CN113292591A - Synthesis method and application of 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane - Google Patents

Synthesis method and application of 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane Download PDF

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CN113292591A
CN113292591A CN202110700303.4A CN202110700303A CN113292591A CN 113292591 A CN113292591 A CN 113292591A CN 202110700303 A CN202110700303 A CN 202110700303A CN 113292591 A CN113292591 A CN 113292591A
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bis
tetramethyldisiloxane
isocyanatoalkyl
silane
alkyl
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高胜波
刘嵚
陈辉
李庆
李越
祁拥军
郑泽
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Tangshan Sanfu New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C07F7/0872—Preparation and treatment thereof
    • C07F7/0889—Reactions not involving the Si atom of the Si-O-Si sequence
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/778—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur 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
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon

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Abstract

The invention discloses a synthesis method and application of 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane, and relates to the technical field of compound synthesis. The synthesis method effectively reduces the input cost of raw materials by utilizing the mode of obtaining the alkyl carbamate silane by reacting cyanate, alkyl alcohol and chloroalkane silane; the trimethyl chlorosilane is used as a protective agent to protect the secondary amine on the alkyl carbamate double-end socket, so that the generation of polymerization reaction phenomena such as byproducts and the like in the cracking process is prevented. The synthesis method has the advantages of simple process, short synthesis time, high synthesis efficiency, high yield of finished products up to more than 95%, and contribution to industrial mass production. The 1, 3-bis (isocyanate alkyl) -1,1,3, 3-tetramethyldisiloxane is applied as a preparation raw material in polyurethane, coating, sealant and polyether modified products.

Description

Synthesis method and application of 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane
Technical Field
The invention relates to the technical field of compound synthesis, in particular to a synthesis method and application of 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane.
Background
In the prior art, dimethyl carbonate and 1, 3-bis (chloropropyl) -1,1,3, 3-tetramethyldisiloxane are mostly adopted to react to produce alkyl carbamate, and then the alkyl carbamate is cracked to obtain the subsequent corresponding product. In the prior art, alkyl carbamate prepared by reacting 1, 3-bis (chloropropyl) -1,1,3, 3-tetramethyldisiloxane with dimethyl carbonate has low yield, more raw materials are used in the early stage, more byproducts are generated in the cracking process, and the products are difficult to separate. The yield of the alkyl carbamate prepared by the reaction is low.
Therefore, it is a most important issue to provide a new synthesis process that can further increase the yield of alkyl carbamate, shorten the synthesis preparation time, and prevent the occurrence of byproducts and the like in the cracking process, while reducing the raw material input cost.
Disclosure of Invention
In order to solve the technical problems, the invention provides a synthesis method and application of 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane.
In order to realize the technical purpose, the invention adopts the following scheme: the synthesis method of 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane comprises the following steps:
the method comprises the following steps: reacting chloroalkane silane, cyanate and alkyl alcohol to synthesize alkyl carbamate silane, wherein the chemical reaction equation is as follows:
Figure BDA0003129518680000011
wherein R is1Represents methine, e.g. -CH2-、
Figure BDA0003129518680000012
Etc.; r2Represents an alkyl group such as methyl or ethyl;
step two: dropping the alkyl carbamate silane into the hydrolytic agent for hydrolysis to obtain the 1, 3-bis (alkyl carbamate esteralkyl) -1,1,3, 3-tetramethyl disiloxane, wherein the reaction time of the second step is from the beginning to the end of the dropping, and the reaction equation is as follows:
Figure BDA0003129518680000021
step three: triethylamine (as an acid-binding agent) is added into 1, 3-bis (carbamic acid alkyl ester alkyl group) -1,1,3, 3-tetramethyl disiloxane in advance, then a protective agent is dripped into the 1, 3-bis (carbamic acid alkyl ester alkyl group) -1,1,3, 3-tetramethyl disiloxane under the action of triethylamine, and the protective agent is dripped in 4 hours at 50 ℃ to obtain trimethylsilyl carbamic acid alkyl ester silane, wherein the reaction equation is as follows:
Figure BDA0003129518680000022
step four: the trimethylsilyl alkyl carbamate silane is cleaved to give 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane, the reaction equation being as follows:
Figure BDA0003129518680000023
preferably, the chloroalkane silane is one or more of chloropropyldimethylmethoxysilane, chloropropyldimethylethoxysilane, chloromethyldimethylmethoxysilane and chloromethyldimethylethoxysilane.
