CN114854204A - Room-temperature vulcanized silicone rubber and preparation method and application thereof - Google Patents
Room-temperature vulcanized silicone rubber and preparation method and application thereof Download PDFInfo
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- CN114854204A CN114854204A CN202210746670.2A CN202210746670A CN114854204A CN 114854204 A CN114854204 A CN 114854204A CN 202210746670 A CN202210746670 A CN 202210746670A CN 114854204 A CN114854204 A CN 114854204A
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- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 134
- 239000004945 silicone rubber Substances 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000008035 bio-based plasticizer Substances 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000004014 plasticizer Substances 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- -1 fatty acid ester Chemical class 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 10
- 239000000194 fatty acid Substances 0.000 claims abstract description 10
- 229930195729 fatty acid Natural products 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 37
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 37
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 37
- 239000005642 Oleic acid Substances 0.000 claims description 37
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 37
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 37
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 37
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- GHBFNMLVSPCDGN-UHFFFAOYSA-N rac-1-monooctanoylglycerol Chemical compound CCCCCCCC(=O)OCC(O)CO GHBFNMLVSPCDGN-UHFFFAOYSA-N 0.000 claims description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 9
- PHYFQTYBJUILEZ-UHFFFAOYSA-N Trioleoylglycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCCCCCCCC)COC(=O)CCCCCCCC=CCCCCCCCC PHYFQTYBJUILEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 claims description 8
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 7
- 229940087068 glyceryl caprylate Drugs 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 125000005456 glyceride group Chemical group 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229940117972 triolein Drugs 0.000 claims description 5
- 239000000263 2,3-dihydroxypropyl (Z)-octadec-9-enoate Substances 0.000 claims description 4
- RZRNAYUHWVFMIP-GDCKJWNLSA-N 3-oleoyl-sn-glycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-GDCKJWNLSA-N 0.000 claims description 4
- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 claims description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 3
- 239000003549 soybean oil Substances 0.000 claims description 3
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 2
- ARGICNMLPHJXTP-UHFFFAOYSA-N [SiH4].C(=C)C(OC(CCC)=NO)C(COC(CCC)=O)OC(CCC)=O Chemical compound [SiH4].C(=C)C(OC(CCC)=NO)C(COC(CCC)=O)OC(CCC)=O ARGICNMLPHJXTP-UHFFFAOYSA-N 0.000 claims description 2
- OUGKFJZADGTJRG-UHFFFAOYSA-N [SiH4].CC(OC(CCC)=NO)C(COC(CCC)=O)OC(CCC)=O Chemical compound [SiH4].CC(OC(CCC)=NO)C(COC(CCC)=O)OC(CCC)=O OUGKFJZADGTJRG-UHFFFAOYSA-N 0.000 claims description 2
- 238000005034 decoration Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims 1
- 238000009413 insulation Methods 0.000 claims 1
- 229920002545 silicone oil Polymers 0.000 abstract description 8
- 239000003921 oil Substances 0.000 abstract description 7
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract description 6
- 229920001971 elastomer Polymers 0.000 abstract description 6
- 239000005060 rubber Substances 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000011368 organic material Substances 0.000 abstract description 2
- 239000004970 Chain extender Substances 0.000 description 27
- 230000000694 effects Effects 0.000 description 14
- 238000004073 vulcanization Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- 229910000077 silane Inorganic materials 0.000 description 6
- 235000015112 vegetable and seed oil Nutrition 0.000 description 5
- 239000008158 vegetable oil Substances 0.000 description 5
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 4
- BAECOWNUKCLBPZ-HIUWNOOHSA-N Triolein Natural products O([C@H](OCC(=O)CCCCCCC/C=C\CCCCCCCC)COC(=O)CCCCCCC/C=C\CCCCCCCC)C(=O)CCCCCCC/C=C\CCCCCCCC BAECOWNUKCLBPZ-HIUWNOOHSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
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- RZRNAYUHWVFMIP-HXUWFJFHSA-N glycerol monolinoleate Natural products CCCCCCCCC=CCCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-HXUWFJFHSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 239000004590 silicone sealant Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 239000010775 animal oil Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-M decanoate Chemical compound CCCCCCCCCC([O-])=O GHVNFZFCNZKVNT-UHFFFAOYSA-M 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229940080812 glyceryl caprate Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920002631 room-temperature vulcanizate silicone Polymers 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
