CN110922600A - Hydroxyalkyl organosilicon compounds, and preparation method and application thereof - Google Patents

Hydroxyalkyl organosilicon compounds, and preparation method and application thereof Download PDF

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CN110922600A
CN110922600A CN201911007733.7A CN201911007733A CN110922600A CN 110922600 A CN110922600 A CN 110922600A CN 201911007733 A CN201911007733 A CN 201911007733A CN 110922600 A CN110922600 A CN 110922600A
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hydroxyalkyl
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diglycidyl ether
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CN110922600B (en
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唐红定
余学成
熊英
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Wuhan University WHU
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    • 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
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • 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
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
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    • 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
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    • 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
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Abstract

The invention discloses a hydroxyl-alkyl organic silicon compound and a preparation method and application thereof. Belonging to the field of organic silicon materials. The hydroxyalkyl organosilicon compound comprises a hydroxyalkyl silane compound, a hydroxyalkyl linear polysiloxane or a hydroxyalkyl silicon resin. Also discloses a preparation method of the hydroxyl alkyl organosilicon compound through the ring-opening reaction of the amino alkyl organosilicon compound and the epoxy compound. The method can synthesize a series of hydroxyl-alkyl organosilicon compounds with different structures and different hydroxyl contents simply and conveniently. The hydroxyl alkyl organosilicon compound can be used for preparing organosilicon modified materials.

Description

Hydroxyalkyl organosilicon compounds, and preparation method and application thereof
Technical Field
The invention relates to the field of organic silicon materials, in particular to a hydroxyl alkyl organic silicon compound and a preparation method and application thereof. The related hydroxyalkyl organosilicon compounds comprise hydroxyalkyl silane compounds, hydroxyalkyl linear polysiloxane or silicone resin.
Background
The organosilicon compound is a compound having at least one organic group bonded to Si in its molecular structure. The main chain of the organosilicon compound often contains Si-O-Si bonds, so that the organosilicon material has the advantages of excellent high and low temperature resistance, oxidation and aging resistance, light aging resistance, mildew resistance, chemical stability, good electrical insulation, low surface energy, low glass transition temperature, low viscosity, good thermal stability, excellent biocompatibility, water resistance, weather resistance, colorless property, no toxicity and the like, and is widely applied to the fields of aviation, automobiles, daily chemicals, wires and cables, medicine and the like.
Combining the excellent properties of silicone with the properties of other polymeric materials can result in excellent material hybridization characteristics. Thus, silicones can be used as modified organic polymers or resins, such as modified acrylic resins, polyester resins, epoxy resins, alkyd resins, phenolic resins, polyurethanes, polyimide resins, and the like. Generally, there are two main methods of physical blending and chemical modification of silicone-modified organic polymers. Among them, the chemical modification method is particularly important. Commonly used reactive silicone intermediates include alkoxy silicon organosilicon compounds, silicon hydroxy organosilicon compounds, hydroxy hydrocarbyl organosilicon compounds, and amino hydrocarbyl organosilicon compounds, among others. The organic silicon compound containing hydroxyl alkyl and the organic silicon compound containing amino alkyl belong to organic silicon compounds with carbon functional groups, and can be used for the reaction of various organic compounds, such as isocyanate, acyl chloride, acid anhydride, epoxy, acrylate double bonds and the like. Polyurethane-polysiloxane copolymers modified by the reaction of a hydroxyl group and an amino group have better hydrolysis and alcoholysis resistance than silicon hydroxyl organosilicon compounds. While the selection of appropriate hydrocarbon and amino groups can alter the properties of the copolymer, for example, improve the compatibility of the soft and hard segments in a heterophasic copolymer system. Compared with the amino-hydrocarbyl organosilicon compound, the hydroxyl-hydrocarbyl organosilicon compound has the advantages of difficult oxidation and yellowing, matching of reaction characteristics with polyether polyol and the like, and is more and more valued.
Hydroxyhydrocarbyl-terminated linear polydimethylsiloxanes are the most common and most widely used hydroxyhydrocarbyl organosilicon compounds. Because the organosilicon modified Polymer material not only contains active hydroxyl alkyl, but also has the characteristics of organosilicon materials such as no color, no odor, high transparency, high and low temperature resistance, physiological inertia, electric insulation, hydrophobicity, small viscosity temperature coefficient and the like, the organosilicon modified Polymer material is widely applied to the preparation of organosilicon modified Polymer materials (Polymer,2001,42:7953.) (Polymer,2009,50: 2320.). However, the low polarity and low surface energy exhibited by the relatively simple structure and long-chain polydimethylsiloxane limit the modification effect. Several patents and literature reports also regarding hydroxyalkyl organosilicon compounds of different structures, for example, CN 107011507A discloses an organosilicon group-containing polyether polyol and its application to foamed polyurethane, which is effective in improving the durability and compression resistance of the modified polyurethane slow-recovery sponge and improving its high and low temperature resistance. Li et al (Polymer Engineering and Science,2007,47: 625) compare the effects of polyurethane modified by long-chain polydimethylsiloxane with single-end dihydroxy hydrocarbon groups (diol with long-chain polysiloxane located at a side chain) and long-chain polydimethylsiloxane with double-end hydroxy hydrocarbon groups (diol with long-chain polysiloxane located at a main chain), and find that the reaction rate of the diol with polysiloxane located at a side chain is faster than that of the diol with polysiloxane located at the main chain, the diol has a better organic silicon surface migration tendency, a better surface modification effect can be obtained with a smaller introduction amount, and meanwhile, the side chain has better compatibility with polyurethane compared with the main chain polysiloxane diol, the modified polyurethane phase separation is small, and the mechanical strength is reduced. Therefore, the hydroxyl-alkyl organosilicon compounds with different structures play an important role in the preparation of organosilicon modified materials.
Common hydroxyl alkyl organosilicon compounds take polysiloxane as a main chain, and hydroxyl alkyl is modified on the polysiloxane main chain through hydrosilylation, such as preparation of double-terminal hydroxyl alkyl polydimethylsiloxane. The preparation process can also be extended to the preparation of other hydroxyhydrocarbyl organosilicon compounds. For example, CN 107011507 a provides a process for the preparation of allyl polyether polyols by hydrosilylation reaction with a hydrogen containing silicone composition. CN 107652434A is prepared by hydrosilylation of polyether monohydric alcohol containing silicon-hydrogen group and linear polysiloxane containing allyl at side chain and both ends. CN 103627002A takes tetramethyldisiloxane, octamethylcyclotetrasiloxane, allyl glycidyl ether and diethylamine as starting materials, and prepares the double-terminal hydroxyalkyl polydimethylsiloxane through three-step reactions of hydrosilylation, equilibrium polymerization and epoxy ring opening. The synthesis processes are complex and difficult to control, the content and molecular structure of the introduced hydroxyl alkyl cannot be easily controlled, and the factors of complicated purification steps, large product loss and the like limit the practical application of the method.
In view of the above, currently available hydroxyalkyl organosilicon compounds are relatively few and are not readily available.