Preferably, the alkyl alcohol is one or more of aliphatic alcohol and aromatic alcohol.
Preferably, the aliphatic alcohol is one or more of methanol, ethanol, propanol, isopropanol, butanol, cyclohexanol, tert-butanol. The aromatic alcohol is one or more of cyclohexanol and benzyl alcohol.
Preferably, the cyanate is one or more of sodium cyanate, potassium cyanate, magnesium cyanate, calcium cyanate, and barium cyanate.
Preferably, the synthesis reaction temperature in the first step is 80-180 ℃, preferably 100-160 ℃, and further preferably 130 ℃; the synthesis pressure is 0-0.3 MPa, preferably 0.1-0.2 MPa; the synthesis time is 11-14 h.
Preferably, the hydrolytic agent in the second step is water, and the volume ratio of the water usage to the carbamate silane usage is 1-5: 1-2; the hydrolysis temperature is 25 to 100 ℃, preferably 65 to 85 ℃, and more preferably 80 ℃.
Preferably, the protective agent is trimethylchlorosilane; in the third step, the molar ratio of the 1, 3-bis (carbamic acid alkyl ester alkyl group) -1,1,3, 3-tetramethyl disiloxane to the triethylamine to the protective agent is 1-2: 2.4-6: 2.2-5.
Preferably, the cracking temperature in step four is 150 ℃ to 280 ℃, preferably 200 ℃ to 250 ℃, and more preferably 220 ℃. The cracking pressure is-0.07 MPa-0.1 MPa. The fourth step of cracking reaction time in the laboratory test process is 8 hours; in the actual production process, the cracking time of 1 ton of material is 24 hours, and the cracking time is related to the material quantity. And (4) after cracking is finished, pumping out the cracking product from the cracking kettle under negative pressure, and finishing the reaction when no product can be pumped out from the cracking kettle.
An application of 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane, and an application of a finished product prepared by the synthesis method as a preparation raw material in polyurethane, coating, sealant and polyether modified products.
Compared with the prior art, the invention has the beneficial effects that: the invention provides a synthesis method of 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane, which is a method for obtaining alkyl carbamate silane by using reaction of cyanate, alkyl alcohol and chloroalkane silane, so that the input cost of raw materials is effectively reduced; the trimethyl chlorosilane is used as a protective agent to protect the secondary amine on the alkyl carbamate double-end socket, so that the generation of polymerization reaction phenomena such as byproducts and the like in the cracking process is prevented. The synthesis method has the advantages of simple process, short synthesis time, high synthesis efficiency, and high yield of the finished product of over 95%, and is favorable for industrial mass production. The 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane is applied as a preparation raw material in the industries of polyurethane, coating, sealant and polyether modification.
Drawings
FIG. 1 is a gas chromatogram of the feed at the start of the third reaction in example 1 of the present invention;
FIG. 2 is a gas chromatogram of an intermediate material in the third reaction step of example 1 according to the present invention;
FIG. 3 is a gas chromatogram of the crude product after the reaction of the third step in example 1 of the present invention is completed;
FIG. 4 is a gas chromatogram of the cracked product of the fourth reaction of example 1.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to fully understand the objects, features and effects of the invention, but the present invention is not limited thereto.
Example 1
A method for synthesizing 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane comprises the following steps:
the first step is as follows: chloropropyl dimethyl methoxy silane, sodium cyanate and methanol react for 13 hours at the temperature of 130 ℃ and the pressure of 0.1MPa according to the molar ratio of 1:2.5:3 to synthesize the methyl carbamate silane.
