CN103483371A - Preparation and application of N-methyl piperazinyl silane coupling agent - Google Patents
Preparation and application of N-methyl piperazinyl silane coupling agent Download PDFInfo
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- CN103483371A CN103483371A CN201310446824.7A CN201310446824A CN103483371A CN 103483371 A CN103483371 A CN 103483371A CN 201310446824 A CN201310446824 A CN 201310446824A CN 103483371 A CN103483371 A CN 103483371A
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- methyl piperazine
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- silane coupling
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Abstract
The invention discloses preparation and application of an N-methyl piperazinyl silane coupling agent. The structural formula of the N-methyl piperazinyl silane coupling agent is shown as the formula (I). According to the invention, tetramethylammonium hydroxide is used as a catalyst; mass polymerization is conducted between the N-methyl piperazinyl silane coupling agent and octamethyl cyclotetrasiloxane to obtain N-methyl piperazinyl polysilicone; the N-methyl piperazinyl polysilicone is further emulsified by an emulsifier to obtain N-methyl piperazinyl polysilicone emulsion which can be used for preparing a fabric softening and finishing agent. Fabrics and products made of the fabrics which are treated with the N-methyl piperazinyl polysilicone have different properties and handle styles when being compared with those treated with aminoethyl aminopropyl polysilicone; wherein the N-methyl piperazinyl polysilicone is synthesized by using the N-methyl piperazinyl silane coupling agent with a novel structure as a raw material. The N-methyl piperazinyl silane coupling agent can meet the requirements of high grading and diversification of the market, and is an indispensable raw material for added-value increment and high functionalization of fibers.
Description
Technical field
The invention belongs to the silicone fine chemicals field, be specifically related to a kind of preparation and purposes of N methyl piperazine base silane coupling agent.
Background technology
Textile softeners in the market is two classes substantially, one class is the aminoethyl aminopropylpolysiloxane, one class is amino-polyether block silicone oil, all for spinning post-finishing, be the most important softening agent of the synthon such as the natural fiber such as cotton, fiber crops, silk, wool spinning product and polyester, nylon, polyacrylonitrile, play the effects such as soft, smooth, fluffy.
Wherein, the aminoethyl aminopropylpolysiloxane is the textile auxiliary agent of current consumption maximum, is called as the king of softening agent.The fabric sofetening of wherethrough reason, smooth, fluffy, crease-resistant etc., it is to be formed by N-2-aminoethyl-3-aminopropyl methyl dimethoxysilane coupling agent (being KBM-602) and prestox ring tetrasilane (being D4) mass polymerization, contain 2 amino on side chain due to it, so soft, but also have following shortcoming:
1. under the effect of light, heat, easily yellowing;
2. natural fiber loses wetting ability, and effect is taken in impact;
3. rebound resilience, smoothness and washing fastness can not be satisfied the demand.
Amino-polyether block silicone oil in the market can be avoided most defects and the deficiency of above-mentioned aminoethyl aminopropylpolysiloxane, but rebound resilience, washing fastness, fluffy sense etc. can't meet the high request of the multi-level functionalization of particular fabric.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art, a kind of preparation and purposes of N methyl piperazine base silane coupling agent is provided.The invention provides a kind of silane coupling agent of novel texture, take it as the synthetic N methyl piperazine based polysiloxane of raw material, the fabric of processing and goods are compared and are had different performances and feel style with amino-polyether block silicone oil from the aminoethyl aminopropylpolysiloxane generally used on market, but superior, the diversified needs of satisfying the market are fibre product high added value, the indispensable raw material of multifunction.N methyl piperazine propyl group methyl dimethoxysilane coupling agent of the present invention also can be used for polymer modifiers, releasing agent, paint additive, brightening agent and cosmetics additive etc. in addition.
The objective of the invention is to be achieved through the following technical solutions:
First aspect, the present invention relates to a kind of N methyl piperazine base silane coupling agent, and its structural formula is as shown in formula I:
Second aspect, the present invention relates to a kind of preparation method of above-mentioned N methyl piperazine base silane coupling agent, N methyl piperazine and chloropropylmethyldimethoxysilane reaction, obtain N methyl piperazine base propyl group methyl dimethoxysilane, i.e. described N methyl piperazine base silane coupling agent.
Preferably, the weight ratio of described N methyl piperazine and chloropropylmethyldimethoxysilane is 54～64: 36～46.
