CN112920609A - Single-component photocuring solid silicone rubber composition and preparation method thereof - Google Patents
Single-component photocuring solid silicone rubber composition and preparation method thereof Download PDFInfo
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- CN112920609A CN112920609A CN202110051981.2A CN202110051981A CN112920609A CN 112920609 A CN112920609 A CN 112920609A CN 202110051981 A CN202110051981 A CN 202110051981A CN 112920609 A CN112920609 A CN 112920609A
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- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 73
- 239000004945 silicone rubber Substances 0.000 title claims abstract description 62
- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 239000007787 solid Substances 0.000 title claims abstract description 30
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 38
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 38
- 229920001971 elastomer Polymers 0.000 claims abstract description 25
- 239000005060 rubber Substances 0.000 claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 8
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 8
- 150000001412 amines Chemical class 0.000 claims abstract description 7
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 7
- 239000000945 filler Substances 0.000 claims abstract description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- -1 polysiloxane Polymers 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 3
- 229920002367 Polyisobutene Polymers 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 230000006835 compression Effects 0.000 claims description 3
- 238000007906 compression Methods 0.000 claims description 3
- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical compound O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052751 metal Chemical class 0.000 claims description 3
- 239000002184 metal Chemical class 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 125000004665 trialkylsilyl group Chemical group 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims 1
- 238000001125 extrusion Methods 0.000 abstract description 17
- 238000004073 vulcanization Methods 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004134 energy conservation Methods 0.000 abstract description 3
- 238000004806 packaging method and process Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 238000001723 curing Methods 0.000 description 13
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- 229920002545 silicone oil Polymers 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- WYUIWUCVZCRTRH-UHFFFAOYSA-N [[[ethenyl(dimethyl)silyl]amino]-dimethylsilyl]ethene Chemical compound C=C[Si](C)(C)N[Si](C)(C)C=C WYUIWUCVZCRTRH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000006459 hydrosilylation reaction Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 2
- DQEYHSVSMPJXLJ-UHFFFAOYSA-N C1(C=CC=C1)[Pt](CC)(C)C Chemical compound C1(C=CC=C1)[Pt](CC)(C)C DQEYHSVSMPJXLJ-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- JMYZLRSSLFFUQN-UHFFFAOYSA-N (2-chlorobenzoyl) 2-chlorobenzenecarboperoxoate Chemical compound ClC1=CC=CC=C1C(=O)OOC(=O)C1=CC=CC=C1Cl JMYZLRSSLFFUQN-UHFFFAOYSA-N 0.000 description 1
- OXYKVVLTXXXVRT-UHFFFAOYSA-N (4-chlorobenzoyl) 4-chlorobenzenecarboperoxoate Chemical compound C1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1 OXYKVVLTXXXVRT-UHFFFAOYSA-N 0.000 description 1
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- IKCLCGXPQILATA-UHFFFAOYSA-N 2-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Cl IKCLCGXPQILATA-UHFFFAOYSA-N 0.000 description 1
- JQZGUQIEPRIDMR-UHFFFAOYSA-N 3-methylbut-1-yn-1-ol Chemical compound CC(C)C#CO JQZGUQIEPRIDMR-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 238000013006 addition curing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DSVRVHYFPPQFTI-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane;platinum Chemical compound [Pt].C[Si](C)(C)O[Si](C)(C=C)C=C DSVRVHYFPPQFTI-UHFFFAOYSA-N 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010070 extrusion (rubber) Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- JUWSSMXCCAMYGX-UHFFFAOYSA-N gold platinum Chemical compound [Pt].[Au] JUWSSMXCCAMYGX-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 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
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- 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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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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 provides a single-component photocuring solid silicone rubber composition and a preparation method thereof, wherein the single-component photocuring solid silicone rubber composition comprises the following components in parts by mass: 100 parts of vinyl silicone rubber crude rubber, 10-50 parts of reinforcing filler, 1-10 parts of filler treating agent, 1-5 parts of release agent, 2-8 parts of hydrogen-containing cross-linking agent, 0.1-1 part of photoactive platinum complex catalyst and 0.01-0.05 part of organic amine assistant, and the material is prepared by stirring and mixing the components in steps. The invention adopts single-component packaging, and has the applicable period of more than one year; the surface of the extrudate is improved, and embrittlement, reversion and heat shrinkage are reduced; the method is applied to thick-wall continuous extrusion molding process products, solves the problem of bubbles generated at low vulcanization rate at high temperature, and has the advantages of long quality guarantee period, energy conservation, low cost, less side effect and the like.