The second step is that: and (3) dropwise adding the methyl carbamate silane into water at the temperature of 80 ℃ for hydrolysis, wherein the volume ratio of the water to the methyl carbamate silane is 3:1, so as to obtain 1, 3-bis (carbamoylpropyl) -1,1,3, 3-tetramethyldisiloxane, and ending the dropwise addition, namely ending the second-step reaction.
The third step: adding triethylamine into 1, 3-bis (carbamic acid methyl ester propyl group) -1,1,3, 3-tetramethyl disiloxane, dropwise adding trimethyl chlorosilane into 1, 3-bis (carbamic acid methyl ester propyl group) -1,1,3, 3-tetramethyl disiloxane at 50 ℃, and completing dropwise adding for 4 hours to obtain trimethylsilyl amino methyl ester silane. Wherein the molar ratio of the 1, 3-bis (carbamoylpropyl) -1,1,3, 3-tetramethyldisiloxane to the triethylamine to the trimethylchlorosilane is 1:3: 3.
The fourth step: the trimethylsilyl methyl carbamate silane is cracked at 220 ℃ and the pressure of-0.07 MPa to obtain the 1, 3-bis (isocyanatopropyl) -1,1,3, 3-tetramethyldisiloxane.
Example 2
A method for synthesizing 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane comprises the following steps:
the first step is as follows: chloropropyl dimethyl methoxy silane, potassium cyanate and ethanol react for 11 hours at 180 ℃ and 0.2MPa according to the molar ratio of 1:2.5:3 to synthesize the urethane silane.
The second step is that: and (3) dropwise adding the urethane silane into water at 100 ℃ for hydrolysis, wherein the volume ratio of the water to the urethane silane is 5:1.5, so as to obtain 1, 3-bis (urethane propyl) -1,1,3, 3-tetramethyldisiloxane, and ending the dropwise addition, namely ending the reaction in the second step.
The third step: adding triethylamine into 1, 3-bis (ethyl carbamate propyl) -1,1,3, 3-tetramethyldisiloxane, then dropwise adding trimethylchlorosilane into 1, 3-bis (ethyl carbamate propyl) -1,1,3, 3-tetramethyldisiloxane at 50 ℃, and completing dropwise adding for 4h to obtain the trimethylsilyl ethyl carbamate silane. Wherein the molar ratio of the 1, 3-bis (carbamoylpropyl) -1,1,3, 3-tetramethyldisiloxane to the triethylamine to the trimethylchlorosilane is 1.5:5: 4.
The fourth step: trimethylsilyl urethane silane was cleaved at 200 ℃ and 0.1MPa to give 1, 3-bis (isocyanatopropyl) -1,1,3, 3-tetramethyldisiloxane.
Example 3
A method for synthesizing 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane comprises the following steps:
the first step is as follows: chloropropyldimethylethoxysilane, magnesium cyanide and tertiary butanol are reacted for 14h according to the molar ratio of 1:2.5:3 at 80 ℃ and the pressure of 0.1MPa to synthesize the tert-butyl carbamate silane.
The second step is that: and (3) dropwise adding the tert-butyl carbamate silane into water at 25 ℃ for hydrolysis, wherein the volume ratio of the water to the tert-butyl carbamate silane is 4:1, so as to obtain 1, 3-bis (tert-butylcarbamoylpropyl) -1,1,3, 3-tetramethyldisiloxane, and ending the dropwise addition, namely ending the reaction in the second step.
The third step: adding triethylamine into 1, 3-bis (tert-butylcarbamoylpropyl) -1,1,3, 3-tetramethyldisiloxane, dropwise adding trimethylchlorosilane into 1, 3-bis (tert-butylcarbamoylpropyl) -1,1,3, 3-tetramethyldisiloxane at 50 ℃, and completing dropwise adding for 4h to obtain the trimethylsilyl carbamic acid tert-butyl ester silane, wherein the molar ratio of the 1, 3-bis (tert-butylcarbamoylpropyl) -1,1,3, 3-tetramethyldisiloxane to the triethylamine to the trimethylchlorosilane is 2:6: 5.