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- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on 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; Adhesives based on derivatives of such polymers
- C09J183/04—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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
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- C08K2201/011—Nanostructured additives
Abstract
The invention relates to room-temperature vulcanized silicone rubber and a preparation method and application thereof, and relates to the field of organic materials. The silicon rubber comprises the following raw materials in parts by weight: 130-270 parts of silicon rubber base material, 4-8 parts of cross-linking agent, 0.01-0.05 part of catalyst and 0.2-2.25 parts of bio-based plasticizer; the bio-based plasticizer is selected from a fatty acid plasticizer and/or a fatty acid ester plasticizer. The room temperature vulcanized silicone rubber adopts the bio-based plasticizer, so that the processability of the rubber material is improved, the tensile modulus of the room temperature vulcanized silicone rubber after curing is reduced, the elongation at break is improved, and the bio-based plasticizer replaces white oil or dimethyl silicone oil, so that the production cost is reduced and the environmental protection is ensured.
Description
Technical Field
The invention relates to the field of organic materials, in particular to room-temperature vulcanized silicone rubber and a preparation method and application thereof.
Background
Room Temperature Vulcanizing (RTV) silicone rubber has the characteristics of convenient use, such as liquid use, vulcanization under room temperature conditions and the like, and higher thermal stability and weather resistance, and is widely applied to building sealing and industrial electronics. The low-modulus silicone rubber has the stress-strain characteristics of low stress and high elongation, and is suitable for sealing building expansion joints and concrete facilities, so that the low-modulus silicone rubber can bear large deformation caused by temperature, humidity, stress and the like. The conventional vulcanization mechanism is adopted to prepare the RTV silicone rubber with low modulus performance after vulcanization, a base polymer with high relative molecular mass is used, and the technical problems of high consistency, difficult mixing processing, difficult extrusion and use and the like are caused correspondingly.
Plasticizers are a class of low volatile materials that are miscible with polymeric materials and reduce their modulus, increasing their processability, and can improve the flow or reduce cohesion of polymeric materials by the addition of plasticizers. The addition of a plasticizer to the silicone rubber improves its use properties and workability, resulting in a decrease in modulus after vulcanization. The plasticizer used for preparing the room temperature vulcanized silicone rubber at present mainly comprises white oil, MDT type silicone oil, dimethyl silicone oil and the like. But the addition of a large amount of silicone oil for plasticization also brings about the problem of plasticizer migration after rubber vulcanization, and the added methyl silicone oil does not participate in the vulcanization of the rubber and does not contribute to the elasticity of the rubber. If dimethyl silicone oil is added to the silicone rubber as a plasticizer, the dielectric constant of the silicone rubber is reduced despite the effect of reducing the elastic modulus. In addition, in order to reduce cost, some enterprises use white oil to replace dimethyl silicone oil, the prepared silicone rubber has an oil leakage phenomenon, and the white oil can cause the problems of volume shrinkage and hardening of the silicone rubber after volatilization.
In addition, the use of chain extenders also reduces the modulus of the silicone rubber. By adding the chain extender, the basic polymer is crosslinked, the molecular chain is linearly lengthened, the crosslinking density of the network structure is reduced, good extrusion using fluidity can be ensured, and the vulcanized rubber has low modulus characteristic. However, the use of chain extenders also has problems of being too costly and of having low compatibility with the polymer.
