CN115368399A - Preparation method and application of high-efficiency stabilizer for dealcoholized room temperature vulcanized silicone rubber - Google Patents
Preparation method and application of high-efficiency stabilizer for dealcoholized room temperature vulcanized silicone rubber Download PDFInfo
- Publication number
- CN115368399A CN115368399A CN202211205800.8A CN202211205800A CN115368399A CN 115368399 A CN115368399 A CN 115368399A CN 202211205800 A CN202211205800 A CN 202211205800A CN 115368399 A CN115368399 A CN 115368399A
- Authority
- CN
- China
- Prior art keywords
- stirring
- room temperature
- stabilizer
- silicone rubber
- boiling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003381 stabilizer Substances 0.000 title claims abstract description 45
- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 27
- 239000004945 silicone rubber Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 35
- 239000000126 substance Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- -1 ester compound Chemical class 0.000 claims abstract description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 13
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000007789 sealing Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 9
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 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 5
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 4
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000001069 triethyl citrate Substances 0.000 claims description 4
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000013769 triethyl citrate Nutrition 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- ULOZDEVJRTYKFE-UHFFFAOYSA-N diphenyl oxalate Chemical compound C=1C=CC=CC=1OC(=O)C(=O)OC1=CC=CC=C1 ULOZDEVJRTYKFE-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 20
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000011112 process operation Methods 0.000 abstract description 2
- 239000002210 silicon-based material Substances 0.000 abstract description 2
- 239000000565 sealant Substances 0.000 description 23
- 238000003860 storage Methods 0.000 description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 17
- 239000003054 catalyst Substances 0.000 description 17
- 229910052719 titanium Inorganic materials 0.000 description 13
- 239000010936 titanium Substances 0.000 description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 10
- 239000003292 glue Substances 0.000 description 10
- 238000001514 detection method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 5
- 239000013522 chelant Substances 0.000 description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000012974 tin catalyst Substances 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001263 acyl chlorides Chemical group 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 150000003141 primary amines Chemical group 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 2
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 1
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 1
- 125000006414 CCl Chemical group ClC* 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- 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
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
The invention discloses a preparation method and application of a high-efficiency stabilizer for dealcoholized room temperature vulcanized silicone rubber, and belongs to the technical field of new organic silicon materials. The technical scheme is that the preparation method comprises the following steps: 1) Adding the ester compound into a three-mouth bottle, and stirring at the temperature of 45-70 ℃ to remove low-boiling-point substances; 2) Dripping a silane coupling agent into a three-mouth bottle for many times at the temperature of 60-70 ℃, preserving heat, stirring for reaction, and stirring to remove low-boiling-point substances; 3) Dripping benzoyl chloride into a three-necked bottle, heating to 45-70 ℃, and stirring to remove low-boiling-point substances; 4) Cooling to room temperature, and sealing to obtain the stabilizer. The alcohol type efficient stabilizer prepared by the invention has the advantages of light color, no odor, environmental protection, low raw material price, simple process operation and high yield, and solves the technical problems of complex preparation process, poor stability and high preparation cost.
Description
Technical Field
The invention relates to the technical field of new organic silicon materials, and particularly relates to a preparation method and application of an efficient stabilizer for dealcoholized room temperature vulcanized silicone rubber.
Background
The dealcoholized room temperature vulcanized silicone rubber is prepared by taking hydroxyl-terminated polydimethylsiloxane as a base rubber, methyl trimethoxy silane as a cross-linking agent, active nano calcium carbonate and fumed silica as reinforcing materials, and matching a coupling agent, a catalyst and the like. With the coming of the 5G network era and the rapid development of the industries such as photovoltaic industry, electronic appliances, new energy automobiles and the like, the dealcoholized room temperature vulcanized silicone rubber has the advantages of excellent weather resistance, high and low temperature resistance, radiation resistance, good sealing property, no corrosion to most base materials, no pollution, no toxicity, environmental protection, convenient use, low price and the like, and is widely applied to a plurality of fields such as buildings, electronic appliances, aerospace, automobile manufacturing, solar photovoltaic industry and the like. However, in the preparation process of the dealcoholized room temperature vulcanized silicone rubber, the base material contains partial residual hydroxyl and intramolecular water, so that the storage stability is poor; on the other hand, the titanium catalyst is inevitably yellowed, which seriously influences the use.