Disclosure of Invention
The invention aims to overcome the defects that the synthetic process of hydroxyl-alkyl organic silicon compounds in the prior art is complex and difficult to control, the content and the molecular structure of introduced hydroxyl-alkyl cannot be easily controlled, the purification steps are complicated, the product loss is large and the like, and provides a class of hydroxyl-alkyl organic silicon compounds and a preparation method and application thereof. The hydroxy-hydrocarbyl organosilicon compound is obtained by the ring-opening reaction of the amino-hydrocarbyl organosilicon compound and an epoxy compound. The method can synthesize a series of hydroxyl-alkyl organosilicon compounds with different structures and different hydroxyl contents simply and conveniently.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, there is provided a hydroxyalkyl linear polysiloxane, the structure of which is any one of the following:
Figure BDA0002243258720000031
wherein: r1、R2Is phenyl or methyl;
R3、R4is methyl, methoxy, ethoxy, β -acryloyloxyethoxy or β -methacryloyloxyethoxy;
R5is H, phenyl or alkyl;
R6is a group shown as follows:
Figure BDA0002243258720000032
R7is a group shown as follows:
Figure BDA0002243258720000033
a is 1 or 3;
m, n and y are natural numbers.
In a second aspect, there is provided a hydroxy-hydrocarbon silicon resin, comprising: the structure of the hydroxy hydrocarbon silicon resin is shown in any one of the following formulas:
Figure BDA0002243258720000041
wherein:
R3、R4is methyl, methoxy, ethoxy, β -acryloyloxyethoxy or β -methacryloyloxyethoxy;
R5is H, phenyl or alkyl;
R6is a group shown as follows:
Figure BDA0002243258720000042
a is 1 or 3.
In a third aspect, there is provided a class of hydrocarbylsilane compounds characterized by: the structure of the hydroxyalkyl silane compound is shown as follows:
Figure BDA0002243258720000043
wherein:
R5is H, phenyl or alkyl;
R8is a group shown as follows:
Figure BDA0002243258720000051
R9、R10、R11is methyl, trimethylsiloxy, methoxy, ethoxy;
a is 1 or 3;
b is 1 or 2 or 3.
In a fourth aspect, a method for preparing the above hydroxyalkyl linear polysiloxane is provided, wherein the reaction formula is shown as formula I, and the method comprises the following steps:
under the protection of inert gas, uniformly mixing an organic silicon compound containing aminoalkyl or iminoalkyl with an epoxy compound, adding a proper amount of catalyst, and reacting at 30-50 ℃ for 24-72h to obtain hydroxyalkyl linear polysiloxane;
the molar amount of the aminoalkyl group or the aminohydrocarbylene group of the added organosilicon compound containing an aminoalkyl group or an aminohydrocarbylene group is the same as the molar amount of the epoxy group in the added epoxy compound;
the linear polysiloxane containing amino hydrocarbon group or imino hydrocarbon group is prepared by the method disclosed in patent document CN 109369880A, or directly purchased from silicone oil containing amino group or imino group in the market;
the catalyst is one of LiCl, LiBr and LiI, and accounts for 0.5-2 wt% of the total mass of the raw materials;
the epoxy compound (OCHCH)nR6The epoxy resin is one of ethylene oxide, propylene oxide, isopropyl glycidyl ether, n-butyl glycidyl ether, allyl glycidyl ether, benzyl glycidyl ether, tertiary carbonic acid glycidyl ester, methacrylic acid glycidyl ester and acrylic acid glycidyl ester;
the epoxy compound (OCHCH) in said stepnR7The material is one of diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, hexanediol diglycidyl ether, resorcinol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, and cyclohexane-1, 2-dicarboxylic acid diglycidyl ester;
Figure BDA0002243258720000061
wherein:
R1、R2is phenyl or methyl;
R3、R4is methyl, methoxy, ethoxy, β -acryloyloxyethoxy or β -methacryloyloxyethoxy;
R5h, cyclohexyl, phenyl, alkyl;
R6is a group shown as follows:
Figure BDA0002243258720000062
R7is a group shown as follows:
Figure BDA0002243258720000063
a is 1 or 3;
m and n are natural numbers.
In a fifth aspect, a method for preparing the above hydroxy-hydrocarbon-based silicone resin is provided, wherein the reaction formula is shown as formula II, and the method comprises the following steps:
under the protection of nitrogen, uniformly mixing silicon resin containing aminoalkyl or alkylene with epoxy compound (wherein the molar weight of the aminoalkyl or alkylene is equal to the molar weight of the epoxy group), adding a proper amount of catalyst, and reacting at 30-50 ℃ for 24-72h to obtain the hydroxy-hydrocarbon silicon resin;
the silicon resin containing amino or imino is aminoalkyl or alkylene silicon resin;
the catalyst is one of LiCl, LiBr and LiI, and accounts for 0.5-2 wt% of the total mass of the raw materials;
the epoxy compound (OCHCH)nR6The epoxy resin is one of ethylene oxide, propylene oxide, isopropanol glycidyl ether, n-butanol glycidyl ether, allyl alcohol glycidyl ether, benzyl alcohol glycidyl ether, tertiary carbonic acid glycidyl ester, methacrylic acid glycidyl ester and acrylic acid glycidyl ester;
Figure BDA0002243258720000071
wherein:
R3、R4is methyl, methoxy, ethoxy, β -acryloyloxyethoxy or β -methacryloyloxyethoxy;
R5h, cyclohexyl, phenyl, alkyl;
R6is a group shown as follows:
Figure BDA0002243258720000072
a is 1 or 3;
m and n are natural numbers.
In a sixth aspect, there is provided a method for preparing the above silane compound with hydroxyalkyl group, wherein the reaction formula is shown as formula III, comprising the following steps:
under the protection of inert gas at 30-50 deg.C, silane compound (R) containing amino hydrocarbon group or imino hydrocarbon group11)(R10)(R9)Si(CH2)aNH(R5) With epoxy compounds (OCHCH)bR8(wherein the molar weight of the aminoalkyl or the imido is equal to the molar weight of the epoxy group) is uniformly mixed, and then a proper amount of catalyst is added to stir and react for 24-72h, so as to obtain the hydroxyalkyl silane compound;
the aminoalkyl or aminoalkyl-containing silane compound (R)11)(R10)(R9)Si(CH2)aNH(R5) Gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldiethoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma-aminopropyltris (trimethylsiloxy) silane, gamma-aminopropylmethyldi (trimethylsiloxy) silane, α -aminomethyltriethoxysilane, α -aminomethyltrimethoxysilane, α -aminomethylmethyldiethoxysilane, α -aminomethylmethyldimethoxysilane, α -aminomethyltris (trimethylsiloxy), α -aminomethylmethyldi (trimethylsiloxy) silane;
the catalyst is one or more of LiCl, LiBr and LiI, the mass percentage of the catalyst in the total mass of the raw materials is 0.5-2 wt%,
the epoxy compound (OCHCH)nR8The epoxy resin is one of ethylene oxide, propylene oxide, diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, hexanediol diglycidyl ether, resorcinol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, glycerol triglycidyl ether, isopropyl glycidyl ether, n-butyl glycidyl ether, allyl glycidyl ether, benzyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate, glycidyl versatate, and cyclohexane-1, 2-dicarboxylic acid diglycidyl ester;
Figure BDA0002243258720000081
wherein:
R5is H, phenyl or alkyl;
R8is a group shown as follows:
Figure BDA0002243258720000091
R9、R10、R11is methyl, trimethylsiloxy, methoxy, ethoxy;
a is 1 or 3;
b is 1 or 2 or 3.