Preferably, described temperature of reaction is 110～115 ℃, and the reaction times is 200～240min, and reaction pressure is normal pressure.
The third aspect, the present invention relates to a kind of purposes of aforesaid N methyl piperazine base silane coupling agent, described N methyl piperazine base silane coupling agent is for the preparation of fabric softener, polymer modifiers, releasing agent, paint additive, brightening agent or cosmetics additive.
Preferably, described N methyl piperazine base silane coupling agent and prestox ring tetrasilane bulk polymerization generate the N methyl piperazine based polysiloxane, and the N methyl piperazine based polysiloxane emulsion that the emulsification of described N methyl piperazine based polysiloxane makes is fabric softener.
Preferably, the weight ratio of described N methyl piperazine base silane coupling agent and prestox ring tetrasilane is 3.5～5: 95～96.5.
Preferably, described bulk polymerization is to take Tetramethylammonium hydroxide as catalyzer, and temperature of reaction is 100～105 ℃, and the reaction times is 8～9h, and reaction pressure is normal pressure.
Fourth aspect, the present invention relates to a kind of N methyl piperazine based polysiloxane, and its structural formula is as shown in formula II:
m=60～1000 wherein, n=2～20.
Preferably, described N methyl piperazine based polysiloxane is to take Tetramethylammonium hydroxide as catalyzer, by aforesaid N methyl piperazine base silane coupling agent and the tetrasilane mass polymerization of prestox ring and.
Compared with prior art, the present invention has following beneficial effect:
1, with the aminoethyl aminopropylpolysiloxane, compare, the N methyl piperazine based polysiloxane has following advantages:
1) under the prerequisite that guarantees flexibility, the performances such as the fabric whiteness of processing, fluffy sense and smoothness occupy first of all kinds of amino modified polysiloxanes;
2) fabric hydrophilic is better;
3) drape of fabric, tensile strength, anti-wrinkle are better;
4) aspect such as antistatic, anti-pilling property of fabric is better.
2, with amino-polyether block silicone oil, compare, the N methyl piperazine based polysiloxane has better rebound resilience, washing fastness and fluffy sense, can meet the advantages such as demand of particular fabric.
3, the preparation from N methyl piperazine base propyl group methyl dimethoxysilane coupling agent to N methyl piperazine based polysiloxane and silicon breast thereof, the simple easy handling of production technique, whole production process is nontoxic to be produced without the three wastes, and yield is greater than 95%.
The accompanying drawing explanation
By reading the detailed description of non-limiting example being done with reference to the following drawings, it is more obvious that the other features, objects and advantages of patent of the present invention will become:
The 1H NMR spectrogram that Fig. 1 is N methyl piperazine base propyl group methyl dimethoxysilane;
The 13C NMR spectrogram that Fig. 2 is N methyl piperazine base propyl group methyl dimethoxysilane.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.Following examples will contribute to those skilled in the art further to understand the present invention, but not limit in any form the present invention.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make some distortion and improvement.These all belong to protection scope of the present invention.
the preparation of embodiment 1, N methyl piperazine base silane coupling agent
The concrete circuit of preparation of the N methyl piperazine based polysiloxane that the present embodiment relates to is as follows:
(1) take N methyl piperazine and chloropropylmethyldimethoxysilane makes N methyl piperazine base propyl group methyl dimethoxysilane, i.e. N methyl piperazine base silane coupling agent as main raw material; By product is N methyl piperazine base hydrochloride, and reaction equation is as follows:
Wherein, the consumption of N methyl piperazine and chloropropylmethyldimethoxysilane is as shown in table 1.
The N methyl piperazine base silane coupling agent that the present embodiment makes is for the preparation of fabric softener, polymer modifiers, releasing agent, paint additive, brightening agent or cosmetics additive.
the preparation of embodiment 2～10, N methyl piperazine base silane coupling agent
In the preparation of N methyl piperazine base propyl group methyl dimethoxysilane, the weight ratio of N methyl piperazine and chloropropylmethyldimethoxysilane is as shown in table 1 respectively.
The N methyl piperazine base silane coupling agent made is for the preparation of fabric softener, polymer modifiers, releasing agent, paint additive, brightening agent or cosmetics additive.
