CN111004395A - Preparation method of low-solvent block type polyether amino silicone oil - Google Patents
Preparation method of low-solvent block type polyether amino silicone oil Download PDFInfo
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- CN111004395A CN111004395A CN201911332014.2A CN201911332014A CN111004395A CN 111004395 A CN111004395 A CN 111004395A CN 201911332014 A CN201911332014 A CN 201911332014A CN 111004395 A CN111004395 A CN 111004395A
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 81
- 229920000570 polyether Polymers 0.000 title claims abstract description 81
- 229920013822 aminosilicone Polymers 0.000 title claims abstract description 39
- 239000002904 solvent Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229920002545 silicone oil Polymers 0.000 claims abstract description 49
- 239000004593 Epoxy Substances 0.000 claims abstract description 45
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000004945 emulsification Methods 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 19
- 150000001412 amines Chemical class 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 34
- 239000004744 fabric Substances 0.000 abstract description 6
- 239000003960 organic solvent Substances 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 229910052710 silicon Inorganic materials 0.000 abstract description 5
- 239000010703 silicon Substances 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 42
- 230000035484 reaction time Effects 0.000 description 12
- 239000003377 acid catalyst Substances 0.000 description 9
- 238000006459 hydrosilylation reaction Methods 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 7
- 229920001296 polysiloxane Polymers 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000004753 textile Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 206010010356 Congenital anomaly Diseases 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- -1 aminoethyl aminopropyl dimethyl siloxane Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 229940008099 dimethicone Drugs 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 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
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/647—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
The invention relates to a preparation method of low-solvent block type polyether amino silicone oil, belonging to the technical field of organic silicon. The method comprises the following steps: (1) preparation of epoxy-terminated intermediate: uniformly mixing hydrogen-terminated silicone oil, allyl epoxy polyether and DMF, stirring, heating to 70-80 ℃, adding a proper amount of catalyst, reacting for 2-4 hours, and cooling to obtain an epoxy-terminated intermediate; (2) preparation of block polyether amino silicone oil: mixing the epoxy terminated intermediate prepared in the step (1) with polyetheramine, reacting at 80-110 ℃ for 5-8h to obtain a mixture, cooling to room temperature, adding an emulsifier accounting for 8-12% of the total mass of the mixture into the mixture for emulsification, and adjusting the pH value to 6-7 to obtain the low-solvent block polyether amino silicone oil. The method has simple preparation process and easily obtained preparation raw materials, greatly reduces the use of organic solvents, and the prepared soft finishing agent can endow the fabric with thick, stiff, smooth and hand feeling style so as to overcome the defects of the prior art.
Description
Technical Field
The invention relates to a preparation method of low-solvent block type polyether amino silicone oil, belonging to the technical field of organic silicon.
Background
In 1940, American Patnode uses dimethyldichlorosilane for waterproof treatment of fiber, and opens up the application of organic silicon in the textile field. Over 70 years of development, silicone textile auxiliaries have undergone a mechanical mixture of dimethicone (first generation silicone finish); hydroxyl silicone oil emulsions (second generation silicone finishes); functional group-modified silicone oils (third-generation silicone finishing agents) such as polyether/epoxy silicone oil (CGF), amino silicone oil, carboxyl silicone oil, polyether/amino silicone oil, and the like, and block-type silicone finishing agents having a linear structure, so-called ternary block copolymerized silicone oils, which have newly appeared in recent years.
In the hand feeling finishing agent of the textile in the market at present, amino silicone oil is required to be used. The main chain of the amino silicone oil is formed by a bond with excellent flexibility, amino groups with different structures are introduced on the side chain according to different amino silane coupling agents, and the amino groups have chemical characteristics of stronger polarity, reactivity, adsorbability and the like, so that the amino silicone oil has congenital advantages in the textile hand feeling finishing effect. Common amino silicone oil, such as aminoethyl aminopropyl dimethyl siloxane, is a softener widely applied in the textile industry, has the functions of improving the hand feeling of fabrics, making the fabrics soft, smooth, elastic, crease-resistant and the like, is friendly to human bodies, and is popular. The good application performance of the amino silicone oil is derived from the fact that the amino silicone oil can form a smooth low-energy organic silicon film on the surface of a fiber by using a silicon methyl group to face outwards, a dipole bond and a cationized amino group to point to a fiber interface, but the arrangement mode enables the fiber to present certain hydrophobicity, reduces the hygroscopicity of the fabric and the wearing comfort, is generally easy to break emulsion and yellow, and is sensitive to high-value, high-electrolyte, high-temperature and high-shear force, poor in compatibility and the like.
