CN113861406B - Method for preparing silane modified polyether by utilizing dichlorosilane - Google Patents
Method for preparing silane modified polyether by utilizing dichlorosilane Download PDFInfo
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- CN113861406B CN113861406B CN202111280908.9A CN202111280908A CN113861406B CN 113861406 B CN113861406 B CN 113861406B CN 202111280908 A CN202111280908 A CN 202111280908A CN 113861406 B CN113861406 B CN 113861406B
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- Prior art keywords
- catalyst
- allyl
- modified polyether
- dichlorosilane
- polypropylene glycol
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- 239000004526 silane-modified polyether Substances 0.000 title claims abstract description 43
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 28
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910000077 silane Inorganic materials 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 13
- -1 alkoxy hydrogen Chemical compound 0.000 claims abstract description 11
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims abstract description 9
- 239000006227 byproduct Substances 0.000 claims abstract description 7
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 7
- 238000005886 esterification reaction Methods 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 36
- 239000002253 acid Substances 0.000 claims description 15
- 150000001412 amines Chemical group 0.000 claims description 12
- 150000002576 ketones Chemical class 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical compound CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 claims description 6
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical group CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 claims description 5
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 claims description 5
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 5
- 229920005591 polysilicon Polymers 0.000 claims description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 150000003058 platinum compounds Chemical class 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005052 trichlorosilane Substances 0.000 claims description 4
- UFFBMTHBGFGIHF-UHFFFAOYSA-N (2,6-Me2C6H3)NH2 Natural products CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000000565 sealant Substances 0.000 abstract description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 13
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000004970 Chain extender Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 125000001891 dimethoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- FEXBEKLLSUWSIM-UHFFFAOYSA-N 2-Butyl-4-methylphenol Chemical compound CCCCC1=CC(C)=CC=C1O FEXBEKLLSUWSIM-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/3311—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group
- C08G65/3312—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group acyclic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Polyethers (AREA)
Abstract
The invention provides a method for preparing silane modified polyether by utilizing dichlorosilane. The method comprises the following steps: s1, carrying out hydrosilation chain extension on double-end allyl polypropylene glycol and dichlorosilane in the presence of a first Pt catalyst to obtain chain-extended double-end allyl polypropylene glycol ether; s2, carrying out esterification reaction on the chain-extended double-end allyl polypropylene glycol ether obtained in the step S1 and alcohol to obtain allyl-terminated silane modified polyether with a siloxy chain; s3, carrying out hydrosilation reaction on the allyl end capped silane modified polyether subjected to the chain extension of the siloxy obtained in the step S2 and alkoxy hydrogen-containing silane under the action of a second Pt catalyst, and obtaining the catalyst. The silane modified polyether which can be used for preparing the sealant is successfully prepared by utilizing the byproduct dichlorosilane in the presence of the first Pt catalyst, and the byproduct is effectively utilized. The method provided by the invention has low cost.
Description
Technical Field
The invention relates to the technical field of synthesis of silane modified polyether polymers, in particular to a method for preparing silane modified polyether by utilizing dichlorosilane.
Background
The dichlorosilane has active chemical property and extremely high danger, is inflammable and explosive, can be exploded in a very wide concentration range after being mixed with air, and is one of the most dangerous process products in the production of polysilicon and trichlorosilane monomers. How to treat dichlorosilane effectively is the focus of most concern for polysilicon and monomer manufacturers. Many enterprises cannot effectively treat dichlorosilane by adopting simple hydrolysis, neutralization and other measures. The loss of elements such as silicon, chlorine and the like is caused, and meanwhile, the potential safety hazard is also high, and the environment is polluted. The silicon hydrogen bond and the silicon chlorine bond in the dichlorosilane have higher reactivity, the highly acidic direct esterification is difficult to obtain the neutral dimethoxysilane with high purity, the boiling point and flash point of the dichlorosilane are extremely low, and the storage condition is harsh, so that the utilization and development of the dichlorosilane are limited, and most monomer enterprises at present adopt the catalytic disproportionation of the dichlorosilane to convert the dichlorosilane into other stable chlorosilane.
At present, silane modified polyether is chain-extended by methylene dichloride, small molecular alcohol containing binary or polyhydric hydroxyl, amino-containing imino compound or ether alcohol, and the small molecular compound is easy to remove from a system, but after chain extension, the bond energy of bonds such as C-O-C, C-N-O is insufficient, and only the chain extension effect is achieved, so that the heat resistance of the polyether cannot be improved.