In order to solve the problems of poor storage stability, easy yellowing and the like of the existing dealcoholization type room temperature vulcanized silicone rubber, the prior art provides a plurality of methods for preparing dealcoholization type room temperature vulcanized silicone rubber, and patent CN1507468A uses a modified organic tin to avoid adding a stabilizer, but cannot stabilize a titanium catalyst, and residual moisture in rubber material can consume a part of the titanium catalyst, so that the storage stability of the rubber material is poor, the rubber material is easy to yellow, and the reaction degree of the organic tin is not easy to control. The patent CN106047273A prepares a cyclic silazane compound stabilizer, improves the storage performance of an alcohol type sealant by capturing free alcohol in a rubber material, but the stabilizer has low yield and high preparation cost, is only used in combination with alkoxy-terminated polydimethylsiloxane, does not provide example data for use in combination with hydroxyl-terminated polydimethylsiloxane, and does not obviously improve the storage performance of the alcohol type sealant prepared by taking hydroxyl-terminated polydimethoxysiloxane as a base rubber.
At present, the problems of high viscosity peak, poor storage stability, easy yellowing, high preparation cost of a stabilizer, complex process and the like of an alcohol type sealant prepared by taking hydroxy-terminated polydimethylsiloxane as a base adhesive exist.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the stabilizer can efficiently remove residual hydroxyl and intramolecular water in a base material, and is easy to form chemical coordination with a titanium catalyst, so that the titanium catalyst is effectively stabilized, the titanium catalyst is prevented from migrating, the viscosity peak is reduced, the yellowing performance of the alcohol-type sealant is improved, and the storage stability of the dealcoholized room-temperature vulcanized silicone rubber is improved from the source.
The technical scheme of the invention is as follows:
the first aspect discloses a preparation method of a high-efficiency stabilizer for dealcoholized room temperature vulcanized silicone rubber, which is characterized by comprising the following steps:
1) Adding the ester compound into a three-mouth bottle, and stirring to remove low-boiling-point substances;
2) Dripping a silane coupling agent into a three-mouth bottle for many times, preserving heat, stirring for reaction, and stirring to remove low-boiling-point substances;
3) Cooling to below 40 ℃, dripping benzoyl chloride into a three-neck bottle, heating and stirring to remove low-boiling-point substances;
4) Cooling to room temperature, and sealing to obtain the stabilizer.
Preferably, the step 1) of removing the low-boiling-point substances is carried out at the temperature of 45-70 ℃ and the stirring time of-0.08 MPa-0.09 MPa for 10-50min.
Preferably, the temperature for the heat preservation stirring reaction in the step 2) is 60-70 ℃, the reaction time is 180-300 min, and the low-boiling-point substance removal is carried out under the conditions of-0.08 MPa-0.09 MPa and stirring.
Preferably, in the step 3), the dripping time is 60-120min, the temperature for removing low-boiling-point substances is 45-70 ℃, and the stirring time is 30-120 min under the condition of-0.08-0.09 MPa.
Preferably, the ester compound is one or more of triethyl citrate, ethyl acetoacetate and diphenyl oxalate.
Preferably, the silane coupling agent is one or more of aminopropyltrimethoxysilane, aminopropylmethyldimethoxysilane and aminopropyltriethoxysilane.
Preferably, the molar ratio of the ester compound, the silane coupling agent and the benzoyl chloride is 1: (1-2): (0.5-1).
In a second aspect, the application of the high-efficiency stabilizer in the preparation of dealcoholization type room temperature vulcanized silicone rubber is disclosed.
