CN114591538B - Methylacetylacetonyl silane stabilizer and preparation method and application thereof - Google Patents
Methylacetylacetonyl silane stabilizer and preparation method and application thereof Download PDFInfo
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- CN114591538B CN114591538B CN202210305971.1A CN202210305971A CN114591538B CN 114591538 B CN114591538 B CN 114591538B CN 202210305971 A CN202210305971 A CN 202210305971A CN 114591538 B CN114591538 B CN 114591538B
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- 239000003381 stabilizer Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XRXORTOTZHTOIT-UHFFFAOYSA-N CCC(CC(C[SiH3])=O)=O Chemical compound CCC(CC(C[SiH3])=O)=O XRXORTOTZHTOIT-UHFFFAOYSA-N 0.000 title claims description 7
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 38
- -1 methyl acetylacetone silane Chemical compound 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 10
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004321 preservation Methods 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000000706 filtrate Substances 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 229920002379 silicone rubber Polymers 0.000 claims description 32
- 239000004945 silicone rubber Substances 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- QAZYYQMPRQKMAC-FDGPNNRMSA-L calcium;(z)-4-oxopent-2-en-2-olate Chemical compound [Ca+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O QAZYYQMPRQKMAC-FDGPNNRMSA-L 0.000 claims description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- AIWZOHBYSFSQGV-LNKPDPKZSA-M sodium;(z)-4-oxopent-2-en-2-olate Chemical compound [Na+].C\C([O-])=C\C(C)=O AIWZOHBYSFSQGV-LNKPDPKZSA-M 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000010953 base metal Substances 0.000 claims 1
- 229910001510 metal chloride Inorganic materials 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000002210 silicon-based material Substances 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 238000003860 storage Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 239000000565 sealant Substances 0.000 description 5
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FVUAJWNWAHUQLZ-UHFFFAOYSA-N [chloro(dimethyl)silyl] hypochlorite Chemical class ClO[Si](C)(C)Cl FVUAJWNWAHUQLZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000010073 coating (rubber) Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical group [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000004590 silicone sealant Substances 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
-
- 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
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
-
- 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
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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)
Abstract
The invention discloses a methyl acetylacetone silane stabilizer, and belongs to the technical field of preparation of organic silicon materials. The technical scheme is as follows: the adhesive comprises the following components in parts by mass: 50-200 parts of organic solvent, 15-60 parts of metal acetylacetonate complex, 5-50 parts of dimethyldichlorosilane and a preparation method of methyl acetylacetone silane stabilizer, wherein the preparation method comprises the following steps: (1) Mixing the acetylacetone-based metal complex and an organic solvent to obtain a mixed solution, and dropwise adding dimethyldichlorosilane into the mixed solution under the stirring condition; (2) after the dropwise adding is finished, heating and carrying out heat preservation reaction; (3) Filtering after the reaction is finished, and distilling the filtrate under reduced pressure to remove the low solvent to obtain the product, namely the methyl acetylacetone silane stabilizer. The methyl acetylacetone silane stabilizer prepared by the invention has simple preparation process, the solvent can be recycled, the generated metal chloride can be used as a byproduct, the raw materials are easy to obtain, the requirement on equipment is low, and the industrial production is easy to realize.
Description
Technical Field
The invention relates to the technical field of preparation of organic silicon materials, in particular to a methyl acetylacetone silane stabilizer and a preparation method and application thereof.
Background
The dealcoholized silicone rubber has the advantages of no corrosion to metal, no cracking in the vulcanization process and the like, and is widely applied to the fields of electronics, electrics, buildings, automobiles and the like. The dealcoholized silicone rubber is prepared by taking methyltrimethoxysilane as a crosslinking agent and taking organic titanium and organic tin as catalysts.