Disclosure of Invention
In order to solve the problems, the invention provides room-temperature vulcanized silicone rubber, which improves the processability of rubber materials, reduces the tensile modulus of the room-temperature vulcanized silicone rubber after curing and improves the elongation at break by adopting a bio-based plasticizer, and ensures the environmental protection while reducing the production cost by replacing white oil or dimethyl silicone oil with the bio-based plasticizer.
In order to achieve the purpose, the invention provides room-temperature vulcanized silicone rubber which comprises the following raw materials in parts by weight:
the bio-based plasticizer is selected from a fatty acid plasticizer and/or a fatty acid ester plasticizer. In one embodiment, the silicone rubber comprises the following raw materials in parts by weight:
the bio-based plasticizer is selected from a fatty acid plasticizer and/or a fatty acid ester plasticizer. In one embodiment, the bio-based plasticizer comprises at least 1 of the following raw materials: epoxidized soybean oil, oleic acid, caprylic/capric glyceride, glyceryl trioleate, glyceryl monooleate or glyceryl monocaprylate.
The molecular structures of the bio-based plasticizer are shown in figures 1-6, the bio-based plasticizer exists in natural animal and vegetable oil, resources are rich, components are stable, cost is low, and the prepared plasticizer product is stable in quality and is non-toxic.
In one embodiment, the silicone rubber base comprises the following raw materials in parts by weight:
80-120 parts of alpha, omega-dihydroxy polydimethylsiloxane
50-150 parts of nano calcium carbonate.
The viscosity of the alpha, omega-dihydroxy polydimethylsiloxane at 25 ℃ is 10000 mPas, 20000 mPas or 80000 mPas.
By adopting the raw materials in parts by weight, the prepared silicone rubber has the advantages of low modulus and high displacement.
In one embodiment, the cross-linking agent comprises at least 1 of the following raw materials: methyl tributyrinoxime silane, vinyl tributyrinoxime silane or methyl trimethoxysilane.
In one embodiment, the catalyst comprises at least 1 of the following feedstocks: dibutyltin dilaurate or dibutyltin diacetate.
The invention also provides a preparation method of the room temperature vulcanized silicone rubber, which comprises the following steps: mixing the silicon rubber base material, the cross-linking agent, the catalyst and the bio-based plasticizer, and stirring the silicon rubber to obtain the silicon rubber.
In one embodiment, the preparation method of the silicone rubber base comprises the following steps: mixing alpha, omega-dihydroxy polydimethylsiloxane and nano calcium carbonate, and stirring the base materials to obtain the nano calcium carbonate.
In one embodiment, the vacuum degree of the silicon rubber stirring is 0.06-0.12MPa, and the stirring time of the silicon rubber is 30-50 min; the vacuum degree of the base material stirring is 0.06-0.12MPa, and the base material stirring time is 1.5-2.5 h.
The invention also provides application of the room temperature vulcanized silicone rubber in building expansion joint sealing, concrete facility joint sealing, heat preservation and decoration integrated plate bonding, or weather-proof joint filling sealing of stone and curtain walls.
Compared with the prior art, the invention has the following beneficial effects:
according to the room-temperature vulcanized silicone rubber and the preparation method and application thereof, the room-temperature vulcanized silicone rubber adopts the bio-based plasticizer, so that the processability of a rubber material is improved, the tensile modulus of the cured silicone rubber is reduced, and the elongation at break is improved; meanwhile, the bio-based plasticizer replaces white oil and dimethyl silicone oil which are plasticizers in the traditional process, and the bio-based plasticizer exists in natural animal and vegetable oil and is non-toxic, rich in resources and stable in components, so that the production cost is reduced, and the environmental protection property is ensured.
