CN108191905B - Rosin modified organosilane containing multiple active groups, preparation method thereof and silicone rubber modified by same - Google Patents
Rosin modified organosilane containing multiple active groups, preparation method thereof and silicone rubber modified by same Download PDFInfo
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- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 46
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 42
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 title claims abstract description 42
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000004945 silicone rubber Substances 0.000 title claims abstract description 31
- 150000001282 organosilanes Chemical class 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000126 substance Substances 0.000 claims description 43
- 229920002545 silicone oil Polymers 0.000 claims description 22
- -1 propylene pimaric acid Chemical compound 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000006229 carbon black Substances 0.000 claims description 17
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 16
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- MHVJRKBZMUDEEV-UHFFFAOYSA-N (-)-ent-pimara-8(14),15-dien-19-oic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)C=C1CC2 MHVJRKBZMUDEEV-UHFFFAOYSA-N 0.000 claims description 10
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- MHVJRKBZMUDEEV-APQLOABGSA-N (+)-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@](C=C)(C)C=C2CC1 MHVJRKBZMUDEEV-APQLOABGSA-N 0.000 claims description 8
- DLOSDQIBVXBWTB-UHFFFAOYSA-N 1-[dimethyl(propyl)silyl]oxyethanamine Chemical compound CCC[Si](C)(C)OC(C)N DLOSDQIBVXBWTB-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 3
- MCLXOMWIZZCOCA-UHFFFAOYSA-N 3-[methoxy(dimethyl)silyl]propan-1-amine Chemical compound CO[Si](C)(C)CCCN MCLXOMWIZZCOCA-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 241000872198 Serjania polyphylla Species 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 230000002209 hydrophobic effect Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- 238000004073 vulcanization Methods 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 42
- 239000002253 acid Substances 0.000 description 29
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- 238000010521 absorption reaction Methods 0.000 description 21
- 239000000203 mixture Substances 0.000 description 20
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 16
- PXYRCOIAFZBLBN-HQJFNQTASA-N fumaropimaric acid Chemical compound C([C@]12C=C([C@H](C[C@@H]11)[C@H]([C@@H]2C(O)=O)C(O)=O)C(C)C)C[C@@H]2[C@]1(C)CCC[C@@]2(C)C(O)=O PXYRCOIAFZBLBN-HQJFNQTASA-N 0.000 description 14
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 14
- 229910052710 silicon Inorganic materials 0.000 description 13
- 239000010703 silicon Substances 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 6
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- GLISOBUNKGBQCL-UHFFFAOYSA-N 3-[ethoxy(dimethyl)silyl]propan-1-amine Chemical class CCO[Si](C)(C)CCCN GLISOBUNKGBQCL-UHFFFAOYSA-N 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000007551 Shore hardness test Methods 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
-
- 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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses rosin modified organosilane containing multiple active groups, a preparation method thereof and silicon rubber modified by the same, and the rosin modified organosilane containing multiple active groups has a structural formula as follows:
wherein, in the step (A),
,
n is 0 or 1; a. the1＝OCH2CH3、OCH3Or CH3，A2＝OCH2CH3、OCH3Or CH3，A3＝OCH2CH3、OCH3Or CH3And A is1,A2And A3May not be all CH3. According to the multi-active-group rosin modified silicone rubber, rosin is subjected to copolymerization and vulcanization, and is uniformly dispersed in the silicone rubber in a block mode, so that the high and low temperature resistance and the mechanical property of the silicone rubber are remarkably improved; the preparation method is simple and environment-friendly.
Description
Technical Field
The invention relates to rosin modified organosilane containing multiple active groups, a preparation method thereof and silicon rubber modified by the same, belonging to the field of functional silicon rubber.