The fourth step: the trimethylsilyl carbamic acid tert-butyl ester silane is cracked at the temperature of 150 ℃ and the pressure of-0.07 MPa to obtain the 1, 3-bis (isocyanatopropyl) -1,1,3, 3-tetramethyldisiloxane.
Example 4
A method for synthesizing 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane comprises the following steps:
the first step is as follows: chloropropyldimethylethoxysilane, barium cyanate and benzyl alcohol react for 11 hours at 180 ℃ and 0.2MPa according to the molar ratio of 1:2.5:3 to synthesize the benzyl carbamate silane.
The second step is that: dropwise adding the benzyl carbamate silane into water at 100 ℃ for hydrolysis, wherein the volume ratio of the water to the benzyl carbamate silane is 5:2, so as to obtain 1, 3-bis (benzyl carbamate propyl) -1,1,3, 3-tetramethyldisiloxane, and finishing the dropwise adding, namely finishing the second-step reaction.
The third step: adding triethylamine into 1, 3-bis (carbamic acid phenylmethylester propyl) -1,1,3, 3-tetramethyldisiloxane, dropwise adding trimethylchlorosilane into 1, 3-bis (carbamic acid phenylmethylester propyl) -1,1,3, 3-tetramethyldisiloxane at 50 ℃, and finishing dropwise adding for 4h to obtain trimethylsilyl amino phenylmethylester silane, wherein the molar ratio of 1, 3-bis (carbamic acid phenylmethylester propyl) -1,1,3, 3-tetramethyldisiloxane to triethylamine to trimethylchlorosilane is 1:5: 4.
The fourth step: trimethylsilyl benzyl carbamate silane is cracked at 200 ℃ and 0.1MPa to obtain 1, 3-bis (isocyanatopropyl) -1,1,3, 3-tetramethyldisiloxane.
Example 5
A method for synthesizing 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane comprises the following steps:
the first step is as follows: chloromethyl dimethyl methoxy silane, sodium cyanate and methanol react according to the molar ratio of 1:2.5:3 at 100 ℃ and the pressure of 0.1MPa to synthesize 13.5h of methyl carbamate silane.
The second step is that: and (3) dropwise adding the methyl carbamate silane into water at 45 ℃ for hydrolysis, wherein the volume ratio of the water to the methyl carbamate silane is 1:2, so as to obtain 1, 3-bis (carbamoylmethyl) -1,1,3, 3-tetramethyldisiloxane, and ending the dropwise addition, namely ending the second-step reaction.
The third step: adding triethylamine into 1, 3-bis (carbamoylmethylyl-methyl) -1,1,3, 3-tetramethyldisiloxane, dropwise adding trimethylchlorosilane into 1, 3-bis (carbamoylmethylyl-methyl) -1,1,3, 3-tetramethyldisiloxane at 50 ℃, and finishing dropwise adding for 4h to obtain trimethylsilylcarbamatomethylsilane, wherein the molar ratio of 1, 3-bis (carbamoylmethylyl-methyl) -1,1,3, 3-tetramethyldisiloxane to triethylamine to trimethylchlorosilane is 1:2.4: 2.2.
The fourth step: the trimethylsilyl methyl carbamate silane is cracked at 160 ℃ and the pressure of-0.07 MPa to obtain the 1, 3-bis (isocyanatomethyl) -1,1,3, 3-tetramethyldisiloxane.
Example 6
A method for synthesizing 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane comprises the following steps:
the first step is as follows: chloromethyl dimethyl ethoxy silane, potassium cyanate and ethanol react according to the molar ratio of 1:2.5:3 at 160 ℃ and the pressure of 0.2MPa to synthesize 11.5h of urethane silane.
The second step is that: and (3) dropwise adding the urethane silane into water at 85 ℃ for hydrolysis, wherein the volume ratio of the water to the urethane silane is 1:1, so as to obtain 1, 3-bis (urethane methyl) -1,1,3, 3-tetramethyldisiloxane, and ending the dropwise addition, namely ending the second-step reaction.