The mechanism of the invention is as follows:
the invention utilizes the primary amine group in the amino silane coupling agent to carry out chemical reaction with the ester group in the ester compound to remove the alcohol micromolecule substance. The acyl chloride group in benzoyl chloride reacts with the residual secondary amine group in the amino silane coupling agent to remove hydrogen chloride. Thereby chemically grafting the ester compound and the benzoyl chloride into the molecular structure of the amino silane coupling agent. the-C (= O) -N-C (= O) -structure in the product is easily hydrolyzed by reaction with water, thereby removing the moisture remaining in the silicone rubber. In addition, the dicarbonyl nitrogen-containing structure is easy to form chemical coordination with titanium and tin, and the structural stability of the catalyst in the alcohol type glue is improved. The benzene ring structure in the product improves the high temperature resistance of the product and further enhances the high-temperature storage stability of the alcohol-type adhesive. The siloxane groups in the product enhance the system compatibility with the alcohol-type silicone rubber, and are beneficial to uniform dispersion in the rubber.
Compared with the prior art, the invention has the beneficial effects that:
(1) The alcohol-type efficient stabilizer prepared by the invention is prepared by taking the ester compound, the silane coupling agent and the benzoyl chloride as raw materials and carrying out chemical reaction, has light color, no odor, environmental protection, low raw material price, simple process operation and high yield, and solves the technical problems of complex preparation process, poor stability and high preparation cost.
(2) The high-efficiency stabilizer is applied to dealcoholized room temperature vulcanized silicone rubber, can easily remove water in powder and stabilize a titanium catalyst, and avoids the migration of the titanium catalyst in a system to cause chain breakage of a long-chain molecular structure in the rubber, so that the strength is reduced, and the application value is lost.
(3) The high-efficiency stabilizer provided by the invention is reacted with water for hydrolysis, so that residual moisture in the silicone rubber is removed. And the catalyst is easy to form chemical coordination with titanium and tin, so that the structural stability of the catalyst in the alcohol type glue is improved. The benzene ring structure improves the high temperature resistance of the product and further enhances the high-temperature storage stability of the alcohol-type adhesive. The siloxane groups contained enhance the system compatibility with the alcohol-type silicone rubber and facilitate uniform dispersion in the rubber.
Drawings
FIG. 1 is an infrared spectrum of the high efficiency stabilizer of the product in example 1.
Detailed Description
In the present application, the stirring speed is a medium-low speed and the rotation speed is 800 to 1000r/min, unless otherwise specified.
Example 1
A preparation method of a high-efficiency stabilizer for dealcoholized room temperature vulcanized silicone rubber comprises the following steps:
1) Adding 65 g of ethyl acetoacetate into a three-necked bottle, heating to 50 ℃, and removing low-boiling-point substances under negative pressure of-0.08 MPa for 30 min; the low-boiling-point substances are removed because the ester raw materials can absorb moisture in the air in the process of storing at room temperature, partial hydrolysis is generated, alcohol micromolecule substances are generated, and partial micromolecule substances of industrial-grade raw materials can remain, so that the low-boiling-point substances possibly existing in the raw materials are removed at the temperature, and the purity of the raw materials is ensured.
2) 85 g of aminopropyl methyl dimethoxy silane is dripped into a three-necked bottle for 3 times, the mixture is kept at 60 ℃ and stirred for reaction for 240min, and low-boiling-point substances are removed by stirring at-0.08 Mpa.
3) When the temperature is cooled to below 40 ℃, 60g of benzoyl chloride is dripped into a three-neck flask within 90min, and the mixture is stirred and reacted for 90min under negative pressure at 50 ℃; removing low-boiling-point substances;
4) The mixture was cooled to room temperature to obtain 174.3 g of the high potency stabilizer with a yield of 83%, and the product was stored under sealed conditions.
As can be seen from the IR spectrum in FIG. 1, 2971cm -1 Is characterized by a characteristic peak of CH3-C (= O) -R, 2360cm -1 The characteristic peak of secondary amine shows that the primary amine group of aminopropylmethyldimethoxysilane chemically reacts with the ester group of ethyl acetoacetate to remove ethanol. 1706cm -1 The characteristic peak of R-C (= O) -CH 2-C (= O) -R further shows that ethyl acetoacetate removes ethanol and reacts with amino. 1074cm -1 The characteristic peak of methyldimethoxysilane indicates that the silicon methoxy group of the silane coupling agent is retained during the reaction. Further illustrated is the reaction of ethyl acetoacetate with amino groups. 1541.64cm -1 The characteristic peak of benzene ring indicates that acyl chloride group in benzoyl chloride and residual secondary amine group in amino silane coupling agent are reacted chemically to remove hydrogen chloride, and the infrared spectrogram shows that the concentration is 750cm -1 -700cm -1 There is no strong absorption peak, which indicates no C-Cl group remained, further indicating the completion of the benzoyl chloride reaction.