Background
Silicone rubber is a high-molecular elastic material with organic and inorganic properties, has excellent weather resistance, ozone resistance, physiological inertia and the like, and is widely applied to the industries of electronics, electricity, construction, medical treatment, health care and the like. However, the silicon rubber molecules Si-O-Si bond has longer length and larger bond angle, Si-O is easy to rotate, the chain is in a spiral structure and has high flexibility and weak intermolecular interaction force, so the mechanical property is poorer, and the development of biomass resources to improve the mechanical property of the silicon rubber is very urgent at present when petroleum resources are deficient and the environment pollution is serious.
Disclosure of Invention
The invention provides rosin modified organosilane containing multiple active groups, a preparation method thereof and silicon rubber modified by the same, the obtained block rosin modified silicon rubber can be applied to the industries of electronic appliances, medical treatment and health, automobiles, coatings and the like, rosin is uniformly dispersed in the silicon rubber through copolymerization and vulcanization, the preparation method is simple and environment-friendly, and the mechanical property and the high and low temperature resistance of the silicon rubber are obviously improved.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a rosin modified organosilane containing multiple active groups has a structural formula as follows:
According to the preparation method of the rosin modified organosilane containing the multiple active groups, the raw material rosin is firstly subjected to acyl chlorination and then reacts with the organosilane at room temperature for 12 +/-2 hours, so that the rosin modified organosilane containing the multiple active groups is obtained.
In order to enhance the modification effect on organosilane, the raw material rosin is at least one of fumaropimaric acid or acrylpimaric acid; the organosilane is at least one of aminopropyltriethoxysilane, aminopropylmethyldiethoxysilane, aminopropyldimethylethoxysilane, aminopropyltrimethoxysilane, aminopropylmethyldimethoxysilane or aminopropyldimethylmethoxysilane.
The structural formula of the silicone rubber modified by the rosin modified organosilane containing multiple active groups is as follows:
the rosin has the advantages of high yield, reproducibility, biodegradability and the like, and the stable structure of the rigid hydrogenated phenanthrene ring skeleton of the rosin can be introduced into a high polymer material through chemical reaction, so that a petrochemical aromatic ring raw material can be replaced, and the mechanical property, the high and low temperature resistance, the adhesion property and other properties of the silicon rubber are effectively improved; the invention utilizes the natural green resource product-rosin and skillfully solves the problem of uniform dispersion of the rosin in the silicone rubber.
The block type rosin modified silicone rubber comprises the following raw material components: 100 parts of hydroxyl-terminated dimethyl silicone oil, 20-30 parts of white carbon black, 20-30 parts of rosin modified organosilane containing multiple active groups, 1-30 parts of cross-linking agent and 0.2-2 parts of catalyst; the parts are parts by mass.
The mechanism is as follows: when the silicone rubber raw material is prepared, under the action of a catalyst, the silicon ethoxy (silicon methoxy) in the cross-linking agent and the base rubber are subjected to dealcoholization reaction to generate ethoxy (methoxy) terminated polysiloxane, part of ethoxy (methoxy) in the base rubber absorbs water vapor in the air and is hydrolyzed into silicon hydroxyl, and the generated silicon hydroxyl and unhydrolyzed terminal silicon ethoxy (silicon methoxy) are subjected to dealcoholization condensation reaction to form cross-linking so as to form the silicone rubber film.
In order to further improve the mechanical property of the material, the viscosity of the hydroxyl-terminated dimethyl silicone oil is 20000-50000 mpa.s.
In order to further promote the synergistic effect among the components and simultaneously improve the temperature resistance and the mechanical property of the rubber, the white carbon black is hydrophobic gas-phase white carbon black with the particle size of 7-40 nm.
In order to further improve the mechanical property and the temperature resistance of the rubber, the preparation method of the rosin modified organosilane containing multiple active groups comprises the following steps: firstly, acylating and chlorinating raw material rosin, and then reacting with organosilane at room temperature for 12 +/-2 hours to obtain rosin modified organosilane containing multiple active groups.
More preferably, the raw material rosin is at least one of fumaric pimaric acid and acrylic pimaric acid.