Drawings
FIG. 1 is a schematic diagram of the molecular structure of oleic acid in the context of the invention;
FIG. 2 is a schematic representation of the molecular structure of epoxidized soybean oil in accordance with the present disclosure;
FIG. 3 is a schematic diagram of the molecular structure of glycerol monooleate in the present invention;
FIG. 4 is a schematic representation of the molecular structure of glyceryl monocaprylate in the present disclosure;
FIG. 5 is a schematic diagram of the molecular structure of triolein in the context of the invention;
FIG. 6 is a schematic diagram of the molecular structure of caprylic/capric glyceride in the disclosure;
fig. 7 is a graph showing the results of the effects of different types of plasticizers on the mechanical properties of silicone rubber in experimental examples, wherein the abscissa, from left to right, is a blank group without adding a vegetable oil plasticizer, the silicone rubber 13 of comparative example 1 (the mass percentage of ZL-08 chain extender is 0.6%), the silicone rubber 1 of example 1 (the bio-based plasticizer is oleic acid), the silicone rubber 2 of example 1 (the bio-based plasticizer is caprylic capric acid glyceride), the silicone rubber 3 of example 1 (the bio-based plasticizer is glycerol trioleate), the silicone rubber 4 of example 1 (the bio-based plasticizer is glycerol monooleate), and the silicone rubber 5 of example 1 (the bio-based plasticizer is glycerol monocaprylate);
FIG. 8 is a graph showing the effect of different amounts of oleic acid and ZL-08 chain extender on tensile strength of silicone rubber;
FIG. 9 is a graph of the results of the effect of different amounts of oleic acid and ZL-08 chain extender on elongation at break of silicone rubber.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Defining:
room temperature vulcanization type silicone rubber: it is a silicone rubber that can be cured in situ at room temperature without the need for heat and pressure.
α, ω -dihydroxy polydimethylsiloxane: also known as 107 silicone rubber.
Reagents, materials and equipment used in the embodiment are all commercially available sources unless otherwise specified; unless otherwise specified, all the methods are conventional in the art.
Example 1
Different bio-based plasticizers are adopted to prepare the room temperature vulcanized silicone rubber.
Firstly, preparing a silicon rubber base material.
Adding 100 parts of 107 silicon rubber and 50 parts of nano calcium carbonate into a power mixer at room temperature, and stirring for 2 hours under the conditions that the vacuum degree is 0.094MPa and the temperature is 120 ℃ to obtain the silicon rubber base material.
And secondly, preparing room temperature vulcanized silicone rubber.
Cooling the silicon rubber base material to room temperature, adding a cross-linking agent into the silicon rubber base material, wherein the cross-linking agent is 5 parts of methyl tributyl ketoxime silane and 1 part of vinyl tributyroxime silane, and then adding a catalyst, wherein the catalyst is 0.03 part of dibutyltin dilaurate;
in order to compare the influence of adding different bio-based plasticizers on the performance of the silicone rubber, after adding a catalyst, respectively adding 0.45 part of oleic acid, 0.45 part of caprylic/capric glyceride, 0.45 part of glycerol trioleate, 0.45 part of glycerol monooleate and 0.45 part of glycerol monocaprylate, stirring for 30min under the condition that the vacuum degree is 0.094MPa, and discharging to obtain the silicone rubber: the silicone rubber comprises silicone rubber 1 (oleic acid is used as a bio-based plasticizer), silicone rubber 2 (glyceryl caprylate and caprate is used as a bio-based plasticizer), silicone rubber 3 (glyceryl trioleate is used as a bio-based plasticizer), silicone rubber 4 (glyceryl monooleate is used as a bio-based plasticizer), and silicone rubber 5 (glyceryl monocaprylate is used as a bio-based plasticizer). Storing in a glue barrel for later use.
Example 2
The room temperature vulcanized silicone rubber is prepared by adopting oleic acid with different addition amounts.
Firstly, preparing a silicon rubber base material.
Adding 100 parts of 107 silicon rubber and 50 parts of nano calcium carbonate into a power mixer at room temperature, and stirring for 2 hours under the conditions that the vacuum degree is 0.094MPa and the temperature is 120 ℃ to obtain the silicon rubber base material.
Secondly, preparing the room temperature vulcanized silicone rubber.