Disclosure of Invention
In order to solve the defect of improving the performance of the polyether by chain extension of the silane modified polyether at present, a silane modified polyether polymer prepared by chain extension of dichlorosilane and a preparation method thereof are provided, the preparation method can effectively utilize the dichlorosilane, and the silane modified polyether prepared by the preparation method has good heat resistance and other mechanical properties.
The method for preparing silane modified polyether by utilizing dichlorosilane provided by the invention comprises the following steps:
s1, carrying out hydrosilation chain extension on double-end allyl polypropylene glycol and dichlorosilane in the presence of a first Pt catalyst to obtain chain-extended double-end allyl polypropylene glycol ether (TM 1);
s2, carrying out esterification reaction on the chain-extended double-end allyl polypropylene glycol ether obtained in the step S1 and alcohol to obtain allyl-terminated silane modified polyether (TM 2) with a siloxy chain;
s3, carrying out hydrosilation reaction on the allyl terminated silane modified polyether subjected to the chain extension of the siloxy obtained in the step S2 and alkoxy hydrogen-containing silane under the action of a second Pt catalyst, and obtaining silane modified polyether (TM 3).
According to the invention, the silane modified polyether with high heat resistance is successfully synthesized by using the dichlorosilane as the chain extender, and the obtained sealant has high heat resistance and can effectively utilize the dichlorosilane.
In a preferred embodiment of the present invention, the dichlorosilane of the present invention is a by-product of a polysilicon and trichlorosilane synthesis system.
In the present invention, the first Pt catalyst may be a Pt catalyst commonly used in the art, such as an isopropanol solution of chloroplatinic acid, which is an amine coordinated platinum compound in step S1 in a preferred embodiment of the present invention. Platinum compounds in which chloroplatinic acid is coordinated with highly sterically hindered amines obtained by reaction of organic amines and ketones are preferred. Among them, the organic amine is preferably 2, 6-methylaniline, 2, 6-diisopropylaniline or N-phenylaniline, and more preferably 2, 6-diisopropylaniline. The ketone is preferably mesityl oxide, butanedione or acetylacetonate, and more preferably mesityl oxide. Wherein, chloroplatinic acid: organic amine: the molar ratio of ketone is preferably 1: (1-2): (1-2).
In a preferred embodiment of the present invention, the preparation method of the first Pt catalyst comprises the steps of: mixing organic amine, ketone and solvent, micro-refluxing for 10-20 h, cooling to room temperature, deep cooling, filtering, mixing the obtained solid with tetrahydrofuran solution of chloroplatinic acid, performing coordination reaction for 2-3 h under micro-refluxing, recrystallizing and drying to obtain the product. Among them, the solvent is preferably methanol, ethanol or isopropanol. When the alkoxy hydrogen-containing silane is trimethoxy hydrogen-containing silane, the solvent is preferably methanol or isopropanol, and when the alkoxy hydrogen-containing silane is triethoxy hydrogen-containing silane, the solvent is preferably ethanol or isopropanol.
In a preferred embodiment of the present invention, the first Pt catalyst is used in such an amount that Pt in the reaction system is used in an amount of 5 to 100ppm, preferably 20 to 50ppm, based on the total amount of the reaction materials (i.e., all the reaction materials in step S1).
In a preferred embodiment of the invention, the molecular weight of the polypropylene glycol in the double ended allyl polypropylene glycol may be 200, 400, 1000, 2000 or 4000, preferably 4000.
In a preferred embodiment of the present invention, in step S1, the molar ratio of the double-ended allyl polypropylene glycol to the dichlorosilane is (1.5 to 2.5): 1, and more preferably (1.9 to 2.1): 1.
In a preferred embodiment of the present invention, the step S1 is specifically: activating the double-end allyl polypropylene glycol and the first Pt catalyst for 0.1-1 h at the temperature of minus 50-minus 15 ℃, dropwise adding dichlorosilane at the temperature of minus 50-minus 15 ℃, reacting for 1-8 h at the temperature of keeping the temperature, and removing unreacted raw materials to obtain the chain-extended double-end allyl polypropylene glycol ether (namely the double-end allyl polypropylene glycol ether with increased molecular weight). Wherein the activation temperature is preferably-30 to-15 ℃, the activation time is preferably 5 to 20min, and the heat preservation time is preferably 2 to 5h.