More preferably, the organosilane is at least one of aminopropyltriethoxysilane, aminopropylmethyldiethoxysilane, aminopropyldimethylethoxysilane, aminopropyltrimethoxysilane, aminopropylmethyldimethoxysilane or aminopropyldimethylmethoxysilane.
In order to simultaneously take account of the hardness and the strength of the rubber, the cross-linking agent is tetraethoxysilane.
To ensure reaction efficiency, the catalyst was dibutyltin dilaurate.
The preparation method of the multi-active-group rosin modified silicone rubber comprises the steps of adding hydroxyl-terminated dimethyl silicone oil and white carbon black into a three-roller machine, grinding and mixing uniformly, transferring into a vacuum planetary stirrer, carrying out vacuum stirring and dehydration for 2-5h at the temperature of 100 ℃ and 150 ℃, cooling to room temperature in a sealed manner, adding the rosin modified organosilane containing the multi-active groups, stirring for 15 +/-2 min at the temperature of 500 ℃ and 1000r/min, adding a cross-linking agent and a catalyst, stirring for 15 +/-2 min at the temperature of 500 ℃ and 1000r/min, carrying out vacuum defoaming, pouring into a mold, and curing for 6d at the room temperature to obtain the multi-active-group rosin modified silicone rubber.
The prior art is referred to in the art for techniques not mentioned in the present invention.
According to the multi-active-group rosin modified silicone rubber, rosin is subjected to copolymerization and vulcanization, and is uniformly dispersed in the silicone rubber in a block mode, so that the high and low temperature resistance and the mechanical property of the silicone rubber are remarkably improved; the preparation method is simple and environment-friendly.
Drawings
FIG. 1 is a FT-IR spectrum of acrylpimaric acid-modified aminopropyltriethoxysilane in example 1.
FIG. 2 shows the propylenedisalicylic acid-modified aminopropyltriethoxysilane of example 113C NMR spectrum.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
In the embodiment, the room temperature is 25 +/-5 ℃, and the stirring speed is 800 r/min;
example 1
Weighing 50 parts of acrylpimaric acid, 50 parts of dichloromethane and 50 parts of oxalyl chloride, adding the weighed materials into a single-neck flask, refluxing for 4 hours at 50 ℃, removing low-boiling-point substances to obtain acrylpimaric acid chloride, dropwise adding the acrylpimaric acid chloride into a three-neck flask containing a mixture of 60 parts of aminopropyltriethoxysilane, 30 parts of triethylamine and 50 parts of dichloromethane, reacting for 12 hours at room temperature, filtering, and removing the low-boiling-point substances to obtain the acrylpimaric acid modified aminopropyltriethoxysilane.
100 parts of hydroxyl-terminated dimethyl silicone oil (50000mpa.s, 107 silicone oil, Hubei New Sihai chemical industry Co., Ltd.) and 25 parts of white carbon black (the particle size is 7-40nm) are added into a three-roll mill to be milled and mixed uniformly, the mixture is transferred into a vacuum planetary stirrer to be stirred, dehydrated and dried for 2 hours under vacuum at 120 ℃, sealed and cooled to room temperature, 20 parts of acrylpimaric acid modified aminopropyltriethoxysilane is added to be stirred for 15 minutes, then 14 parts of ethyl orthosilicate and 0.5 part of dibutyltin dilaurate are added to be stirred for 15 minutes, vacuum defoamation is carried out, the mixture is poured into a mold to be cured for 6 days under room temperature, and the acrylpimaric acid modified silicone rubber with multiple active groups is obtained.
FIG. 1 is a FT-IR spectrum of acrylpimaric acid-modified aminopropyltriethoxysilane in example 1.
Acrylpimaric acid modified aminopropylTriethoxy silane (TEOS): 3319cm-1Is a characteristic absorption peak of an N-H bond, 1079cm-1Is a characteristic absorption peak of a silicon-oxygen-carbon bond, 957cm-1Is a characteristic absorption peak of silicon ethoxy. Which indicates the successful synthesis of the acrylpimaric acid modified aminopropyl triethoxysilane.