The third step: adding triethylamine into 1, 3-bis (carbamic acid carbethoxymethyl) -1,1,3, 3-tetramethyldisiloxane, then dropwise adding trimethylchlorosilane into 1, 3-bis (carbamic acid carbethoxymethyl) -1,1,3, 3-tetramethyldisiloxane at 50 ℃, and obtaining trimethylsilyl carbamic acid ester silane after 4h of dropwise adding, wherein the molar ratio of 1, 3-bis (carbamic acid carbethoxymethyl) -1,1,3, 3-tetramethyldisiloxane to triethylamine to trimethylchlorosilane is 1.5:4: 3.
The fourth step: trimethylsilyl carbamate silane was cleaved at 185 ℃ and 0.1MPa to give 1, 3-bis (isocyanatomethyl) -1,1,3, 3-tetramethyldisiloxane.
Example 7
A method for synthesizing 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane comprises the following steps:
the first step is as follows: chloromethyl dimethyl ethoxy silane, potassium cyanate and benzyl alcohol react for 13 hours at 140 ℃ and 0.1MPa according to the molar ratio of 1:2.5:3 to synthesize the carbamic acid benzyl ester silane.
The second step is that: adding water into the carbamic acid benzyl ester silane at the temperature of 55 ℃ for hydrolysis, wherein the volume ratio of the water to the carbamic acid benzyl ester silane is 5:1, so as to obtain 1, 3-bis (carbamic acid benzyl ester methyl group) -1,1,3, 3-tetramethyl disiloxane, and finishing the dropwise addition, namely finishing the second step reaction.
The third step: adding triethylamine into 1, 3-bis (carbamic acid phenylmethyl) 1,1,3, 3-tetramethyldisiloxane, then dropwise adding trimethylchlorosilane into 1, 3-bis (carbamic acid phenylmethyl) 1,1,3, 3-tetramethyldisiloxane at 50 ℃, and obtaining trimethylsilyl carbamic acid phenylmethyl silane after 4h of dropwise addition, wherein the molar ratio of 1, 3-bis (carbamic acid phenylmethyl) 1,1,3, 3-tetramethyldisiloxane to triethylamine to trimethylchlorosilane is 2:5: 4.
The fourth step: trimethylsilyl benzyl carbamate silane is cracked at 175 ℃ and 0.1MPa to obtain 1, 3-bis (isocyanatomethyl) -1,1,3, 3-tetramethyldisiloxane.
In the practical operation process of the above embodiment, the selected synthesis reaction device is a full-automatic organic synthesis reaction device, the device is made of stainless steel, the specification and model are DDS-1000 and DDS-14, and the manufacturer: shanghai investigation instruments Ltd. The hydrolysis unit who selects for use is italian VELLP HU6 hydrolysis unit, and the device is stainless steel, and specification model is HU6, and the producer: german and auspicious technologies, Inc. The cracking device who chooses for use is the cracking reaction cauldron, and the device is stainless steel material, and specification model is USC-6, and the producer: hebei Zhongyu instruments and Equipment, Inc.
The product detection method comprises the following steps: the product is liquid, and the whole process adopts gas chromatography detection (area normalization method);
the detection device comprises: lunans Rainbow gas chromatograph SP-7890.
Sample injector: and (4) splitting.
Separating the column: capillary, column number DB-5 (column length 30m, column diameter 0.32mm, film thickness 0.5 μm).
A detector: FID (flame ionization detector).
Detecting the gas pressure of each item of equipment: column head pressure 0.1 MP; tail blowing 0.1 MP; hydrogen 0.1 MP; empty hydrogen 0.1 MP.
Flow of carrier gas in each part of detection equipment: column flow rate: 5 ml/min; shunting: 20 ml/min; purging: 10 ml/min.
Detecting the temperature of the equipment: sample injector: 270 ℃; a detector: 280 ℃.