In a seventh aspect, the application of the hydroxyalkyl organosilicon compound in modified polyurethane, polyester resin, acrylate resin and epoxy resin is provided.
The modified polyurethane resin is described as follows:
under the protection of inert gas, adding the mixture of polyether or polyester polyol and the hydroxyl alkyl organic silicon compound of the claim into the mixed solution of diisocyanate, a proper amount of catalyst and organic solvent, and stirring for reaction for 2-4h to obtain the organic silicon modified polyurethane resin.
The invention has the advantages and beneficial effects that:
(1) the hydroxyl alkyl organosilicon compound has the advantages of adjustable structure and controllable hydroxyl content, namely, the compound can be obtained by ring-opening reaction of different amino alkyl or imino alkyl organosilicon compounds and different epoxy compounds, such as ethylene oxide, propylene oxide and glycidyl derivatives. Wherein, the organosilicon chain segment can be positioned at a side chain or a main chain, and the hydroxyl alkyl can be monohydric alcohol or polyhydric alcohol. Hydroxyhydrocarbyl organosilicon compounds having alkoxysilyl groups (said hydroxyalkyl silane compound of type 3) are also available, the additional introduction of alkoxysilyl groups allowing moisture curing in the modified polymer system, providing additional Si-O-Si crosslinks, increasing the crosslink density and strength of the modified polymer, improving surface properties, and the like. Hydroxyhydrocarbyl organosilicon compounds containing acrylate double bonds or vinyl or phenyl groups may also be obtained (by selecting R in different glycidyl derivatives)8Groups) can expand the application range of the hydroxyl-functionalized organosilicon compounds.
(2) The hydroxyl organic silicon compound is introduced into the high molecular polymer, and the viscosity of the prepolymer of the high molecular polymer is reduced along with the increase of the content of organic silicon due to the introduction of polysiloxane with low surface energy and low viscosity, so that the dosage of the organic solvent can be reduced, and the problem of Volatile Organic Compounds (VOC) of the polymer can be partially solved.
(3) The synthesis method is solvent-free, can mildly and effectively change the organic silicon compound containing the amino alkyl or the imino alkyl into the hydroxyl alkyl which is stable and difficult to be oxidized through the ring-opening reaction with the epoxy compound under the reaction condition at room temperature, and has simple operation process.
(4) The synthesis method has the advantages of cheap and easily available raw materials and simple and feasible preparation process.
Drawings
FIG. 1 is a FT-IR spectrum of the hydroxyalkyl silane compound prepared in example 1.
FIG. 2 is a schematic representation of the preparation of the hydroxyalkylsilane compound of example 11H-NMR spectrum.
FIG. 3 is a schematic representation of the preparation of the hydroxyalkylsilane compound of example 113C-NMR spectrum.
FIG. 4 is a HR-MS spectrum of the hydroxyalkylsilane compound prepared in example 1.
FIG. 5 is a FT-IR spectrum of a urethane resin modified with a hydroxyalkyl silane compound prepared in example 1.
FIG. 6 shows modification of polyurethane resin with hydroxyalkyl silane compound prepared in example 11H-NMR spectrum.
FIG. 7 shows modification of polyurethane resin with hydroxyalkyl silane compound prepared in example 113C-NMR spectrum.
FIG. 8 is a comparative scanning electron microscope image of cured products of polyurethane resins modified with a hydroxyalkyl silane compound having different silicone contents prepared in example 1.
FIG. 9 is a thermogravimetric analysis chart of cured products of the polyurethane resin modified with the hydroxyalkyl silane compound having different silicone contents prepared in example 1
Detailed Description
The features and advantages of the present invention will be further understood from the following detailed description taken in conjunction with the accompanying drawings. The examples provided are merely illustrative of the method of the present invention and do not limit the remainder of the disclosure in any way.
Example 1
The structural formula for preparing the hydroxyalkyl silane compound is shown as follows:
Figure BDA0002243258720000101
[ wherein,
Figure BDA0002243258720000102
R5cyclohexyl radical, R11＝R10＝R9Trimethylsiloxy, a-3, and b-2.]
The preparation steps are as follows, and the reaction formula is as follows:
Figure BDA0002243258720000111
[ wherein,
Figure BDA0002243258720000112
R5cyclohexyl radical, R11＝R10＝R9Trimethylsiloxy, a-3, and b-2.]
(1) Under the protection of argon, 36.8g (0.1mol) of chloropropyltris (trimethylsiloxy) silane and 100g (1mol) of cyclohexylamine are placed in a 500mL three-necked bottle, heated to 120 ℃ and reacted for 24-78h, the reaction degree is detected by gas chromatography during the reaction, after the reaction is completed, the reaction product is decompressed and filtered to remove impurities such as ammonium salt, and then the filtrate is heated to 120 ℃ and 130 ℃ and decompressed by an oil pump to 100pa, and the 110-degree fraction is obtained by decompression and fractionation, namely (N-cyclohexyl) iminotris (trimethylsiloxy) silane. The chemical reaction equation is as follows:
Figure BDA0002243258720000113
(2) under the protection of argon, 43.6g (0.1mol) of (N-cyclohexyl) aminopropylidene tris (trimethylsiloxy) silane prepared in the step (1), 8.7g (0.05mol) of ethylene glycol diglycidyl ether and 0.5g of lithium bromide are added into a 100mL three-necked flask, heated to 30 ℃ and stirred for reaction for 48 hours, so that the hydroxyalkyl silane compound can be obtained. The reaction progress was monitored by Thin Layer Chromatography (TLC) during the reaction (the ratio of developing solvent EA: DCM: EA: MeOH ═ 6:2:10: 1). The chemical reaction equation is as follows:
Figure BDA0002243258720000114
the infrared spectrum, nuclear magnetic hydrogen spectrum, nuclear magnetic carbon spectrum and high resolution mass spectrum of the hydroxyalkyl silane compound are respectively shown in FIGS. 1 to 4. From the FT-IR spectrum of FIG. 1, it can be seen that the absorption peak of Si-O-Si appears at 1057cm-1To (3). 1251,842 and 755cm-1Three peaks are Si (CH)3)3Characteristic peak of (2). 3416cm-1Absorption peakIs a characteristic peak of-OH. From FIG. 21H NMR spectrum can see that the single peak at 0.1-0.1 ppm is Si-CH3The proton peak of (1). In addition, 0.5-0.2ppm of multiplet is Si-CH2-proton peak of (a). And multiple peaks at 2.6-2.3ppm represent N-CH2-and proton peaks of N-CH-. And the integral area ratio of each peak is consistent with a theoretical value. From FIG. 313The C NMR spectrum showed that the peak at 0.0ppm was Si-CH3The carbon peak of (2). Peaks at 51.3, 51.9 and 57.9ppm C are N-CH2C peaks of-and N-CH 10.0ppm C peak represents Si-CH2-carbon peak of (a). Three C peaks at 69.0-57.8ppm represent O-CH2-and carbon peak of O-CH-. The high resolution mass spectrum shows that the molecular weight of the synthesized molecules is consistent with the theoretical value. These results indicate that the hydrocarbyloxysilane compounds were successfully synthesized.