FIG. 2 shows the propylenedisalicylic acid-modified aminopropyltriethoxysilane of example 113C NMR spectrum.
The preparation method comprises the steps of carrying out modification on the acrylpimaric acid by the aminopropyltriethoxysilane13C NMR spectrum identification: in the range of 123 and 148ppm, the peaks belong to the characteristic chemical shift peaks of CH ═ C, 178ppm to the characteristic chemical shift peaks of C ═ O, and 58 and 18ppm to the characteristic chemical shift peaks of Si — O — C. By passing13C NMR spectrum analysis shows that the acrylpimaric acid modified aminopropyl triethoxysilane is successfully synthesized.
Example 2
Weighing 50 parts of acrylpimaric acid, 50 parts of dichloromethane and 50 parts of oxalyl chloride, adding the weighed materials into a single-neck flask, refluxing for 4 hours at 50 ℃, removing low-boiling-point substances to obtain acrylpimaric acid chloride, dropwise adding the acrylpimaric acid chloride into a three-neck flask containing a mixture of 60 parts of aminopropylmethyldiethoxysilane, 30 parts of triethylamine and 50 parts of dichloromethane, reacting for 12 hours at room temperature, filtering, and removing the low-boiling-point substances to obtain the acrylpimaric acid modified aminopropylmethyldiethoxysilane.
FT-IR spectrum of the acrylpimaric acid modified aminopropylmethyldiethoxysilane: 3319cm-1Is a characteristic absorption peak of an N-H bond, 1079cm-1Is a characteristic absorption peak of a silicon-oxygen-carbon bond, 957cm-1Is a characteristic absorption peak of silicon ethoxy. The successful synthesis of the acrylpimaric acid modified aminopropyl methyldiethoxysilane is illustrated.
Modification of aminopropyl methyl diethoxy silane with acrylic pimaric acid13C NMR spectrum identification: in the range of 123 and 148ppm, the peaks belong to the characteristic chemical shift peaks of CH ═ C, 178ppm to the characteristic chemical shift peaks of C ═ O, and 58 and 18ppm to the characteristic chemical shift peaks of Si — O — C. By passing13C NMR spectrum analysis shows that the acrylpimaric acid modified aminopropyl methyl diethoxy silane is successfully synthesized.
100 parts of hydroxyl-terminated dimethyl silicone oil (50000mpa.s, 107 silicone oil, Hubei New Sihai chemical industry Co., Ltd.) and 25 parts of white carbon black (the particle size is 7-40nm) are added into a three-roll mill to be milled and mixed uniformly, the mixture is transferred into a vacuum planetary stirrer to be stirred, dehydrated and dried for 2 hours under vacuum at 120 ℃, sealed and cooled to room temperature, 20 parts of acrylpimaric acid modified aminopropylmethyldiethoxysilane is added to be stirred for 15 minutes, then 16 parts of ethyl orthosilicate and 0.5 part of dibutyltin dilaurate are added to be stirred for 15 minutes, vacuum defoamation is carried out, the mixture is poured into a mold to be cured for 6 days under room temperature, and the multi-active group acrylpimaric acid modified silicone rubber is obtained.
Example 3
50 parts of acrylpimaric acid, 50 parts of methylene chloride and 50 parts of oxalyl chloride were weighed into a single-neck flask and charged to 50 parts℃Refluxing for 4h, removing low-boiling-point substances to obtain acrylpimaric acyl chloride, dropwise adding the acrylpimaric acyl chloride into a three-neck flask containing a mixture of 60 parts of aminopropyl dimethylethoxysilane, 30 parts of triethylamine and 50 parts of dichloromethane, reacting at room temperature for 12h, filtering, and removing the low-boiling-point substances to obtain the acrylpimaric acid modified aminopropyl dimethylethoxysilane.