Cooling the silicon rubber base material to room temperature, adding a cross-linking agent into the silicon rubber base material, wherein the cross-linking agent is 5 parts of methyl tributyl ketoxime silane and 1 part of vinyl tributyroxime silane, and then adding a catalyst, wherein the catalyst is 0.03 part of dibutyltin dilaurate;
in order to compare the influence of different addition amounts of oleic acid on the performance of the silicone rubber, the oleic acid with different addition amounts is respectively added, the mass percentage of the oleic acid in (the silicone rubber base material, the crosslinking agent and the catalyst) is 0, 0.3%, 0.6%, 1% and 1.5%, then the mixture is stirred for 30min under the condition that the vacuum degree is 0.094MPa, and the material is discharged, so that the silicone rubber is obtained: silicon rubber 6 (the mass percent of oleic acid is 0), silicon rubber 7 (the mass percent of oleic acid is 0.3%), silicon rubber 8 (the mass percent of oleic acid is 0.6%), silicon rubber 9 (the mass percent of oleic acid is 1%), and silicon rubber 10 (the mass percent of oleic acid is 1.5%). Storing in a glue barrel for later use.
Comparative example 1
The room temperature vulcanized silicone rubber is prepared by adopting ZL-08 chain extenders with different addition amounts.
Firstly, preparing a silicon rubber base material.
Adding 100 parts of 107 silicon rubber and 50 parts of nano calcium carbonate into a power mixer at room temperature, vacuumizing, and stirring for 2 hours at the vacuum degree of 0.094MPa and the temperature of 120 ℃ to obtain the silicon rubber base material.
And secondly, preparing room temperature vulcanized silicone rubber.
Cooling the silicon rubber base material to room temperature, adding a cross-linking agent into the silicon rubber base material, wherein the cross-linking agent is 5 parts of methyl tributyl ketoxime silane and 1 part of vinyl tributyroxime silane, and then adding a catalyst, wherein the catalyst is 0.03 part of dibutyltin dilaurate;
in order to compare the influence of different addition amounts of ZL-08 chain extenders on the performance of the silicone rubber, respectively adding different addition amounts of ZL-08 chain extenders, wherein the mass percentage of ZL-08 chain extenders in (silicone rubber base material + cross-linking agent + catalyst) is 0, 0.3%, 0.6%, 1% and 1.5%, then carrying out vacuum stirring for 30min, the vacuum degree is 0.094MPa, and discharging to obtain the silicone rubber composition: silicon rubber 11 (the mass percent of ZL-08 chain extender is 0), silicon rubber 12 (the mass percent of ZL-08 chain extender is 0.3%), silicon rubber 13 (the mass percent of ZL-08 chain extender is 0.6%), silicon rubber 14 (the mass percent of ZL-08 chain extender is 1%) and silicon rubber 15 (the mass percent of ZL-08 chain extender is 1.5%). Storing in a glue barrel for later use.
Examples of the experiments
The silicone rubbers 1 to 15 obtained in the above examples and comparative examples were subjected to a performance test.
The test method comprises the following steps:
surface drying time: the test method adopted is that the test is carried out according to the method B in GB/T13477.5-2002 (the sample is filled in a mould frame, a scraper is used for scraping, and a finger contacts three different parts until no sample is adhered to the finger);
curing speed: according to the detection method, with reference to GB/T29595-2013, a proper amount of prepared sealant is filled in a test template with a thickness gradient groove, the test template is placed under 60% RH, and after vulcanization is carried out at room temperature for 24 hours, the test template is lifted from the thinnest part of the thickness gradient of a sealing clamp until the sealant adheres to the template, and the thickness of the vertical section of the test template is measured;
tensile strength and elongation at break: according to the test of GB/T528-2009, dumbbell-type sample bars are adopted, the thickness of the sample is 2.0mm +/-0.2 mm, the tensile rate is 20mm/min, and the average value of the tensile strength and the elongation at break of 3 sample bars is taken as the test result.