Description
Technical Field
The invention relates to the technical field of organic silicon rubber, in particular to a single-component photocuring solid silicon rubber composition and a preparation method thereof, and especially relates to a thick-wall continuous extrusion molding process product.
Background
Silicone rubbers have excellent properties such as weather resistance, electrical properties, low compression set, heat resistance, and cold resistance, and are widely used in various fields, including electrical devices, automobiles, buildings, medical care, and foods. For example, it can be used as a spacer for an optical disk used in a computer; bread and cake molds; a gasket for construction; automotive parts such as connector seals, spark plug caps, etc.; medical catheters, and the like. Now, the demand for silicone rubber is increasing, and development of silicone rubber having excellent characteristics is desired.
The photocuring technology is an advanced technology which utilizes ultraviolet light to initiate liquid materials with chemical activity to rapidly polymerize and crosslink and instantly solidify into solid materials, has the advantages of rapid solidification, low energy consumption, high efficiency, no pollution and the like, and completely accords with the principle of '3E': energy (Energy saving), Ecology (ecological environment protection) and Economy (Economy), and is an environment-friendly green technology. At present, most of photocuring organosilicon materials are modified, and the curing mechanism is mainly free radical curing containing acrylate groups or acrylamide groups; cationic curing of epoxy, vinyl ether or styrene containing groups; and (3) addition curing of sulfydryl and vinyl. The free radical organic silicon photocuring system has the defects of large volume shrinkage, oxygen inhibition and the like; the cationic organic silicon photocuring system has the advantages of no oxygen inhibition interference, good thick film curing, small volume shrinkage, strong adhesive force, wear resistance, high hardness and the like, but has lower curing rate; mercapto silicone curing systems have a very foul odor. And the traditional hydrosilylation as a photocuring system is rarely reported.
In the known industrial extrusion processes for silicone rubbers, highly reactive peroxides such as bis-2, 4-dichlorobenzoyl peroxide, 2-monochlorobenzoyl peroxide or 4-monochlorobenzoyl peroxide are used as vulcanization catalysts. Such catalysts produce, under vulcanization, unavoidable by-products, such as chlorobenzoic acid, which can impair the mechanical properties of the vulcanizates by so-called reversion; however, peroxide systems have pot lives of up to one month at 25 ℃ with a suitable cure rate. In addition, metal catalyst systems such as complexes of platinum tetramethyldivinyldisiloxane (Karsted platinum gold catalysts) are used as vulcanization catalysts, which have pot lives of only 1 to 48 hours at 25 ℃ and are therefore designed as two-component systems which form the final reactive one-component compositions of matter immediately before extrusion. In the presently preferred forming method for the hot vulcanization system the wall temperature of the furnace can reach 500 c, typically 250-450 c. The strong temperature gradient and low heat transfer rate of the silicone rubber composition may lead to reversion and surface embrittlement on the extruded article, causing cracking during moderate elongation and so-called reversion leading to depolymerization. The surface temperature of thick-walled extruded articles can be increased to above 300 ℃ while the inner part of the article has a much lower temperature, so that the thick-walled article is not fully cured in the inner part, which results in a low rate of vulcanization at higher temperatures with blistering and heat shrinkage. The patent CN101039999A proposes the use of a light-activated curable silicone composition for the preparation of thick-walled moldings or thick-walled coatings, but does not indicate that it can be used in thick-walled extrusion processes.
The photocuring organic silicon rubber initiates crosslinking after being irradiated by ultraviolet light, and the problem that bubbles are generated at a low vulcanization rate at a high temperature due to a strong temperature gradient and a low heat transfer speed in a heat transfer process is solved. However, photocurable silicones, which are the mechanism of hydrosilylation cure, are generally designed as two components due to their dark reaction. Patent CN108473769A proposes a silicone rubber composition, a method for producing the same, and a silicone rubber extrusion molded article, but does not indicate that it can be prepared as a one-component silicone rubber composition.