Column box:
order of the scale Rate (. degree.C./min) End temperature (. degree.C.) Retention time (min)
Initial - 80.0 1.0
1 st order 10.0 100.0 0
2 order 15.0 140.0 0
3 order 25.0 280.0 10
The detection purpose is as follows:
1. and verifying that trimethylchlorosilane is added into the 1, 3-bis (carbamatoalkyl) -1,1,3, 3-tetramethyldisiloxane in the third step under the action of triethylamine to obtain the trimethylsilyl carbamate silane, so that whether the next step of reaction is influenced by unreacted amino ester is prevented.
2. Verifying the purity and yield of the crude product of 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane obtained by the fourth step of trimethylsilyl carbamate silane cracking.
Experimental groups: the finished product prepared in example 1 above was selected as the experimental group.
The experimental results are as follows:
FIG. 1 is a gas chromatogram of the feed at the start of the reaction in the third step of example 1. The axis of abscissa in the graph represents the time of peak appearance of the substance in the instrument, the axis of ordinate represents the peak height of the substance, data 1.313 is the time of peak appearance of triethylamine, and data 2.318 is the time of peak appearance of carbamate. The unreacted feed peaks are evident from FIG. 1.
FIG. 2 is a gas chromatogram of the middle of the reaction in the third step of example 1. The axis of abscissa in the graph represents the time of peak of a substance in an instrument, the axis of ordinate represents the peak height of the substance, the data is 1.313 of the time of peak of triethylamine, 2.318 of the time of peak of carbamate, and 2.438 of the time of peak of trimethylsilyl carbamate. From FIG. 2, two peaks of product and starting material can be observed after the reaction has proceeded for a while.
FIG. 3 is a gas chromatogram of the crude product after the reaction of the third step in example 1. The abscissa axis in the graph represents the peak-off time of a substance in an instrument, the ordinate axis represents the peak height of the substance, and the peak-off time 2.413 is the peak type of trimethylsilyl carbamate. From fig. 3, it can be observed that there are substantially no other raw material peaks after purification. And the data in table 1 show that 97.1% of the material after the third step reaction is concentrated in the peak time of 2.413, which indicates that the material has very low content of other materials except trimethylsilyl carbamate and the purity meets the requirement.
TABLE 1 table of purity of the material after the end of the third reaction step
Figure BDA0003129518680000091
FIG. 4 is a peak diagram of crude 1, 3-bis (isocyanatopropyl) -1,1,3, 3-tetramethyldisiloxane obtained by the fourth step of cracking trimethylsilyl carbamate silane at 220 ℃ and under a pressure of-0.07 MPa. In FIG. 4, the axis of abscissa indicates the time of appearance of a substance in an instrument, the axis of ordinate indicates the peak height of the substance, and the ratio of the peak area at a peak appearance time of 1.968 indicates the content of 1, 3-bis (isocyanatopropyl) -1,1,3, 3-tetramethyldisiloxane; the peak area ratio at a peak-off time of 2.083 represents the content of (1-isocyanatopropyl-3-carbamoylmethylpropyl) -1,1,3, 3-tetramethyldisiloxane. It is observed from FIG. 4 that the material still has a part of incomplete reaction to become a product after cracking, and there is one in which the trimethylsilyl group is removed but the product is not completely changed. As a result of the data shown in Table 2, it was confirmed that the yield of 1, 3-bis (isocyanatopropyl) -1,1,3, 3-tetramethyldisiloxane was 95.7% after the fourth reaction step.
TABLE 2 table of purity of product after the fourth reaction step
Figure BDA0003129518680000101
The final products of the remaining 6 groups of examples and comparative examples were subjected to gas chromatography and the product yields are shown in table 3. The product yield of the examples is significantly improved compared to the comparative examples.
