CN116515117A - Hyperbranched quaternary ammonium salt polyether amino silicone oil and preparation method thereof - Google Patents

Abstract

The invention relates to hyperbranched quaternary ammonium salt polyether amino silicone oil and a preparation method thereof, wherein 100 parts of branched hydrogen-containing silicone oil, allyl polyether and allyl epoxy polyether are adopted as raw materials, the molar ratio of allyl to silyl is 1.0-1.1, a catalyst and a solvent (the solvent accounts for 1-30% of the weight of the reactant) are added, the temperature is raised to 70-120 ℃, and the reaction is carried out for 2-12 hours, so that the branched polyether epoxy silicone oil is obtained. Then, a tertiary amine compound was added according to tertiary amine group/epoxy group= (1.5 to 2.0): 1 molar ratio, adding glacial acetic acid (the molar number is 1.0-1.1 of the molar number of tertiary amino groups), heating to 70-110 ℃, and reacting for 4-48 h to obtain the hyperbranched quaternary ammonium salt polyether amino silicone oil. According to the invention, the branched structure hydrogen-containing silicone oil is introduced, the branched polyether epoxy silicone oil is constructed through the hydrosilylation reaction of allyl epoxy polyether, and then the branched polyether epoxy silicone oil is subjected to the epoxy amination reaction with the difunctional structure tertiary amine compound, so that the bonding acting force of the silicone oil and fabric fibers can be improved, the fiber friction coefficient is further reduced, and the soft hand feeling is improved.

Description

A kind of hyperbranched quaternary ammonium salt polyether amino silicone oil and preparation method thereof

technical field

The invention relates to the technical field of silicone oil synthesis, in particular to a hyperbranched quaternary ammonium salt polyether amino silicone oil and a preparation method thereof.

Background technique

In order to overcome the above-mentioned shortcomings of traditional amino silicone oil, various methods have been used to improve it, such as epoxy modification or modification of hydrophilic groups such as carboxyl groups, side chain or main chain polyether modification, and the modified silicone oil is stable. The performance is improved, but the feel is deviated.

The patent (CN104452311B) provides a preparation method of a side chain modified silicone softener, which is used to prepare a silicone softener with high-efficiency hydrophilicity and good flexibility. The patent (US5807956) uses double epoxy polysiloxane and amino polyether to prepare block polyether silicone oil. Compared with traditional side chain amino silicone oil, amino groups are introduced into the main chain to maintain its softness. The polyether segment can further obtain better hydrophilic properties. Patents (CN104650363B and CN104650364B) use diethylenetriamine to react with epoxy groups to form a hyperbranched network structure, and combine hyperbranched polymers with linear polyether amino block silicones to develop new silicone softeners. Has a new modified silicone chemical structure.

However, the primary amine group on the main chain of the block silicone oil still has the same fabric "yellowing" problem as the amino silicone oil. Therefore, it is possible to replace the primary amine group by introducing a quaternary ammonium group on the main chain of the block polyether amino silicone oil. Mainly use epoxy silicone oil and polyether amine as raw materials, and use quaternization reagents for cationic modification to obtain main chain quaternization polyether block amino silicone oil. The quaternization reagents include epoxypropyl trimethyl chloride Ammonium, dimethyl sulfate, epichlorohydrin, ethyl chloroacetate and epoxy polyether, etc. The patent (CN114016297A) uses polyether epoxy silicone oil and diethylenetriamine to react to generate block polyether amino silicone oil, and then dehydrates with long-chain fatty acid or alkyl lactone to form a ring at high temperature, and finally adds a quaternizing agent to prepare a low Hydrophilic block polyether amino silicone oil with yellowing properties. Under acidic conditions, epoxy compounds can react with tertiary amines to form quaternary ammonium salts. Patent EP-A-282720 describes a kind of terminal diepoxy polysiloxane and terminal bis-tertiary amine compound to react under acidic conditions to form long-chain quaternary ammonium salt polysiloxane, which can reduce the tendency of hair elution. This patent does not involve the synthesis of polyether chain segments and branched structures. Therefore, the inventors of the present application tried to use hyperbranched hydrogen-containing silicone oil as the main body, introduce (epoxy) polyether chain segments through hydrosilylation, and react with epoxy groups and tertiary amine compounds to generate quaternary ammonium-containing Salt structure hyperbranched hydrophilic polyether amino silicone oil.