Example 2
The structural formula for preparing the hydroxyalkyl silane compound is shown as follows:
Figure BDA0002243258720000121
[ wherein R8Methyl, R5Is phenyl, R11＝R10Methoxy radical, R9Methyl, a 1, b 1.]
The preparation steps are as follows, and the reaction formula is as follows:
Figure BDA0002243258720000122
[ wherein R8Methyl, R5Is phenyl, R11＝R10Methoxy radical, R9Methyl, a 1, b 1.]
Under the protection of argon, (N-phenyl) iminomethylmethyldimethoxysilane (21.1 g, 0.1mol), propylene oxide (2.9 g, 0.05mol) and lithium iodide (0.5 g) were put into a 100mL three-necked flask, heated to 30 ℃ and reacted with stirring for 48 hours to obtain a hydrocarbyloxysilane compound.
Example 3
The structural formula for preparing the hydroxyalkyl silane compound is shown as follows:
Figure BDA0002243258720000123
[ wherein,
Figure BDA0002243258720000124
R5cyclohexyl radical, R11＝R10R is trimethylsiloxy, R9Methyl, a-3, b-3.]
The preparation steps are as follows, and the reaction formula is as follows:
Figure BDA0002243258720000125
[ wherein,
Figure BDA0002243258720000126
R5cyclohexyl radical, R11＝R10R is trimethylsiloxy, R9Methyl, a-3, b-3.]
Under the protection of argon, (N-cyclohexyl) aminopropylidene methyldi (trimethylsiloxy) silane (7.22 g, 0.03mol), trimethylolpropane triglycidyl ether (3.02 g, 0.01mol) and lithium chloride (0.1 g) were charged in a 100mL three-necked flask, and the mixture was heated to 30 ℃ and stirred for reaction for 48 hours to obtain an hydroxyalkyl silane compound.
Example 4
The structural formula for preparing the hydroxyalkyl silane compound is shown as follows:
Figure BDA0002243258720000131
[ wherein,
Figure BDA0002243258720000132
R5cyclohexyl radical, R11＝R10Ethoxy, R9Methyl, a-3, b-3.]
The preparation steps are as follows, and the reaction formula is as follows:
Figure BDA0002243258720000133
[ wherein,
Figure BDA0002243258720000134
R5cyclohexyl radical, R11＝R10Ethoxy, R9Methyl, a-3, b-3.]
Under the protection of argon, (N-cyclohexyl) aminopropylidene methyldiethoxysilane (8.19 g, 0.03mol), trimethylolethane triglycidyl ether (2.88 g, 0.01mol) and lithium iodide (0.2 g) were charged in a 100mL three-necked flask, and the mixture was heated to 40 ℃ and stirred for reaction for 72 hours to obtain a hydroxyalkyl silane compound.
Example 5
The structural formula for preparing the hydroxyalkyl silane compound is shown as follows:
Figure BDA0002243258720000135
[ wherein,
Figure BDA0002243258720000136
R5cyclohexyl radical, R11＝R10＝R9Ethoxy, a-3, and b-3.]The preparation steps are as follows, and the reaction formula is as follows:
Figure BDA0002243258720000137
[ wherein,
Figure BDA0002243258720000138
R5cyclohexyl radical, R11＝R10＝R9Ethoxy, a-3, and b-3.]Under the protection of argon, (N-cyclohexyl) aminopropylidene triethoxysilane (9.09 g, 0.03mol), glycerol triglycidyl ether (2.74 g, 0.01mol) and lithium iodide (0.3 g) were charged into a 100mL three-necked flask, heated to 50 ℃ and stirred for reaction for 72 hours to obtain a hydroxyalkyl silane compound.
Example 6
The formula for preparing the hydroxyalkyl linear polysiloxane compound is shown as follows:
Figure BDA0002243258720000141
[ wherein R1＝R2Is phenyl, R3(iii) β -acryloyloxyethoxy, R4Methyl, R5Cyclohexyl radical, R6＝H，a＝3。]
The preparation steps are as follows, and the reaction formula is as follows:
Figure BDA0002243258720000142
[ wherein R1＝R2Is phenyl, R3(iii) β -acryloyloxyethoxy, R4Methyl, R5Cyclohexyl radical, R6＝H，a＝3。]
Under the protection of argon, 10.34g (0.004mol) of amino-terminated linear polysiloxane prepared by CN 109369880A, 0.70g (0.016mol) of ethylene oxide and 0.2g of lithium bromide are added into a 100mL pressure reaction bottle, heated to 40 ℃, stirred and reacted for 48 hours to obtain the hydroxyl-terminated linear polysiloxane compound.
Example 7
The formula for preparing the hydroxyalkyl linear polysiloxane compound is shown as follows:
Figure BDA0002243258720000143
[ wherein R1＝R2Is phenyl, R3＝R4Methoxy radical, R5Cyclohexyl radical, R6Methyl, a 3.]
The preparation steps are as follows, and the reaction formula is as follows:
Figure BDA0002243258720000144
[ wherein R1＝R2Is phenyl, R3＝R4Methoxy radical, R5Cyclohexyl radical, R6Methyl, a 3.]
Under the protection of argon, 23.0g (0.01mol) of amino-terminated linear polysiloxane prepared by CN 104387546A, 1.74g (0.03mol) of propylene oxide and 0.5g of lithium bromide are added into a 100mL pressure reaction bottle, heated to 50 ℃, stirred and reacted for 60 hours, and low-boiling-point substances are pumped out to obtain the hydroxyl linear polysiloxane compound.
Example 8
The formula for preparing the hydroxyalkyl linear polysiloxane compound is shown as follows:
Figure BDA0002243258720000151
[ wherein R1Methyl, R2Is phenyl, R3＝R4(iii) β -methacryloyloxyethoxy, R5Is phenyl, R6I.e. isopropoxymethyl, a 1.]
The preparation steps are as follows, and the reaction formula is as follows:
Figure BDA0002243258720000152
[ wherein R1Methyl, R2Is phenyl, R3＝R4(iii) β -methacryloyloxyethoxy, R5Is phenyl, R6I.e. isopropoxymethyl, a 1.]
26.08g (0.01mol) of amino-terminated phenyl-containing linear polysiloxane prepared in CN 104387546A, 2.32g (0.02mol) of isopropyl glycidyl ether and 0.3g of lithium chloride were put into a 100mL three-necked flask under the protection of argon, heated to 30 ℃ and stirred to react for 48 hours, thereby obtaining a hydroxyalkyl linear polysiloxane compound.