FT-IR spectrogram of the acrylpimaric acid modified aminopropyl dimethylethoxysilane: 3319cm-1Is a characteristic absorption peak of an N-H bond, 1079cm-1Is a characteristic absorption peak of a silicon-oxygen-carbon bond, 957cm-1Is a characteristic absorption peak of silicon ethoxy. The successful synthesis of the acrylpimaric acid modified aminopropyl dimethylethoxysilane is illustrated.
Modification of aminopropyl dimethylethoxysilane with acrylic pimaric acid13C NMR spectrum identification: in the range of 123 and 148ppm, the peaks belong to the characteristic chemical shift peaks of CH ═ C, 178ppm to the characteristic chemical shift peaks of C ═ O, and 58 and 18ppm to the characteristic chemical shift peaks of Si — O — C. By passing13C NMR spectrum analysis shows that the acrylpimaric acid modified aminopropyl dimethylethoxysilane is successfully synthesized.
100 parts of hydroxyl-terminated dimethyl silicone oil (50000mpa.s, 107 silicone oil, Hubei New Sihai chemical industry Co., Ltd.) and 25 parts of white carbon black (the particle size is 7-40nm) are added into a three-roll mill to be milled and mixed uniformly, the mixture is transferred into a vacuum planetary stirrer to be stirred, dehydrated and dried for 2 hours under vacuum at 120 ℃, sealed and cooled to room temperature, 30 parts of acrylpimaric acid modified aminopropyl dimethyl ethoxy silane is added to be stirred for 15 minutes, then 18 parts of ethyl orthosilicate and 0.5 part of dibutyltin dilaurate are added to be stirred for 15 minutes, vacuum defoaming is carried out, the mixture is poured into a mold to be cured for 6 days under room temperature, and the multi-active group acrylpimaric acid modified silicone rubber is obtained.
Example 4
Weighing 50 parts of acrylpimaric acid, 50 parts of dichloromethane and 50 parts of oxalyl chloride, adding the mixture into a single-neck flask, refluxing for 4 hours at 50 ℃, removing low-boiling-point substances to obtain acrylpimaric acid chloride, dropwise adding the acrylpimaric acid chloride into a three-neck flask containing a mixture of 60 parts of aminopropyl trimethoxysilane, 30 parts of triethylamine and 50 parts of dichloromethane, reacting for 12 hours at room temperature, filtering, and removing the low-boiling-point substances to obtain the acrylpimaric acid modified aminopropyl trimethoxysilane.
FT-IR spectrum of the acryl pimaric acid modified aminopropyl trimethoxy silane: 3319cm-1Is a characteristic absorption peak of an N-H bond, 1079cm-1Is a characteristic absorption peak of a silicon-oxygen-carbon bond, 940cm-1Is a characteristic absorption peak of the silicon methoxyl group. Which indicates that the acrylpimaric acid modified aminopropyl trimethoxy silane is successfully synthesized.
Modification of aminopropyl trimethoxysilane by acrylic pimaric acid13C NMR spectrum identification: in the range of 123 and 148ppm, the peak belongs to the characteristic chemical shift of CH ═ C in the phenanthrene ring structure of the rosin structure, 178ppm belongs to the characteristic chemical shift of C ═ O, and 50ppm belongs to the characteristic chemical shift of Si-O-C. By passing13C NMR spectrum analysis shows that the acrylpimaric acid modified aminopropyl trimethoxy silane is successfully synthesized.
100 parts of hydroxyl-terminated dimethyl silicone oil (50000mpa.s, 107 silicone oil, Hubei New Sihai chemical industry Co., Ltd.) and 25 parts of white carbon black (the particle size is 7-40nm) are added into a three-roll mill to be milled and mixed uniformly, the mixture is transferred into a vacuum planetary mixer to be stirred, dehydrated and dried for 2 hours under vacuum at 120 ℃, sealed and cooled to room temperature, 20 parts of acrylpimaric acid modified aminopropyl trimethoxy silane is added to be stirred for 15 minutes, then 14 parts of ethyl orthosilicate and 0.5 part of dibutyltin dilaurate are added to be stirred for 15 minutes, vacuum defoamation is carried out, the mixture is poured into a mould to be solidified for 6 days under room temperature, and the multi-active group acrylpimaric acid modified silicone rubber is.
