CN104927057A

CN104927057A - Organic silicon feeling agent and preparation method thereof

Info

Publication number: CN104927057A
Application number: CN201510294008.8A
Authority: CN
Inventors: 高鹏东; 徐运欢; 孙东明
Original assignee: GUANGZHOU SILOK POLYMER CO Ltd
Current assignee: GUANGZHOU SILOK POLYMER CO Ltd
Priority date: 2015-05-31
Filing date: 2015-05-31
Publication date: 2015-09-23
Anticipated expiration: 2035-05-31
Also published as: CN104927057B

Abstract

The invention belongs to the technical field of macromolecules, and discloses an organic silicon feeling agent and a preparation method thereof. The feeling agent comprises a compound (of which the formula is show in the description), wherein in the formula of the compound, x is equal to 8-18, y is equal to 1-5, and z is equal to 1-5. According to the invention, novel aminophenyl modified silicone oil is obtained, can be used as the feeling agent, has the characteristics of good antifouling property, rapid dryness, fluff hand feeling, high stability and the like, and meets requirements of the market.

Description

A kind of organic silicon hand feeling agent and preparation method thereof

Technical field

The invention belongs to technical field of macromolecules, be specifically related to a kind of new organic silicon hand feeling agent and preparation method thereof.

Background technology

Feel weighs the requisite important indicator of leather quality.Except retanning and dryness finalization, in covering with paint, especially at top coat, use some hand feeling agents, can bring about tangible results to the final feel of leather goods.Therefore, the application of hand feeling agent is paid attention to by tannery always deeply.Conventional hand feeling agent has wax and the large class of organosilicon two.The leather effect of shadow taking wax as the non-ionic type hand feeling agent that obtains of raw material and surface slip agent process is not good, and take organosilicon as the obtained special hand feeling agent of raw material, owing to adopting D more ₄the technique of open loop repolymerization, emulsification, molecular weight, is easy to migration, thus causes non-resistant defect.

Summary of the invention

For these reasons, applicant is through years of researches, and obtain a kind of novel organosilicon hand feeling agent, this hand feeling agent has the feature of didirtresistance, quick-drying, fuzzy hand, good stability, is more applicable to the needs in market.

Specifically, the invention provides:

A kind of organic silicon hand feeling agent: containing following compound

Wherein x=8-18; Y=1-5, z=1-5;

Described organic silicon hand feeling agent containing following compound is preferably:

Organic silicon hand feeling agent described above, its preparation method includes but not limited to following:

Step 1: by compound (II) and compound (III) in 7% sodium hydroxide solution, reflux 1 hour under 110-120 DEG C of condition, slowly steam methyl alcohol, after methyl alcohol all steams, stopped reaction, with toluene extraction water hydrolysis products, underpressure distillation removing toluene, namely obtains ol cpds (IV);

Step 2: in the following order by compound (IV), 0.01mol/ml (CH ₃) ₄nOH catalyzer 8.7ml, H ₂o and D ₄disposablely join in reaction vessel, at N ₂protect and at 95 DEG C, after hydrolysis reaction 40min, be warming up to 95 ~ 123 DEG C, while vacuumize dehydration limit polyreaction;

Step 3: after being aggregated to 4 ~ 6h, stops vacuumizing and logical nitrogen, adds 0.01 ~ 0.1g/ml trimethyl silanol as end-blocking degradation water solution in system, be warming up to 125 DEG C, after end-blocking degraded confined reaction 4h, logical nitrogen, heat up 155 DEG C, abolish catalyzer 0.5h; At 110 ~ 155 DEG C, adopt oil pump to vacuumize remove low-boiling-point substance (<10mmHg), obtain the water white compound with certain viscosity.

The present invention obtains being a kind of new aminophenyl modified silicon oil, and this silicone oil can be used as hand feeling agent and uses, and it has antifouling, quick-drying, fuzzy hand, good stability feature, is more applicable to the needs in market.

Embodiment

Below by way of the description of embodiment, the invention will be further described, but this is not limitation of the present invention, those skilled in the art are according to basic thought of the present invention, various amendment or improvement can be made, but only otherwise depart from basic thought of the present invention, all within the scope of the present invention.