Example 9
The formula for preparing the hydroxyalkyl linear polysiloxane compound is shown as follows:
Figure BDA0002243258720000153
[ wherein R1＝R2＝R3＝R4Methyl, R5＝H，R6N-butyl and a 3.]
The reaction formula is shown as follows:
Figure BDA0002243258720000154
[ wherein R1＝R2＝R3＝R4Methyl, R5＝H，R6N-butyl and a 3.]
Under the protection of argon, 80.0g (0.01mol) of amino silicone oil (Mn-8000, Dow Corning OFX-8040A), 2.6g (0.02mol) of n-butyl glycidyl ether and 1.5g of lithium bromide are added into a 250mL three-necked bottle, heated to 40 ℃, stirred and reacted for 72 hours to obtain the hydroxyalkyl linear polysiloxane compound.
Example 10
The formula for preparing the hydroxyalkyl linear polysiloxane compound is shown as follows:
Figure BDA0002243258720000155
[ wherein R1＝R2＝R3＝R4Methyl, R5＝H，R6Allyloxy, a 3.]
The preparation steps are as follows, and the reaction formula is as follows:
Figure BDA0002243258720000161
[ wherein R1＝R2＝R3＝R4Methyl, R5＝H，R6Allyloxy, a 3.]
Under the protection of argon, α, 50.0g (0.01mol) of omega-bisaminopropyl-terminated polydimethylsiloxane (ATPS, Mn-5000, Jiangxi star fire), 2.28g (0.02mol) of allyl glycidyl ether and 1.5g of lithium bromide are added into a 250mL three-neck bottle, heated to 35 ℃, stirred and reacted for 60 hours, and then the hydroxyl alkyl linear polysiloxane compound is obtained.
Example 11
The formula for preparing the hydroxyalkyl linear polysiloxane compound is shown as follows:
Figure BDA0002243258720000162
[ wherein R1＝R2＝R3＝R4Methyl, R5＝H，
Figure BDA0002243258720000163
a＝3。]
The preparation steps are as follows, and the reaction formula is as follows:
Figure BDA0002243258720000164
[ wherein R1＝R2＝R3＝R4Methyl, R5＝H，
Figure BDA0002243258720000165
a＝3。]
Under the protection of argon, α, 50.0g (0.01mol) of omega-bisaminopropyl-terminated polydimethylsiloxane (ATPS, Mn-5000, Jiangxi star fire), 2.60g (0.02mol) of diglycidyl ether and 1.5g of lithium bromide are added into a 250mL three-necked bottle, heated to 50 ℃, stirred and reacted for 72 hours to obtain the hydroxyl alkyl linear polysiloxane compound.
Example 12
The formula for preparing the hydroxyalkyl linear polysiloxane compound is shown as follows:
Figure BDA0002243258720000166
[ wherein R1＝R2Is phenyl, R3(iii) β -acryloyloxyethoxy, R4Methyl, R5A cyclohexyl group is added to the reaction mixture,
Figure BDA0002243258720000167
Figure BDA0002243258720000168
a＝1。]
the reaction steps are as follows, and the reaction formula is as follows:
Figure BDA0002243258720000171
[ wherein R1＝R2Is phenyl, R3(iii) β -acryloyloxyethoxy, R4Methyl, R5A cyclohexyl group is added to the reaction mixture,
Figure BDA0002243258720000172
Figure BDA0002243258720000173
a＝1。]
under the protection of argon, 10.3g (0.004mol) of amino-terminated linear polysiloxane obtained in CN 109369880A, 4.04g (0.02mol) of butanediol diglycidyl ether and 0.2g of lithium bromide were put into a 100mL three-necked flask, heated to 40 ℃ and stirred to react for 70 hours to obtain a hydroxyalkyl linear polysiloxane compound.
Example 13
The formula for preparing the hydroxyalkyl linear polysiloxane compound is shown as follows:
Figure BDA0002243258720000174
[ wherein R1Methyl, R2Is phenyl, R3＝R4Ethoxy, R5The compound is a compound of the formula (I) butyl group,
Figure BDA0002243258720000175
a＝3。]
the reaction steps are as follows, and the reaction formula is as follows:
Figure BDA0002243258720000176
[ wherein R1Methyl, R2Is phenyl, R3＝R4Ethoxy, R5The compound is a compound of the formula (I) butyl group,
Figure BDA00022432587200001710
a＝3。]
23g (0.01mol) of amino-terminated linear polysiloxane obtained in CN 109369880A, 2.3g (0.01mol) of hexanediol diglycidyl ether, and 0.2g of lithium bromide were charged in a 100mL three-necked flask under an argon atmosphere, and the mixture was heated to 40 ℃ and stirred to react for 70 hours to obtain a hydroxyalkyl linear polysiloxane compound.
Example 14
The formula for preparing the hydroxyalkyl linear polysiloxane compound is shown as follows:
Figure BDA0002243258720000177
[ wherein R1＝R2Methyl, R3＝R4(iii) β -acryloyloxyethoxy, R5A cyclohexyl group is added to the reaction mixture,
Figure BDA0002243258720000178
Figure BDA0002243258720000179
a＝3。]
the reaction steps are as follows, and the reaction formula is as follows:
Figure BDA0002243258720000181
[ wherein R1＝R2Methyl, R3＝R4(iii) β -acryloyloxyethoxy, R5A cyclohexyl group is added to the reaction mixture,
Figure BDA0002243258720000182
Figure BDA0002243258720000183
a＝3。]
under the protection of argon, 10.43g (0.004mol) of amino-terminated linear polysiloxane prepared in CN 109369880A, 0.86g (0.004mol) of neopentyl glycol diglycidyl ether and 0.2g of lithium bromide were put into a 100mL three-necked flask, heated to 50 ℃ and stirred to react for 70 hours to obtain a hydroxyalkyl linear polysiloxane compound.
Example 15
The formula for preparing the hydroxyalkyl linear polysiloxane compound is shown as follows:
Figure BDA0002243258720000184
[ wherein R1＝R2Methyl, R3＝R4(iii) β -acryloyloxyethoxy, R5＝H，
Figure BDA0002243258720000185
a＝3。]
The reaction steps are as follows, and the reaction formula is as follows:
Figure BDA0002243258720000186
[ wherein R1＝R2Methyl, R3＝R4(iii) β -acryloyloxyethoxy, R5＝H，
Figure BDA0002243258720000187
a＝3。]
Under the protection of argon, 10.40g (0.004mol) of amino-terminated linear polysiloxane prepared by CN 109369880A, 0.87g (0.004mol) of diethylene glycol diglycidyl ether and 0.2g of lithium iodide are added into a 100mL three-necked bottle, heated to 40 ℃, and stirred for reaction for 60 hours to obtain the hydroxyalkyl linear polysiloxane compound.