Example 2
Different from the example 1, 95 g of aminopropyltrimethoxysilane was added dropwise into a three-necked flask in 3 times in the step 2), and the flask was cooled to room temperature under the same conditions as in the example to obtain 184.8 g of the high-potency stabilizer with a yield of 84%, and the flask was sealed and stored.
Example 3
Different from the embodiment 1, in the step 2), 115 g of aminopropyltriethoxysilane is added into a three-mouth bottle in 3 times, other conditions are the same as the embodiment 1, cooling is carried out to room temperature to obtain 196.8 g of efficient stabilizer, the yield is 82%, and the efficient stabilizer is stored in a sealed mode.
Example 4
1) Adding 70 g of triethyl citrate into a three-necked bottle, heating to 50 ℃, and removing low-boiling-point substances under the negative pressure of 0.09Mpa for 30 min;
2) Dropwise adding 45 g of aminopropyl methyl dimethoxysilane into a three-necked bottle for 3 times, keeping the temperature and stirring for reaction for 240min at 60 ℃, and stirring to remove low-boiling-point substances at 0.09 Mpa;
3) When the temperature is cooled to below 40 ℃, 25 g of benzoyl chloride is dripped into the three-neck flask within 90min, and the mixture is stirred and reacted for 90min under negative pressure at 50 ℃; removing low-boiling-point substances; cooling to room temperature to obtain 121.8 g of high-efficiency stabilizer with yield of 87%, and sealing for storage.
Example 5
1) Adding 70 g of triethyl citrate into a three-necked bottle, heating to 50 ℃, and removing low-boiling-point substances under negative pressure of-0.08 Mpa for 30 min;
2) Dropwise adding 50 g of aminopropyl trimethoxy silane into a three-necked bottle for 3 times, carrying out heat preservation and stirring reaction for 300min at the temperature of 60 ℃, and stirring and removing low-boiling-point substances at the pressure of-0.08 MPa;
3) When the temperature is cooled to below 40 ℃, 25 g of benzoyl chloride is dripped into a three-neck flask within 90min, and low-boiling-point substances are removed by stirring and reacting for 90min under negative pressure at 70 ℃; cooling to room temperature to obtain 130.4 g of high-efficiency stabilizer with the yield of 89.9%, and sealing for storage.
Examples 6-10 were alcohol-type sealants prepared using the high-potency stabilizers prepared in examples 1-5 and comparative examples 1-3 were alcohol-type sealants prepared without the high-potency stabilizers prepared in this application, and the alcohol-type sealants prepared in examples 6-10 and comparative examples 1-3 were subjected to performance tests to determine the respective properties of conventional (room temperature vulcanization), aged (70) o C aging for 7 days) and surface drying, curing and mechanical properties after 12 months of room temperature storage, the test was performed under standard conditions (temperature (23 ± 2) ° C, relative humidity (50 ± 5)%), and the product performance test results are detailed in table 1. Surface drying time: testing according to GB/T13477.5-; tensile strength and elongation at break: testing according to GB/T528-2009; the deep curing time test method comprises the following steps: the sample was poured into a wedge-shaped groove 20mm in height and 20mm in width, cured at 23. + -.2 ℃ and 50. + -.5% relative humidity, and the depth of cure (mm) was measured at regular intervals and when completely cured, the time was recorded.
Example 6
1000 g of 107 glue with the viscosity of 20000 mPa.s, 900 g of active nano calcium carbonate and 100 g of dimethyl silicone oil are added into a 5L high-speed dispersion glue making machine, the temperature is raised to 120 ℃, and the premix is obtained after vacuum pumping and dehydration for 60 min. And cooling to room temperature, adding 60g of methyltrimethoxysilane, 10 g of KH-550 and 10 g of the high-efficiency stabilizer prepared in example 1, stirring at a low speed for 30min under normal pressure, then adding 10 g of titanate chelate and 1.0 g of organic tin catalyst, and stirring in vacuum for 30min to obtain the alcohol-type sealant, wherein the product performance detection results are detailed in Table 1.