Described D ₄for octamethylcyclotetrasiloxane, purchased from Beijing Hang Pingguichuan Chemical Co., Ltd..

Embodiment 1

Step 1: 1.8mol compound (II), 0.5mol compound (III), 300ml 7% sodium hydroxide solution are added in reaction vessel successively, reflux 1 hour under 110-120 DEG C of condition, slowly steam methyl alcohol, after methyl alcohol all steams, stopped reaction, at room temperature use toluene extraction water hydrolysis products, underpressure distillation removing toluene, namely obtains ol cpds (IV);

Table 1 product (IV) physical property

Outward appearance (range estimation)	Refractive index/25 DEG C	Viscosity cps (25 DEG C of rotational viscosimeters)	Yield %
				Colourless transparent liquid	1.5075	78.30	98.55

Step 2: in the following order by 0.4mol compound (IV), 0.01mol/ml (CH ₃) ₄nOH catalyzer 1ml, 100mlH ₂o and 0.6molD ₄join successively in reaction vessel, at N ₂protect and at 95 DEG C, after hydrolysis reaction 40min, be warming up to 95 ~ 123 DEG C, while vacuumize dehydration limit polyreaction;

Table 2 product (V) physical property

Outward appearance (range estimation)	Refractive index/25 DEG C	Viscosity cps (25 DEG C of rotational viscosimeters)	Yield %
				Colourless transparent liquid	1.4947	82.0	98.83

Step 3: after being aggregated to 4h, stops vacuumizing and logical nitrogen, adds 0.01g/ml trimethyl silanol 1000ml as end-blocking degradation water solution, be warming up to 125 DEG C in system, and after end-blocking degraded confined reaction 4h, logical nitrogen, heats up 155 DEG C, abolish catalyzer 0.5h; At 110 DEG C, adopt oil pump to vacuumize remove low-boiling-point substance (<10mmHg), obtain the water white compound with certain viscosity.

Table 3 product (I-1) physical property

According to infrared spectrogram:

1067cm ^-1, 1024cm ^-1show containing Si-O-Si; 843cm ^-1show containing trimethyl silicane structure; 2959cm ^-1, 1260cm ^-1and 803cm ^-1show containing silicon methyl structural; 1431cm ^-1show containing phenyl ring; 1220cm ^-1near be Si (CH ₂) ₃nH ₂(CH ₂) ₂nH ₂absorption peak;

According to nmr spectrum ¹h-NMR:

δ=0.08 is Si-CH ₃middle H absorption peak; δ=0.56 is Si-CH ₂the absorption peak of-middle H; δ=1.30 be in-CH ₂the absorption peak (-CH that removing is directly connected with Si of-middle H ₂-).

Embodiment 2

Step 1: 0.9mol compound (II), 0.3mol compound (III), 7% sodium hydroxide solution are added in reaction vessel successively, reflux 1 hour under 110-120 DEG C of condition, slowly steam methyl alcohol, after methyl alcohol all steams, stopped reaction, with toluene extraction water hydrolysis products, underpressure distillation removing toluene, namely obtains ol cpds (IV);

Table 4 product (IV) physical property

Outward appearance (range estimation)	Refractive index/25 DEG C	Viscosity cps (25 DEG C of rotational viscosimeters)	Yield %
				Colourless transparent liquid	1.5057	79.60	98.70

Step 2: in the following order by 0.23mol compound (IV), 0.1mol/ml (CH ₃) ₄nOH catalyzer 1.3ml, 100mlH ₂o and 0.4molD4 joins in reaction vessel, at N ₂protect and at 95 DEG C, after hydrolysis reaction 40min, be warming up to 95 ~ 123 DEG C, while vacuumize dehydration limit polyreaction;

Table 5 product (V) physical property

Outward appearance (range estimation)	Refractive index/25 DEG C	Viscosity cps (25 DEG C of rotational viscosimeters)	Yield %
				Colourless transparent liquid	1.4846	84.12	98.59

Table 6 product (I-2) physical property

According to infrared spectrogram:

1073cm ^-1, 1028cm ^-1show containing Si-O-Si; 862cm ^-1show containing trimethyl silicane structure; 3007cm ^-1, 1310cm ^-1and 843cm ^-1show containing silicon methyl structural; 1516cm ^-1show containing phenyl ring; 1263cm ^-1near be Si (CH ₂) ₃nH ₂(CH ₂) ₂nH ₂absorption peak.