In a preferred embodiment of the present invention, in step S1, a solvent is further included, i.e., the double-ended allyl polypropylene glycol, the first Pt catalyst, and the solvent are activated at-50 to-15 ℃ for 0.1 to 1 hour. Wherein the solvent can be cyclohexane, n-hexane, n-heptane and other inert solvents, and the addition amount of the solvent is 50-80 wt% of the double-end allyl polypropylene glycol.
In the method of the invention, the step S1 is an important step, and the dichlorosilane can be effectively and successfully chain-extended with the double-end allyl polypropylene glycol through hydrosilation reaction to prepare the chain-extended double-end allyl polypropylene glycol ether (namely the double-end allyl polypropylene glycol ether with increased molecular weight).
In a preferred embodiment of the present invention, in step S2, the molar ratio of the alcohol to the chain-extended double-ended allyl polypropylene glycol ether obtained in step S1 is (2 to 3): 1, preferably (2.1 to 2.5): 1. wherein the temperature of the esterification reaction in the step S2 is 50-130 ℃. Among them, the alcohol is preferably methanol or ethanol.
In a preferred embodiment of the present invention, the specific steps of step S3 include: mixing the allyl-terminated silane modified polyether with the siloxy chain extension obtained in the step S2 with a second Pt catalyst, activating for 0.5-4 h at 30-80 ℃, dropwise adding trialkoxy hydrogen-containing silane, and then carrying out heat preservation reaction for 1-8 h. Among them, the second Pt catalyst is preferably an isopropanol solution of chloroplatinic acid. The second Pt catalyst is used in such an amount that the amount of Pt in the reaction system is preferably 5 to 100ppm, more preferably 10 to 30ppm, based on the total amount of the reaction materials (i.e., all the reaction materials in the S3 step). In a preferred embodiment of the present invention, the alkoxy hydrogen-containing silane is trimethoxy hydrogen-containing silane, triethoxy hydrogen-containing silane or methyl dimethoxy hydrogen-containing silane, preferably trimethoxy hydrogen-containing silane, and when the alkoxy hydrogen-containing silane is trimethoxy hydrogen-containing silane, the mechanical properties of the obtained sealant are better. The molar ratio of the alkoxy hydrosilane to the siloxy-extended allyl-terminated silane-modified polyether obtained in step S2 is preferably (1.2 to 1.5): 1.
In step S3, the pH of the reaction system is preferably adjusted to 3-5 prior to activation of the allyl-terminated silane-modified polyether of the siloxane chain extension obtained in step S2 with the second Pt catalyst. The pH of the reaction system may be adjusted using an organic acid, which may be oxalic acid, citric acid, acetic acid, etc., preferably acetic acid.
In the step S3, the activation temperature is preferably 40-60 ℃, the activation time is preferably 5-20 min, and the heat preservation time is preferably 2-5 h.
The invention also aims at providing the silane modified polyether TM3 prepared by the preparation method.
The invention also aims to provide the preparation method or application of the silane modified polyether TM3 prepared by the preparation method in preparation of sealant.
The beneficial effects of the invention are as follows:
(1) The invention uses the byproduct dichlorosilane in polysilicon and organosilicon monomer trichlorosilane as a chain extender to successfully prepare macromolecular silane modified polyether in the presence of the first Pt catalyst, effectively uses the byproducts, and the sealant prepared by the silane modified polyether prepared by the method has high heat resistance and good mechanical property.