Example 7
Different from example 6, the high-efficiency stabilizer prepared in example 2 is added in example 7, and the product performance detection results of the obtained alcohol-type sealant are shown in table 1.
Example 8
Different from the embodiment 6, the embodiment 8 adds the high-efficiency stabilizer prepared in the embodiment 3, and the alcohol type sealant obtained has the product performance detection results shown in the table 1.
Example 9
Different from the embodiment 6, the embodiment 9 adds the high-efficiency stabilizer prepared in the embodiment 4, and the alcohol type sealant obtained has the product performance detection results shown in the table 1.
Example 10
Different from the embodiment 6, the high-efficiency stabilizer prepared in the embodiment 5 is added in the embodiment 10, and the product performance detection result of the obtained alcohol type sealant is detailed in the table 1.
Comparative example 1
1000 g of 107 glue with the viscosity of 20000 mPas, 900 g of active nano calcium carbonate and 100 g of dimethyl silicone oil are added into a 5L high-speed dispersion glue making machine, the temperature is raised to 120 ℃, and the premix is obtained after vacuum pumping and dehydration for 60 min. Cooling to room temperature, adding 60g of methyl trimethoxy silane and 10 g of KH-550, stirring at normal pressure and low speed for 30min, then adding 10 g of titanate chelate and 1.0 g of organic tin catalyst, and stirring in vacuum for 30min to obtain the alcohol type sealant, wherein the product performance detection results are detailed in Table 1.
Comparative example 2
1000 g of 107 glue with the viscosity of 20000 mPa.s, 900 g of active nano calcium carbonate and 100 g of dimethyl silicone oil are added into a 5L high-speed dispersion glue making machine, the temperature is raised to 120 ℃, and the mixture is vacuumized and dehydrated for 60min to obtain the premix. Cooling to room temperature, adding 60g of methyltrimethoxysilane, 10 g of KH-550 and 10 g of hexamethyldisilazane, stirring at a low speed for 30min at normal pressure, then adding 10 g of titanate chelate and 1.0 g of organotin catalyst, and stirring for 30min under vacuum to obtain the alcohol type sealant, wherein the product performance detection results are detailed in Table 1.
Comparative example 3
1000 g of 107 glue with the viscosity of 20000 mPa.s, 900 g of active nano calcium carbonate and 100 g of dimethyl silicone oil are added into a 5L high-speed dispersion glue making machine, the temperature is raised to 120 ℃, and the premix is obtained after vacuum pumping and dehydration for 60 min. Cooling to room temperature, adding 60g of methyl trimethoxy silane, 10 g of KH-550 and 10 g of gamma-isocyanatopropyl trimethoxy silane, stirring at low speed for 30min under normal pressure, then adding 10 g of titanate chelate and 1.0 g of organotin catalyst, and stirring for 30min under vacuum to obtain the alcohol type sealant, wherein the product performance detection results are detailed in Table 1.
TABLE 1
As can be seen from the comparison of the data of examples 6-10 and comparative examples 1-3, the alcohol type sealants prepared by the high-efficiency stabilizer prepared in the application of examples 6-10 have excellent surface drying and curing performance under the conventional conditions, the good surface drying and curing effect can be still kept after 7 days of heat aging at 70 ℃ and 12 months of room temperature storage, the tensile strength and the elongation at break of the sealant are not obviously changed compared with the conventional performance, and the storage time can reach 12 months; although the alcohol-type sealant prepared in the comparative examples 1 to 3 has surface drying and curing properties under the conventional conditions and has better mechanical properties, the alcohol-type sealant is not cured after 7 days of thermal aging at 70 ℃ and 12 months of room temperature storage, the tensile strength and the elongation at break of the alcohol-type sealant are obviously reduced, and the storage time is shorter, because the high-efficiency stabilizer disclosed by the invention is easy to form chemical coordination with titanium and tin, the structural stability of the catalyst in the alcohol-type sealant is improved, the titanium catalyst is prevented from migrating in a system, a long-chain molecular structure in the sealant is broken, the strength is reduced, the application value is lost, and the titanium and tin catalysts are prevented from losing the reactivity so as to prolong the storage time of the alcohol-type sealant. The high-efficiency stabilizer can also be hydrolyzed by reacting with water, so that residual moisture in the silicon rubber is removed, the consumption of the moisture in a system to a cross-linking agent and a catalyst is reduced, and the structure of a benzene ring contained in the high-efficiency stabilizer can also improve the high-temperature resistance of the product, thereby further enhancing the high-temperature storage stability of the alcohol-type rubber.