Table 1
Test out in conjunction with temperature, reaction times, reaction pressure the reaction yield that each embodiment is corresponding as shown in table 1, known, consider yield and production efficiency, optimum technology prepared by N methyl piperazine base propyl group methyl dimethoxysilane of the present invention is: the weight ratio of N methyl piperazine and chloropropylmethyldimethoxysilane is 61～62: 38～39.
the application of embodiment 11, N methyl piperazine base silane coupling agent
The N methyl piperazine base silane coupling agent that the embodiment 8 of take makes is example for the preparation of fabric softener, and concrete steps are:
A, with the N methyl piperazine base propyl group methyl dimethoxysilane and the prestox ring tetrasilane that make, (can be also DMC, select prestox ring tetrasilane in the present embodiment) bulk polymerization makes N methyl piperazine base amino silicones, and its equation is as follows:
Due to N methyl piperazine base propyl group methyl dimethoxysilane, for the preparation of the N methyl piperazine based polysiloxane, when the latter is applied to after-finishing of textile products, molecular weight is less than 5000, and the fabric sofetening degree of processing is inadequate, is greater than 80000, the emulsification difficulty.So being chosen between 5000～80000 of N methyl piperazine based polysiloxane molecular weight, therefore m is limited between 60～1000; Simultaneously, when the N methyl piperazine based polysiloxane made is applied to after-finishing of textile products, require the ammonia value between 0.15～0.5, therefore n is limited between 2～20.And in N methyl piperazine base amino silicones, the weight ratio of m, n and reaction raw materials is closely related, therefore, in the present invention, the weight ratio of N methyl piperazine base propyl group methyl dimethoxysilane and prestox ring tetrasilane can be 3.5～5: 95～96.5.For study N methyl piperazine base propyl group methyl dimethoxysilane with prestox ring tetrasilane the optimum amount ratio in above-mentioned weight ratio scope, in the present embodiment, the consumption of N methyl piperazine base propyl group methyl dimethoxysilane and prestox ring tetrasilane is made as respectively shown in 10 kinds of proportionings of table 2;
B, N methyl piperazine based polysiloxane make N methyl piperazine based polysiloxane emulsion through emulsifying agent emulsification, and the aftertreatment for textiles is specially: be applied to cotton, wash/cotton, the softening of the fabric such as cotton/regenerated cellulose fibre.
Table 2
The N methyl piperazine based polysiloxane emulsion that the N methyl piperazine based polysiloxane of further selecting above each combination to make obtains through emulsification is carried out the evaluation of softening agent performance to cotton textiles, polyester-cotton blend, blended fabric.
In the evaluation experiment,
Flexibility, smoothness, fluffy sense: untrimmed cloth specimen feel rank is decided to be 1 grade, and flexibility, smoothness, fluffy sense are divided into to 5 grades from the poorest to optimum, by 10 experts, is evaluated respectively, and comprehensive average rank is final conclusion.
The xanthochromia degree: adopt SBDY-1 digital display whiteness instrument to detect whiteness, the less whiteness of numerical value is better, and the larger whiteness of data is lower.
Rebound resilience: measure 5 through 5 latitudes with reference to GB/T3819-1997 " mensuration of textile fabric folding line recovery is replied horn cupping ", ask wrinkle recovery angle mean value.
Washing fastness: full-automatic testing machine of shrinkage, household detergent 1g/L, 40 ℃ of washing 30min, wash 5 times, feel, wetting ability and the rebound resilience of fabric after the test washing.
Wetting ability: the fabric after finishing composition arranges is laid on beaker, drips 1 with standard dropper from the place of distance fabric 2cm height and drip, the static lower fabric exhaustion needed time of water of measuring.
Test result is as shown in table 3:
Table 3
As shown in Table 3, the fabric that N methyl piperazine based polysiloxane emulsion of the present invention is processed has good flexibility, fluffy sense, smoothness, xanthochromia degree, rebound resilience, washing fastness, wetting ability; Wherein, optimum performance is selected embodiment 6,7,8,9; While being about to N methyl piperazine base silane coupling agent of the present invention for the preparation of fabric finishing agent, the weight ratio of N methyl piperazine base silane coupling agent and prestox ring tetrasilane is preferably 3.5～5: 95～96.5.
embodiment 12, performance comparison test
The purpose of the present embodiment is to select aminoethyl aminopropylpolysiloxane, amino-polyether block silicone oil, (embodiment 8 for the N methyl piperazine based polysiloxane, proportioning 8) to cotton, wash/cotton, cotton/regenerated cellulose fibre fabric carries out the evaluation of softening agent performance, assessment method is with embodiment 11, and the experiment correlation data sees the following form 4:
The structural formula of above-mentioned aminoethyl aminopropylpolysiloxane is:
wherein, m=60～1000, n=2～20.The concrete Magnasoft307 that adopts Mitugao New Material Group.
Above-mentioned amino-polyether block silicone oil specifically adopts the Magnasoft238 of Mitugao New Material Group.
Table 4
As shown in Table 4, N methyl piperazine based polysiloxane of the present invention is compared with the aminoethyl aminopropylpolysiloxane, has following advantage:
1) under the prerequisite that guarantees flexibility, the performances such as the fabric whiteness of processing, fluffy sense and smoothness occupy first of all kinds of amino modified polysiloxanes;
2) fabric hydrophilic is better;
3) drape of fabric, tensile strength, anti-wrinkle are better.
N methyl piperazine based polysiloxane of the present invention is compared with amino-polyether block silicone oil, has rebound resilience, washing fastness, fluffy sense better, can meet the advantages such as demand of particular fabric.
Above specific embodiments of the invention are described.It will be appreciated that, the present invention is not limited to above-mentioned specific implementations, and those skilled in the art can make various distortion or modification within the scope of the claims, and this does not affect flesh and blood of the present invention.N methyl piperazine based polysiloxane of the present invention also is not limited to prepare fabric softener, and its structural characteristic has determined that it also can be used for preparing polymer modifiers, releasing agent, paint additive, brightening agent or cosmetics additive etc.
Claims (10)
1. a N methyl piperazine base silane coupling agent, is characterized in that, its structural formula is as shown in formula I:
2. the preparation method of a N methyl piperazine base silane coupling agent as claimed in claim 1, it is characterized in that, N methyl piperazine and chloropropylmethyldimethoxysilane reaction, obtain N methyl piperazine base propyl group methyl dimethoxysilane, i.e. described N methyl piperazine base silane coupling agent.
3. the preparation method of N methyl piperazine base silane coupling agent as claimed in claim 2, is characterized in that, the weight ratio of described N methyl piperazine and chloropropylmethyldimethoxysilane is 54～64: 36～46.
4. the preparation method of N methyl piperazine base silane coupling agent as claimed in claim 2, is characterized in that, described temperature of reaction is 110～115 ℃, and the reaction times is 200～240min, and reaction pressure is normal pressure.
5. the purposes of a N methyl piperazine base silane coupling agent as claimed in claim 1, it is characterized in that, described N methyl piperazine base silane coupling agent is for the preparation of fabric softener, polymer modifiers, releasing agent, paint additive, brightening agent or cosmetics additive.
6. the purposes of N methyl piperazine base silane coupling agent as claimed in claim 5, it is characterized in that, described N methyl piperazine base silane coupling agent and prestox ring tetrasilane bulk polymerization generate the N methyl piperazine based polysiloxane, and the N methyl piperazine based polysiloxane emulsion that the emulsification of described N methyl piperazine based polysiloxane makes is fabric softener.
7. the purposes of N methyl piperazine base silane coupling agent as claimed in claim 6, is characterized in that, the weight ratio of described N methyl piperazine base silane coupling agent and prestox ring tetrasilane is 3.5～5: 95～96.5.
8. the purposes of N methyl piperazine base silane coupling agent as described as claim 6 or 7, is characterized in that, described bulk polymerization is to take Tetramethylammonium hydroxide as catalyzer, and temperature of reaction is 100～105 ℃, and the reaction times is 8～9h, and reaction pressure is normal pressure.
9. a N methyl piperazine based polysiloxane, is characterized in that, its structural formula is as shown in formula II:
m=60～1000 wherein, n=2～20.
10. N methyl piperazine based polysiloxane as claimed in claim 9, it is characterized in that, described N methyl piperazine based polysiloxane is to take Tetramethylammonium hydroxide as catalyzer, by N methyl piperazine base silane coupling agent as claimed in claim 1 and prestox ring tetrasilane bulk polymerization and obtain.
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| CN110820353A (en) * | 2019-10-24 | 2020-02-21 | 苏州联胜化学有限公司 | Hydrophilic silicone oil and preparation method thereof |
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| CN110820353A (en) * | 2019-10-24 | 2020-02-21 | 苏州联胜化学有限公司 | Hydrophilic silicone oil and preparation method thereof |
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