CN117024745A - Method for preparing organosilicon polyol based on mercapto-alkene light-click reaction - Google Patents
Method for preparing organosilicon polyol based on mercapto-alkene light-click reaction Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 22
- 229920005862 polyol Polymers 0.000 title claims abstract description 21
- 150000003077 polyols Chemical class 0.000 title claims abstract description 14
- 238000012650 click reaction Methods 0.000 title claims abstract description 12
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 41
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920002545 silicone oil Polymers 0.000 claims abstract description 21
- -1 polysiloxane Polymers 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 10
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- 239000010703 silicon Substances 0.000 claims description 15
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 14
- 244000028419 Styrax benzoin Species 0.000 claims description 7
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 7
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 7
- 229960002130 benzoin Drugs 0.000 claims description 7
- 235000019382 gum benzoic Nutrition 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 claims description 6
- SHLSSLVZXJBVHE-UHFFFAOYSA-N 3-sulfanylpropan-1-ol Chemical compound OCCCS SHLSSLVZXJBVHE-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 4
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 3
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- ULGGZAVAARQJCS-UHFFFAOYSA-N 11-sulfanylundecan-1-ol Chemical compound OCCCCCCCCCCCS ULGGZAVAARQJCS-UHFFFAOYSA-N 0.000 claims description 2
- MJQWABQELVFQJL-UHFFFAOYSA-N 3-Mercapto-2-butanol Chemical compound CC(O)C(C)S MJQWABQELVFQJL-UHFFFAOYSA-N 0.000 claims description 2
- HABNNYNSJFKZFE-UHFFFAOYSA-N 3-Mercapto-2-methylpentanol Chemical compound CCC(S)C(C)CO HABNNYNSJFKZFE-UHFFFAOYSA-N 0.000 claims description 2
- UGZAJZLUKVKCBM-UHFFFAOYSA-N 6-sulfanylhexan-1-ol Chemical compound OCCCCCCS UGZAJZLUKVKCBM-UHFFFAOYSA-N 0.000 claims description 2
- XJTWZETUWHTBTG-UHFFFAOYSA-N 8-sulfanyloctan-1-ol Chemical compound OCCCCCCCCS XJTWZETUWHTBTG-UHFFFAOYSA-N 0.000 claims description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 22
- 239000011248 coating agent Substances 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 15
- 239000010985 leather Substances 0.000 abstract description 10
- 239000002649 leather substitute Substances 0.000 abstract description 10
- 230000009257 reactivity Effects 0.000 abstract description 9
- 238000002360 preparation method Methods 0.000 abstract description 8
- 150000003138 primary alcohols Chemical class 0.000 abstract description 8
- 150000003333 secondary alcohols Chemical class 0.000 abstract description 6
- 239000004758 synthetic textile Substances 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 230000003373 anti-fouling effect Effects 0.000 abstract description 5
- 239000004814 polyurethane Substances 0.000 abstract description 5
- 229920002635 polyurethane Polymers 0.000 abstract description 4
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 abstract description 4
- 230000002209 hydrophobic effect Effects 0.000 abstract description 3
- 239000003607 modifier Substances 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- 150000001298 alcohols Chemical class 0.000 abstract description 2
- 239000012948 isocyanate Substances 0.000 abstract description 2
- 150000002513 isocyanates Chemical class 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000005375 organosiloxane group Chemical group 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920013822 aminosilicone Polymers 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- DDJSWKLBKSLAAZ-UHFFFAOYSA-N cyclotetrasiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1 DDJSWKLBKSLAAZ-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003573 thiols Chemical class 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/392—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing sulfur
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses a method for preparing organosilicon polyol based on mercapto-alkene light-click reaction. The double bond in the polyvinyl polysiloxane (vinyl silicone oil) and the sulfhydryl in the sulfhydryl monomer are utilized to perform light-click reaction to synthesize the organosilicon alcohol with polyhydroxy (functionality not less than 2), and the-OH and carbon chain in the organosilicon polyol are directly connected, so that the organosilicon alcohol can react with isocyanate to improve the hydrophobic and antifouling properties of polyurethane and PU synthetic leather coatings, and can also be used as a modifier of the organosilicon coatings to improve the surface tension, recoating property, adhesion, solvent resistance and the like of the organosilicon coatings. In addition, the preparation method of the organic silanol provided by the invention has the advantages that the-OH can be at the end (linear chain type) or at the side group (side chain type), and can be primary alcohol (1) 0 Alcohols) may also be secondary alcohols (2) 0 Alcohol), the functionality, the point location and the reactivity are controllable, and new materials are provided for development of leather, synthetic leather, textile and other coating materials such as hydrophobicity, antifouling and the like.