Contents of the invention

The object of the present invention is to provide a kind of hyperbranched quaternary ammonium polyether amino silicone oil and its preparation method, to overcome the deficiencies in the prior art.

The technical scheme for solving the technical problems of the present invention is: adopt 100 parts of branched hydrogen-containing silicone oil, allyl polyether and allyl epoxy polyether as raw materials, and the molar ratio of allyl/hydrosilyl is 1.0 to 1.1, Add a catalyst and a solvent (the solvent accounts for 1-30% by weight of the reactants), raise the temperature to 70-120° C., and react for 2-12 hours to obtain branched polyether epoxy silicone oil. Next, add the tertiary amine compound, feed according to the molar ratio of tertiary amino group/epoxy group=(1.5～2.0):1, add glacial acetic acid (the number of moles is 1.0～1.1 of the number of moles of the tertiary amino group, and heat up to 70-110 °C, react for 4-48 hours to obtain hyperbranched quaternary ammonium polyether amino silicone oil.

The structural formula of branched hydrogen-containing silicone oil is as follows,

Wherein, the value of a+b is an integer from 30 to 300, a>or=1, b>or=1;

The structural formula of allyl polyether is as follows,

Wherein, the value of (p+q) is an integer ranging from 10 to 35;

The structural formula of allyl epoxy polyether is as follows,

Wherein, the value of (x+y) is an integer ranging from 10 to 35;

The catalyst is selected from the isopropanol solution of hexahydrate chloroplatinic acid, and the amount used is 5-20 ppm based on the total weight of raw materials calculated as platinum element.

The solvent is isopropanol, ethylene glycol butyl ether, ethylene glycol tert-butyl ether, diethylene glycol butyl ether, propylene glycol, dipropylene glycol, tripropylene glycol, 2-methyl-1,3-propanediol, dimethyl-1, 3-propanediol, butanediol, methyl-1,3-butanediol, dimethyl-1,2-butanediol, pentanediol, methyl-2,4-pentanediol, dimethyl- One or more of 2,4-pentanediol, methoxy-1,2-propanediol, triethylene glycol, and methyl-1,3,5-pentanetriol.

The molecular structure general formula of tertiary amine compound is as follows:

Wherein, m+n=0-50, and is an integer; R2 is a saturated hydrocarbon group with 1-3 carbon numbers, linear or branched.

The beneficial effects of the present invention are:

In terms of structure, the present invention introduces hydrogen-containing silicone oil with a branched structure, and constructs a branched polyether epoxy silicone oil through the hydrosilylation reaction of allyl epoxy polyether, and then combines it with a tertiary amine with a bifunctional structure The compound undergoes epoxy amination reaction to form a hyperbranched structural block polyether amino silicone oil through An+B ₂ , which can improve the bonding force between the silicone oil and the fabric fiber, further reduce the fiber friction coefficient, and improve the soft feel.

In order to control the reaction crosslinking degree of the present invention and avoid problems such as gelation of silicone oil in the process of epoxy amination, firstly, this patent introduces allyl polyether, by controlling the relationship between the compound and allyl epoxy polyether Ratio, second, the use of tertiary amine compounds instead of primary/secondary amine compounds not only forms a quaternary ammonium salt structure in one step, improves the hydrophilicity of silicone oil, but also controls the degree of crosslinking of hyperbranched quaternary ammonium salt polyether amino silicone oil to avoid Over-crosslinking produces gels that are easy to produce.

Detailed ways

The following examples are illustrative, and are only used to explain the present invention, and should not be construed as limiting the present invention.

Example 1

100.0g branched hydrogen-containing silicone oil (a=5, b=25), 103.0g allyl polyether (p=7, q=3) and 200.0g allyl epoxy polyether (x=15, y =17) join in the four-necked flask that thermometer and reflux condenser are housed, under stirring condition, add 0.4g hexahydrate chloroplatinic acid isopropanol solution (platinum element concentration 5000ppm), isopropanol 4.0g, at 120 Stir the reaction at ℃ for 2 hours, and the silicon hydrogen reaction is complete. Then, add 32.2g of tetramethylpropylenediamine and 32.7g of glacial acetic acid, raise the temperature to 70℃, and react for 48h to obtain hyperbranched quaternary ammonium polyether amino silicone oil.

