CN117567714B - Organosilicon hydrophilic flame-retardant finishing agent and preparation method thereof - Google Patents

Organosilicon hydrophilic flame-retardant finishing agent and preparation method thereof Download PDF

Info

Publication number
CN117567714B
CN117567714B CN202410072934.XA CN202410072934A CN117567714B CN 117567714 B CN117567714 B CN 117567714B CN 202410072934 A CN202410072934 A CN 202410072934A CN 117567714 B CN117567714 B CN 117567714B
Authority
CN
China
Prior art keywords
flame retardant
finishing agent
tryptophan
compound
preparing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202410072934.XA
Other languages
Chinese (zh)
Other versions
CN117567714A (en
Inventor
贺剑
储海龙
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangzhou Xin Tian Xin Mstar Technology Ltd
Original Assignee
Guangzhou Xin Tian Xin Mstar Technology Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangzhou Xin Tian Xin Mstar Technology Ltd filed Critical Guangzhou Xin Tian Xin Mstar Technology Ltd
Priority to CN202410072934.XA priority Critical patent/CN117567714B/en
Publication of CN117567714A publication Critical patent/CN117567714A/en
Application granted granted Critical
Publication of CN117567714B publication Critical patent/CN117567714B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6523—Compounds of group C08G18/3225 or C08G18/3271 or polyamines of C08G18/38
    • C08G18/6529—Compounds of group C08G18/3225 or polyamines of C08G18/38
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/572—Five-membered rings
    • C07F9/5728—Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
    • C08G18/3889—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having nitrogen in addition to phosphorus
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C08G18/61—Polysiloxanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/579—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them modified by compounds containing phosphorus
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/20—Treatment influencing the crease behaviour, the wrinkle resistance, the crease recovery or the ironing ease
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/30—Flame or heat resistance, fire retardancy properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/50—Modified hand or grip properties; Softening compositions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)

Abstract

The invention relates to the technical field of fabric finishing, and discloses an organosilicon hydrophilic flame retardant finishing agent and a preparation method thereof. After finishing the cotton fabric, the hydrophilicity of the cotton fabric can be effectively improved, and the water absorption and moisture absorption performance of the cotton fabric can be improved. And the organic silicon chain segment of the main chain can ensure that the cotton fabric has good flexibility and wrinkle resistance while keeping the hydrophilicity. The organic silicon hydrophilic flame retardant finishing agent has the advantages that the phosphate structure, the nitrogen-containing heterocycle and the organic siloxane in the molecular main chain form a nitrogen-phosphorus-silicon synergistic flame retardant effect, so that the cotton fabric shows excellent flame retardant performance.

Description

Organosilicon hydrophilic flame-retardant finishing agent and preparation method thereof
Technical Field
The invention relates to the technical field of fabric finishing, in particular to an organosilicon hydrophilic flame retardant finishing agent and a preparation method thereof.
Background
With the continuous improvement of living standard, people have pursued higher quality of life, and more importance is attached to clothing wear, and cotton fabrics have the advantages of light warmth retention, strong hygroscopicity, good air permeability and the like, and have wide application in the aspects of high-grade fabric clothing, special clothing protection and the like. In order to endow the cotton fabric with the characteristics of flexibility, flame retardance and the like, the cotton fabric needs to be finished; the current finishing agent mainly comprises polyether finishing agent, organic silicon finishing agent and the like.
The organosilicon finishing agent can well improve the flexibility, crease resistance and hand feeling of the fabric, but the traditional organosilicon finishing agent has hydrophobicity, and the hydrophilicity and hygroscopicity of the finished fabric can be reduced. Patent CN111607969B discloses that a highly hydrophilic silicone finish is prepared from chlorine-containing monomers, epoxy-terminated silicone oils, polyetheramines, and the like as raw materials. But the silicone finish does not impart flame retardant properties to cotton fabrics. The invention aims to prepare the organosilicon hydrophilic flame-retardant finishing agent, which is applied to finishing of fabrics such as cotton fabrics and the like, and improves the properties of hydrophilicity, softness, flame retardance and the like of the fabrics.
Disclosure of Invention
The invention solves the technical problems that: the organic silicon hydrophilic flame-retardant finishing agent is applied to finishing of fabrics such as cotton fabrics and the like, and improves the properties of hydrophilicity, softness, flame retardance and the like of the fabrics.
The technical scheme provided by the invention is as follows:
an organosilicon hydrophilic flame-retardant finishing agent comprises the following raw materials in proportion of (0.4-0.75) mol (0.25-0.6) mol (0.001-0.0015) mol of amino-terminated polysiloxane, phenyl phosphate di (ether tryptophan) compound, diisocyanate compound and dibutyl tin dilaurate.
The structural formula of phenyl phosphate di (ether tryptophan) is as follows:
。
the diisocyanate compound includes toluene-2, 4-diisocyanate and diphenylmethane-4, 4' -diisocyanate.
Further, the preparation method of the organosilicon hydrophilic flame retardant finishing agent comprises the following steps: adding N, N-dimethylformamide, amino-terminated polysiloxane, phenyl phosphate di (ether tryptophan) compound and diisocyanate compound into a flask, stirring and dissolving, introducing nitrogen, adding dibutyltin dilaurate, reacting at 60-80 ℃ for 2-4h, cooling, pouring the solution into ethanol for precipitation, filtering, washing with ethanol, and drying to obtain the organosilicon hydrophilic flame-retardant finishing agent.
Further, the preparation method of the phenyl phosphate di (ether tryptophan) compound comprises the following steps:
(1) Adding a reaction solvent, 2- [2- (2-chloroethoxy) ethoxy ] ethanol and triethylamine into a flask, adding phenylphosphonic dichloride at the temperature of between-5 and 0 ℃, stirring for 10 to 30 minutes, heating to 25 to 35 ℃, reacting for 3 to 6 hours, removing the solvent by rotary evaporation, washing with petroleum ether, and drying to obtain the intermediate 1. The reaction route is as follows:
。
(2) Adding 1, 4-dioxane, an intermediate 1, N- (tert-butoxycarbonyl) -L-tryptophan, a catalyst and cosolvent water into a flask, heating to 75-90 ℃, reacting for 8-24h, removing the 1, 4-dioxane by rotary evaporation, adding ethyl acetate and water for extraction, drying an organic phase, removing the ethyl acetate by rotary evaporation, washing petroleum ether, adding an intermediate product into dichloromethane, adding trifluoroacetic acid (TFA), reacting for 3-5h at 20-35 ℃, removing the solvent by rotary evaporation, and recrystallizing the product by ethyl acetate to obtain the phenyl phosphate di (ether tryptophan) compound. The reaction route is as follows:
。
further, the ratio of the reaction solvent, 2- [2- (2-chloroethoxy) ethoxy ] ethanol, triethylamine and phenylphosphonic acid dichloride in the step (1) is (3-5) L (1.9-2.4) mol (2-2.4) mol to 1mol.
Further, the reaction solvent comprises dichloromethane, chloroform and toluene.
Further, in the step (2), the ratio of 1, 4-dioxane, intermediate 1, N- (tert-butoxycarbonyl) -L-tryptophan, catalyst and water is (3-4) L, 1mol (2-2.5) mol (2.4-2.8) mol (0.8-1.5) L. Further, the catalyst comprises sodium hydride, sodium hydroxide and potassium hydroxide.
The invention has the technical effects that: the invention takes cheap and easily available 2- [2- (2-chloroethoxy) ethoxy ] ethanol, phenylphosphonic dichloride, N- (tert-butoxycarbonyl) -L-tryptophan and the like as raw materials to prepare phenyl phosphate di (ether tryptophan) compound which contains two amino groups and is subjected to polymerization reaction with amino-terminated polysiloxane and diisocyanate compound to obtain the novel organosilicon hydrophilic flame retardant finishing agent; the main chain of the finishing agent contains hydrophilic ether bond, carboxyl and ureido groups, so that the dispersibility of the organic silicon finishing agent in water is improved, the solution is uniform and stable, and the centrifugal stability is excellent.
After the organosilicon hydrophilic flame retardant finishing agent is used for finishing cotton fabrics, the hydrophilicity of the cotton fabrics can be effectively improved, and the water absorption and moisture absorption properties of the cotton fabrics are improved. And the organic silicon chain segment of the main chain can ensure that the cotton fabric has good flexibility and wrinkle resistance while keeping the hydrophilicity. And the main chain of the finishing agent molecule contains a nontoxic and environment-friendly tryptophan structural unit, and the introduction of an amino acid structure is beneficial to improving the biocompatibility of the finishing agent.
The organic silicon hydrophilic flame retardant finishing agent has the advantages that the phosphate structure, the nitrogen-containing heterocycle and the organic siloxane in the molecular main chain of the organic silicon hydrophilic flame retardant finishing agent form a nitrogen-phosphorus-silicon synergistic flame retardant effect, nitrogen-phosphorus elements can promote cotton fabrics to form carbon during combustion, organic silicon is combusted and pyrolyzed to generate inorganic silicon oxide, and a continuous and stable barrier layer is formed with the carbon layer, so that oxygen is isolated, and the combustion process is inhibited. The continuous burning time and smoldering time during burning are obviously reduced, the damage length is reduced, and the cotton fabric shows excellent flame retardant property.
Detailed Description
The invention will be further illustrated with reference to specific examples.
Amino-terminated polysiloxanes: CAS number 106214-84-0. The structural formula is as follows:
。
2- [2- (2-chloroethoxy) ethoxy ] ethanol: CAS number 5197-62-6.
Phenylphosphonic acid dichloride: CAS number 824-72-6.
N- (tert-butoxycarbonyl) -L-tryptophan: CAS number 13139-14-5.
Toluene-2, 4-diisocyanate: CAS number 584-84-9.
Diphenylmethane-4, 4' -diisocyanate: CAS number 101-68-8.
Example 1
(1) 250mL of toluene solvent, 128mmol of 2- [2- (2-chloroethoxy) ethoxy ] ethanol and 130mmol of triethylamine are added into a flask, 60mol of phenylphosphonic dichloride is added at the temperature of minus 5 ℃, stirring is carried out for 30min, the temperature is increased to 25 ℃ for reaction for 6h, the solvent is removed by rotary evaporation, and the intermediate 1 is obtained by washing with petroleum ether and drying.
(2) Into a flask were added 120mL of 1, 4-dioxane, 40mmol of intermediate 1, 100mmol of N- (tert-butoxycarbonyl) -L-tryptophan, 112mmol of catalyst sodium hydroxide and 60mL of water, the temperature was raised to 90 ℃, the reaction was conducted for 12 hours, the 1, 4-dioxane was removed by rotary evaporation, ethyl acetate and water were added for extraction, the organic phase was dried, ethyl acetate was removed by rotary evaporation, after washing with petroleum ether, the intermediate product was added to 400mL of methylene chloride, 620mmol of trifluoroacetic acid (TFA) was added, the reaction was conducted for 4 hours at 35 ℃, the solvent was removed by rotary evaporation, and the product was recrystallized with ethyl acetate to obtain phenyl phosphate bis (ether tryptophan).
(3) 400mL of N, N-dimethylformamide, 75mmol of amino-terminated polysiloxane, 25mmol of phenyl phosphate di (ether tryptophan) compound and 100mmol of diphenylmethane-4, 4' -diisocyanate are added into a flask, nitrogen is introduced after stirring and dissolving, 0.12mmol of dibutyltin dilaurate is added for reaction at 70 ℃ for 2 hours, the solution is poured into ethanol for precipitation after cooling, and the solution is filtered, washed by ethanol and dried to obtain the organosilicon hydrophilic flame retardant finishing agent.
Example 2
(1) 300mL of methylene chloride solvent, 144mmol of 2- [2- (2-chloroethoxy) ethoxy ] ethanol and 144mmol of triethylamine are added into a flask, 60mol of phenylphosphonic dichloride is added at the temperature of 0 ℃, the mixture is stirred for 30min, the temperature is increased to 25 ℃ for reaction for 6h, the solvent is removed by rotary evaporation, and the mixture is washed by petroleum ether and dried to obtain the intermediate 1.
(2) To the flask were added 160mL of 1, 4-dioxane, 40mmol of intermediate 1, 100mmol of N- (t-butoxycarbonyl) -L-tryptophan, 102mmol of potassium hydroxide as a catalyst and 55mL of water, the mixture was heated to 75℃and reacted for 24 hours, the 1, 4-dioxane was removed by rotary evaporation, ethyl acetate and water were added for extraction, the organic phase was dried, ethyl acetate was removed by rotary evaporation, after washing with petroleum ether, the intermediate product was added to 400mL of methylene chloride, 620mmol of trifluoroacetic acid (TFA) was added, the reaction was carried out for 5 hours at 20℃and the solvent was removed by rotary evaporation, and the product was recrystallized from ethyl acetate to give phenyl phosphate bis (ether tryptophan).
(3) 300mL of N, N-dimethylformamide, 60mmol of amino-terminated polysiloxane, 40mmol of phenyl phosphate di (ether tryptophan) compound and 100mmol of diphenylmethane-4, 4' -diisocyanate are added into a flask, nitrogen is introduced after stirring and dissolving, 0.1mmol of dibutyltin dilaurate is added for reaction for 4 hours at 60 ℃, the solution is poured into ethanol for precipitation after cooling, and the solution is washed by ethanol and dried to obtain the organosilicon hydrophilic flame retardant finishing agent.
Example 3
(1) 180mL of chloroform solvent, 114mmol of 2- [2- (2-chloroethoxy) ethoxy ] ethanol and 120mmol of triethylamine are added into a flask, 60mol of phenylphosphonic dichloride is added at the temperature of 0 ℃, the mixture is stirred for 10min, the temperature is increased to 35 ℃ for reaction for 3h, the solvent is removed by rotary evaporation, and the mixture is washed by petroleum ether and dried to obtain the intermediate 1.
(2) 120mL of 1, 4-dioxane, 40mmol of intermediate 1, 80mmol of N- (tert-butoxycarbonyl) -L-tryptophan, 96mmol of sodium hydride as a catalyst and 32mL of water are added into a flask, the temperature is raised to 80 ℃, the reaction is carried out for 8 hours, the 1, 4-dioxane is removed by rotary evaporation, ethyl acetate and water are added for extraction, an organic phase is dried, the ethyl acetate is removed by rotary evaporation, after petroleum ether is washed, the intermediate product is added into 500mL of dichloromethane, 750mmol of trifluoroacetic acid (TFA) is added, the reaction is carried out for 3 hours at 25 ℃, the solvent is removed by rotary evaporation, and the product is recrystallized by ethyl acetate to obtain phenyl phosphate di (ether tryptophan) compound.
(3) 300mL of N, N-dimethylformamide, 40mmol of amino-terminated polysiloxane, 60mmol of phenyl phosphate di (ether tryptophan) compound and 100mmol of toluene-2, 4-diisocyanate are added into a flask, nitrogen is introduced after stirring and dissolution, 0.15mmol of dibutyltin dilaurate is added for reaction at 80 ℃ for 2 hours, the solution is poured into ethanol for precipitation after cooling, and the solution is filtered, washed by ethanol and dried to obtain the organosilicon hydrophilic flame retardant finishing agent.
Comparative example 1
400mL of N, N-dimethylformamide, 100mmol of amino-terminated polysiloxane and 100mmol of diphenylmethane-4, 4' -diisocyanate are added into a flask, nitrogen is introduced after stirring and dissolution, 0.12mmol of dibutyltin dilaurate is added for reaction, the reaction is carried out for 2 hours at 70 ℃, the solution is poured into ethanol for precipitation after cooling, filtering, ethanol washing and drying are carried out, and the finishing agent is obtained.
Comparative example 2
400mL of N, N-dimethylformamide, 100mmol of phenyl phosphate di (ether tryptophan) compound and 100mmol of diphenylmethane-4, 4' -diisocyanate are added into a flask, nitrogen is introduced after stirring and dissolution, 0.12mmol of dibutyltin dilaurate is added for reaction at 70 ℃ for 2 hours, the solution is cooled and poured into ethanol for precipitation, filtration, ethanol washing and drying are carried out, and the finishing agent is obtained.
Adding the finishing agent into water, stirring at high speed to prepare a solution with the mass concentration of 5-50g/L, adding the finishing agent into a centrifuge tube, rotating at 3000r/min for 30min, and observing the centrifugal stability of the emulsion.
Table 1 centrifugal stability test of emulsions
Examples 1 to 3 use amino-terminated polysiloxane, phenyl phosphate di (ether tryptophan) compound and diisocyanate compound to carry out polymerization reaction to obtain the organosilicon hydrophilic flame retardant finishing agent, and the molecular main chain contains hydrophilic ether bond, carboxyl and ureido groups, so that the dispersibility of the organosilicon finishing agent in water is improved, the solution is uniform and stable, and the centrifugal stability is excellent.
In comparative example 1, polymerization reaction is carried out by using amino-terminated polysiloxane and diphenylmethane-4, 4' -diisocyanate, and phenyl phosphate di (ether tryptophan) compound is not added, so that the obtained finishing agent does not contain hydrophilic ether bond, and when the mass concentration is large, the centrifugal stability of the finishing agent solution is poor, and demulsification is carried out.
Adding the finishing agent into water, stirring and dispersing at high speed to prepare finishing liquid with the mass concentration of 20g/L, adding cotton fabric into the finishing liquid, performing twice-soaking and twice-rolling finishing by adopting a rolling machine, controlling the temperature of the finishing liquid to be 40 ℃, and then baking at 180 ℃ to obtain 60 s.
With reference to AATCC 79-2000 standard water dripping method, the hydrophilicity of the cotton fabric after finishing is tested, and the longer the time, the better the hydrophilicity.
With reference to the standard of GB/T3819-1997, the fabric crease recovery angle of cotton fabric is measured by a fabric crease elastometer, and the larger the crease recovery angle is, the better the fabric flexibility and crease resistance are.
Table 2 cotton fabric performance test
The silicone hydrophilic flame retardant finishes of examples 1 to 3 contain ether linkages, carboxyl groups, ureido groups) Hydrophilic groups can effectively improve the hydrophilicity of the cotton fabric after finishing the cotton fabric, and are beneficial to improving the water absorption and moisture absorption properties of the cotton fabric. And the organic silicon chain segment of the main chain can ensure that the cotton fabric has good flexibility and wrinkle resistance while keeping the hydrophilicity.
Adding the finishing agent into water, stirring and dispersing at high speed to prepare finishing liquid with mass concentration of 20g/L and 50g/L respectively, adding cotton fabric into the finishing liquid, performing twice-soaking and twice-rolling finishing by adopting a rolling machine, controlling the temperature of the finishing liquid to be 40 ℃, and then baking at 180 ℃ to obtain 60 s.
The flame retardant property of the finished cotton fabric is tested according to the method of GB/T5455-2014.
Table 3 flame retardancy test of cotton fabrics
Table 4 flame retardant performance test of cotton fabrics
Examples 1 to 3 utilize amino-terminated polysiloxane, phenyl phosphate di (ether tryptophan) compound and diisocyanate compound to carry out polymerization reaction to obtain organosilicon hydrophilic flame retardant finishing agent, after finishing cotton fabric, phosphate, nitrogen-containing heterocycle and organosiloxane in the molecular main chain of the finishing agent form nitrogen-phosphorus-silicon synergistic flame retardant effect, nitrogen-phosphorus element can promote cotton fabric to form charcoal during combustion, organosilicon burns and pyrolyzes to generate inorganic silicon oxide, and forms a continuous and stable barrier layer with the charcoal layer, thereby being beneficial to isolating oxygen and inhibiting combustion process. The continuous burning time and smoldering time during burning are obviously reduced, the damage length is reduced, and the cotton fabric shows excellent flame retardant property.
The finishing agent of comparative example 1 is free of phenyl phosphate di (ether tryptophan) compound, contains no nitrogen-phosphorus flame retardant structure, and has the worst flame retardant property; comparative example 2 was not added with amino-terminated polysiloxane, did not form nitrogen-phosphorus-silicon synergistic flame retardant effect, and was poor in flame retardant property.

Claims (8)

1. The organosilicon hydrophilic flame retardant finishing agent is characterized by comprising the following raw materials in proportion of (0.4-0.75) mol (0.25-0.6) 1mol (0.001-0.0015) mol of amino-terminated polysiloxane, phenyl phosphate di (ether tryptophan) compound, diisocyanate compound and dibutyl tin dilaurate;
the structural formula of the phenyl phosphate di (ether tryptophan) compound is as follows:
；
the diisocyanate compound includes toluene-2, 4-diisocyanate and diphenylmethane-4, 4' -diisocyanate.
2. A method for preparing the silicone hydrophilic flame retardant finish according to claim 1, comprising the steps of: adding N, N-dimethylformamide, amino-terminated polysiloxane, phenyl phosphate di (ether tryptophan) compound and diisocyanate compound into a flask, stirring and dissolving, introducing nitrogen, adding dibutyltin dilaurate, reacting, cooling for precipitation, filtering, washing and drying to obtain the organosilicon hydrophilic flame-retardant finishing agent.
3. The method for preparing the organosilicon hydrophilic flame retardant finishing agent according to claim 2, wherein the reaction temperature is 60-80 ℃ and the reaction time is 2-4h.
4. The method for preparing the silicone hydrophilic flame retardant finishing agent according to claim 2, wherein the method for preparing the phenyl phosphate di (ether tryptophan) compound comprises the following steps:
(1) Adding a reaction solvent, 2- [2- (2-chloroethoxy) ethoxy ] ethanol and triethylamine into a flask, adding phenylphosphonic dichloride at the temperature of between-5 and 0 ℃, stirring for 10 to 30 minutes, heating to 25 to 35 ℃, reacting for 3 to 6 hours, removing the solvent by rotary evaporation, washing and drying to obtain an intermediate 1;
(2) Adding 1, 4-dioxane, an intermediate 1, N- (tert-butoxycarbonyl) -L-tryptophan, a catalyst and cosolvent water into a flask, heating to 75-90 ℃, reacting for 8-24 hours, removing the 1, 4-dioxane by rotary evaporation, extracting, washing, adding an intermediate product into dichloromethane, adding trifluoroacetic acid, reacting for 3-5 hours at 20-35 ℃, removing the solvent by rotary evaporation, and recrystallizing the product to obtain the phenyl phosphate di (ether tryptophan) compound.
5. The method for preparing a hydrophilic flame retardant silicone finish according to claim 4, wherein the ratio of the reaction solvent, 2- [2- (2-chloroethoxy) ethoxy ] ethanol, triethylamine, and phenylphosphonic acid dichloride in step (1) is (3-5) L (1.9-2.4) mol (2-2.4) 1mol.
6. The method for preparing the hydrophilic flame retardant finishing agent according to claim 5, wherein the reaction solvent comprises methylene chloride, chloroform and toluene.
7. The method for preparing a hydrophilic flame retardant silicone finish according to claim 4, wherein the ratio of 1, 4-dioxane, intermediate 1, N- (t-butoxycarbonyl) -L-tryptophan, catalyst and cosolvent water in step (2) is (3-4) L1 mol (2-2.5) mol (2.4-2.8) mol (0.8-1.5) L.
8. The method for preparing the silicone hydrophilic flame retardant finishing agent according to claim 7, wherein the catalyst comprises sodium hydride, sodium hydroxide and potassium hydroxide.
CN202410072934.XA 2024-01-18 2024-01-18 Organosilicon hydrophilic flame-retardant finishing agent and preparation method thereof Active CN117567714B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202410072934.XA CN117567714B (en) 2024-01-18 2024-01-18 Organosilicon hydrophilic flame-retardant finishing agent and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202410072934.XA CN117567714B (en) 2024-01-18 2024-01-18 Organosilicon hydrophilic flame-retardant finishing agent and preparation method thereof