(2) The method provided by the invention effectively utilizes byproducts and has low cost.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to examples. The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
Example 1
The embodiment of the invention provides a method for preparing silane modified polyether by utilizing dichlorosilane, which comprises the following steps:
1)A-PPG-SiCl 2 ext> Synthesisext> ofext> PPGext> -ext> Aext>
Mixing 204g of polypropylene glycol (A-PPG 4000-A) with end capped by allyl and 110g of cyclohexane, adding a first Pt catalyst, wherein the dosage of the first Pt catalyst is 20ppm of the total amount of reaction raw materials in the reaction system, activating for 20min at-20-15 ℃, then dropwise adding 2.66g of dichlorosilane at-20-15 ℃, preserving heat for 2h, and heating to 20 ℃ to remove unreacted dichlorosilane to obtain 316.4g of cyclohexane solution of TM1;
the preparation method of the first Pt catalyst comprises the following steps:
0.5g of 2, 6-diisopropylaniline, 0.28g of mesityl oxide and 10ml of isopropanol are added into a 50ml three-neck flask, heated to 80 ℃ for micro reflux for 15 hours, cooled to room temperature, cooled to-20 ℃ for deep cooling, filtered, and the obtained yellowish green powder is subjected to coordination reaction with 1.4g of chloroplatinic acid (1.4 g refers to the mass of chloroplatinic acid) in tetrahydrofuran solution at 60-65 ℃ for 2 hours to obtain an orange yellow powdery catalyst, and after recrystallisation of dichloromethane, the orange yellow powdery catalyst is dried for later use.
2)A-PPG-Pr-Si(OCH 3 ) 2 Ext> -ext> Prext> -ext> PPGext> -ext> Aext> synthesisext>
Gasifying 1.76g of methanol into a pressurizing device, adding the cyclohexane solution of TM1 obtained in 1) into the pressurizing device, heating to 90-95 ℃, maintaining 2kg of pressure, preserving heat for 2h, cooling and decompressing, and removing hydrogen chloride and excessive methanol to obtain 300.5g of cyclohexane solution of TM2 (the mass of TM2 is 190.5 g);
3) Synthesis of silane-modified polyethers
Activating the cyclohexane solution of the TM2 obtained in the step 2) and the isopropanol solution of the chloroplatinic acid serving as a second Pt catalyst at 60 ℃ for 1h, wherein the isopropanol solution of the chloroplatinic acid serving as the second Pt catalyst is used for enabling Pt in a reaction system to be 15ppm of the total amount of reaction raw materials in the step, dropwise adding 7.6g trimethoxy hydrogen-containing silane into the reaction system, reacting at 65-70 ℃ for 2h under the condition of heat preservation, monitoring the mass percent of the trimethoxy hydrogen-containing silane by a GC internal standard to be less than or equal to 0.5%, and removing the solvent and unreacted trimethoxy hydrogen-containing silane by reduced pressure distillation to obtain 195.56g of nearly colorless transparent silane modified polyether (TM 3).
Example 2
The method provided in this embodiment is the same as that in embodiment 1, and the only difference is that the preparation method of the first Pt catalyst is different, and in this embodiment, the preparation method of the first Pt catalyst is as follows:
adding 0.36g of 2, 6-methylaniline, 0.26g of butanedione and 10ml of isopropanol into a 50ml three-neck flask, heating to slightly reflux the system for 15h, cooling to room temperature, deep cooling to-20 ℃, filtering, carrying out coordination reaction on the obtained yellow powder and 1.5g of chloroplatinic acid tetrahydrofuran solution for 2h at 60-65 ℃ to obtain a yellow powdery catalyst, recrystallizing dichloromethane, and drying for later use.
This example gives 316.28g of TM1 in cyclohexane, and 196.46g of a nearly colorless transparent silane-modified polyether (TM 3) are finally obtained.
Example 3
The method provided in this embodiment is the same as that in embodiment 1, and the only difference is that the preparation method of the first Pt catalyst is different, and in this embodiment, the preparation method of the first Pt catalyst is as follows:
1.01-g N-phenylaniline, 0.6g of acetylacetone and 15ml of isopropanol are added into a 50ml three-neck flask, the mixture is heated to a system micro reflux state for 15h, cooled to room temperature, cooled to minus 20 ℃, filtered, and the obtained yellow powder is subjected to coordination reaction with 1.5g of chloroplatinic acid tetrahydrofuran solution at 60-65 ℃ for 2h to obtain a yellow powdery catalyst, and after recrystallisation of dichloromethane, the yellow powdery catalyst is dried for standby.
This example gives 316.04g of TM1 in cyclohexane, yielding 196.12g of a nearly colorless transparent silane-modified polyether (TM 3).
Example 4
The method provided in this example is the same as that of example 1, except that in this example the first Pt catalyst is an isopropanol solution of chloroplatinic acid.
This example gives 315.82TM1 as a cyclohexane solution 199.92g of a nearly colorless transparent silane-modified polyether (TM 3).