Although the present invention has been described in detail by referring to the drawings in connection with the preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or alterations to the embodiments of the present invention may be made by those skilled in the art without departing from the spirit and scope of the present invention, and such modifications or alterations are intended to be within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. The preparation method of the high-efficiency stabilizer for the dealcoholized room temperature vulcanized silicone rubber is characterized by comprising the following steps of:
1) Adding the ester compound into a three-mouth bottle, and stirring to remove low-boiling-point substances;
2) Dripping a silane coupling agent into a three-mouth bottle for many times, preserving heat, stirring for reaction, and stirring to remove low-boiling-point substances;
3) Cooling to below 40 ℃, dripping benzoyl chloride into a three-neck bottle, heating and stirring to remove low-boiling-point substances;
4) Cooling to room temperature, and sealing to obtain the stabilizer.
2. The method for preparing the high efficiency stabilizer for dealcoholized room temperature vulcanized silicone rubber according to claim 1, wherein the removal of low boiling substances in step 1) is carried out at a temperature of 45 ℃ to 70 ℃ under a pressure of-0.08 Mpa to-0.09 Mpa with a stirring time of 10 to 50min.
3. The method for preparing the high efficiency stabilizer for dealcoholized room temperature vulcanized silicone rubber according to claim 1, wherein the temperature for the heat preservation and stirring reaction in step 2) is 60 ℃ to 70 ℃, the reaction time is 180min to 300min, and the removal of the low boiling point substances is performed by stirring at-0.08 Mpa to-0.09 Mpa.
4. The method for preparing the high efficiency stabilizer for dealcoholized room temperature vulcanized silicone rubber according to claim 1, wherein in the step 3), the dropping time is 60 to 120min, the temperature for removing low boiling substances is 45 ℃ to 70 ℃, and the stirring time is 30min to 120min under the conditions of-0.08 Mpa to-0.09 Mpa.
5. The method for preparing the high efficiency stabilizer for the dealcoholized silicone rubber composition according to claim 1, wherein the ester compound is one or more of triethyl citrate, ethyl acetoacetate and diphenyl oxalate.
6. The method for preparing the efficient stabilizer for the dealcoholized room temperature vulcanized silicone rubber according to claim 1, wherein the silane coupling agent is one or more of aminopropyltrimethoxysilane, aminopropylmethyldimethoxysilane and aminopropyltriethoxysilane.
7. The method for preparing the high efficiency stabilizer for the dealcoholized silicone rubber vulcanizate at room temperature according to claim 1, wherein the molar ratio of the ester compound, the silane coupling agent and the benzoyl chloride is 1: (1-2): (0.5-1).