Example 16
The formula for preparing the hydroxyalkyl linear polysiloxane compound is shown as follows:
Figure BDA0002243258720000188
[ wherein R1Methyl, R2Is phenyl, R3＝R4(iii) β -methacryloyloxyethoxy, R5＝H，
Figure BDA0002243258720000189
Figure BDA00022432587200001810
a＝3。]
The reaction formula is shown as follows:
Figure BDA0002243258720000191
[ wherein R1Methyl, R2Is phenyl, R3＝R4(iii) β -methacryloyloxyethoxy, R5＝H，
Figure BDA0002243258720000192
Figure BDA0002243258720000193
a＝3。]
Under the protection of argon, 10.43g (0.004mol) of amino-terminated linear polysiloxane prepared by CN 109369880A, 1.05g (0.004mol) of triethylene glycol diglycidyl ether and 0.2g of lithium iodide are added into a 100mL three-necked bottle, heated to 40 ℃, and stirred for reaction for 60 hours to obtain the hydroxyalkyl linear polysiloxane compound.
Example 17
The formula for preparing the hydroxyalkyl linear polysiloxane compound is shown as follows:
Figure BDA0002243258720000194
[ wherein R1Methyl, R2Is phenyl, R3＝R4(iii) β -acryloyloxyethoxy, R5＝H，
Figure BDA0002243258720000195
a＝3。]
The reaction formula is shown as follows:
Figure BDA0002243258720000196
[ wherein R1Methyl, R2Is phenyl, R3＝R4(iii) β -acryloyloxyethoxy, R5＝H，
Figure BDA0002243258720000197
a＝3。]
Under the protection of argon, 10.40g (0.004mol) of amino-terminated linear polysiloxane prepared in CN 109369880A, 0.89g (0.004mol) of resorcinol diglycidyl ether and 0.4g of lithium iodide were put into a 100mL three-necked flask, heated to 40 ℃ and stirred to react for 60 hours to obtain a hydroxyalkyl linear polysiloxane compound.
Example 18
The formula for preparing the hydroxyalkyl linear polysiloxane compound is shown as follows:
Figure BDA0002243258720000198
[ wherein R1Methyl, R2Is phenyl, R3＝R4(iii) β -acryloyloxyethoxy, R5＝H，
Figure BDA0002243258720000199
a＝3。]
The reaction formula is shown as follows:
Figure BDA0002243258720000201
[ wherein R1Methyl, R2Is phenyl, R3＝R4(iii) β -acryloyloxyethoxy, R5＝H，
Figure BDA0002243258720000202
a＝3。]
Under the protection of argon, 10.40g (0.004mol) of amino-terminated linear polysiloxane prepared by CN 109369880A, 1.14g (0.004mol) of cyclohexane-1, 2-dicarboxylic acid diglycidyl ester and 0.4g of lithium iodide are added into a 100mL three-necked flask, heated to 40 ℃ and stirred for reaction for 60 hours to obtain the hydroxyalkyl linear polysiloxane compound.
Example 19
The formula for preparing the hydroxyalkyl linear polysiloxane compound is shown as follows:
Figure BDA0002243258720000203
[ wherein R1Methyl, R2Is phenyl, R3＝R4(iii) β -acryloyloxyethoxy, R5＝H，
Figure BDA0002243258720000204
Figure BDA0002243258720000205
a＝3。]
The reaction formula is shown as follows:
Figure BDA0002243258720000206
[ wherein R1Methyl, R2Is phenyl, R3＝R4(iii) β -acryloyloxyethoxy, R5＝H，
Figure BDA0002243258720000207
Figure BDA0002243258720000208
a＝3。]
Under the protection of argon, 10.40g (0.004mol) of amino-terminated linear polysiloxane prepared from CN 109369880A, 1.36g (0.004mol) of bisphenol A diglycidyl ester and 0.4g of lithium iodide are added into a 100mL three-necked flask, heated to 40 ℃ and stirred for reaction for 60 hours to obtain the hydroxyalkyl linear polysiloxane compound.
Example 20
The formula for preparing the hydroxyalkyl linear polysiloxane compound is shown as follows:
Figure BDA0002243258720000209
[ wherein R1＝R2＝R3＝R4Methyl, R5＝H，R6Is benzyl.]
The reaction formula is shown as follows:
Figure BDA0002243258720000211
[ wherein R1＝R2＝R3＝R4Methyl, R5＝H，R6Is benzyl.]
50.0g (0.01mol) of side-chain type aminosilicone oil prepared according to a literature method (Dulisweed et al, printing and dyeing assistant, 2010, 27 (6): 16-19.), 6.57g (0.04mol) of benzyl glycidyl ether and 1.5g of lithium bromide were added to a 250mL three-necked flask under the protection of argon gas, heated to 35 ℃ and stirred for reaction for 60 hours to obtain the hydroxyalkyl linear polysiloxane compound.
Example 21
The formula for preparing the hydroxyalkyl linear polysiloxane compound is shown as follows:
Figure BDA0002243258720000212
[ wherein R1＝R2＝R3＝R4Methyl, R5＝H，
Figure BDA0002243258720000213
]
The reaction formula is shown as follows:
Figure BDA0002243258720000214
[ wherein R1＝R2＝R3＝R4Methyl, R5＝H，
Figure BDA0002243258720000215
]
50.0g (0.01mol) of side-chain type aminosilicone oil prepared according to a literature method (Dulisweed et al, printing and dyeing assistant, 2010, 27 (6): 16-19.), 5.68g (0.04mol) of glycidyl acrylate and 1.5g of lithium bromide were added to a 250mL three-necked flask under the protection of argon gas, heated to 40 ℃ and stirred for reaction for 60 hours to obtain the hydroxyalkyl linear polysiloxane compound.
Example 22
The formula for preparing the hydroxyalkyl linear polysiloxane compound is shown as follows:
Figure BDA0002243258720000216
[ wherein R1＝R2＝R3＝R4Methyl, R5＝H，
Figure BDA0002243258720000221
]
The reaction formula is shown as follows:
Figure BDA0002243258720000222
[ wherein R1＝R2＝R3＝R4Methyl, R5＝H，
Figure BDA0002243258720000223
]
50.0g (0.01mol) of side-chain type aminosilicone oil prepared according to a literature method (Dulisweed et al, printing and dyeing assistant, 2010, 27 (6): 16-19.), 6.28g (0.04mol) of glycidyl methacrylate and 1.5g of lithium bromide were put into a 250mL three-necked flask under the protection of argon gas, heated to 40 ℃ and stirred for reaction for 60 hours to obtain the hydroxyalkyl linear polysiloxane compound.
Example 23
The structural formula for preparing the hydroxy-hydrocarbon silicon resin is shown as follows:
Figure BDA0002243258720000224
[ wherein R5＝H，
Figure BDA0002243258720000225
a＝3。]
The reaction formula is shown as follows:
Figure BDA0002243258720000226
[ wherein R5＝H，
Figure BDA0002243258720000227
a＝3。]
Under the protection of argon, 22g (0.001mol) of active amino-containing organic silicon resin SR22000 (Shanghai EMST electronic materials Co., Ltd.), 2.28g (0.01mol) of glycidyl versatate and 1.5g of lithium bromide are added into a 250mL three-necked bottle, heated to 40 ℃ and stirred for reaction for 60 hours to obtain the hydroxyl silicone resin.