According to nmr spectrum ¹h-NMR:

δ=0.09 is Si-CH ₃middle H absorption peak; δ=0.57 is Si-CH ₂the absorption peak of-middle H; δ=1.30 be in-CH ₂the absorption peak (-CH that removing is directly connected with Si of-middle H ₂-).

Embodiment 3

1, starting material and specification: hand feeling agent 116A1 (fine hair sense) is purchased from Shanghai and be full of Chemical Co., Ltd.; TX-10 emulsifying agent, TX-4 emulsifying agent, Glacial acetic acid are purchased from Wuhan Hong Xinkang Fine Chemical Co., Ltd.

2, emulsifying process: washing/cleaning equipment, add water and the emulsifying agent (weight ratio is the mixture that the TX-10 emulsifying agent of 1:1 and TX-4 emulsifying agent are made) of 40% under normal temperature, rapid stirring makes it even.After about 15min, slowly drip metering hand feeling agent, stir and reach homogeneous system, about 1 ~ 2h.Drip dilution water, stir, add Glacial acetic acid adjust ph to 5 ~ 6.

Comparative example 1 is that the emulsifying agent of the hand feeling agent 116A1 and 5% of 12% is prepared and obtained; Comparative example 2 is that the emulsifying agent of the hand feeling agent 116A1 and 12% of 12% is prepared and obtained.

Mensuration product performance index is as shown in table 7:

Table 7 product performance index

The cardinal principle using emulsifying agent to ensure that emulsion has good stability.Under the prerequisite ensureing stability of emulsion, emulsifier is more few better.As shown in Table 7, the hand feeling agent of gained of the present invention only need mix with a small amount of compound emulsifying agent and can obtain stable emulsion, and emulsion intercalation method is better than the emulsion of comparative example 1, comparative example 2.

Embodiment 4: the application on high-grade pig leather for making garment

Get hand feeling agent and comparative example 2 prepared by the present invention of depositing half a year, obtain emulsion by the method described in embodiment 3, get 3 brown front pig leather for making garments (sprayed the end, in, bright layer), spray hand feeling agent emulsion thereon, the results are shown in Table 8.

Quick-drying is tested: the feel oxidant layer at brown front pig leather for making garment surface spraying thickness being 0.8mm, observes its time of drying.

Table 8 hand feeling agent Performance comparision

Known by table 8, the hand feeling agent that embodiment 1, embodiment 2 prepare has good dirt resistance, quick-drying and fuzzy hand.Stability after emulsion storage half a year is better than 116A1, and the fine hair sense of pig leather after placing half a year of the hand feeling agent process simultaneously prepared through embodiment 1 and embodiment 2 is all better than 116A1, shows that the hand feeling agent weather resistance that the present invention obtains is good.

Claims

1. an organic silicon hand feeling agent, is characterized in that: hand feeling agent contains

Wherein x=8-18; Y=1-5, z=1-5.

2. a kind of organic silicon hand feeling agent according to claim 1, is characterized in that:

3. a kind of organic silicon hand feeling agent according to claim 1, is characterized in that:

4. a kind of organic silicon hand feeling agent according to claim 1, its preparation method is:

Step 1: compound (II), compound (III), 7% sodium hydroxide solution are added in reaction vessel successively, reflux 1 hour under 110-120 DEG C of condition, slowly steam methyl alcohol, after methyl alcohol all steams, stopped reaction, with toluene extraction water hydrolysis products, underpressure distillation removing toluene, namely obtains ol cpds (IV);

Step 2: in the following order by compound (IV), 0.01mol/ml (CH ₃) ₄nOH catalyzer, H ₂o and D ₄join successively in reaction vessel, at N ₂protect and at 95 DEG C, after hydrolysis reaction 40min, be warming up to 95 ~ 123 DEG C, while vacuumize dehydration limit polyreaction;