8. Use of the high potency stabilizer according to any of claims 1-7 in the preparation of a dealcoholized room temperature vulcanized silicone rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211205800.8A CN115368399B (en) | 2022-09-30 | 2022-09-30 | Preparation method and application of efficient stabilizer for dealcoholized room temperature vulcanized silicone rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211205800.8A CN115368399B (en) | 2022-09-30 | 2022-09-30 | Preparation method and application of efficient stabilizer for dealcoholized room temperature vulcanized silicone rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115368399A true CN115368399A (en) | 2022-11-22 |
| CN115368399B CN115368399B (en) | 2023-05-09 |
Family
ID=84073916
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211205800.8A Active CN115368399B (en) | 2022-09-30 | 2022-09-30 | Preparation method and application of efficient stabilizer for dealcoholized room temperature vulcanized silicone rubber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115368399B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103725009A (en) * | 2014-01-02 | 2014-04-16 | 湖北环宇化工有限公司 | Preparation method of fast curing dealcoholization type transparent room-temperature silicon sulfide rubber |
| CN109824863A (en) * | 2019-02-22 | 2019-05-31 | 上海稻畑精细化工有限公司 | A kind of preparation method of polyurethane curing agent |
| CN110922936A (en) * | 2019-12-13 | 2020-03-27 | 东莞市博君来胶粘材料科技有限公司 | Dealcoholized silicone adhesive and preparation method and application thereof |
| CN113956840A (en) * | 2021-11-26 | 2022-01-21 | 海南师范大学 | Dealcoholized room temperature vulcanized silicone rubber sealant and preparation method thereof |
-
2022
- 2022-09-30 CN CN202211205800.8A patent/CN115368399B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103725009A (en) * | 2014-01-02 | 2014-04-16 | 湖北环宇化工有限公司 | Preparation method of fast curing dealcoholization type transparent room-temperature silicon sulfide rubber |
| CN109824863A (en) * | 2019-02-22 | 2019-05-31 | 上海稻畑精细化工有限公司 | A kind of preparation method of polyurethane curing agent |
| CN110922936A (en) * | 2019-12-13 | 2020-03-27 | 东莞市博君来胶粘材料科技有限公司 | Dealcoholized silicone adhesive and preparation method and application thereof |
| CN113956840A (en) * | 2021-11-26 | 2022-01-21 | 海南师范大学 | Dealcoholized room temperature vulcanized silicone rubber sealant and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115368399B (en) | 2023-05-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107286897B (en) | Single-component low-viscosity dealcoholized organic silicon pouring sealant and preparation method thereof | |
| CN110305621B (en) | Dealcoholized room-temperature curing organosilicon sealant and preparation method thereof | |
| CN109280533B (en) | Single-component dealcoholized transparent silicone sealant and preparation method and application thereof | |
| CN110003842B (en) | Single-component dealcoholized room temperature vulcanized organopolysiloxane composition | |
| EP0239437B1 (en) | A room temperature-curable organopolysiloxane composition | |
| CN101353563A (en) | Single-component silicone fluid sealant for solar energy cell assembly and manufacturing method thereof | |
| CN104388039B (en) | Dealcoholized type room temperature vulcanized organosilicon sealant of single component high transparency and preparation method thereof | |
| CN104558612B (en) | A kind of alkoxy end-capped polysiloxane polymer and preparation method thereof | |
| CN107523259B (en) | Preparation of alpha-570 coupling agent modified organosilicon sealant | |
| CN108329473B (en) | Composition containing high phenyl polysiloxane and packaging material or optical film comprising composition | |
| CN109054715B (en) | Modified silane sealant for LED backlight source and preparation method thereof | |
| CN108517198A (en) | A kind of single-component room-temperature vulcanized organosilicon adhesive and preparation method thereof | |
| CN109181623B (en) | Silicone sealant for fast curing photovoltaic module and preparation method thereof | |
| CN113337245A (en) | Dealcoholized photovoltaic module sealant and preparation method thereof | |
| CN111440323A (en) | Synthesis method of alkoxy-terminated organic silicon polyether copolymer and preparation of sealant thereof | |
| CN114621724A (en) | Bi-component organosilicon sealant and preparation method thereof | |
| CN111117556A (en) | Silicone rubber sealant capable of adsorbing VOCs gas and preparation method thereof | |
| CN114316897A (en) | Silicone sealant and preparation method thereof | |
| CN112210341B (en) | Double-vulcanization system building sealant and preparation method thereof | |
| CN108219739B (en) | Deep-cured single-component ketoxime-removed organic silicon adhesive and preparation method thereof | |
| CN109666448A (en) | A kind of photovoltaic module dealcoholized type sealant and preparation method thereof | |
| CN115368399A (en) | Preparation method and application of high-efficiency stabilizer for dealcoholized room temperature vulcanized silicone rubber | |
| CN103772426B (en) | Organic silicon resin with high refractive index, preparation method and application thereof | |
| CN113462350B (en) | Weather-resistant adhesive | |
| CN103436028B (en) | Room temperature curing type one-component thermostable silica gel and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |