CN107385966A - A kind of leather-like dyeing assistant of novel organosilicon and preparation method thereof - Google Patents
A kind of leather-like dyeing assistant of novel organosilicon and preparation method thereof Download PDFInfo
- Publication number
- CN107385966A CN107385966A CN201710597333.0A CN201710597333A CN107385966A CN 107385966 A CN107385966 A CN 107385966A CN 201710597333 A CN201710597333 A CN 201710597333A CN 107385966 A CN107385966 A CN 107385966A
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- Prior art keywords
- leather
- compound
- preparation
- dyeing assistant
- novel organosilicon
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Links
- 0 C1[C@@]2C1C*CC2 Chemical compound C1[C@@]2C1C*CC2 0.000 description 3
- JVQUBHIPPUVHCN-UHFFFAOYSA-N CCCCC(CN)N Chemical compound CCCCC(CN)N JVQUBHIPPUVHCN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/642—Compounds containing nitrogen
- D06P1/6426—Heterocyclic compounds
-
- 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 System
- C07F7/02—Silicon compounds
- C07F7/025—Silicon compounds without C-silicon linkages
Abstract
The invention discloses leather-like dyeing assistant of a kind of novel organosilicon and preparation method thereof, belong to leather dyeing technical field.Technical scheme main points are：A kind of leather-like dyeing assistant of novel organosilicon, its structural formula are, the invention further particularly discloses the preparation method of the leather-like dyeing assistant of the novel organosilicon, its specific synthetic route is：
Description
Technical field
The invention belongs to leather dyeing technical field, and in particular to a kind of leather-like dyeing assistant of novel organosilicon and
Its preparation method.
Background technology
Leather coloring can improve leather outward appearance, improve its commodity value, most in addition to bottom leather, industry leather, true qualities leather
Light leather will be dyed in production, and this is the important procedure of light leather production.Dyeing not only assigns the various tones of leather, and
And require that color is uniform, it is bright in colour, and there is higher colorfastness, while to reduce the dye content of waste liquid.
In modern leather industry, suede is not covered with paint, lacquer, colour wash, etc., and requires color uniformity, full color, pure color；For front
Leather, it is the improved inexorable trend of leather technology to redye dab, and this undoubtedly proposes higher requirement to dyeing.Organosilicon is a kind of
The new function material of excellent combination property, development is quick, is widely used, and the silicon oxygen bond that bond energy is very high, tool are contained in strand
There is prominent heat resistance, while because its intermolecular active force is relatively low and the high-flexibility of strand, therefore its polymer has
Relatively low surface tension and glass transition temperature, in addition it also there is physiological inertia, gas permeability and hydrophobicity so that
Leather and fur products has good sanitation performance, thus is widely used in leather manufacture.Application of the organosilicon in leather manufacture
Have from water field to covering with paint, particularly waterproof, softness, feel, modification etc..Organic Silicon Smoothing Agent for Leather, its main component are exactly
Polysiloxane, the organosilicone elastic film formed have smooth silk-like handle and waterproof antiwear, it is smooth to assign leather
Feel and certain glossiness and flexibility, water resistance also greatly improve, and elasticity, wearability, resistance to deflection also make moderate progress,
And the gas permeability and water vapor permeability of leather can be kept.Organic Silicon Smoothing Agent for Leather mainly has two kinds of solvent-borne type and emulsion-type, and this two
Kind formulation is all that the silicone oil that hand feeling agent uses all is modified silicon oil, and the modification of silicone oil can be seen based on organosilicon polymer
It is product that the part methyl in dimethicone is substituted by carbon functional group, special organic group or polyether segment to do.It is polyether-modified
Silicone oil, amino-hydrocarbon modification silicone oil, epoxyhydrocarbyl modified silicon oil, carboxylic alkyl modified silicon oil and hydroxyl alkyl modified silicon oil are organosilicon hands
Feel the main component kind of agent.Polyurethane-type organosilicon brightener uses double methylol dimethyl polysiloxane modified polyurethanes,
The leather primed for acrylic resin, can obtain the excellent coating of high luster, resistance to deflection, and light durable compared with
It is good.However, the shortcomings that above-mentioned organosilicon Colourate for leather is all high molecular polymer, and generally existing is water-soluble poor.
The content of the invention
Present invention solves the technical problem that there is provided, a kind of molecular structure is simple and water-soluble preferable novel organosilicon
Leather-like dyeing assistant and preparation method thereof.
The present invention adopts the following technical scheme that a kind of leather-like dyeing of novel organosilicon helps to solve above-mentioned technical problem
Agent, it is characterised in that the structural formula of the organic silicon leather dyeing is
The preparation method of the leather-like dyeing assistant of novel organosilicon of the present invention, it is characterised in that concretely comprise the following steps：
(1) trichlorosilane and sodium methoxide react in solvent ethylene glycol dimethyl ether obtains trimethoxy silane；
(2) compound 1 and (Boc)2O first carries out double Boc protections, then with tetrafluoro boric acid nitrous in the isopropyl of chiral catalyst four
Nitroso substitution is carried out in the presence of base oxygen titanium and R- xenols and chiral transfer generates compound 2；
(3) nitroso in Zn/AcOH and dichloromethane of compound 2 is sloughed after being reduced into amino under trifluoroacetic acid effect
Boc groups obtain compound 3；
(4) compound 3 is reacted with trimethoxy silane in water obtains the leather-like dyeing assistant of novel organosilicon；
Reaction equation in preparation process is：
Further preferably, the detailed process of step (1) is：Sodium methoxide is added to solvent ethylene glycol two in reaction vessel
In methyl ether, then trichlorosilane is added in the ethylene glycol dimethyl ether solution of sodium methoxide and reacts 0.5h in 10-30 DEG C, be evaporated off anti-
Solvent is answered to obtain sterling trimethoxy silane, the wherein molar ratio of trichlorosilane and sodium methoxide is 1:3, use sodium methoxide energy
Enough generations for effectively avoiding tetramethoxy-silicane and dimethoxy chlorosilane, and reaction condition is very gentle.
Further preferably, the detailed process of step (2) is：Under nitrogen protection by compound 1 and (Boc)2O is added to two
In chloromethanes, alkaline reagent is added, is stirred at room temperature to reaction and terminates rear concentrated solvent, be diluted with water, then adds ethyl acetate extraction
Take, organic phase is cleaned repeatedly with saturation NaCl solution, the double protection intermediates of Boc is concentrated under reduced pressure to give, under nitrogen protection by Boc
Double protection intermediates and dry pyridine are added in dry acetonitrile, are cooled to -10 DEG C and are added tetrafluoro boric acid nitrous and chiral catalysis
Agent tetra isopropyl oxygen titanium (Ti (O-i-Pr)4) and R- xenols (R- (-) BINOL), low temperature is stirred to reaction terminate after add second
Acetoacetic ester dissolves, and is cleaned twice with watery hydrochloric acid, then with saturation NaHCO3Solution cleans twice, is finally cleaned with saturation NaCl solution
Twice, concentration organic phase obtains compound 2, and wherein alkaline reagent is triethylamine, DIEA or potassium carbonate, compound 1, (Boc)2O
Molar ratio with alkaline reagent is 1:2.2:2, the molar ratio of tetrafluoro boric acid nitrous and compound 1 is 1.1:1, it is chiral
Catalyst tetra isopropyl oxygen titanium and R- xenols and the mass ratio that feeds intake of compound 1 are respectively 1% and 1%.
Further preferably, the detailed process of step (3) is：Compound 2 is dissolved in dichloromethane, adds glacial acetic acid and zinc
Powder, saturation NaCO is added after reacting at room temperature 10min3The pH of solution regulation reaction system is alkalescence, adds ethyl acetate extraction,
Stand, layering, pour out lower floor's aqueous phase, organic phase uses saturation NaCO again3Solution cleans once, is finally cleaned with saturation NaCl solution
Three times, organic phase is concentrated, concentrate and trifluoroacetic acid are added in dichloromethane, reaction 0.5h is stirred at room temperature and obtains compound
3, the molar ratio of wherein zinc powder and compound 2 is 5:1.
Further preferably, the detailed process of step (4) is：Compound 3 and water are added in reaction vessel and persistently stirred
Mix, add trimethoxy silane after being heated to 60 DEG C of reaction 15min, continue to react 2h in 60 DEG C, then heat to 75 DEG C of distillations
3h is reacted, the leather-like dyeing assistant of novel organosilicon, wherein compound 3 and the throwing of trimethoxy silane are obtained after aqueous solvent is evaporated off
It is 1 to expect mol ratio:4.
The present invention has the advantages that compared with prior art：
1st, the comprehensive existing organic silicon leather dyeing of the present invention, selection is very good using hydrophily and can make
Piperidine ring for dyeing auxiliaries is essential groups, chiral amino group is introduced on piperidine ring, then hand over trimethoxy silane
Connection reaction obtains non-polymeric organic silicon leather dyeing, and the leather-like dyeing assistant of the novel organosilicon is water-soluble preferably,
Chemical bond and physical absorption can occur with leather and dyestuff, it is purer to make to dye the leather color come, more bright-coloured, and can increase
The absorptivity of dyestuff, the dosage of dyestuff is saved, reduce the concentration of dyestuff in dyeing waste liquid, and then reduce the pollution to environment.
2nd, preparation method of the invention has that reaction condition is gentle, simple to operate, cost is cheap, is easy to purifying, environment friend
The characteristics of good and suitable industrialized production.
Embodiment
The above of the present invention is described in further details by the following examples, but this should not be interpreted as to this
The scope for inventing above-mentioned theme is only limitted to following embodiment, and all technologies realized based on the above of the present invention belong to this hair
Bright scope.
Embodiment 1
Sodium methoxide 65g (1.2mol) is added in solvent ethylene glycol dimethyl ether 200mL in reaction bulb, in 10 DEG C of conditions
It is lower that trichlorosilane 54g (0.4mol) is added drop-wise in the ethylene glycol dimethyl ether solution of sodium methoxide, drip after 10 DEG C of reactions
0.5h, reaction dissolvent is evaporated off and obtains sterling trimethoxy silane 116g, purity 99.8%.
Embodiment 2
Sodium methoxide 65g (1.2mol) is added in solvent ethylene glycol dimethyl ether 200mL in reaction bulb, in 20 DEG C of conditions
It is lower that trichlorosilane 54g (0.4mol) is added drop-wise in the ethylene glycol dimethyl ether solution of sodium methoxide, drip after 20 DEG C of reactions
0.5h, reaction dissolvent is evaporated off and obtains sterling trimethoxy silane 117g, purity 99.9%.
Embodiment 3
Sodium methoxide 65g (1.2mol) is added in solvent ethylene glycol dimethyl ether 200mL in reaction bulb, in 30 DEG C of conditions
It is lower that trichlorosilane 54g (0.4mol) is added drop-wise in the ethylene glycol dimethyl ether solution of sodium methoxide, drip after 30 DEG C of reactions
0.5h, reaction dissolvent is evaporated off and obtains sterling trimethoxy silane 120g, purity 99.8%.
Embodiment 4
Under nitrogen protection by the 10g of compound 1 (0.1mol) and (Boc)2O 48g (0.22mol) are added to dichloromethane
In 200mL, triethylamine 20g (0.2mol) is added, concentrated solvent after reaction 5h is stirred at room temperature, is diluted with water, then adds acetic acid second
Ester is extracted, and organic phase is washed three times with saturated sodium-chloride, is then concentrated under reduced pressure to give the double protection intermediates of Boc.Under nitrogen protection
The double protection intermediates of obtained Boc and dry pyridine 20mL are added in dry acetonitrile 200mL, are placed in -10 DEG C of cold hydrazine
Add tetrafluoro boric acid nitrous 13g (0.11mol) and chiral catalyst tetra isopropyl oxygen titanium 0.1g and R- xenol 0.1g, low temperature
Ethyl acetate 200mL dissolving is added after stirring reaction 30min, with 0 DEG C of 1mol/L watery hydrochloric acid Rapid Cleaning twice, then with satisfying
And NaHCO3Solution cleans twice, is finally cleaned twice with saturation NaCl solution, and concentration organic phase obtains the 31g of compound 2.
Embodiment 5
The 33g of compound 2 (0.1mol) is dissolved in dichloromethane 200mL, adds glacial acetic acid 60g and zinc powder 32g
(0.5mol), reacts at room temperature 10min, and reaction adds saturation NaCO after terminating3The pH of solution regulation reaction system is alkalescence,
Ethyl acetate extraction is added, is stood, layering, pours out lower floor's aqueous phase, organic phase uses saturation NaCO again3Solution cleans once, finally
Cleaned three times with saturation NaCl solution, concentrate organic phase, concentrate and trifluoroacetic acid 50mL are added in dichloromethane, room temperature
Stirring reaction 0.5h obtains the 105g of compound 3.
Embodiment 6
The 11.5g of compound 3 (0.1mol) is added in three-necked flask with water 200mL and continues to stir, is heated to 60 DEG C
Trimethoxy silane 49g (0.4mol) is added after reacting 15min, continues to react 2h in 60 DEG C, it is anti-to then heat to 75 DEG C of distillations
3h is answered, the leather-like dyeing assistant of novel organosilicon is obtained after aqueous solvent is evaporated off55g。
Embodiment 7
Sample test
The present embodiment is carried out to the resulting leather-like dyeing assistant of novel organosilicon using test, and application experiment is three
Carried out in dynamic stainless steel rotary drum, it is raw materials used to remove from office (thickness 1mm) for ox-hide.
Technique for applying：Weigh-retanning：Carried out by same technique；Neutralize：Liquor ratio (1.5), temperature (35 DEG C), sodium bicarbonate
(2.0wt%), rotate (60min, it is desirable to neutralize saturating), final ph (6.2-6.5)；Washing：30min；Dyeing：Liquor ratio (3.0),
Temperature (55 DEG C), levelling agent (0.5wt%), rotate (10min), dyestuff (appropriate), rotate (60min), mix fatting agent
(20wt%), rotate (60min), formic acid (1.5wt%), rotate (30min), the leather-like dyeing assistant of novel organosilicon is (suitable
Amount), rotate (30min)；Collect waste liquid, wash, go out drum, hang dry it is dry.
Main Analysis detects the physical property and Color of finished product.Finished product physical property detection include tensile property,
Tear resistance, performance of bursting apart and permeable gas, Color include the dye-uptake of colorfastness, full color degree and dyestuff
Deng.
The leather-like dyeing assistant dosage of the novel organosilicon of table 1 influences (dye dosage 2.0wt%) to waste liquid
The dye dosage of table 2 contrasts (the leather-like dyeing assistant dosage 1.5wt% of novel organosilicon)
As can be seen from Table 1 when the timing of dye dosage one, increase the leather-like dyeing assistant dosage of novel organosilicon, dyestuff quilt
The amount of absorption is more, and its leather color and luster is denseer.The leather-like timing of dyeing assistant dosage one of novel organosilicon as can be seen from Table 2,
Increase dye dosage, its waste liquid color and luster is deeper, and the absorptivity of dyestuff is lower.Show the leather-like dyeing of novel organosilicon of the present invention
Auxiliary agent has the obvious effect for promoting leather fiber to absorb dyestuff.
The crust leather quantitative measurement result of table 3
From table 3, after adding the leather-like dyeing assistant of novel organosilicon, for improving crust leather tensile property, bursting apart property
Can and tear resistance etc. be respectively provided with certain effect, this is due to that the molecule of this product enters in leather fiber and can promote skin
Caused by certain crosslinking is produced between the molecule of leather fiber, the leather-like dyeing assistant of this novel organosilicon contains a variety of functional groups, both
It can in itself act on, can also be acted on the tanning agent being incorporated on leather fiber molecule, therefore increase leather fiber molecule with leather fiber
Between crosslinking degree.
Embodiment above describes the general principle of the present invention, main features and advantages, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, the original for simply illustrating the present invention described in above-described embodiment and specification
Reason, under the scope for not departing from the principle of the invention, various changes and modifications of the present invention are possible, and these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (10)
1. a kind of leather-like dyeing assistant of novel organosilicon, it is characterised in that the structural formula of the organic silicon leather dyeing is
A kind of 2. preparation method of the leather-like dyeing assistant of novel organosilicon described in claim 1, it is characterised in that specific step
Suddenly it is：
(1) trichlorosilane and sodium methoxide react in solvent ethylene glycol dimethyl ether obtains trimethoxy silane；
(2) compound 1 and (Boc)2O first carries out double Boc protections, then with tetrafluoro boric acid nitrous in chiral catalyst tetra isopropyl oxygen
Nitroso substitution is carried out in the presence of titanium and R- xenols and chiral transfer generates compound 2；
(3) nitroso in Zn/AcOH and dichloromethane of compound 2 sloughs Boc after being reduced into amino under trifluoroacetic acid effect
Group obtains compound 3；
(4) compound 3 is reacted with trimethoxy silane in water obtains the leather-like dyeing assistant of novel organosilicon；
Reaction equation in preparation process is：
3. the preparation method of the leather-like dyeing assistant of novel organosilicon according to claim 2, it is characterised in that step (1)
Detailed process be：Sodium methoxide is added in solvent ethylene glycol dimethyl ether in reaction vessel, then trichlorosilane is added to
0.5h is reacted in the ethylene glycol dimethyl ether solution of sodium methoxide and in 10-30 DEG C, reaction dissolvent is evaporated off and obtains sterling trimethoxy silicon
Alkane.
4. the preparation method of the leather-like dyeing assistant of novel organosilicon according to claim 3, it is characterised in that：Described three
The molar ratio of chlorosilane and sodium methoxide is 1:3.
5. the preparation method of the leather-like dyeing assistant of novel organosilicon according to claim 2, it is characterised in that step (2)
Detailed process be：Under nitrogen protection by compound 1 and (Boc)2O is added in dichloromethane, adds alkaline reagent, room
Temperature stirring terminates rear concentrated solvent to reaction, is diluted with water, then adds ethyl acetate extraction, and organic phase is cleaned with saturation NaCl solution
Repeatedly, the double protection intermediates of Boc are concentrated under reduced pressure to give, under nitrogen protection add the double protection intermediates of Boc and dry pyridine
To drying in acetonitrile, it is cooled to -10 DEG C and adds tetrafluoro boric acid nitrous and chiral catalyst tetra isopropyl oxygen titanium and R- xenols, it is low
Temperature stirring adds ethyl acetate dissolving after terminating to reaction, cleaned twice with watery hydrochloric acid, then with saturation NaHCO3Solution cleaning two
It is secondary, finally cleaned twice with saturation NaCl solution, concentration organic phase obtains compound 2.
6. the preparation method of the leather-like dyeing assistant of novel organosilicon according to claim 5, it is characterised in that：The alkali
Property reagent is triethylamine, DIEA or potassium carbonate, compound 1, (Boc)2The molar ratio of O and alkaline reagent is 1:2.2:2, four
Fluoboric acid nitrous and the molar ratio of compound 1 are 1.1:1, chiral catalyst tetra isopropyl oxygen titanium and R- xenols and chemical combination
The mass ratio that feeds intake of thing 1 is respectively 1% and 1%.
7. the preparation method of the leather-like dyeing assistant of novel organosilicon according to claim 2, it is characterised in that step (3)
Detailed process be：Compound 2 is dissolved in dichloromethane, adds glacial acetic acid and zinc powder, saturation is added after reacting at room temperature 10min
NaCO3The pH of solution regulation reaction system is alkalescence, adds ethyl acetate extraction, stands, layering, pours out lower floor's aqueous phase, have
Machine mutually uses saturation NaCO again3Solution cleans once, is finally cleaned three times with saturation NaCl solution, organic phase is concentrated, by concentrate
It is added to trifluoroacetic acid in dichloromethane, reaction 0.5h is stirred at room temperature and obtains compound 3.
8. the preparation method of the leather-like dyeing assistant of novel organosilicon according to claim 7, it is characterised in that：The zinc
Powder and the molar ratio of compound 2 are 5:1.
9. the preparation method of the leather-like dyeing assistant of novel organosilicon according to claim 2, it is characterised in that step (4)
Detailed process be：Compound 3 and water are added in reaction vessel and continue to stir, is added after being heated to 60 DEG C of reaction 15min
Enter trimethoxy silane, continue to react 2h in 60 DEG C, then heat to 75 DEG C of distillation reaction 3h, be evaporated off obtaining after aqueous solvent new
Organic silicon leather dyeing.
10. the preparation method of the leather-like dyeing assistant of novel organosilicon according to claim 9, it is characterised in that describedization
The molar ratio of compound 3 and trimethoxy silane is 1:4.
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| CN201710597333.0A CN107385966A (en) | 2017-07-20 | 2017-07-20 | A kind of leather-like dyeing assistant of novel organosilicon and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020234379A1 (en) * | 2019-05-21 | 2020-11-26 | Janssen Pharmaceutica Nv | Processes and intermediates for preparing a btk inhibitor |
| CN114853662A (en) * | 2021-02-05 | 2022-08-05 | 四川青木制药有限公司 | Preparation method of chiral hydrazinylpiperidine derivative |
| NL2033083B1 (en) | 2022-09-20 | 2024-03-26 | Stahl Int B V | Grafted polymer of mono-unsaturated polycarboxylic acid as dyeing auxiliary or as re-tanning agent for leather |
-
2017
- 2017-07-20 CN CN201710597333.0A patent/CN107385966A/en active Pending
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| BOGDAN MARCINIEC ET AL.: "Ruthenium-catalyzed dealkenative N-silylation of amines by substituted vinylsilanes", 《DALTON TRANS.》 * |
| KEN TAKAKI ET AL.: "Synthesis of lanthanide(II)–imine complexes and their use in carbon–carbon and carbon–nitrogen unsaturated bond transformation", 《TETRAHEDRON》 * |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020234379A1 (en) * | 2019-05-21 | 2020-11-26 | Janssen Pharmaceutica Nv | Processes and intermediates for preparing a btk inhibitor |
| CN113906011A (en) * | 2019-05-21 | 2022-01-07 | 詹森药业有限公司 | Processes and intermediates for preparing BTK inhibitors |
| CN114853662A (en) * | 2021-02-05 | 2022-08-05 | 四川青木制药有限公司 | Preparation method of chiral hydrazinylpiperidine derivative |
| CN114853662B (en) * | 2021-02-05 | 2024-01-12 | 四川青木制药有限公司 | Process for preparing chiral hydrazinopiperidine derivatives |
| NL2033083B1 (en) | 2022-09-20 | 2024-03-26 | Stahl Int B V | Grafted polymer of mono-unsaturated polycarboxylic acid as dyeing auxiliary or as re-tanning agent for leather |
| WO2024063646A1 (en) | 2022-09-20 | 2024-03-28 | Stahl International B.V. | Grafted polymer of mono-unsaturated polycarboxylic acid as dyeing auxiliary or as re-tanning agent for leather |
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