In view of the foregoing, there is a need for improvements in the prior art that overcome the deficiencies of the prior art.
Disclosure of Invention
The invention aims to provide a single-component photocuring solid silicone rubber composition and a preparation method thereof, which adopt single-component packaging and have the applicable period time of more than one year; the surface of the extrudate is improved, and embrittlement, reversion and heat shrinkage are reduced; the method is applied to thick-wall continuous extrusion molding process products, solves the problem of bubbles generated at low vulcanization rate at high temperature, and has the advantages of long quality guarantee period, energy conservation, low cost, less side effect and the like.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a single-component photocuring solid silicone rubber composition comprises the following components in parts by mass: 100 parts of vinyl silicone rubber raw rubber, 10-50 parts of reinforcing filler, 1-10 parts of filler treating agent, 1-5 parts of release agent, 2-8 parts of hydrogen-containing cross-linking agent, 0.1-1 part of photoactive platinum complex catalyst and 0.01-0.05 part of organic amine assistant.
According to the scheme, the raw vinyl silicone rubber has a molecular weight of 50-80 ten thousand, and the vinyl content is 0.05-1.2%. Raw rubbers with different vinyl contents are preferably mixed for use to improve the mechanical properties of the vulcanized silicone rubber product, such as tensile strength, elongation, tear strength, compression set; the mass ratio of the raw rubber with high vinyl content to the raw rubber with low vinyl content is 100: 1-1: 10, and more preferably 10: 1-1: 1.
According to the scheme, the reinforcing filler is fumed silica or precipitated silica, and the specific surface area is 150-400 m2/g。
According to the scheme, the filler treating agent is any one or a mixture of more than one of dimethyldialkoxysilane, diphenyl silanediol and silazane. Silazanes are preferred, hexamethyldisilazane, and combinations of hexamethyldisilazane and 1, 3-divinyl-1, 1,3, 3-tetramethyldisilazane are particularly preferred.
According to the scheme, the release agent is any one or a mixture of more than one of higher fatty acid and metal salt thereof, liquid polyisobutylene, azo compound and ester wax.
According to the scheme, the hydrogen-containing cross-linking agent is straight-chain, cyclic or branched-chain hydrogen-containing polysiloxane, and the hydrogen content is 0.5-1.6%; the molar ratio of Si-H units to Si-vi units in the hydrogenpolysiloxane is 0.5: 1-10: 1, and more preferably 1: 1-3: 1.
According to the above scheme, the photoactive platinum complex catalyst is a cyclopentadienyl-trialkyl-platinum compound substituted with an alkyl group or a trialkylsilyl group; more preferably, the alkyl cyclopentadienyl-trimethyl-platinum, especially preferred, methyl cyclopentadienyl-trimethyl-platinum.
According to the scheme, the organic amine assistant is any one or a mixture of more than one of 2, 2-bipyridine, 2,2, 2-tripyridine, dimethylglyoxime and N, N, N, N-tetramethylethylenediamine.
A preparation method of a single-component photocuring solid silicone rubber composition comprises the following steps:
1) raw vinyl silicone rubber, reinforcing filler, filler treating agent and release agent are refined into base rubber in an internal mixer;
2) cooling the base rubber, and then mixing and stirring the base rubber, the hydrogen-containing cross-linking agent and the organic amine auxiliary agent uniformly in an internal mixer;
3) adding the photoactive platinum complex catalyst, and mixing and stirring uniformly.
The forming method of the single-component photocuring solid silicone rubber composition comprises the following steps: and putting the prepared solid silicone rubber composition into continuous extrusion equipment, extruding a thick-wall molded product by the extrusion equipment, and curing the product after the product is irradiated by UV curing equipment. The continuous extrusion apparatus includes a single screw extruder, a twin screw extruder or a gear extruder. The UV device includes a high-pressure mercury lamp, a metal halide lamp, a UV-LED lamp, and more preferably, a UV-LED lamp. The wavelength of UV light for initiating vulcanization is 200-400 nm; the UV energy is 500-3000 mW/cm 2; the illumination time is 2-60 s. The distance between the molded extrudate and the light source is 1-10 cm, and more preferably 3-8 cm. The thickness of the thick-walled extrudate is 5 to 25mm, more preferably 8 to 20 mm.
The invention has the beneficial effects that:
the curing mechanism of the invention is hydrosilylation crosslinking reaction, and the single-component packaging is adopted, so that the applicable period of more than one year is realized; because heating equipment and cooling equipment are not needed, energy is saved, and cost is reduced; the thermal stress of the extrudate prepared by the method is much lower than that of the extrudate subjected to thermal vulcanization, the surface of the extrudate is improved, and embrittlement, reversion and thermal shrinkage are reduced; the method is applied to thick-wall continuous extrusion molding process products, and solves the problem of bubbles generated at low vulcanization rate at high temperature; has the advantages of long shelf life, energy conservation, low cost, less side effects and the like.
Detailed Description
The technical solution of the present invention will be described with reference to the following examples.
Example 1:
the invention provides a single-component photocuring solid silicone rubber composition and a preparation method thereof, wherein the single-component photocuring solid silicone rubber composition comprises the following steps: 85 parts of raw vinyl silicone rubber having a vinyl content of 0.9% and a molecular weight of 60 ten thousand, 15 parts of raw vinyl silicone rubber having a vinyl content of 0.05% and a molecular weight of 65 ten thousand are put into an internal mixing kneader, and 35 parts of 200m rubber are sequentially put into the internal mixing kneader while stirring at room temperature2Uniformly stirring fumed silica, 9 parts of hexamethyldisilazane and 2 parts of zinc stearate release agent, heating to 170 ℃, stirring at constant temperature for 70min, starting vacuum, continuously heating and stirring for 60min under the condition that the vacuum degree is-0.085 MPa, and cooling to obtain the silicone rubber base adhesive. In the dark or under the condition of filtering light (yellow light, wavelength 600-650 nm), putting the silicon rubber base rubber into an open mill, sequentially adding 4.58 parts of straight-chain type hydrogen-containing silicon oil with hydrogen content of 0.75 percent and 0.026 part of 2,2, 2-terpyridine (diluted by vinyl silicone oil with viscosity of 1000 mpa.s) with concentration of 0.3 percent at room temperature, kneading uniformly, adding 0.15 part of methylcyclopentadienyl-trimethyl-platinum with concentration of 0.5 percent, and continuing to knead uniformly.
The silicon rubber composition is placed in the dark or under the condition of filtering light (yellow light, the wavelength is 600-650 nm), and the applicable period of time is observed. In addition, part of the composition was fed into a single screw extruder with a screw diameter of 50mm and a screw length-diameter ratio L/D of 14, the screw rotation speed was controlled,the extrusion linear speed is 7.2m/min, a silicone tube with the inner diameter of 2mm and the wall thickness of 8mm is extruded, and the silicone tube passes through the silicone tube with the length of 50cm, the wavelength of 365nm and the energy of 2500mW/cm at a constant speed2And a cylindrical UV-LED lamp with an inner diameter of 95 mm. The resulting silicone tube was tested for complete curing and the bubble conditions in the tube were observed using a magnifying glass, the results are shown in table 1.
Example 2:
the invention provides a single-component photocuring solid silicone rubber composition and a preparation method thereof, wherein the single-component photocuring solid silicone rubber composition comprises the following steps: 60 parts of raw vinyl silicone rubber having a vinyl content of 0.6% \ molecular weight of 75 ten thousand, 40 parts of raw vinyl silicone rubber having a vinyl content of 0.1% and a molecular weight of 55 ten thousand are put into an internal mixing kneader, and 30 parts of 250m rubber are sequentially put into the internal mixing kneader while stirring at room temperature2The preparation method comprises the following steps of uniformly stirring/g fumed silica, 7.5 parts of hexamethyldisilazane, 2 parts of 1, 3-divinyl-1, 1,3, 3-tetramethyldisilazane and 3 parts of liquid polyisobutene, heating to 180 ℃, stirring at a constant temperature for 60min, starting vacuum, continuously heating and stirring for 60min under the condition that the vacuum degree is-0.09 MPa, and cooling to obtain the silicone rubber base adhesive. In the dark or under the condition of filtering light (yellow light, wavelength 600-650 nm), putting silicone rubber base rubber into an open mill, sequentially adding 2.2 parts of MT structure branched chain type hydrogen-containing silicone oil with hydrogen content of 1.0% and 0.01 part of 2, 2-bipyridyl (diluted by vinyl silicone oil with viscosity of 1000mpa. s.) at room temperature, uniformly kneading, then adding 0.46 part of (trimethylsilyl-cyclopentadiene) trimethyl platinum with concentration of 0.25%, and continuously kneading uniformly.
Placing the silicon rubber composition in the dark or under the condition of filtering light (yellow light, the wavelength is 600-650 nm), and observing the applicable period; in addition, part of the composition was fed into a single screw extruder with a screw diameter of 50mm and a screw length-diameter ratio L/D of 14, the screw speed was controlled so that the linear extrusion speed was 6.5m/min, a silicone tube with an inner diameter of 4mm and a wall thickness of 12mm was extruded, and the composition passed through a silicone tube with a length of 60cm, a wavelength of 360nm and an energy of 3000mW/cm at a constant vertical speed2And a cylindrical UV-LED lamp with an inner diameter of 90 mm. The resulting silicone tube was tested for complete curing and the bubble conditions in the tube were observed using a magnifying glass, the results are shown in table 1.
Example 3:
the invention provides a single-component photocuring solid silicone rubber composition and a preparation method thereof, wherein the single-component photocuring solid silicone rubber composition comprises the following steps: 73 parts of raw vinyl silicone rubber having a vinyl content of 1.0% and a molecular weight of 58 ten thousand, 27 parts of raw vinyl silicone rubber having a vinyl content of 0.2% and a molecular weight of 60 ten thousand were put into an internal kneading machine, and 28 parts of 250m rubber were put into the internal kneading machine in this order while stirring at room temperature2And uniformly stirring/g precipitation-method white carbon black, 7.3 parts of hexamethyldisilazane, 1.5 parts of 1, 3-divinyl-1, 1,3, 3-tetramethyldisilazane and 2.5 parts of 2, 2-azobisisobutyronitrile, heating to 160 ℃, stirring at a constant temperature for 80min, starting vacuum, continuously heating and stirring for 50min under the condition that the vacuum degree is-0.095 MPa, and cooling to obtain the silicone rubber base adhesive. The silicone rubber-based rubber is put into an open mill in the dark or under the condition of filtering light (yellow light, wavelength 600-650 nm), 2.26 parts of tetramethylcyclotetrasiloxane with hydrogen content of 1.67% and 0.028 parts of dimethylglyoxime (diluted by vinyl silicone oil with viscosity of 1000 mpa.s) with concentration of 0.3% are sequentially put into the open mill at room temperature and are uniformly kneaded, 0.28 part of (phenyldimethylsilyl-cyclopentadiene) trimethylplatinum with concentration of 0.3% is added, and the uniform kneading is continued.
Placing the silicon rubber composition in the dark or under the condition of filtering light (yellow light, the wavelength is 600-650 nm), and observing the applicable period; in addition, part of the composition was fed into a single screw extruder with a screw diameter of 50mm and a screw length-diameter ratio L/D of 14, the screw speed was controlled so that the linear extrusion speed was 6.8m/min, a silicone tube with an inner diameter of 5mm and a wall thickness of 18mm was extruded, and the silicone tube passed vertically at a constant speed over a length of 65cm, a wavelength of 350nm and an energy of 2800mW/cm2And a cylindrical UV-LED lamp with an inner diameter of 120 mm. The resulting silicone tube was tested for complete curing and the bubble conditions in the tube were observed using a magnifying glass, the results are shown in table 1.
Example 4:
the invention provides a single-component photocuring solid silicone rubber composition and a preparation method thereof, wherein the single-component photocuring solid silicone rubber composition comprises the following steps: 58 parts of raw vinyl silicone rubber having a vinyl content of 1.2% and a molecular weight of 63 ten thousand, 42 parts of raw vinyl silicone rubber having a vinyl content of 0.15% and a molecular weight of 50 ten thousand are charged into an internal mixing kneader, and 26 parts of a mixture of 300m are successively charged at room temperature while stirring2White carbon black in a precipitation method of 7.8 portionsHexamethyldisilazane and 2.8 parts of ester wax are uniformly stirred, heated to 165 ℃, stirred at a constant temperature for 65min, then vacuumized, continuously heated and stirred for 70min under the condition that the vacuum degree is-0.09 MPa, and cooled to obtain the silicone rubber base rubber. In the dark or under the condition of filtering light (yellow light, wavelength 600-650 nm), the silicone rubber base rubber is put into an open mill, 4.67 parts of straight-chain type hydrogen-containing silicone oil with 0.85% hydrogen content and 0.04 part of N, N, N, N-tetramethylethylenediamine (diluted by vinyl silicone oil with 1000mpa.s viscosity) with the concentration of 0.25% are sequentially put into the open mill at room temperature, and are uniformly kneaded, 0.27 part of (triethylsilyl-cyclopentadiene) trimethyl platinum with the concentration of 0.5% is added, and the mixture is continuously kneaded uniformly.
Placing the silicon rubber composition in the dark or under the condition of filtering light (yellow light, the wavelength is 600-650 nm), and observing the applicable period; in addition, part of the composition was fed into a single screw extruder with a screw diameter of 50mm and a screw length-diameter ratio L/D of 14, the screw speed was controlled so that the linear extrusion speed was 5.5m/min, a silicone tube with an inner diameter of 5mm and a wall thickness of 12mm was extruded, and the silicone tube passed vertically at a constant speed over a length of 40cm, a wavelength of 320nm and an energy of 2000mW/cm2Cylindrical UV-LED lamp with inner diameter of 110 mm. The resulting silicone tube was tested for complete curing and the bubble conditions in the tube were observed using a magnifying glass, the results are shown in table 1.
Comparative example 1:
the silicone rubber-based rubber obtained in example 1 was put into an open mill, and 4.58 parts of a straight-chain type hydrogen-containing silicone oil having a hydrogen content of 0.75% and 0.48 part of ethynylcyclohexanol having a concentration of 10% (diluted with 1000mpa.s viscosity vinyl silicone oil) were sequentially put into the open mill and kneaded uniformly at room temperature, and then 0.15 part of a platinum catalyst having a concentration of 0.5% was put into the open mill and kneaded uniformly.
The silicone rubber composition described above was left to stand at room temperature and observed for an applicable period of time. In addition, part of the composition is put into a single-screw extruder, the diameter of a screw is 50mm, the length-diameter ratio L/D of the screw is 14, the rotating speed of the screw is controlled, the linear speed of extrusion is 7.2m/min, a silicone tube with the inner diameter of 2mm and the wall thickness of 8mm is extruded, the composition vertically passes through a cylindrical drying tunnel with the length of 50cm, the temperature of 550 ℃ and the inner diameter of 65mm at a constant speed, and then horizontally passes through a drying tunnel with the length of 5m and the temperature of 200 ℃. The silicone tube obtained after cooling was tested for complete solidification and the bubble conditions in the tube were observed using a magnifying glass, the results are shown in table 1.
Comparative example 2:
the silicone rubber-based rubber obtained in example 3 was put into an open mill, 2.26 parts of tetramethylcyclotetrasiloxane having a hydrogen content of 1.67% and 0.83 part of methylbutynol (diluted with 1000mpa.s viscosity vinyl silicone oil) were sequentially put into the mill at room temperature, kneaded uniformly, and then 0.28 part of 0.3% cassettplatinum catalyst was added, and kneaded uniformly.
The silicone rubber composition described above was left to stand at room temperature and observed for an applicable period of time. In addition, part of the composition is put into a single-screw extruder, the diameter of a screw is 50mm, the length-diameter ratio L/D of the screw is 14, the rotating speed of the screw is controlled, the linear speed of extrusion is 6.8m/min, a silicone tube with the inner diameter of 5mm and the wall thickness of 18mm is extruded, the composition vertically passes through a cylindrical drying tunnel with the length of 65cm, the temperature of 600 ℃ and the inner diameter of 80mm at a constant speed, and then horizontally passes through a drying tunnel with the length of 3m and the temperature of 250 ℃. The resulting silicone tube was tested for complete curing and the bubble conditions in the tube were observed using a magnifying glass, the results are shown in table 1.