During the preparation process of the silicone rubber, the moisture in the rubber material can cause the generation of free methanol, thereby causing the dealcoholized silicone rubber to have poor storage stability, and the storage period is only 3-6 months. The storage stability of the dealcoholized silicone rubber is usually improved by adding a stabilizer. For example, the invention patent (CN 201310675531.6) discloses a room temperature vulcanized single-component dealcoholized silicone rubber sealant and a preparation method thereof, hexamethyldisilazane is used as a storage stabilizer to remove residual moisture in a system and improve storage of the dealcoholized silicone rubber sealant; the invention patent (CN 202010246591.6) discloses a silyl-terminated polyether-polyacrylate sealant and a preparation method thereof, and vinyl trimethoxy silane is used as a water removal agent to obtain a stable sealant; the invention patent (CN 201711386980.3) discloses a single-component self-leveling silicone sealant composition and a sealant for concrete joints and a preparation method thereof, and the prepared silicone rubber has the advantage of storage stability by taking vinyl trimethoxy silane as a water removal agent; the invention patent (CN 201611066315.1) discloses a silicone rubber coating layer which is deeply cured in a closed environment, wherein the deep curing of the silicone rubber is enhanced by a dicarbonyl compound (ethyl acetoacetate and the like), so that the stability of a catalyst can be improved. At present, the main measure for improving the storage stability of the dealcoholized silicone rubber is to achieve the aim of reducing the generation of methanol by taking water in a stabilizer consumption system as a main aim, and has certain limitation.
In addition, a method of adding a beta-diketone (acetylacetone or the like) is also adopted as a stabilizer, and the reaction of methanol and hydroxyl-terminated polydimethylsiloxane is reduced by controlling the catalytic activity of organic titanium and organic tin. However, the beta-diketone cannot react with water in the system and cannot capture free alcohol in the system. However, there has not been a high-efficiency stabilizer which aims to simultaneously achieve water consumption, free alcohol trapping and catalyst activity change.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: overcomes the defects of the prior art, provides a methyl acetylacetone silane stabilizer which is easy to hydrolyze and alcoholyze, reacts with water and free methanol in the rubber material, and further improves the stability of the dealcoholized silicone rubber.
The technical scheme of the invention is as follows:
in a first aspect, a methyl acetylacetonate silane stabilizer is disclosed, which comprises the following components in parts by mass:
50-200 parts of organic solvent
Acetylacetone-based metal complex 15-60 parts
5-50 parts of dimethyldichlorosilane
Preferably, the organic solvent is one or more of benzene, toluene, xylene, acetonitrile, acetone, pentane, methylcyclohexane and octane.
Preferably, the acetylacetone-based metal complex is one or more of potassium acetylacetonate, calcium acetylacetonate, and sodium acetylacetonate.
In a second aspect, a method of preparing a methyl acetylacetonate silane stabilizer is disclosed, comprising the steps of:
(1) Mixing the acetylacetone-based metal complex and an organic solvent to obtain a mixed solution, and dropwise adding dimethyldichlorosilane into the mixed solution under the stirring condition;
(2) After the dropwise adding is finished, heating and carrying out heat preservation reaction;
(3) Filtering after the reaction is finished, and distilling the filtrate under reduced pressure to remove the low solvent to obtain the product, namely the methyl acetylacetone silane stabilizer.
Preferably, the reaction temperature of the heat preservation reaction in the step (2) is 40-100 ℃, and the time of the heat preservation reaction is 4-16 h.
Preferably, the vacuum degree of the reduced pressure distillation in the step (3) is between-0.06 MPa and 0.1MPa, the time is between 30min and 180min, and the temperature is between 40 and 120 ℃.
In a third aspect, the use of a methylacetylacetonylsilane stabilizer in the preparation of silicone rubber is disclosed.
The mechanism of the invention is as follows:
the acetylacetone-based metal complex and dimethyl dichlorosilane are subjected to substitution reaction in an organic solvent to generate dimethyl acetylacetone silane and metal chloride. The presence of the inert organic solvent prevents the hydrolytic polycondensation of dimethyldichlorosilane, promoting the reaction between the acetylacetonato-based metal complex and the dichlorodimethylsiloxane.
The dimethyl acetylacetone silane has very high activity and is easy to react with water molecules and methanol. When the stabilizer is used as a stabilizer of dealcoholized silicone rubber, the dimethyl acetylacetone silane reacts with water molecules to generate dimethyl silicon glycol and acetylacetone. Dimethylacetoacetylsilane will also react with methanol to form acetylacetone and dimethyldimethoxysilane. The generated acetylacetone and dimethyl acetylacetone silane can generate a coordination chemical structure with titanium ions and tin ions in the catalyst, so that the migration of the catalyst is avoided or the catalyst plays a role in catalysis in advance, and the reaction of methanol and hydroxyl-terminated polydimethylsiloxane is inhibited. Therefore, the methyl acetylacetone silane stabilizer can improve the storage stability of the dealcoholized silicone rubber in three aspects of water consumption, methanol capture and catalyst activity inhibition.