The existing synthesis process of block polyether/amino modified organosilicon mostly adopts a route of firstly synthesizing an organosilicon chain segment with functionalized end group and then reacting the organosilicon chain segment with polyether amine modified by reactive end group, and because the compatibility of the organosilicon chain segment and the polyether chain segment is poor, in order to improve the compatibility of the two chain segments and the controllability of reaction, a large amount of organic solvents such as isopropanol or ethylene glycol monobutyl ether are often needed to be used. Under the current large background that the requirements for environmental protection and safety in China are more and more strict and the restriction requirements for solvents in European Union are increasing, how to reduce or avoid the use of organic solvents is a big problem faced by people. In addition, the segmented reaction has a series of problems of long line, complex process, high operation intensity of workers, low process controllability and the like. Therefore, the synthesis process route of the block polyether/amino modified silicone softener with short flow and no or little organic solvent is developed, which meets the development trend of green, efficient and low-cost industries and has extremely high necessity.
Disclosure of Invention
The invention provides a preparation method of low-solvent block type polyether amino silicone oil, which has the advantages of simple preparation process, easily obtained preparation raw materials and greatly reduced use of organic solvents, and the soft finishing agent prepared from the polyether amino silicone oil can endow thick, stiff and smooth fabric with hand feeling style so as to overcome the defects of the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of low-solvent block polyether amino silicone oil comprises the following steps:
(1) preparation of epoxy-terminated intermediate: uniformly mixing hydrogen-terminated silicone oil, allyl epoxy polyether and N-N Dimethylformamide (DMF), stirring, heating to 70-80 ℃, adding a proper amount of catalyst, reacting for 2-4 hours, and cooling to obtain an epoxy-terminated intermediate, wherein the molar ratio of the hydrogen-terminated silicone oil to the allyl epoxy polyether is 1: 1.8-2.2;
(2) preparation of block polyether amino silicone oil: mixing and stirring the epoxy-terminated intermediate prepared in the step (1) and polyether amine according to a molar ratio of 1: 1-1.6, reacting for 5-8h at 80-110 ℃ to obtain a mixture, cooling to room temperature, adding an emulsifier accounting for 8-12% of the total mass of the mixture into the mixture for emulsification, and adjusting the pH value to 6-7 to obtain the low-solvent block polyether amino silicone oil.
The invention takes hydrogen-terminated silicone oil as a raw material, and reacts with allyl epoxy polyether under the action of chloroplatinic acid catalyst and a small amount of solvent DMF to generate an epoxy-terminated intermediate; and then the self-made epoxy-terminated intermediate reacts with polyetheramine to generate the block type polyether amino silicone oil.
The invention is characterized in that:
1. allyl epoxy polyether replaces acrylic glycidyl ether in the prior art, so that a solvent is added for reaction in the first step of polyether amino silicone oil synthesis, allyl epoxy polyether and amino polyether are used as functional monomers in a distribution block polymerization manner, and a flexible polyether chain segment and amino are introduced into a main chain of a siloxane molecule at the same time;
2. in the prior art, the preparation method of polyether amino silicone oil is that a solvent is added for reaction in the second step of synthesis, the adding amount of the solvent exceeds 50% of the total amount of reaction raw materials, and the solvent generally adopts isopropanol, tetrahydrofuran, methanol and the like; in the synthesis reaction in the invention, no solvent is added in the second step, but a very small amount (5-15%) of DMF (dimethyl formamide) solvent is added in the first step to react with terminal hydrogen-containing silicone oil and allyl epoxy polyether to generate an epoxy-terminated intermediate.
Preferably, the molar ratio of the hydrogen-terminated silicone oil to the allyl epoxy polyether in the step (1) is 1: 2.
preferably, the solvent N-N Dimethylformamide (DMF) in the step (1) is used in an amount of 5-15% by weight based on the total weight of the raw materials.
Preferably, the catalyst in the step (1) is chloroplatinic acid.
Preferably, glacial acetic acid is used to adjust the pH in step (2).
Preferably, the molar ratio of the terminal epoxy intermediate to the polyetheramine in the step (2) is 1: 1.2 to 1.4.
Preferably, the polyether amine in the step (2) is polyether amine D-230, polyether amine ED-600 or polyether amine ED-900.
Preferably, the emulsifier in the step (2) is emulsifier AEO-3 or emulsifier AEO-9.
The invention relates to low-solvent block polyether amino silicone oil prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention overcomes the defects of common amino silicone oil, simple polyether and simple epoxy modified silicone oil, has good hydrophilicity, is more firmly combined in a chemical bond form when acting with fabrics, is more washable, and has the softening effect of common amino silicone oil;
2. the low-solvent block silicone oil prepared by the invention has stable quality, greatly reduces the use of organic solvent in the preparation process, and is beneficial to the transportation and storage of the silicone oil.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples. It is to be understood that the practice of the invention is not limited to the following examples, and that any variations and/or modifications may be made thereto without departing from the scope of the invention.
In the present invention, all parts and percentages are by weight, unless otherwise specified, and the equipment and materials used are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1
A preparation method of low-solvent block type polyether amino silicone oil comprises the following specific steps:
(1) 100g of terminal hydrogen-containing silicone oil, 12g of allyl epoxy polyether and 5.6g of N-N Dimethylformamide (DMF) are uniformly mixed, stirred, heated to 80 ℃, added with 0.3ml of chloroplatinic acid catalyst, kept warm, reacted for 3h, cooled to 30 ℃ and taken out to obtain the terminal epoxy intermediate.
In this example, the molar ratio of hydrogen-terminated silicone oil to allyl epoxy polyether is 1: 2, the molecular weight of the hydrogen-containing silicone oil at the middle end is 8000, and the molecular weight of the allyl epoxy polyether is 480.
(2) Uniformly mixing 80g of the epoxy-terminated intermediate prepared in the step (1) with 2.8g of polyether amine (D230) (the molar ratio of the epoxy-terminated intermediate to the polyether amine is 1: 1.2), stirring, heating to 80 ℃, continuing to react for 6 hours until the solution becomes transparent, cooling to room temperature, adding glacial acetic acid to adjust the pH of the system to 6-7, finally adding 8.3g of fatty alcohol-polyoxyethylene ether (AEO-3), and stirring at room temperature to obtain the block polyether amino silicone oil.
Example 2:
the preparation method of the low-solvent block type polyether amino silicone oil comprises the following specific steps of example 1: (1) 100g of terminal hydrogen-containing silicone oil, 9.6g of allyl epoxy polyether and 5.6g of N-N Dimethylformamide (DMF) are uniformly mixed, stirred, heated to 80 ℃, added with 0.3ml of chloroplatinic acid catalyst, kept warm for reaction for 3h, cooled to 30 ℃ and taken out to obtain the terminal epoxy intermediate.
In this example, the molar ratio of the added terminal hydrogen-containing silicone oil to the allyl epoxy polyether is 1: 2, the molecular weight of the hydrogen-containing silicone oil at the middle end is 10000, and the molecular weight of the allyl epoxy polyether is 480.
(2) And (2) uniformly mixing 80g of epoxy-terminated intermediate and 2.2g of polyether amine (D230), stirring, heating to 80 ℃, reacting for 6 hours until the solution becomes transparent, cooling to room temperature, adding glacial acetic acid to adjust the temperature to 6-7, finally adding 8.2g of fatty alcohol-polyoxyethylene ether (AEO-3), and stirring at room temperature to obtain the block polyether amino silicone oil. Wherein the molar ratio of the epoxy terminated intermediate to the polyetheramine is 1: 1.2.
example 3:
the preparation method of the low-solvent block type polyether amino silicone oil comprises the specific steps of (1) uniformly mixing 100g of terminal hydrogen-containing silicone oil, 12g of allyl glycidyl ether and 5.6g of N-N Dimethylformamide (DMF), stirring, heating to 80 ℃, adding 0.3ml of chloroplatinic acid catalyst, keeping the temperature for reaction for 3 hours, cooling to 30 ℃, and taking out the terminal epoxy intermediate.
In this example, the molar ratio of the added terminal hydrogen-containing silicone oil to the allyl epoxy polyether is 1: 2, the molecular weight of the hydrogen-containing silicone oil at the middle end is 8000, and the molecular weight of the allyl epoxy polyether is 480.
(2) Uniformly mixing 80g of epoxy terminated intermediate and 10.8g of polyether amine (ED-900), stirring and heating to 80 ℃ for reaction for 6 hours until the solution becomes transparent, cooling to room temperature, adding glacial acetic acid to adjust the temperature to 6-7, finally adding 9.1g of fatty alcohol-polyoxyethylene ether (AEO-3), and stirring at room temperature to obtain the block polyether amino silicone oil. Wherein the molar ratio of the epoxy terminated intermediate to the polyetheramine is 1: 1.2.
example 4:
the preparation method of the low-solvent block type polyether amino silicone oil comprises the following specific steps of example 1: (1) 100g of terminal hydrogen-containing silicone oil, 12g of allyl epoxy polyether and 5.6g of N-N Dimethylformamide (DMF) are uniformly mixed, stirred, heated to 80 ℃, added with 0.3ml of chloroplatinic acid catalyst, kept warm, reacted for 3h, cooled to 30 ℃ and taken out to obtain the terminal epoxy intermediate.
In this example, the molar ratio of the added terminal hydrogen-containing silicone oil to the allyl epoxy polyether is 1: 2, the molecular weight of the hydrogen-containing silicone oil at the middle end is 8000, and the molecular weight of the allyl epoxy polyether is 480.
(2) Uniformly mixing 80g of the epoxy-terminated intermediate and 3.2g of polyether amine (D230) (the molar ratio of the epoxy-terminated intermediate to the polyether amine is 1: 1.4), stirring, heating to 80 ℃, reacting for 6 hours until the solution becomes transparent, cooling to room temperature, adding glacial acetic acid to adjust the solution to 6-7, finally adding 8.3g of fatty alcohol-polyoxyethylene ether (AEO-9), and stirring at room temperature to obtain the block polyether amino silicone oil.
The properties of the block polyether amino silicone oil emulsion and the yield of the product are shown in Table 1.
TABLE 1
| Serial number | Molecular weight (g/mol) of terminal epoxy silicone oil | Molecular weight of polyetheramine (g/mol) | Epoxy value/(g/mol) | Yield/%) | Emulsifier | Appearance of the emulsion |
| Example 1 | 8000 | D-230 | 0.0016 | 96.4% | AEO-3 | Colorless and transparent |
| Example 2 | 10000 | D-230 | 0.0044 | 86.7% | AEO-3 | Colorless and translucent |
| Example 3 | 8000 | ED-900 | 0.0032 | 90.2% | AEO-3 | Colorless and transparent |
| Example 4 | 8000 | D-230 | 0.0061 | 81.7% | AEO-9 | Milky white color |
Tables 1, 2, 3 and 4 correspond to examples 1, 2, 3 and 4, respectively, and it can be seen from the data in Table 1 that the lower the epoxy value, the higher the yield of the polyether amino block silicone oil. The yield was high (96.4%) with the combination of epoxy-terminated silicone oil (M = 8000) and polyetheramine D-230, because the macromolecular double-ended epoxy silicone oil was not easily reacted with the amino polyether, the block reaction of the hydrophilic amino polyether and the lipophilic double-ended epoxy silicone oil could not be fully completed.
In order to verify the effect and search for the optimal reaction ratio and conditions, the inventor conducts a single-factor test on the preparation method of the low-solvent block type polyether amino silicone oil, and the specific process is as follows:
1. in the hydrosilylation reaction, the mole ratio of a reactant has a certain influence on the conversion rate of the double bonds of the terminal hydrogen-containing silicone oil, during the reaction process, the allyl groups may have isomerization reaction to generate products which are not beneficial to the addition reaction, so that Si-H bonds are remained, and the remained Si-H bonds are more active and are easy to generate crosslinking-gelation, thus damaging the stability of the products. We set the reaction temperature to 80 ℃, the reaction time to 3 hours, the chloroplatinic acid catalyst amount to 0.3ml, and the solvent amount to 5% of the total mass of the reactants, and adjust the molar ratio of the terminal hydrogen-containing silicone oil to the allyl epoxy polyether, and study the effect on the hydrosilylation reaction, the results are shown in table 2.
TABLE 2 influence of the molar ratio of the reactants on the conversion of the terminal hydrogen-containing silicone oil double bonds
| Ratio of amounts of reactant species | Conversion (%) | Appearance of Silicone oil |
| 1：1.8 | 89.32% | Colorless and transparent |
| 1：1.9 | 92.65% | Colorless and transparent |
| 1：2.0 | 94.91% | Light yellow and transparent |
| 1：2.1 | 95.57% | Light yellow and transparent |
| 1：2.2 | 95.89% | Yellow transparent |
As can be seen from Table 2, the Si-H bond conversion rate gradually increased with the increase in the amount of allyl glycidyl ether used, and became stable when n (terminal hydrogen-containing silicone oil) = n (allyl epoxy polyether) = about 1: 2. Comprehensively considering, selecting n (terminal hydrogen-containing silicone oil): n (allyl epoxy polyether) = 1: 2.
2. In the hydrosilylation reaction, the amount of the Pt catalyst is very critical, and if the amount of the catalyst is insufficient, the reaction conversion rate is low, the reaction time is long, and the production efficiency is influenced. Also, if the catalyst is in excess, the reaction will be too rapid to be easily controlled, jeopardizing production safety. In addition, the Pt catalyst is expensive and high in cost, and the excessive use of the Pt catalyst also causes waste and environmental pollution. The mol ratio of hydrogen-terminated silicone oil to allyl epoxy polyether is set to be 1: 2. the reaction was carried out at 80 ℃ for 3 hours with the amount of solvent accounting for 5% of the total mass of the reactants, and the effect of chloroplatinic acid catalyst on hydrosilylation was investigated, and the results are shown in Table 3.
TABLE 3 influence of catalyst dosage on the conversion of terminal hydrogen-containing silicone oil double bonds
| Amount of catalyst used (ml) | Conversion (%) | Appearance of Silicone oil |
| 0.15ml | 79.52% | Opalescent and opaque |
| 0.2ml | 82.97% | Colorless and transparent |
| 0.25ml | 87.49% | Light yellow and transparent |
| 0.3ml | 93.36% | Light yellow and transparent |
| 0.35ml | 94.10% | Yellow brown transparent |
As can be seen from Table 3, as the amount of catalyst used in the system increases, the probability of collision of Si-H bonds with the Pt catalyst increases and the conversion rate increases. When the catalyst amount reaches 0.3ml, the conversion rate tends to be stable. Then the catalyst dosage is increased, the color of the product is deepened, and the catalyst dosage is selected to be 0.3ml (to the total mass of reactants) in comprehensive consideration.
3. In the hydrosilylation reaction, the reaction time is a problem related to the production efficiency and the production cost, and is also a key factor influencing the product quality. In this experiment, we set the molar ratio of terminal hydrogen-containing silicone oil to allyl epoxy polyether to 1: 2. the effect of hydrosilylation reaction was investigated at a reaction temperature of 80 ℃ with a solvent amount of 5% of the total mass of the reactants and a chloroplatinic acid catalyst amount of 0.3ml, and the results are shown in Table 4.
TABLE 4 influence of reaction time on the conversion of terminal hydrogen-containing silicone oil double bonds
| Reaction time (h) | Conversion (%) | Appearance of Silicone oil |
| 1.5h | 81.29% | Opalescent and opaque |
| 2h | 84.97% | Colorless and transparent |
| 2.5h | 88.48% | Light yellow and transparent |
| 3h | 92.08% | Light yellow and transparent |
| 3.5h | 92.86% | Yellow transparent |
As can be seen from Table 4, when the reaction time was less than 3 hours, the Si-H bond conversion rate gradually increased with the increase of the reaction time, and when the reaction time was 3 hours, the Si-H bond conversion rate tended to be stable, and the Si-H bond conversion rate did not change significantly with the continued increase of the reaction time. This is probably because efficient collisions between molecules require some time for the reaction to be more complete. The reaction time is selected to be 3H by comprehensively considering the conversion rate of Si-H bonds and cost factors.