Example 5
Weighing 50 parts of fumaropimaric acid, 50 parts of dichloromethane and 65 parts of oxalyl chloride, adding the materials into a single-neck flask, refluxing for 4 hours at 50 ℃, removing low-boiling-point substances to obtain fumaropimaric acid chloride, dropwise adding the fumaropimaric acid chloride into a three-neck flask containing 90 parts of aminopropyltriethoxysilane, 36 parts of triethylamine and 50 parts of dichloromethane, reacting for 12 hours at room temperature, filtering, and removing the low-boiling-point substances to obtain the fumaropimaric acid modified aminopropyltriethoxysilane.
FT-IR spectrum of fumaropimaric acid modified aminopropyltriethoxysilane: 3319cm-1Is a characteristic absorption peak of an N-H bond, 1079cm-1Is a characteristic absorption peak of a silicon-oxygen-carbon bond, 957cm-1Is a characteristic absorption peak of silicon ethoxy. The successful synthesis of fumaropimaric acid modified aminopropyl triethoxysilane is demonstrated.
Modified by fumaric pimaric acid and aminopropyl triethoxysilane13C NMR spectrum identification: in the range of 123 and 148ppm, the peaks belong to the characteristic chemical shift peaks of CH ═ C, 178ppm to the characteristic chemical shift peaks of C ═ O, and 58 and 18ppm to the characteristic chemical shift peaks of Si — O — C. By passing13C NMR spectrum analysis shows that the fumaropimaric acid modified aminopropyl triethoxysilane is successfully synthesized.
100 parts of hydroxyl-terminated dimethyl silicone oil (50000mpa.s, 107 silicone oil, Hubei New Sihai chemical industry Co., Ltd.) and 25 parts of white carbon black (the particle size is 7-40nm) are added into a three-roll mill to be milled and mixed uniformly, the mixture is transferred into a vacuum planetary stirrer to be stirred, dehydrated and dried for 2 hours under vacuum at 120 ℃, sealed and cooled to room temperature, 20 parts of fumaropimaric acid modified aminopropyl triethoxysilane is added to be stirred for 15 minutes, then 14 parts of ethyl orthosilicate and 0.5 part of dibutyltin dilaurate are added to be stirred for 15 minutes, vacuum defoamation is carried out, the mixture is poured into a mold to be cured for 6 days under room temperature, and the multi-active group fumaropimaric acid modified silicone rubber is obtained.
Example 6
Weighing 50 parts of fumaropimaric acid, 50 parts of dichloromethane and 65 parts of oxalyl chloride, adding the materials into a single-neck flask, refluxing for 4 hours at 50 ℃, removing low-boiling-point substances to obtain fumaropimaric acid chloride, dropwise adding the fumaropimaric acid chloride into a three-neck flask containing 90 parts of aminopropyl trimethoxy silane, 36 parts of triethylamine and 50 parts of dichloromethane, reacting for 12 hours at room temperature, filtering, and removing the low-boiling-point substances to obtain the fumaropimaric acid modified aminopropyl trimethoxy silane.
FT-IR spectrum of fumaropimaric acid modified aminopropyl trimethoxy silane: 3319cm-1Is a characteristic absorption peak of an N-H bond, 1079cm-1Is a characteristic absorption peak of a silicon-oxygen-carbon bond, 940cm-1Is a characteristic absorption peak of the silicon methoxyl group. The successful synthesis of fumaropimaric acid modified aminopropyl trimethoxysilane is illustrated.
