160-180 ℃ under the pressure of 15MPa, and reasonably setting specific vulcanization temperature and time according to data obtained by an MDR vulcanization curve;
the test results of the examples and comparative examples are detailed in Table 1.
TABLE 1
1 Compression set at 25% strain, 204 ℃, tested at 70 hours using an O-ring of AS 568-214.
As is clear from examples 1 and 2 and 3, the combination of the tetrapropylfluororubber and the acid fumed silica is preferably a combination of the TX101 vulcanizing agent and the combination of TX101 and odorless DCP in terms of light transmittance and comprehensive physical properties.
As can be seen from examples 2 and 4, when the acid gas phase white carbon black is added in the formulation, the addition of a small amount of nano MgO (1 part) can reduce T90, promote crosslinking (which is shown as a great increase in CRI), effectively improve the hardness and modulus of the vulcanized rubber, and greatly reduce the permanent compression set of the vulcanized rubber at 204 ℃.
As is clear from example 4 and comparative example 2, comparative example 3 and comparative example 4, the nano magnesium oxide preferably has a particle size of 100nm or less. The addition of the components is preferably less than 5 parts, and the performance is not obviously improved when the components are more than 5 parts, and the content of metal elements in the vulcanized rubber formula is easily increased by times. The effect of adding nano MgO in the formula is obviously better than that of nano ZnO.
As is clear from the results of examples 3 and comparative example 1, when the total amount of peroxide in the compound vulcanizing agent composition is 1 part and TAIC is 3 parts, the transmittance of the product is still good, the hardness of the vulcanized rubber is low, the 100% modulus of elongation is low, and the permanent compression set is large, which is not beneficial to practical application.
As is clear from example 8, the addition of a low fraction of polytetrafluoroethylene fine powder can moderately improve the overall physical properties of the vulcanized rubber and also moderately improve the light transmittance.
As is clear from example 9, the addition of the alkali vapor phase white carbon black can obtain a vulcanized rubber formulation with higher transmittance and has excellent overall physical properties.
In summary, the present invention effectively overcomes the disadvantages of the prior art and has high industrial utility value.
While the invention has been described with respect to preferred embodiments thereof, it will be understood by those skilled in the art that various modifications and additions may be made without departing from the scope of the invention. Equivalent embodiments of the present invention will be apparent to those skilled in the art having the benefit of the teachings disclosed herein, when considered in the light of the foregoing disclosure, and without departing from the spirit and scope of the invention; meanwhile, any equivalent changes, modifications and evolution of the above embodiments according to the essential technology of the present invention still fall within the scope of the technical solution of the present invention.
Claims (6)
1. The tetrafluoro rubber composition comprises the following raw materials in parts by weight:
a vulcanizing agent;
The vulcanizing agent is 1.5 parts of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, or 0.5 part of 1, 3-bis (tert-butylperoxyisopropyl) benzene and 1.0 part of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, or 0.3 part of 1, 3-bis (tert-butylperoxyisopropyl) benzene and 1.2 parts of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane;
the solar light transmittance of the tetrapropylacetone rubber composition is more than or equal to 25 percent, and the visible light transmittance is more than or equal to 2.5 percent;
the white carbon black is selected from gas phase white carbon black, and the gas phase white carbon black is selected from gas phase white carbon black with acidic surface.
2. The tetrapropylating fluororubber composition according to claim 1, wherein the tetrapropylating fluororubber composition has a solar transmittance of not less than 35% and a visible light transmittance of not less than 3.5%.
3. The tetrapropylfluororubber composition according to claim 1, wherein said tetrapropylfluororubber free of vinylidene fluoride units is selected from the group consisting of Aflas 100,150 series, aflas series 600 series, and crude rubber.
4. The tetrapropylating fluororubber composition according to claim 1, wherein said polytetrafluoroethylene fine powder has a particle diameter of 2 to 5. Mu.m.
5. The method for producing a tetrafluoro rubber composition as claimed in any one of claims 1 to 4, wherein the method comprises mixing a tetrafluoro rubber containing no vinylidene fluoride unit, polytetrafluoroethylene fine powder, white carbon black, adding a vulcanizing agent and triallyl isocyanurate, and mixing to obtain a rubber compound, and subjecting the rubber compound to primary vulcanization and secondary vulcanization to produce the tetrafluoro rubber composition.
6. Use of the tetrapropylfluororubber composition as defined in any one of claims 1 to 4 in the field of semiconductors.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1547594A (en) * | 2001-09-26 | 2004-11-17 | 霓佳斯株式会社 | Moldings of fluororubbers and process for their production |
| CN105111642A (en) * | 2015-07-30 | 2015-12-02 | 巨化集团技术中心 | Tetrapropyl fluoro rubber with low-compression permanent deformation performance and preparation method for tetrapropyl fluoro rubber |
| CN106188996A (en) * | 2016-08-03 | 2016-12-07 | 广州加士特密封技术有限公司 | A kind of antiknock rubber o-ring material and preparation method thereof |
| CN113544160A (en) * | 2019-03-08 | 2021-10-22 | Ａｇｃ株式会社 | Crosslinked rubber |
| CN114437476A (en) * | 2022-03-11 | 2022-05-06 | 江苏中煜橡塑科技有限公司 | Fluororubber sealing ring with extrusion deformation resistance and preparation method thereof |
| CN116496703A (en) * | 2023-04-25 | 2023-07-28 | 浙江祥隆科技有限公司 | EVA photovoltaic packaging adhesive film and preparation method thereof |
-
2023
- 2023-09-19 CN CN202311209843.8A patent/CN117050446B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1547594A (en) * | 2001-09-26 | 2004-11-17 | 霓佳斯株式会社 | Moldings of fluororubbers and process for their production |
| CN105111642A (en) * | 2015-07-30 | 2015-12-02 | 巨化集团技术中心 | Tetrapropyl fluoro rubber with low-compression permanent deformation performance and preparation method for tetrapropyl fluoro rubber |
| CN106188996A (en) * | 2016-08-03 | 2016-12-07 | 广州加士特密封技术有限公司 | A kind of antiknock rubber o-ring material and preparation method thereof |
| CN113544160A (en) * | 2019-03-08 | 2021-10-22 | Ａｇｃ株式会社 | Crosslinked rubber |
| CN114437476A (en) * | 2022-03-11 | 2022-05-06 | 江苏中煜橡塑科技有限公司 | Fluororubber sealing ring with extrusion deformation resistance and preparation method thereof |
| CN116496703A (en) * | 2023-04-25 | 2023-07-28 | 浙江祥隆科技有限公司 | EVA photovoltaic packaging adhesive film and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| 吴宏富.《中国粉体工业通鉴 第三卷》.中国建材工业出版社,2007,第179-180页. * |
| 填料改性氟橡胶的制备及性能研究;任兴丽;蒋兴荣;;弹性体(04);第38-42页 * |
| 王孝达.《金属工艺学》.高等教育出版社,2011,第65-66页. * |
| 聚四氟乙烯微粉-四丙氟橡胶复合材料性能研究;黄达;肖建斌;;化工生产与技术(06);第1-4页 * |
| 贾德民.《新型材料科学与技术 高分子材料卷（上册）》.华南理工大学出版社,2021,第540页. * |
| 陈红兰.《无机化工产品检验》.地质出版社,2014,第170页. * |
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