Examples of the use of Hydrocarbyl organosilicon Compounds
The hydroxyhydrocarbyl organosilicon compound of example 1 was used to prepare an organosilicon-modified polyurethane. The prepolymer structure is terminated by isocyanate and has the following structure:
Figure BDA0002243258720000231
[ wherein
Figure BDA0002243258720000232
R5Cyclohexyl radical, R9＝R10＝R11R is trimethylsiloxy, R84,4' -methyldicyclohexyl, R9Is a polyether structural unit，a＝3，b＝2。]
The method comprises the following specific steps:
under the protection of argon, 13.1g (0.05mol) of 4,4' -dicyclohexylmethane diisocyanate (HMDI), 0.05g of dibutyltin dilaurate, 10.0g of toluene and 10.0g of butyl acetate are added into a 250mL three-necked bottle, stirred uniformly and heated to 60 ℃, then a mixed solution of 12.47g (0.018mol) of polyether triol N307, 2.84g (0.0027mol) of a hydroxyl alkyl silane compound, 10.0g of toluene and 10.0g of tetrahydrofuran is dropwise added, and after 6 hours of reaction, the-NCO-terminated organic silicon modified polyurethane resin prepolymer is obtained.
The infrared spectrum, nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum of the prepolymer of the hydroxyalkyl silane compound-modified polyurethane resin (SPU) are shown in FIGS. 5 to 7, respectively. 2264cm can be seen from the infrared spectrum shown in FIG. 5-1The peak is the characteristic peak of the residual-NCO. And 844 and 757cm-1The peak is Si- (CH)3)3Characteristic peak. Comparing the nuclear magnetic map of the polyurethane resin without silicone, Si-CH is present at 0ppm of the nuclear magnetic hydrogen spectrum shown in FIG. 63Characteristic proton peak of (1). The nuclear magnetic carbon spectrum shown in FIG. 7 shows Si-CH at 0ppm3Characteristic carbon peak of (2). These results show that the hydroxyalkyl silane compound was successfully incorporated into the polyurethane resin to produce a hydroxyalkyl silane compound-modified polyurethane resin.
Preparation of organosilicon modified polyurethane resin film
The organic silicon modified polyurethane resin prepolymer is laid on a polytetrafluoroethylene template or a glass plate, and is solidified into a colorless and transparent film after being placed for 10 hours until the solvent is basically volatilized and then being placed for 1 day.
The electron microscope images of the silicone-free Polyurethane (PU) and the polyurethane (SPU) films modified with the hydroxyalkyl silane compound of example 1 containing different mass fractions are shown in fig. 8. From FIG. 8 it can be seen that the silicone-free Polyurethane (PU) had a significant microphase separation (FIG. 8A), whereas the microphase separation was significantly reduced after the introduction of 10 wt% of the hydroxyalkylsilane compound of example 1, and as the amount of introduction continued to increase, the smoothness of the membrane surface increased and the microphase separation continued to decrease. It was shown that the hydroxyalkyl silane compound of example 1 has good compatibility with the polyurethane segment and can significantly improve the degree of microphase separation on the surface of the polyurethane resin film.
The Thermogravimetric (TGA) patterns of the silicone-free Polyurethane (PU) and the polyurethane resin (SPU) film modified with the hydroxyalkyl silane compound of example 1 containing different mass fractions are shown in fig. 9. The data analysis is tabulated in Table 1, from which it can be seen that a significant increase in 50% thermogravimetric temperature and ash content of 10% by weight of the polyurethane resin modified with the hydroxyalkyl silane compound of example 1 (SPU-10) is seen. While continuing to introduce the hydroxyalkyl silane compound of example 1, both T50% and T5% were progressively lower because the hydroxyalkyl silane compound of example 1 was a diol and the soft segment N307 used to synthesize the modified polyurethane (SPU) was a polyester triol, the modified polyurethane (SPU) had less reduction in crosslink density when a small amount (<10 wt%) of the hydroxyalkyl silane compound of example 1 was introduced, while the silicone groups introduced significantly improved the thermal stability of the modified polyurethane (SPU). When the hydroxyalkyl silane compound of example 1 was further introduced, the cross-linking density of the modified polyurethane (SPU) decreased to a greater extent, resulting in a gradual deterioration in its thermal stability. It is shown that the heat resistance and the thermal stability of the organosilicon modified polyurethane resin (SPU) can be effectively controlled by controlling the type and the content of the added hydroxyalkyl silane compound.
TABLE 1 thermogravimetric analysis of PU and SPUs
Figure BDA0002243258720000241
1：T5The temperature at which the weight loss on heating is 5%;2：T50is 50% of thermal weight loss; the temperature of (d);3: the ash is the mass fraction of the ash at 600 ℃.
Tensile property test data for silicone-free Polyurethane (PU) and polyurethane resin (SPU) films modified with different mass fractions of the hydroxyalkyl silane compound of example 1 are shown in table 2 below. As can be seen from Table 2 below, as the content of the hydroxyalkyl silane compound incorporated in example 1 gradually increased, the tensile strength at break of SPU decreased first and then increased, and the elongation at break increased first and then decreased, indicating that controlling the content of the hydroxyalkyl silane compound incorporated in example 1 is effective in controlling the tensile properties of the silicone-modified polyurethane resin (SPU).
Table 2 tensile Strength at Break and elongation at Break of PU and SPU
Figure BDA0002243258720000251
The water contact angle data for silicone-free Polyurethane (PU) and polyurethane resin (SPU) films modified with different mass fractions of the hydroxyalkyl silane compound of example 1 are shown in table 3. As can be seen from Table 3, the introduction of only 10% by weight of the hydroxyhydrocarbyl silane compound of example 1 resulted in a sharp increase in the water contact angle (77.6 ℃) of the hydrophilic PU film to 100.1 °, followed by a further increase in the amount of the hydroxyhydrocarbyl silane compound of example 1, with a significant decrease in the rate of increase in the water contact angle. It is shown that the incorporation of a smaller amount of the hydroxyalkyl silane compound of example 1 is effective in increasing the hydrophobicity of the silicone-modified polyurethane resin (SPU).
TABLE 3 Water contact angles of PU and SPU
Figure BDA0002243258720000252
The coefficients of friction for the silicone-free Polyurethane (PU) and the film of polyurethane resin (SPU) modified with different mass fractions of the hydroxyalkyl silane compound of example 1 are shown in table 4. As can be seen from the following table, the introduction of 10% by weight of the hydroxyalkyl silane compound of example 1 greatly reduced the coefficient of friction of the silicone resin (SPU), indicating that the introduction of a small amount of the hydroxyalkyl silane compound of example 1 effectively improved the abrasion resistance of the surface of the silicone resin (SPU).
TABLE 4 coefficients of friction for PU and SPU
Figure BDA0002243258720000253
Figure BDA0002243258720000261
1: the friction coefficient refers to the friction coefficient when a Taber friction machine is used for friction test1000 times the mass (mg) lost per revolution of friction. A lower coefficient of friction indicates better wear resistance.