Example 2

100.0g branched hydrogen-containing silicone oil (a=5, b=150), 20.0g allyl polyether (p=10, q=2) and 20.3g allyl epoxy polyether (x=7, y =3) join in the four-neck flask that thermometer and reflux condenser are housed, under stirring condition, add 0.2g hexahydrate chloroplatinic acid isopropanol solution (platinum element concentration 5000ppm), ethylene glycol butyl ether 30.0g, Stir the reaction at 100°C for 6 hours, and the silicon hydrogen reaction is complete. Then, add 41.3g of tertiary amine polyether (m=10, n=0) and 9.1g of glacial acetic acid, raise the temperature to 80°C, and react for 24h to obtain hyperbranched quaternary Ammonium polyether amino silicone oil.

Example 3

100.0g branched hydrogen-containing silicone oil (a=10, b=100), 50.0g allyl polyether (p=10, q=10) and 200.3g allyl epoxy polyether (x=15, y =20) join in the four-necked flask that thermometer and reflux condenser are housed, under stirring condition, add 1.4g hexahydrate chloroplatinic acid isopropyl alcohol solution (platinum element concentration 5000ppm), ethylene glycol tert-butyl ether 105.0g , stirred and reacted at 100°C for 9 hours, the silicon hydrogen reaction was complete, then, added 274.5g tertiary amine polyether (m=15, n=10) and 28.1g glacial acetic acid, raised the temperature to 80°C, and reacted for 12h to obtain hyperbranched Quaternary ammonium polyether amino silicone oil.

Example 4

100.0g branched hydrogen-containing silicone oil (a=20, b=200), 120.5g allyl polyether (p=15, q=20) and 120.0g allyl epoxy polyether (x=14, y =14) join in the four-necked flask that thermometer and reflux condenser are housed, under stirring condition, add 1.4g hexahydrate chloroplatinic acid isopropanol solution (platinum element concentration 5000ppm), isopropanol 80.0g, in 100 Stir the reaction at ℃ for 10 hours, the silicon hydrogen reaction is complete, then, add 261.5g tertiary amine polyether (m=25, n=25) and glacial acetic acid 11.7g, raise the temperature to 110℃, react for 4h, and obtain the hyperbranched quaternary ammonium salt Polyether amino silicone oil.

Example 5

100.0g branched hydrogen-containing silicone oil (a=50, b=250), 80.0g allyl polyether (p=7, q=3) and 60.0g allyl epoxy polyether (x=10, y =2) join in the four-necked flask that thermometer and reflux condenser are housed, under stirring condition, add 0.5g hexahydrate chloroplatinic acid isopropanol solution (platinum element concentration 5000ppm), isopropanol 50.0g, at 70 Stir the reaction at ℃ for 6 hours, and the silicon hydrogen reaction is complete. Then, add 18.5g of tetramethylpropylenediamine and 19.7g of glacial acetic acid, raise the temperature to 90℃, and react for 12h to obtain hyperbranched quaternary ammonium polyether amino silicone oil.

comparative example

Add 100.0g branched hydrogen-containing silicone oil (a=50, b=250) and 160.0g allyl epoxy polyether (x=10, y=2) into a four-necked flask equipped with a thermometer and a reflux condenser , under stirring conditions, add 0.5g hexahydrate chloroplatinic acid isopropanol solution (platinum element concentration 5000ppm), isopropanol 50.0g, stir and react at 70°C for 6 hours, the silicon hydrogen reaction is complete, then add diethylenetri 39.6 g of amine was heated up to 90° C., reacted for 12 hours, and 76.5 g of glacial acetic acid was added to obtain hyperbranched polyether amino silicone oil with relatively high viscosity.

Application implementation comparison

The method of sample preparation is as follows: the softening agents prepared in the above examples and comparative examples were formulated into 20% aqueous solutions respectively, and the red polyester knitted fabric was used as the cloth sample, and the dosage was 20g/L, dipped and rolled, and baked at 180°C. Dry for 90 seconds, and the prepared sample A, sample B, sample C, sample D, sample E, and comparative sample correspond to embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5, and comparative example respectively.