Compared with the prior art, the invention has the following beneficial effects:
1. the methyl acetylacetone silane stabilizer prepared by the invention has simple preparation process, the solvent can be recycled, the generated metal chloride can be used as a byproduct, the raw materials are easy to obtain, the requirement on equipment is low, and the industrial production is easy to realize;
2. the methyl acetylacetone silane stabilizer prepared by the invention has the functions of consuming water, capturing methanol and inhibiting the activity of a catalyst, and has higher yield;
3. the methyl acetylacetone silane stabilizer prepared by the invention is used as a stabilizer of dealcoholized silicone rubber, and can prolong the storage life to 18 months.
Drawings
FIG. 1 is an IR spectrum of the product of example 1 of the present invention.
Detailed Description
The stabilizers of examples 1-4 were prepared by the following procedure using methylacetylacetonosilane:
weighing acetylacetone-based metal complex, placing toluene in a three-necked bottle, dropwise adding dimethyldichlorosilane into the three-necked bottle under stirring, and finishing dropwise adding within one hour. After the dropwise addition, the temperature is raised, and the reaction is carried out in a heat preservation manner. Filtering, distilling the filtrate under reduced pressure to remove no fraction to obtain a red liquid product, namely methyl acetylacetone silane, and sealing for storage.
The specific contents, reaction conditions and yields of the respective substances in examples 1 to 4 are shown in Table 1:
TABLE 1
The reduced pressure distillation and the reduction are to remove the organic solvent from the product, and the temperature and the vacuum degree of the reduction are set according to the different boiling points of the organic solvent. The IR spectrum of example 1 is shown in FIG. 1. 2964cm -1 is-CH 3 The stretching vibration peak of (1) is a methyl group bonded to a silicon atom in the product, 1724cm -1 Characteristic absorption peak of acetylacetone, 1412cm -1 Is a characteristic peak of bonding of acetylacetone and silicon, 1313cm -1 Is a characteristic peak of bonding Si and hydrocarbon, 1058cm -1 And 1016cm -1 Further illustrating the bonding of acetylacetone to silicon for the characteristic peak of Si-O-C. From the IR spectrum, acetylacetone had bonded to methylsilane to form dimethylacetosilane.
Examples 5 to 8
The method for preparing the dealcoholized silicone rubber using the stabilizers prepared in examples 1 to 4 was as follows:
adding 1000g of 107 glue with the viscosity of 20000 mPas, 900g of active nano calcium carbonate and 100g of dimethyl silicone oil into a dispersion glue making machine, heating to 120 ℃, and vacuumizing and dehydrating for 60 minutes to obtain the premix. Cooling to room temperature, adding 48g of methyltrimethoxysilane, 5g of KH-560 and 10g of the stabilizer methyl acetylacetone silane prepared in examples 1-4, stirring at low speed for 30 minutes under normal pressure, then adding 12g of titanate chelate and 0.5g of organic tin catalyst, vacuumizing and stirring for 30 minutes to obtain the dealcoholized silicone rubber.
Comparative example 1 differs from examples 5-8 in that: the dealcoholized silicone rubbers were prepared without adding the stabilizer methylacetylacetonosilane, and the other reaction conditions and the respective amounts of substances were the same as in examples 5 to 8.
Comparative examples 2 to 4 differ from examples 5 to 8 in that: in the preparation of dealcoholized silicone rubbers, 10g of vinyltrimethoxysilane, 10g of hexamethyldisilazane and 10g of acetylacetone were added, and the reaction conditions and the amounts of the respective substances were the same as in examples 5 to 8.
The surface dry tack-free performance of the silicon rubber after conventional (room temperature vulcanization) and aging (aging for 3 days at 90 ℃) is mainly tested, according to the test of GB16776-2005, under the standard conditions (temperature (23 +/-2) DEG C and relative humidity (50 +/-5)%), the surface dry time of the single-component silicon rubber is within 3 hours, and the tack-free time is qualified within 24 hours. The dealcoholized silicone rubber is sealed and stored in a rubber bottle, and then is aged for 3 days at 90 ℃, which is equivalent to 18 months of storage at room temperature.