And II, testing results.
1. Different types of plasticizers affect the mechanical properties of the silicone rubber.
Fig. 7 shows the effect of adding different kinds of bio-based plasticizers on the mechanical properties of silicone rubber, wherein the abscissa, from left to right, represents a blank group without adding vegetable oil plasticizer, silicone rubber 13 of comparative example 1 (the mass percentage of ZL-08 chain extender is 0.6%), silicone rubber 1 of example 1 (the bio-based plasticizer is oleic acid), silicone rubber 2 of example 1 (the bio-based plasticizer is glyceryl caprylate/caprate), silicone rubber 3 of example 1 (the bio-based plasticizer is glyceryl trioleate), silicone rubber 4 of example 1 (the bio-based plasticizer is glyceryl monooleate), and silicone rubber 5 of example 1 (the bio-based plasticizer is glyceryl monocaprylate), and it can be seen from fig. 7 that the blank group without adding vegetable oil plasticizer has the highest elastic modulus and the lowest elongation at break. The elastic modulus of the silicone rubber 1-5 added with the bio-based plasticizer is reduced to a certain degree, wherein the effect of the silicone rubber 4 added with the glycerol monooleate and the silicone rubber 1 added with the oleic acid is most obvious, and the elastic modulus is respectively reduced to 1.10MPa and 1.27 MPa. Meanwhile, the elongation at break of the silicone rubber 1 added with oleic acid is increased to 217% from the original 24%, and the elongation at break of the silicone rubber 2 added with caprylic-capric glyceride and the silicone rubber 3 added with glycerol trioleate is also increased to 119%.
2. Influence of different addition amounts of plasticizer on the mechanical properties of the silicone rubber.
FIG. 8 and FIG. 9 show the effect of different addition amounts of oleic acid and ZL-08 chain extender on the tensile strength and elongation at break of silicone rubber. It can be seen that the modulus of the silicone rubber tends to decrease and the elongation at break tends to increase with increasing addition of oleic acid. Compared with the effect of oleic acid and ZL-08 chain extender, the obvious modulus reduction change occurs when the addition amount of the ZL-08 chain extender reaches 1.5 percent by mass, the elastic modulus is reduced to 1.4MPa, and the elastic modulus is reduced by 17.6 percent compared with a blank group. When the addition amount of the oleic acid is 0.6 percent by mass, the elastic modulus is reduced to 1.27 MPa; when the addition amount is 1.5 percent by mass, the elastic modulus is reduced to 1.05MPa, and is respectively reduced by 25.3 percent and 38.2 percent compared with the blank component. As for elongation at break, the improvement effect of adding oleic acid is also more remarkable than that of adding ZL-08 chain extender, the elongation at break of 1.5% of oleic acid is increased from 24% to 400%, and the elongation at break of ZL-08 with the same addition amount is increased to 209%.
3. Effect of bio-based plasticizers on the vulcanization properties of silicone rubber.
The influence of different addition amounts of oleic acid and ZL-08 chain extender on the vulcanization performance of silicone rubber is shown in the following table, and it can be seen that the addition of oleic acid and ZL-08 chain extender can prolong the surface drying time of silicone sealant and reduce the deep curing speed. When 1.5 mass percent of oleic acid and ZL-08 chain extender are respectively added, the surface drying time is respectively prolonged to 39 minutes and 23 minutes, and the deep curing thicknesses of 6 hours and 24 hours are respectively 0.78mm and 1.57 mm; 0.80mm, 1.58 mm. Oleic acid has a greater impact on the open time of silicone sealants because the long chain molecular structure of oleic acid increases the steric hindrance between the silicone sealant substrates, thereby impeding the progress of crosslinking and curing and extending the open time.