Modification of aminopropyltrimethoxysilane by fumaric pimaric acid13C NMR spectrum identification: in the range of 123 and 148ppm, the peak belongs to the characteristic chemical shift of CH ═ C in the phenanthrene ring structure of the rosin structure, 178ppm belongs to the characteristic chemical shift of C ═ O, and 50ppm belongs to the characteristic chemical shift of Si-O-C. By passing13C NMR spectrum analysis shows that the fumaropimaric acid modified aminopropyl trimethoxy silane is successfully synthesized.
100 parts of hydroxyl-terminated dimethyl silicone oil (50000mpa.s, 107 silicone oil, Hubei New Sihai chemical industry Co., Ltd.) and 25 parts of white carbon black (the particle size is 7-40nm) are added into a three-roll mill to be milled and mixed uniformly, the mixture is transferred into a vacuum planetary mixer to be stirred, dehydrated and dried for 2 hours under vacuum at 120 ℃, sealed and cooled to room temperature, 20 parts of fumaropimaric acid modified aminopropyl trimethoxy silane is added to be stirred for 15 minutes, then 14 parts of ethyl orthosilicate and 0.5 part of dibutyltin dilaurate are added to be stirred for 15 minutes, vacuum defoamation is carried out, the mixture is poured into a mould to be solidified for 6 days under room temperature, and the multi-active group fumaropimaric acid modified silicone rubber is.
Example 7
Weighing 50 parts of fumaropimaric acid, 50 parts of dichloromethane and 65 parts of oxalyl chloride, adding the materials into a single-neck flask, refluxing for 4 hours at 50 ℃, removing low-boiling-point substances to obtain fumaropimaric acid chloride, dropwise adding the fumaropimaric acid chloride into a three-neck flask containing 90 parts of aminopropyl dimethylethoxysilane, 36 parts of triethylamine and 50 parts of dichloromethane, reacting for 12 hours at room temperature, filtering, and removing the low-boiling-point substances to obtain the fumaropimaric acid modified aminopropyl dimethylethoxysilane.
FT-IR spectrogram of fumaropimaric acid modified aminopropyl dimethyl ethoxysilane: 3319cm-1Is a characteristic absorption peak of an N-H bond, 1079cm-1Is a characteristic absorption peak of a silicon-oxygen-carbon bond, 957cm-1Is a characteristic absorption peak of silicon ethoxy. The successful synthesis of the fumaropimaric acid modified aminopropyl dimethyl ethoxy silane is illustrated.
Modified by fumaropimaric acid with aminopropyl dimethylethoxysilane13C NMR spectrum identification: in the range of 123 and 148ppm, the peaks belong to the characteristic chemical shift peaks of CH ═ C, 178ppm to the characteristic chemical shift peaks of C ═ O, and 58 and 18ppm to the characteristic chemical shift peaks of Si — O — C. By passing13C NMR spectrum analysis shows that the fumaropimaric acid modified aminopropyl dimethyl ethoxy silane is successfully synthesized.
100 parts of hydroxyl-terminated dimethyl silicone oil (50000mpa.s, 107 silicone oil, Hubei New Sihai chemical industry Co., Ltd.) and 25 parts of white carbon black (the particle size is 7-40nm) are added into a three-roll mill to be milled and mixed uniformly, the mixture is transferred into a vacuum planetary stirrer to be stirred, dehydrated and dried for 2 hours under vacuum at 120 ℃, sealed and cooled to room temperature, 30 parts of fumaropimaric acid modified aminopropyl dimethyl ethoxy silane is added to be stirred for 15 minutes, then 18 parts of ethyl orthosilicate and 0.5 part of dibutyltin dilaurate are added to be stirred for 15 minutes, vacuum defoaming is carried out, the mixture is poured into a mold to be cured for 6 days under room temperature, and the multi-active group fumaropimaric acid modified silicone rubber is obtained.