The properties of the silicone rubbers prepared in examples 5 to 8 and comparative examples 1 to 4 are shown in Table 2:
TABLE 2
From the results of examples 5-8 and comparative examples 1-4, it can be seen that the dealcoholized silicone rubbers prepared in examples 5-8 by adding the stabilizer methylacetylacetonylsilane of the present invention can maintain good surface drying and tack-eliminating properties at normal temperature and also maintain good surface drying and tack-eliminating properties after aging, while the dealcoholized silicone rubbers prepared in comparative example 1 without adding the stabilizer methylacetylacetonylsilane of the present invention have no surface drying and tack-eliminating after aging. Comparative example 2 was a mercaptan-removed rubber prepared by adding vinyltrimethoxysilane, the surface drying time after aging was as long as 300min, and no tack was removed, and comparative examples 3 and 4 were thiol-removed rubbers prepared by adding 10g of hexamethyldisilazane and 10g of acetylacetone, respectively, and no surface drying and no tack removal after aging; examples 5-8, the silicone rubber prepared was able to ensure good surface drying and tack free properties after aging, mainly because the methyl acetylacetone silane removed free water and alcohol from the silicone rubber, so that the silicone rubber avoided the damage of free alcohol to 107 backbone during aging, and formed inactive trimethyl polysiloxane, which increased the storage stability of the alcohol-based silicone rubber.
The methyl acetylacetone silane stabilizer prepared by the invention has simple preparation process, the solvent can be recycled, the generated metal chloride can be used as a byproduct, the raw materials are easy to obtain, the requirement on equipment is low, and the industrial production is easy to realize; the methyl acetylacetone silane stabilizer prepared by the invention has the functions of consuming water, capturing methanol and inhibiting the activity of a catalyst, and has higher yield; the methyl acetylacetone silane stabilizer prepared by the invention is used as a stabilizer of dealcoholized silicone rubber, and can prolong the storage life to 18 months.
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 substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions are within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (7)
1. The methyl acetylacetonate silane stabilizer is characterized by comprising the following components in parts by mass:
50-200 parts of organic solvent
Acetylacetone base metal complex 15-60 parts
5-50 parts of dimethyldichlorosilane
2. The methyl acetylacetonate silane stabilizer according to claim 1, wherein: the organic solvent is one or more of benzene, toluene, xylene, acetonitrile, acetone, pentane, methylcyclohexane and octane.
3. The methyl acetylacetonate silane stabilizer of claim 1 wherein: the acetylacetone-based metal complex is one or more of potassium acetylacetonate, calcium acetylacetonate and sodium acetylacetonate.
4. The method of preparing a methyl acetylacetonate silane stabilizer according to claim 1 comprising the steps of:
(1) Mixing the acetylacetone-based metal complex and an organic solvent to obtain a mixed solution, and dropwise adding dimethyldichlorosilane into the mixed solution under the stirring condition;
(2) After the dropwise adding is finished, heating and carrying out heat preservation reaction;
(3) Filtering after the reaction is finished, and distilling the filtrate under reduced pressure to remove the low solvent to obtain the product, namely the methyl acetylacetone silane stabilizer.
5. The method of claim 4, wherein the stabilizer is selected from the group consisting of: the reaction temperature of the heat preservation reaction in the step (2) is 40-100 ℃, and the time of the heat preservation reaction is 4-16 h.
6. The method of preparing a methylacetylacetonylsilane stabilizer according to claim 4, wherein: in the step (3), the vacuum degree of reduced pressure distillation is-0.06 MPa-0.1MPa, the time is 30min-180min, and the temperature is 40 ℃ to 120 ℃.
7. Use of a methylacetylacetonylsilane stabilizer according to any one of claims 1-3 in the preparation of silicone rubber.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3804808A (en) * | 1971-10-19 | 1974-04-16 | Ube Industries | Method for polymerizing formaldehyde |
| CN111378402A (en) * | 2020-04-10 | 2020-07-07 | 山东宝龙达实业集团有限公司 | Preparation method and application of hydroxyl scavenging agent |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3804808A (en) * | 1971-10-19 | 1974-04-16 | Ube Industries | Method for polymerizing formaldehyde |
| CN111378402A (en) * | 2020-04-10 | 2020-07-07 | 山东宝龙达实业集团有限公司 | Preparation method and application of hydroxyl scavenging agent |
Non-Patent Citations (1)
| Title |
|---|
| Anionic Polymerization of Hexamethylcyclotrisiloxane with Acetylacetone Initiator To Form Telechelic Polymer;ALOK KUMAR and B.E. EICHINGER;《Macromolecules》;19901231;第23卷;第5358页 * |
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