Hand feeling test: using the hand touch method, with softness and slipperiness as the main performance, it is evaluated by 5 professionals in a comprehensive ranking, and is divided into 1 to 5 grades, with 5 points being the best and 1 point being the worst.

Hygroscopicity: Characterized by static water absorption time, use a standard dropper (25 drops/mL), drop 1 drop of water from a height of 2cm from the fabric to the surface of the flat fabric, and measure the time it takes for the fabric to absorb water droplets under static conditions.

Heat resistance and stability: Silicone oil 20g/L, initially prepared at room temperature and observed for 10 minutes, heated to 60°C, kept for 20 minutes, and observed the phenomenon;

The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the above-mentioned embodiment, and any other changes, modifications, substitutions, combinations, Simplifications should be equivalent replacement methods, and all are included in the protection scope of the present invention.

Claims (8)

1. a kind of hyperbranched quaternary ammonium polyether amino silicone oil, it is characterized in that, is generated by branched polyether epoxy silicone oil and tertiary amine compound, glacial acetic acid reaction, and wherein, the mol ratio of tertiary amino group than epoxy group is ( 1.5～2.0): 1; the raw material formula for the preparation of the branched polyether epoxy silicone oil is: branched hydrogen-containing silicone oil, allyl polyether and allyl epoxy polyether, catalyst, solvent; the branched The structural formula of hydrogen-containing silicone oil is, Wherein, the value of a+b is an integer from 30 to 300, a>or=1, b>or=1; The structural formula of allyl polyether is as follows, Wherein, the value of (p+q) is an integer ranging from 10 to 35; The structural formula of allyl epoxy polyether is as follows, However, the value of (x+y) is an integer of 10-35. 2. hyperbranched quaternary ammonium salt polyether amino silicone oil according to claim 1, is characterized in that, in the preparation raw material of described branched polyether epoxy silicone oil, the mol ratio of allyl/silyl hydrogen is 1.0～ 1.1. 3. The hyperbranched quaternary ammonium polyether amino silicone oil according to claim 1, characterized in that the weight ratio of the solvent to the reactants is 1 to 30%. 4. The hyperbranched quaternary ammonium polyether amino silicone oil according to claim 1, characterized in that the molar number of glacial acetic acid is 1.0 to 1.1 of the molar number of tertiary amino groups. 5. The hyperbranched quaternary ammonium polyether amino silicone oil according to claim 1, characterized in that the catalyst is selected from the hexahydrate water chloroplatinic acid isopropanol solution, and the consumption is calculated as the total weight of raw materials 5-20ppm based on platinum. 6. hyperbranched quaternary ammonium polyether amino silicone oil according to claim 1, is characterized in that, solvent is Virahol, ethylene glycol butyl ether, ethylene glycol tert-butyl ether, diethylene glycol butyl ether, propylene glycol , dipropylene glycol, tripropylene glycol, 2-methyl-1,3-propanediol, dimethyl-1,3-propanediol, butanediol, methyl-1,3-butanediol, dimethyl-1,2- Butanediol, pentanediol, methyl-2,4-pentanediol, dimethyl-2,4-pentanediol, methoxy-1,2 propanediol, triethylene glycol, methyl- One or more of 1,3,5-pentanetriol. 7. hyperbranched quaternary ammonium polyether amino silicone oil according to claim 1, is characterized in that, the molecular structure general formula of tertiary amine compound is: Wherein, m+n=0-50, and is an integer; R2 is a saturated hydrocarbon group with 1-3 carbon numbers, linear or branched. 8. according to the preparation method of claim 1 or 5 or 6 or 7 described hyperbranched quaternary ammonium polyether amino silicone oils, it is characterized in that comprising the following steps, S1) Using 100 parts of branched hydrogen-containing silicone oil, allyl polyether and allyl epoxy polyether as raw materials, the molar ratio of allyl/silyl hydrogen group is 1.0-1.1, adding catalyst and solvent, and the solvent accounts for the reactant The weight ratio is 1-30%, the temperature rises to 70-120°C, and the reaction takes 2-12 hours to obtain branched polyether epoxy silicone oil; S2) Add tertiary amine compound, add glacial acetic acid, the number of moles of glacial acetic acid is 1.0-1.1 of the number of moles of tertiary amino groups, heat up to 70-110°C, react for 4-48 hours, and obtain hyperbranched quaternary ammonium polyether amino silicone oil.