Description
Technical Field
The invention relates to a method for preparing organosilicon polyol based on mercapto-alkene light-click reaction, and belongs to the technical field of organosilicon material preparation.
Background
As an environment-friendly material independent of petroleum resources, the organic silicon has excellent performances of hydrophobicity, antifouling property, weather resistance, wear resistance, insulation, physiological inertia and the like, and has long been widely applied to industries such as leather/synthetic leather coating, automobile polishing, daily chemicals, textile and the like in the form of additives or modifiers. With the development of the organosilicon industry and manufacturing technology, organosilicon is gradually coming into the coating fields of leather/synthetic leather, textile and the like as a coating material.
Chinese patent CN 107675516B discloses an organopolysiloxane table for leather formation, the coating layer is composed of a polysiloxane surface layer, a silica gel adhesive layer and a substrate which are stacked in order from top to bottom. The main raw materials are vinyl polysiloxane and hydrogen-containing polysiloxane, the active groups of reactants are vinyl and silicon hydrogen bonds, the silicon-hydrogen double-component addition reaction system is provided, no byproducts are generated, and the coating has excellent weather resistance, wear resistance, hydrophobicity and self-cleaning functions, and belongs to an environment-friendly coating material.
Although the organic silicon material has a plurality of advantages, all organic silicon is adopted as a coating material, the finished leather is expensive (more than 5 times higher), and the low cost performance makes the organic silicon leather lose market competitiveness. The excellent property of the organosilicon is utilized to modify the existing coating materials such as polyurethane, acrylic resin and the like so as to improve the overall physical property of the coating, and the method is a simple, quick and efficient method. However, the organic silicon raw material has few active groups, uncontrollable points and quantity and poor selectivity in use; secondly, most of the existing-OH silicone oil or amino silicone oil active groups are connected with silicon atoms, the-OH is easy to condense, the amino group is easy to yellow, the stability is poor, and the active groups have lower reactivity due to the shielding effect of a large number of methyl groups on the polysiloxane side chain; furthermore, the low polarity (low surface tension) caused by the low polar groups in the organosilicon raw material causes the problems of insufficient adhesion between the organosilicon raw material and polar substrates, poor surface recoatability and the like when the organosilicon raw material is used as leather, synthetic leather and textile coating. The poor adhesion is manifested by the difficulty in adhesion of the organosilicon coating to the substrate and the low peel strength, such as degumming with sole material when the shoe leather is made into an article; the poor recoatability is manifested in that the coating such as the organic silicon synthetic leather is difficult to be wetted and spread by the surface treatment agent in the surface treatment procedures such as brightening, extinction, printing, color changing and the like, thereby being unfavorable for the appearance and style diversification of products, and the problems limit the further popularization and application of the organic silicon coating material in the fields such as synthetic leather, textile and the like.
Disclosure of Invention
The object of the present invention is to address the above-mentioned deficiencies of the prior art by providing a process for preparing silicone polyols based on mercapto-ene light impact reactions. The double bond in the polyvinyl polysiloxane (vinyl silicone oil) and the light-struck reaction of mercapto in the mercapto monomer are utilized to synthesize the polyhydroxy organosilicon alcohol, and the-OH and carbon chain in the organosilicon polyol are directly connected, so that the polyhydroxy organosilicon alcohol has high stability and reactivity, can react with isocyanate to improve the hydrophobic and antifouling properties of polyurethane and polyurethane synthetic leather coatings, and can also be used as a modifier of the organosilicon coatings to improve the surface tension, recoating property, adhesion, solvent resistance and the like of the organosilicon coatings. In addition, the organosilicon polyol prepared by the method has the-OH at the end (linear chain type) or at the side group (side chain type) and can be primary alcohol (1) 0 Alcohols) may also be secondary alcohols (2) 0 Alcohol) with controllable and adjustable functionality and reactivity, and provides a new material for developing coating materials of high-physical leather, synthetic leather, textile and the like.
The invention provides a method for preparing organosilicon polyol based on mercapto-alkene light-click reaction, which is characterized by comprising the following steps:
firstly, weighing vinyl silicone oil and mercapto alcohol with certain mass according to the mol ratio of-SH to-C=C-of 1.1:1, putting the vinyl silicone oil and the mercapto alcohol into a quartz tube, sequentially adding 1-2% of photoinitiator and normal hexane with the same mass of vinyl silicone oil as solvents, uniformly mixing, placing the mixture into a photochemical reactor, reacting for 1-2 hours at normal temperature under UV light irradiation, collecting a product after the light-striking reaction is finished, placing the product into a rotary evaporator to remove the solvents, washing with water, and distilling under reduced pressure to obtain liquid organic silicon polyol with the yield of not less than 98%;
the method for preparing the organic silicon polyol based on the mercapto-alkene light-click reaction is characterized in that the mercapto alcohol is one of mercapto ethanol, 3-mercapto-1-propanol, 2-mercapto-3-butanol, 3-mercapto-2-methyl-1-pentanol, 6-mercapto-1-hexanol, 8-mercapto-1-octanol and 11-mercapto-1-undecanol.
The method for preparing the organic silicon polyol based on the mercapto-alkene light-click reaction is characterized in that the vinyl polysiloxane is one or the combination of two of double-bond terminated vinyl silicone oil, tetramethyl tetravinyl cyclotetrasiloxane or polyvinyl silicone oil, wherein the mass percentage of vinyl in the double-bond terminated vinyl silicone oil is 0.05-0.43%, and the structural general formula is CH 2 =CH(CH 3 ) 2 -Si-O-[(CH 3 ) 2 SiO] n Si(CH 3 ) 2 CH=CH 2 Wherein n=200 to 3000; wherein the mass percentage of vinyl in the tetramethyl tetravinyl cyclotetrasiloxane is 30 percent, and the structural formula is [ CH ] 3 (CH 2 =CH)SiO] 4 The method comprises the steps of carrying out a first treatment on the surface of the The polyvinyl silicone oil comprises 0.2-2.3% of vinyl by mass, wherein the vinyl is positioned at the end and branched chains.
The method for preparing the organic silicon polyol based on the mercapto-alkene light-click reaction is characterized in that the photoinitiator in the method is one of benzoin, benzoin diethyl ether, benzoin dimethyl ether, 2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-4-methylsulfanyl-phenyl-2-morpholinyl-1-acetone and 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide.
Compared with the prior art, the invention has the following positive effects:
(1) The mercapto-alkene light-click reaction has the characteristics of mild reaction conditions, less side reaction, easy separation of products, high yield and the like. The invention uses the principle of sulfydryl-alkene light-click reaction, is innovatively applied to the preparation of the organic silanol, has mild preparation conditions, can complete the reaction at normal temperature under the induction of UV light, and has high product purity and yield of more than 98 percent.
(2) The functionality of the organosilicon polyol prepared by the invention can be regulated and controlled by the vinyl content of vinyl silicone oil, the site of-OH can be regulated and controlled by the site (such as end or side group) of vinyl in the vinyl silicone oil, and the activity (primary alcohol or secondary alcohol) of-OHCan be obtained by selecting 1 0 And 2 0 Thiol, and thus, by the above methods or combinations, can achieve regulation of functionality, site and reactivity of the silanol.
(3) Compared with the direct connection of the-OH of other silanol and the silicon atom, the-OH of the organosilicon polyol prepared by the invention is connected with the carbon atom, is not easy to polycondensate, has higher stability and higher reactivity with diisocyanate and other monomers, not only increases the types of the organosilicon alcohol, but also provides a novel modified material for the modification of polyurethane coating or organosilicon coating; meanwhile, the preparation method provides a key material for development of functional leather, synthetic leather, textile and other coating materials with hydrophobic, antifouling and other functions.
Detailed Description
The present invention is specifically described below by way of examples, which are given for the purpose of illustration only and are not to be construed as limiting the scope of the present invention, as many insubstantial modifications and variations will be apparent to those skilled in the art in light of the foregoing disclosure, while still falling within the scope of the present invention.
Example 1: preparation of organosilicon diols
100 parts of double bond end capping and 0.43% of vinyl are weighed according to the molar ratio of-SH to-C=C-of 1.1:1, and the structural general formula is CH 2 =CH(CH 3 ) 2 -Si-O-[(CH 3 ) 2 SiO] n Si(CH 3 ) 2 CH=CH 2， The method comprises the steps of placing vinyl siloxane with n=200 and mercaptoethanol into a quartz tube, sequentially adding 1% of photoinitiator benzoin dimethyl ether and n-hexane with vinyl silicone oil and the like as solvents, uniformly mixing, placing into a photochemical reactor, reacting for 1 h at normal temperature under UV light irradiation, collecting a product after the light-struck reaction is finished, placing into a rotary evaporator to remove the solvents, washing with water, and distilling under reduced pressure to obtain liquid organosilicon dihydric alcohol with the yield of 99.6%.
The organosilicon alcohol prepared by the reaction is binary primary alcohol, the OH mass percentage content is 0.26 percent, and the structure is HO-CH 2 -CH 2 -S-CH 2 -CH(CH 3 ) 2 -Si-O-[(CH 3 ) 2 SiO] n Si(CH 3 ) 2 CH-CH 2 -S-CH 2 -CH 2 The OH and the hydroxyl are directly connected with the carbon chain at the end of the organosiloxane, so that the organic siloxane has high stability and reactivity.
Example 2: preparation of organosilicon polyol
100 parts of polyvinyl siloxane is weighed according to the mol ratio of-SH to-C=C-of 1.1:1, the polyvinyl siloxane with the structural general formula of which the vinyl groups are positioned at the end and the branched chains and the mass percent of the vinyl groups is 2.3 percent, and 3-mercapto-1-propanol are put into a quartz tube, then 2 percent of photoinitiator 2, 2-dimethoxy-2-phenyl acetophenone and normal hexane with the mass of polyvinyl silicone oil are sequentially added as solvents, after being evenly mixed, the mixture is placed into a photochemical reactor, the reaction time is 2h at normal temperature under UV light irradiation, after the light-struck reaction is finished, the product is collected and placed into a rotary evaporator to remove the solvents, and then the solvent is subjected to water washing and reduced pressure distillation, so that liquid organic silicon dihydric alcohol is obtained, and the yield is 99.2 percent.
The organosilicon alcohol prepared by the reaction is a multi-primary alcohol, the functionality is not less than 3, the content of-OH in mass percent is 1.39%, and the-OH is distributed at the end and the side chain of the organosiloxane, but is directly connected with a carbon chain, so that the organosilicon alcohol has high stability and reactivity.
Example 3: preparation of organosilicon tetraols
100 parts of tetramethyl tetravinyl cyclotetrasiloxane (30% vinyl by mass, formula [ CH ] were weighed out in a molar ratio of-SH to-C=C-of 1.1:1 3 (CH 2 =CH)SiO] 4 ) And mercaptoethanol is put into a quartz tube, 1.5 percent of photoinitiator 1-hydroxycyclohexyl phenyl ketone and tetramethyl tetravinyl cyclotetrasiloxane and other n-hexane with the same mass are sequentially added as solvents, the solvents are evenly mixed and then are put into a photochemical reactor for reaction for 1.5 h at normal temperature under UV light irradiation, after the light-struck reaction is finished, the products are collected and put into a rotary evaporator for removing the solvents, and then water washing and reduced pressure distillation are carried out to obtain the liquid organosilicon dihydric alcohol with the yield of 98.4 percent.
The organosilicon alcohol prepared by the reaction is quaternary primary alcohol, the functionality is 4, -OH mass percent is 18.2 percent, and the-OH is distributed around the cyclotetrasiloxane, but is directly connected with a carbon chain, so that the organosilicon alcohol has high stability and reactivity.
Claims (4)
1. The method for preparing the organic silicon polyol based on the mercapto-alkene light-click reaction is characterized by comprising the following steps of:
firstly, weighing vinyl silicone oil and mercapto alcohol with certain mass according to the mol ratio of-SH to-C=C-of 1.1:1, putting the vinyl silicone oil and the mercapto alcohol into a quartz tube, sequentially adding 1% -2% of photoinitiator and normal hexane with the same mass of vinyl silicone oil as solvents, uniformly mixing, placing the mixture into a photochemical reactor, reacting at normal temperature under UV light irradiation for 1-2h, collecting a product after the light-irradiation reaction is finished, placing the product into a rotary evaporator to remove the solvents, washing with water, and distilling under reduced pressure to obtain liquid organosilicon polyol with the yield of not less than 98%.
2. The method for preparing the organic silicon polyol based on the mercapto-alkene light spot impact reaction according to claim 1, wherein the mercapto alcohol is one of mercapto ethanol, 3-mercapto-1-propanol, 2-mercapto-3-butanol, 3-mercapto-2-methyl-1-pentanol, 6-mercapto-1-hexanol, 8-mercapto-1-octanol and 11-mercapto-1-undecanol.
3. The method for preparing organosilicon polyol based on mercapto-ene light impact reaction as claimed in claim 1, wherein the vinyl polysiloxane is one or two of double bond terminated vinyl silicone oil, tetramethyl tetravinyl cyclotetrasiloxane or polyvinyl silicone oil, wherein the double bond terminated vinyl silicone oil has a vinyl mass percentage of 0.05-0.43% and a general structural formula of CH 2 =CH(CH 3 ) 2 -Si-O-[(CH 3 ) 2 SiO] n Si(CH 3 ) 2 CH=CH 2 Wherein n=200 to 3000; wherein the mass percentage of vinyl in the tetramethyl tetravinyl cyclotetrasiloxane is 30 percent, and the structural formula is [ CH ] 3 (CH 2 =CH)SiO] 4 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the polyethyleneThe vinyl silicone oil comprises 0.2-2.3% of vinyl by mass, wherein the vinyl is positioned at the end and branched chains.
4. The method for preparing the organic silicon polyol based on the mercapto-alkene light impact reaction according to claim 1, wherein the photoinitiator in the method is one of benzoin, benzoin diethyl ether, benzoin dimethyl ether, 2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-4-methylsulfanyl-phenyl-2-morpholino-1-acetone and 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311149842.9A CN117024745A (en) | 2023-09-07 | 2023-09-07 | Method for preparing organosilicon polyol based on mercapto-alkene light-click reaction |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311149842.9A CN117024745A (en) | 2023-09-07 | 2023-09-07 | Method for preparing organosilicon polyol based on mercapto-alkene light-click reaction |
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| CN117229704A (en) * | 2023-11-10 | 2023-12-15 | 上海福岛新材料科技有限公司 | Super-hydrophobic corrosion-resistant two-component water-based paint |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117229704A (en) * | 2023-11-10 | 2023-12-15 | 上海福岛新材料科技有限公司 | Super-hydrophobic corrosion-resistant two-component water-based paint |
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