Claims (7)

1. A hydroxyalkyl linear polysiloxane, characterized in that it has any one of the following structures:
Figure FDA0002243258710000011
wherein: r1、R2Is phenyl or methyl;
R3、R4is methyl, methoxy, ethoxy, β -acryloyloxyethoxy or β -methacryloyloxyethoxy;
R5is H, phenyl or alkyl;
R6is a group shown as follows:
Figure FDA0002243258710000012
R7is a group shown as follows:
Figure FDA0002243258710000013
a is 1 or 3;
m, n and y are natural numbers.
2. A hydroxy-hydrocarbon silicon resin, characterized in that: the structure of the hydroxy hydrocarbon silicon resin is as follows:
Figure FDA0002243258710000021
wherein:
R3、R4is methyl, methoxy, ethoxy, β -acryloyloxyethoxy or β -methacryloyloxyethoxy;
R5is H, phenyl or alkyl;
R6is a group shown as follows:
Figure FDA0002243258710000022
a is 1 or 3.
3. A hydrocarbylsilane compound characterized by: the structure of the hydroxyalkyl silane compound is shown as follows:
Figure FDA0002243258710000023
wherein:
R5is H, phenyl or alkyl;
R8is a group shown as follows:
Figure FDA0002243258710000031
R9、R10、R11is methyl, trimethylsiloxy, methoxy, ethoxy;
a is 1 or 3;
b is 1 or 2 or 3.
4. The method of preparing the hydroxyalkyl linear polysiloxane of claim 1, wherein the reaction formula of the preparation method is shown as formula I, and the method comprises the following steps:
under the protection of inert gas, uniformly mixing an organic silicon compound containing aminoalkyl or iminoalkyl with an epoxy compound, adding a proper amount of catalyst, and reacting at 30-50 ℃ for 24-72h to obtain hydroxyalkyl linear polysiloxane;
the molar amount of the aminoalkyl group or the aminohydrocarbylene group of the added organosilicon compound containing an aminoalkyl group or an aminohydrocarbylene group is the same as the molar amount of the epoxy group in the added epoxy compound;
the linear polysiloxane containing amino hydrocarbon group or imino hydrocarbon group is prepared by the method disclosed in patent document CN 109369880A, or directly purchased from silicone oil containing amino group or imino group in the market;
the catalyst is one of LiCl, LiBr and LiI, and accounts for 0.5-2 wt% of the total mass of the raw materials;
the epoxy compound (OCHCH)nR6The epoxy resin is one of ethylene oxide, propylene oxide, isopropyl glycidyl ether, n-butyl glycidyl ether, allyl glycidyl ether, benzyl glycidyl ether, tertiary carbonic acid glycidyl ester, methacrylic acid glycidyl ester and acrylic acid glycidyl ester;
the epoxy compound (OCHCH)nR7The material is one of diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, hexanediol diglycidyl ether, resorcinol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, and cyclohexane-1, 2-dicarboxylic acid diglycidyl ester;
Figure FDA0002243258710000041
wherein:
R1、R2is phenyl or methyl;
R3、R4is methyl, methoxy, ethoxy, β -acryloyloxyethoxy or β -methacryloyloxyethoxy;
R5h, cyclohexyl, phenyl, alkyl;
R6is a group shown as follows:
Figure FDA0002243258710000042
R7is a group shown as follows:
Figure FDA0002243258710000043
a is 1 or 3;
m and n are natural numbers.
5. The method for preparing the hydroxyalkyl silicon resin as claimed in claim 2, wherein the reaction formula of the preparation method is shown in formula II, and the method comprises the following steps:
under the protection of nitrogen, uniformly mixing equimolar amount of silicon resin containing aminoalkyl or alkylene with an epoxy compound, adding a proper amount of catalyst, and reacting at 30-50 ℃ for 24-72h to obtain hydroxy-hydrocarbon silicon resin;
the silicon resin containing amino or imino is aminoalkyl or alkylene silicon resin;
the catalyst is one of LiCl, LiBr and LiI, and accounts for 0.5-2 wt% of the total mass of the raw materials;
the epoxy compound (OCHCH)nR6The epoxy resin is one of ethylene oxide, propylene oxide, isopropanol glycidyl ether, n-butanol glycidyl ether, allyl alcohol glycidyl ether, benzyl alcohol glycidyl ether, tertiary carbonic acid glycidyl ester, methacrylic acid glycidyl ester and acrylic acid glycidyl ester;
Figure FDA0002243258710000051
wherein:
R3、R4is methyl, methoxy, ethoxy, β -acryloyloxyethoxy or β -methacryloyloxyethoxy;
R5h, cyclohexyl, phenyl, alkyl;
R6is a group shown as follows:
Figure FDA0002243258710000052
a is 1 or 3;
m and n are natural numbers.
6. The method of claim 3, wherein the reaction formula of the method is represented by formula III, comprising the steps of:
under the protection of inert gas at 30-50 deg.C, adding equimolar amount of silane compound (R) containing amino alkyl or imino alkyl11)(R10)(R9)Si(CH2)aNH(R5) With epoxy compounds (OCHCH)bR8After uniform mixing, adding a proper amount of catalyst, stirring and reacting for 24-72h to obtain a hydroxyalkyl silane compound;
the aminoalkyl or aminoalkyl-containing silane compound (R)11)(R10)(R9)Si(CH2)aNH(R5) Gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldiethoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma-aminopropyltris (trimethylsiloxy) silane, gamma-aminopropylmethyldi (trimethylsiloxy) silane, α -aminomethyltriethoxysilane, α -aminomethyltrimethoxysilane, α -aminomethylmethyldiethoxysilane, α -aminomethylmethyldimethoxysilane, α -aminomethyltris (trimethylsiloxy), α -aminomethylmethyldi (trimethylsiloxy) silane;
the catalyst is one or more of LiCl, LiBr and LiI, the mass percentage of the catalyst in the total mass of the raw materials is 0.5-2 wt%,
the epoxy compound (OCHCH)nR8As ethylene oxide, propylene oxide, diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, hexanediol diglycidyl ether, resorcinol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, glycerol triglycidyl ether, isopropyl glycidyl ether, n-butyl glycidyl ether, allyl glycidyl ether, benzyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate,one of tert-carbonic acid glycidyl ester and cyclohexane-1, 2-dicarboxylic acid diglycidyl ester;
Figure FDA0002243258710000061
wherein:
R5is H, phenyl or alkyl;
R8is a group shown as follows:
Figure FDA0002243258710000071
R9、R10、R11is methyl, trimethylsiloxy, methoxy, ethoxy;
a is 1 or 3;
b is 1 or 2 or 3.
7. Use of the hydroxyalkyl linear polysiloxane of claim 1, the hydroxyalkyl silicon resin of claim 2 or the hydroxyalkyl silicon compound of claim 3 in modified polyurethanes, polyester resins, acrylate resins, epoxy resins.
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