TABLE 1 Effect of different addition amounts of oleic acid and ZL-08 chain extender on vulcanization performance of silicone rubber
In conclusion, the effect of reducing the modulus of the room temperature vulcanized silicone rubber prepared by adopting the bio-based plasticizer is generally more obvious than that of the room temperature vulcanized silicone rubber prepared by adopting the ZL-08 chain extender, wherein the effect of using oleic acid as the bio-based plasticizer is most obvious, and the elongation at break of the room temperature vulcanized silicone rubber is also obviously improved. Meanwhile, the modulus of the room temperature vulcanization type silicone rubber is in a descending trend and the elongation at break is in an increasing trend along with the increase of the addition amount of the oleic acid, when the addition amount of the oleic acid reaches 1.5 mass percent, the elongation at break is increased from 24 percent to 400 percent, and the elongation at break of the silicone rubber prepared by using ZL-08 chain extender with the same addition amount is increased to 209 percent. Moreover, the effect of reducing the surface drying time of the room temperature vulcanization type silicone rubber by the oleic acid is more obvious than that of a ZL-08 chain extender, the surface drying time can be prolonged to 39 minutes by adding 1.5% of the oleic acid, and the reduction of the surface drying time means that the finishing time can be prolonged when glue applying is carried out, so that an operator can finish the rubber for multiple times.
All possible combinations of the technical features of the above embodiments may not be described for the sake of brevity, but should be considered as within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (10)
1. The room-temperature vulcanized silicone rubber is characterized by comprising the following raw materials in parts by weight:
the bio-based plasticizer is selected from a fatty acid plasticizer and/or a fatty acid ester plasticizer.
2. The room temperature vulcanizing silicone rubber as claimed in claim 1, wherein the silicone rubber comprises the following raw materials in parts by weight:
the bio-based plasticizer is selected from a fatty acid plasticizer and/or a fatty acid ester plasticizer.
3. The room temperature vulcanizable silicone rubber of claim 1, wherein the bio-based plasticizer comprises at least 1 of the following raw materials: epoxidized soybean oil, oleic acid, caprylic/capric glyceride, glyceryl trioleate, glyceryl monooleate or glyceryl monocaprylate.
4. The room temperature vulcanizing silicone rubber as claimed in claim 1, wherein the silicone rubber base comprises the following raw materials in parts by weight:
80-120 parts of alpha, omega-dihydroxy polydimethylsiloxane
50-150 parts of nano calcium carbonate.
The viscosity of the alpha, omega-dihydroxy polydimethylsiloxane at 25 ℃ is 10000 mPas, 20000 mPas or 80000 mPas.
5. The room temperature vulcanizing silicone rubber according to claim 1, wherein the crosslinking agent comprises at least 1 of the following raw materials: methyl tributyrinoxime silane, vinyl tributyrinoxime silane or methyl trimethoxysilane.
6. The room temperature vulcanizing silicone rubber of claim 1, wherein the catalyst comprises at least 1 of the following raw materials: dibutyltin dilaurate or dibutyltin diacetate.
7. The method for producing the room temperature vulcanizing silicone rubber as claimed in any one of claims 1 to 6, characterized by comprising the steps of: mixing the silicon rubber base material, the cross-linking agent, the catalyst and the bio-based plasticizer, and stirring the silicon rubber to obtain the silicon rubber.
8. The method of manufacturing according to claim 7, wherein the method of manufacturing the silicone rubber base includes the steps of: mixing alpha, omega-dihydroxy polydimethylsiloxane and nano calcium carbonate, and stirring the base materials to obtain the nano calcium carbonate.
9. The preparation method according to claim 8, wherein the degree of vacuum of the silicone rubber stirring is 0.06-0.12MPa, and the time of the silicone rubber stirring is 30-50 min; the vacuum degree of the base material stirring is 0.06-0.12MPa, and the base material stirring time is 1.5-2.5 h.
10. The use of the room temperature vulcanized silicone rubber of any one of claims 1 to 6 in the sealing of construction expansion joints, concrete facilities joints, bonding of insulation and decoration integrated plates, or weather-resistant joint filling sealing of stone and curtain walls.
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