Example 5
The process provided in this example is the same as that provided in example 1, except that 7.6g of trimethoxy hydrogen containing silane in step 3) is replaced with 6.62g of methyl dimethoxy hydrogen containing silane.
This example gives 194.22g of a near colorless silane-modified polyether (TM 3).
Example 6
The method provided in this example is the same as that provided in example 1, except that:
1. ext> 2.4ext> gext> ofext> dichlorosilaneext> areext> chargedext> inext> stepext> 1ext>)ext>,ext> whereinext> theext> molarext> ratioext> ofext> Aext> -ext> PPGext> -ext> Aext> toext> dichlorosilaneext> isext> 2.1ext>:ext> 1. Step 1) gave 316.33g of TM1 in cyclohexane.
2. Step 3 9.15g trimethoxy hydrogen containing silane was added dropwise.
This example gives 195.96g of a near colorless silane-modified polyether (TM 3).
Comparative example 1
This comparative example provides a method of modifying a polyether with a silane comprising the steps of:
160g of PPG3200 is mixed with 80g of n-heptane after decompression and water removal at 120 ℃, 1.1g of dibutyl tin dilaurate is added, stirring is carried out uniformly, 19.4g of 50% -MDI is dripped into the mixture to react for 2 hours at 50-60 ℃, the content of test-NCO is less than 2%, unreacted MDI is removed by heating and decompression distillation, 11.84g of gKH-550 is added to react for 1 hour at 60-70 ℃, and the unreacted KH-550 is removed by heating and decompression, thus 187.8g of silane modified polyether 1 is obtained.
Comparative example 2
This comparative example provides a method of modifying a polyether with a silane comprising the steps of:
100g of A-PPG4000-OH and 5.1g of 29% sodium methoxide/methanol solution are reacted for 1h at 50 ℃, 1.2g of methylene dichloride is added dropwise for 2h at 40-50 ℃, filtering, neutralizing, adding chloroplatinic acid isopropanol solution, enabling the Pt content to be 30ppm of the mixed reaction raw materials, activating for 0.5h at 60 ℃, 3.36g of trimethoxy hydrogen-containing silane is added dropwise, reacting for 2h at 60-70 ℃ with heat preservation, and distilling to remove low boiling point to obtain 103.1g of silane modified polyether 2.
Experimental example
The silane-modified polyethers provided in the examples and comparative examples of the present invention were used to prepare sealants, respectively, for performance testing.
The preparation method of the sealant comprises the following steps: 100 parts by mass of silane modified polyether, 200 parts by mass of active light calcium carbonate and 60 parts by mass of carbon black (the active light calcium carbonate and the carbon black are dried in advance at 120 ℃ for 24 hours), 80 parts by mass of polypropylene glycol plasticizer and 3 parts by mass of vinyl trimethoxysilane are mixed and stirred uniformly, 1 part by mass of salicylate absorbent and 1 part by mass of 2, 6-butyl-4-methylphenol are added into the mixture, the mixture is stirred until the mixture is uniformly dispersed, 1 part by mass of dibutyltin dilaurate is added into the mixture, and the mixture is stirred uniformly to obtain the sealant.
The sealants prepared using the silane-modified polyethers provided in examples and comparative examples and using the methods described above were tested. Wherein tensile strength, elongation at break and tensile modulus are measured according to GB/T528-2009. The obtained sealant was applied with a tape, the tape was cured under standard conditions for seven days, the cured tape was baked in an oven at 120 ℃, and the time of chalking of the surface of the tape was recorded, and the results were as shown in table 1 below.
TABLE 1 results of sealant performance
Finally, the method of the present invention is only a preferred embodiment and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (12)
1. A method for preparing silane modified polyether by utilizing dichlorosilane, which is characterized by comprising the following steps:
s1, carrying out hydrosilation chain extension on double-end allyl polypropylene glycol and dichlorosilane in the presence of a first Pt catalyst to obtain chain-extended double-end allyl polypropylene glycol ether;
s2, carrying out esterification reaction on the chain-extended double-end allyl polypropylene glycol ether obtained in the step S1 and alcohol to obtain allyl-terminated silane modified polyether with a siloxy chain;
s3, carrying out hydrosilation reaction on the allyl end capped silane modified polyether subjected to the chain extension of the siloxy obtained in the step S2 and alkoxy hydrogen-containing silane under the action of a second Pt catalyst, and obtaining the catalyst.