Comparative example 1
100 parts of hydroxyl-terminated dimethyl silicone oil (50000mpa.s, 107 silicone oil, Hubei New Sihai chemical Co., Ltd.) and 25 parts of white carbon black (particle size 7-40nm) are added into a three-roll mill to be milled and mixed evenly, and the mixture is transferred into a vacuum planetary mixer to be 120 percent℃And (3) stirring in vacuum, dehydrating and drying for 2h, sealing and cooling to room temperature, adding 16 parts of ethyl orthosilicate and 0.5 part of dibutyltin dilaurate, stirring for 15min, defoaming in vacuum, and pouring into a mold for curing at room temperature for 6d to obtain the silicon rubber which is not modified by rosin.
The block type rosin-modified silicone rubbers of examples 1 to 7 and comparative example 1 described above were subjected to performance testing:
1. and (3) testing mechanical properties: and performing mechanical property test in a constant-temperature and constant-humidity detection room according to the standard shown in the national standard GB/T528-2009.
2. Shore hardness test: and performing Shore hardness test in a constant-temperature and constant-humidity detection room according to the standard shown in the national standard GB/T531.1-2008.
The results of the above performance tests are shown in tables 1-2 below:
TABLE 1
TABLE 2
From the above table, it can be seen that: researches find that the rosin uniform block is dispersed in a stable polymer structure, the rigidity of molecular chains of the silicon rubber, the mutual winding of the molecular chains and the like are obviously improved, and the rosin and the white carbon black play a role in synergistically enhancing intermolecular force in the silicon rubber, so that the mechanical property and the thermal stability of the silicon rubber are obviously improved.
Claims (10)
1. The rosin modified organosilane containing multiple active groups is characterized in that: the structural formula is as follows:
2. A process for preparing a rosin-modified organosilane containing multiple reactive groups as claimed in claim 1, wherein: firstly, acylating and chlorinating raw material rosin, and then reacting with organosilane at room temperature for 12 +/-2 hours to obtain rosin modified organosilane containing multiple active groups.
3. The method of claim 2, wherein: the raw material rosin is at least one of fumaric pimaric acid or propylene pimaric acid; the organosilane is at least one of aminopropyltriethoxysilane, aminopropylmethyldiethoxysilane, aminopropyldimethylethoxysilane, aminopropyltrimethoxysilane, aminopropylmethyldimethoxysilane or aminopropyldimethylmethoxysilane.
4. The silicone rubber modified with rosin-modified organosilane containing multiple reactive groups according to claim 1, wherein: the structural formula is as follows:
5. the silicone rubber of claim 4, wherein: the raw material components comprise: 100 parts of hydroxyl-terminated dimethyl silicone oil, 20-30 parts of white carbon black, 20-30 parts of rosin modified organosilane containing multiple active groups, 1-30 parts of cross-linking agent and 0.2-2 parts of catalyst; the parts are parts by mass.
6. The silicone rubber of claim 5, wherein: the viscosity of the hydroxyl-terminated dimethyl silicone oil is 20000-50000 mpa.s.
7. The silicone rubber according to claim 5 or 6, wherein: the white carbon black is hydrophobic gas-phase white carbon black with the particle size of 7-40 nm.
8. The silicone rubber according to claim 5 or 6, wherein: the cross-linking agent is tetraethoxysilane.
9. The silicone rubber according to claim 5 or 6, wherein: the catalyst was dibutyltin dilaurate.
10. The method for producing the silicone rubber according to any one of claims 4 to 9, characterized in that: adding hydroxyl-terminated dimethyl silicone oil and white carbon black into a three-roller machine, grinding and mixing uniformly, then transferring into a vacuum planetary stirrer, carrying out vacuum stirring and dehydration for 2-5h at the temperature of 100-minus one DEG C, sealing and cooling to room temperature, adding rosin modified organosilane containing multiple active groups, stirring for 15 +/-2 min at the temperature of 500-minus one DEG C and 1000r/min, adding a cross-linking agent and a catalyst, stirring for 15 +/-2 min at the temperature of 500-minus one DEG C and 1000r/min, carrying out vacuum defoaming, pouring into a mold, and curing for 6d at the room temperature to obtain the multiple active group rosin modified silicone rubber.
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