TABLE 1 test results of examples and comparative examples
From the results, the single-component photocuring solid silicone rubber composition provided by the invention has an applicable period of more than one year in the dark or under the condition of filtering light (yellow light, wavelength of 600-650 nm), and can meet the quality guarantee period requirement of the single-component solid silicone rubber composition; compared with thermosetting solid silicon rubber compositions, the composition can be completely cured after being illuminated, and solves the problem of bubbles generated at low vulcanization rate at high temperature in thick-wall continuous extrusion molding process products.
The above embodiments are only used for illustrating but not limiting the technical solutions of the present invention, and although the above embodiments describe the present invention in detail, those skilled in the art should understand that: modifications and equivalents may be made thereto without departing from the spirit and scope of the invention and any modifications and equivalents may fall within the scope of the claims.
Claims (9)
1. The single-component photocuring solid silicone rubber composition is characterized by comprising the following components in parts by mass: 100 parts of vinyl silicone rubber raw rubber, 10-50 parts of reinforcing filler, 1-10 parts of filler treating agent, 1-5 parts of release agent, 2-8 parts of hydrogen-containing cross-linking agent, 0.1-1 part of photoactive platinum complex catalyst and 0.01-0.05 part of organic amine assistant.
2. The one-component photocuring solid silicone rubber composition as claimed in claim 1, wherein the raw vinyl silicone rubber has a molecular weight of 50 to 80 ten thousand and a vinyl content of 0.05 to 1.2%. Raw rubbers with different vinyl contents are preferably mixed for use to improve the mechanical properties of the vulcanized silicone rubber product, such as tensile strength, elongation, tear strength, compression set; the mass ratio of the raw rubber with high vinyl content to the raw rubber with low vinyl content is 100: 1-1: 10, and more preferably 10: 1-1: 1.
3. The single-component photocuring solid silicone rubber composition as claimed in claim 1, wherein the reinforcing filler is fumed silica or precipitated silica, and the specific surface area of the reinforcing filler is 150-400 m2/g。
4. The one-component photocuring solid silicone rubber composition according to claim 1, wherein the filler treatment agent is any one or a mixture of more than one of dimethyldialkoxysilane, diphenylsilanediol and silazane.
5. The one-component photocurable solid silicone rubber composition according to claim 1, wherein the release agent is any one or a mixture of more than one of higher fatty acids and metal salts thereof, liquid polyisobutylene, azo compounds, and ester waxes.
6. The one-component photocurable solid silicone rubber composition according to claim 1, wherein the hydrogen-containing cross-linking agent is a linear, cyclic or branched hydrogen-containing polysiloxane, and the hydrogen content is 0.5-1.6%; the molar ratio of Si-H units to Si-vi units in the hydrogenpolysiloxane is 0.5: 1-10: 1.
7. The one-component photocurable solid silicone rubber composition of claim 1, wherein the photoactive platinum complex catalyst is a cyclopentadienyl-trialkyl-platinum compound substituted with an alkyl group or a trialkylsilyl group.
8. The one-component photocurable solid silicone rubber composition according to claim 1, wherein the organic amine auxiliary agent is any one or a mixture of more than one of 2, 2-bipyridine, 2,2, 2-tripyridine, dimethylglyoxime, and N, N-tetramethylethylenediamine.
9. The method for preparing the one-component photocurable solid silicone rubber composition according to claim 1, characterized by comprising the steps of:
1) raw vinyl silicone rubber, reinforcing filler, filler treating agent and release agent are refined into base rubber in an internal mixer;
2) cooling the base rubber, and then mixing and stirring the base rubber, the hydrogen-containing cross-linking agent and the organic amine auxiliary agent uniformly in an internal mixer;
3) adding the photoactive platinum complex catalyst, and mixing and stirring uniformly.
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