TABLE 3 Final product yields
Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative example
Yield/% 95.04491 95.28577 94.96755 95.23849 94.9664 95.11409 89.29659
The invention provides a synthesis method of 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane, which is a method for obtaining carbamate silane by using reaction of cyanate, alkyl alcohol and chloroalkane silane, so that the input cost of raw materials is effectively reduced; the secondary amine on the carbamate double-end socket is protected by using the trimethylchlorosilane as a protective agent, so that the generation of polymerization reaction phenomena such as side products and the like in the cracking process is prevented. The synthesis method has the advantages of simple process, short synthesis time, high synthesis efficiency, high yield of finished products up to more than 95%, and contribution to industrial mass production. The 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane is applied as a preparation raw material in the industries of polyurethane, coating, sealant and polyether modification.
Finally, it is noted that: the above-mentioned list is only the preferred embodiment of the present invention, and naturally those skilled in the art can make modifications and variations to the present invention, which should be considered as the protection scope of the present invention provided they are within the scope of the claims of the present invention and their equivalents.

Claims (10)

1. A method for synthesizing 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane is characterized by comprising the following steps:
the method comprises the following steps: reacting chloroalkane silane, cyanate and alkyl alcohol to synthesize alkyl carbamate silane;
step two: dropwise adding alkyl carbamate silane into a hydrolyzing agent to hydrolyze to obtain 1, 3-bis (alkyl carbamate esteralkyl) -1,1,3, 3-tetramethyldisiloxane;
step three: adding a protective agent into 1, 3-bis (alkyl carbamate alkyl ester) -1,1,3, 3-tetramethyldisiloxane under the action of triethylamine to obtain trimethylsilyl alkyl carbamate silane;
step four: the trimethylsilyl alkyl carbamate silane is cleaved to give 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane.
2. The method for synthesizing 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane in the first step, wherein the chloroalkane silane is one or more of chloropropyldimethylmethoxysilane, chloropropyldimethylethoxysilane, chloromethyldimethylmethoxysilane and chloromethyldimethylethoxysilane; the cyanate is one or more of sodium cyanate, potassium cyanate, magnesium cyanate, calcium cyanate, and barium cyanate; the alkyl alcohol is aliphatic alcohol and/or aromatic alcohol.
3. The method for synthesizing 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane in accordance with claim 2, wherein the aliphatic alcohol is one or more of methanol, ethanol, propanol, isopropanol, butanol, cyclohexanol, tert-butanol; the aromatic alcohol is cyclohexanol and/or benzyl alcohol.
4. The method for synthesizing 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane in accordance with claim 2 or 3, wherein the molar ratio of chloroalkane silane, cyanate and alkyl alcohol is 1:2.5: 3.
5. The method for synthesizing 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane according to claim 4, wherein the synthesis reaction temperature in the first step is 80-180 ℃, the synthesis pressure is 0-0.3 MPa, and the synthesis time is 11-14 h.
6. The method for synthesizing 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane according to claim 1, wherein the hydrolysis agent in the second step is water, and the volume ratio of water to alkyl carbamate silane is 1-5: 1-2.
7. The method for synthesizing 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane according to claim 1 or 6, wherein the hydrolysis temperature in step two is 25 to 100 ℃ and the end of the dropwise addition is the end of step two.
8. The method for synthesizing 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane according to claim 1, wherein the protective agent in step three is trimethylchlorosilane, 1, 3-bis (carbamato alkyl esteralkyl) -1,1,3, 3-tetramethyldisiloxane, triethylamine and trimethylchlorosilane in a molar ratio of 1-2: 2.4-6: 2.2-5; the hydrolysis temperature is 50 ℃, and the hydrolysis time is 4 h.
9. The method for synthesizing 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane in accordance with claim 1, wherein the cracking temperature in step four is 150 ℃ to 280 ℃ and the cracking pressure is-0.07 MPa to 0.1 MPa.
10. Use of 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane, characterized in that the finished product prepared by the method of any one of claims 1-9 of 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane is used as a starting material in the preparation of polyurethane, paint, sealants and polyether modified products.
CN202110700303.4A 2021-06-23 2021-06-23 Synthesis method and application of 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane Pending CN113292591A (en)

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