4. In the hydrosilylation reaction, the reaction temperature is also a key factor affecting the product quality, which is also related to the production efficiency and the production cost. In this experiment, we set the molar ratio of terminal hydrogen-containing silicone oil to allyl epoxy polyether to 1: 2. the effect of the reaction temperature on the hydrosilylation reaction was investigated with a reaction time of 3 hours, a solvent amount of 5% of the total mass of the reactants, and a chloroplatinic acid catalyst amount of 0.3ml, and the results are shown in table 5.
TABLE 5 influence of reaction time on the conversion of terminal hydrogen-containing silicone oil double bonds
| Reaction temperature (. degree.C.) | Conversion (%) | Appearance of Silicone oil |
| 60℃ | 81.34% | Colorless and transparent |
| 70℃ | 83.45% | Colorless and transparent |
| 80℃ | 88.48% | Light yellow and transparent |
| 90℃ | 89.64% | Yellow transparent |
| 100℃ | 91.21% | Grey colour is transparent |
As can be seen from Table 5, when the reaction temperature is lower than 100 ℃, the Si-H bond conversion rate gradually increases with an increase in temperature. When the reaction temperature reaches 100 ℃, the conversion rate of Si-H bonds tends to be stable, and the conversion rate of Si-H bonds does not change obviously when the temperature is continuously increased. This is probably because increasing the temperature is advantageous in increasing the reactivity of Si-H bonds, increasing the probability of collisions between molecules, and thus increasing the conversion rate of Si-H bonds. The reaction temperature can be selected to be 80 ℃ in combination with cost factors.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (9)
1. A preparation method of low-solvent block polyether amino silicone oil is characterized by comprising the following steps:
(1) preparation of epoxy-terminated intermediate: uniformly mixing hydrogen-terminated silicone oil, allyl epoxy polyether and N-N Dimethylformamide (DMF), stirring, heating to 70-80 ℃, adding a proper amount of catalyst, reacting for 2-4 hours, and cooling to obtain an epoxy-terminated intermediate, wherein the molar ratio of the hydrogen-terminated silicone oil to the allyl epoxy polyether is 1: 1.8-2.2;
(2) preparation of block polyether amino silicone oil: mixing the epoxy-terminated intermediate prepared in the step (1) with polyether amine according to a molar ratio of 1: 1-1.6, reacting at 80-110 ℃ for 5-8h to obtain a mixture, cooling to room temperature, adding an emulsifier accounting for 8-12% of the total mass of the mixture into the mixture for emulsification, and adjusting the pH of the system to 6-7 to obtain the low-solvent block polyether amino silicone oil.
2. The method according to claim 1, wherein the molar ratio of the terminal hydrogen-containing silicone oil to the allyl epoxy polyether in the step (1) is 1: 2.
3. the method according to claim 1, wherein the solvent N-N Dimethylformamide (DMF) in step (1) is used in an amount of 5-15% by weight based on the total weight of the starting materials.
4. The production method according to claim 1, characterized in that the catalyst in the step (1) is chloroplatinic acid.
5. The method according to claim 1, wherein the pH value is adjusted by glacial acetic acid in the step (2).
6. The method according to claim 1, wherein the molar ratio of the terminal epoxy intermediate to the polyetheramine in the step (2) is 1: 1.2 to 1.4.
7. The method according to claim 1, wherein the polyetheramine in step (2) is polyetheramine D-230, polyetheramine ED-600 or polyetheramine ED-900.
8. The production method according to claim 1, wherein the emulsifier in the step (2) is an emulsifier AEO-3 or an emulsifier AEO-9.
9. A low-solvent block polyether amino silicone oil prepared by the preparation method of claim 1.
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