2. The method of claim 1, wherein in step S1, the first Pt catalyst is an amine coordinated platinum compound.
3. The method of claim 2, wherein the first Pt catalyst is a highly sterically hindered amine coordinated platinum compound obtained by reacting chloroplatinic acid with an organic amine and a ketone.
4. A method according to claim 3, wherein the dichlorosilane is a byproduct of a polysilicon and trichlorosilane monomer synthesis system;
and/or the organic amine is 2, 6-methylaniline, 2, 6-diisopropylaniline or N-phenylaniline;
and/or the ketone is mesityl oxide, butanedione or acetylacetone.
5. A method according to claim 3, wherein the organic amine is 2, 6-diisopropylaniline;
and/or, the ketone is mesityl oxide.
6. The method according to any one of claims 3 to 5, wherein the chloroplatinic acid: organic amine: the molar ratio of ketone is 1: (1-2): (1-2).
7. The method according to any one of claims 1 to 5, wherein in step S1, the molar ratio of the double-ended allyl polypropylene glycol to the dichlorosilane is (1.5-2.5): 1; the dosage of the first Pt catalyst is 5-100 ppm of the reaction raw material.
8. The method according to any one of claims 1 to 5, characterized in that said step S1 comprises the steps of: activating the double-end allyl polypropylene glycol and the first Pt catalyst for 0.1-1 h at the temperature of minus 50 to minus 15 ℃, dropwise adding dichlorosilane at the temperature of minus 50 to minus 15 ℃, reacting for 1-8 h at the temperature of preserving heat, and removing unreacted raw materials to obtain the chain-extended double-end allyl polypropylene glycol ether.
9. The method according to any one of claims 1 to 5, wherein in step S2, the molar ratio of the alcohol to the chain-extended double-ended allyl polypropylene glycol ether obtained in step S1 is (2 to 3): 1, a step of;
and/or the temperature of the esterification reaction is 50-130 ℃.
10. The method according to any one of claims 1 to 5, wherein the specific step of step S3 is:
and (2) mixing the allyl-terminated silane modified polyether with the siloxy chain extension obtained in the step (S2) with a second Pt catalyst, activating for 0.5-4 hours at the temperature of 30-80 ℃, dropwise adding alkoxy hydrogen-containing silane, and then carrying out heat preservation reaction for 1-8 hours.
11. The method according to claim 10, wherein the amount of the second Pt catalyst is such that the amount of Pt in the reaction system is 5 to 100ppm of the reaction raw material;
and/or the molar ratio of the alkoxy hydrogen-containing silane to the allyl terminated silane modified polyether of the siloxy chain extension obtained in the step S2 is (1.2-1.5): 1.
12. A silane-modified polyether prepared by the process of any one of claims 1 to 11.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1824689A (en) * | 2006-02-17 | 2006-08-30 | 浙江大学 | Synthesis method of silicane coupling agent having long chain polyether chain section |
JP2009185169A (en) * | 2008-02-06 | 2009-08-20 | Chugoku Marine Paints Ltd | New polyorganosiloxane and room temperature-curable silicone composition containing the same as crosslinking agent |
CN109293911A (en) * | 2018-09-30 | 2019-02-01 | 烟台德邦科技有限公司 | A kind of preparation method of end silicone based polyether resin |
CN110117357A (en) * | 2019-04-12 | 2019-08-13 | 浙江新安化工集团股份有限公司 | A kind of silane modified polyether and preparation method thereof |
-
2021
- 2021-11-01 CN CN202111280908.9A patent/CN113861406B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1824689A (en) * | 2006-02-17 | 2006-08-30 | 浙江大学 | Synthesis method of silicane coupling agent having long chain polyether chain section |
JP2009185169A (en) * | 2008-02-06 | 2009-08-20 | Chugoku Marine Paints Ltd | New polyorganosiloxane and room temperature-curable silicone composition containing the same as crosslinking agent |
CN109293911A (en) * | 2018-09-30 | 2019-02-01 | 烟台德邦科技有限公司 | A kind of preparation method of end silicone based polyether resin |
CN110117357A (en) * | 2019-04-12 | 2019-08-13 | 浙江新安化工集团股份有限公司 | A kind of silane modified polyether and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
三氯氢硅制备技术进展;陈其国;韩春;;中国氯碱(09);全文 * |
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