Publications (2)

Publication Number Publication Date
CN117567714A CN117567714A (en) 2024-02-20
CN117567714B true CN117567714B (en) 2024-03-15

Family

ID=89896005

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202410072934.XA Active CN117567714B (en) 2024-01-18 2024-01-18 Organosilicon hydrophilic flame-retardant finishing agent and preparation method thereof

Country Status (1)

Country Link
CN (1) CN117567714B (en)

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1046474A (en) * 1996-07-25 1998-02-17 Sanyo Chem Ind Ltd Treating agent for fiber
CA2488839A1 (en) * 2004-12-02 2006-06-02 The Procter & Gamble Company Liquid fabric softening compositions comprising flame retardant
CN102206921A (en) * 2011-01-21 2011-10-05 北京服装学院 Polyether block amino silicone softening finishing agent, its preparation method and application
JP2014152415A (en) * 2013-02-08 2014-08-25 Matsumoto Yushi Seiyaku Co Ltd Flame-retardant processing agent for fiber, method of producing flame-retardant fiber and flame-retardant fiber
CN106637952A (en) * 2016-12-15 2017-05-10 吴江市北厍盛源纺织品助剂厂 Protein amino acid added textile size and preparation method thereof
CN108586526A (en) * 2018-05-18 2018-09-28 张家港康得新光电材料有限公司 Phosphniline acid esters acrylate oligomer, preparation method and the photocureable coating including it containing fluorenes
CN109594324A (en) * 2018-10-29 2019-04-09 赵建平 A kind of crease proofing agent
WO2019231617A1 (en) * 2018-05-29 2019-12-05 Elitechgroup, Inc. Carborhodamine compounds and methods of preparation thereof
KR20200137111A (en) * 2019-05-29 2020-12-09 현대하이켐(주) Complex flame retardant with inorganic flame retardant and method for preparing of the same
CN113389054A (en) * 2021-06-17 2021-09-14 苏州大上科高新材料有限公司 Flame-retardant anti-ultraviolet finishing process for oxford fabric
CN114773611A (en) * 2022-05-26 2022-07-22 哈尔滨工业大学 Phosphorus-containing oligomeric ester type epoxy resin toughening agent
CN116554808A (en) * 2023-07-10 2023-08-08 山东鲁阳节能材料股份有限公司 Flexible flame-retardant adhesive for cable fabric and preparation method thereof
CN117344546A (en) * 2023-09-01 2024-01-05 福建华峰新材料有限公司 Flame retardant finishing agent and preparation method and application thereof

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1046474A (en) * 1996-07-25 1998-02-17 Sanyo Chem Ind Ltd Treating agent for fiber
CA2488839A1 (en) * 2004-12-02 2006-06-02 The Procter & Gamble Company Liquid fabric softening compositions comprising flame retardant
CN102206921A (en) * 2011-01-21 2011-10-05 北京服装学院 Polyether block amino silicone softening finishing agent, its preparation method and application
JP2014152415A (en) * 2013-02-08 2014-08-25 Matsumoto Yushi Seiyaku Co Ltd Flame-retardant processing agent for fiber, method of producing flame-retardant fiber and flame-retardant fiber
CN106637952A (en) * 2016-12-15 2017-05-10 吴江市北厍盛源纺织品助剂厂 Protein amino acid added textile size and preparation method thereof
CN108586526A (en) * 2018-05-18 2018-09-28 张家港康得新光电材料有限公司 Phosphniline acid esters acrylate oligomer, preparation method and the photocureable coating including it containing fluorenes
WO2019231617A1 (en) * 2018-05-29 2019-12-05 Elitechgroup, Inc. Carborhodamine compounds and methods of preparation thereof
CN109594324A (en) * 2018-10-29 2019-04-09 赵建平 A kind of crease proofing agent
KR20200137111A (en) * 2019-05-29 2020-12-09 현대하이켐(주) Complex flame retardant with inorganic flame retardant and method for preparing of the same
CN113389054A (en) * 2021-06-17 2021-09-14 苏州大上科高新材料有限公司 Flame-retardant anti-ultraviolet finishing process for oxford fabric
CN114773611A (en) * 2022-05-26 2022-07-22 哈尔滨工业大学 Phosphorus-containing oligomeric ester type epoxy resin toughening agent
CN116554808A (en) * 2023-07-10 2023-08-08 山东鲁阳节能材料股份有限公司 Flexible flame-retardant adhesive for cable fabric and preparation method thereof
CN117344546A (en) * 2023-09-01 2024-01-05 福建华峰新材料有限公司 Flame retardant finishing agent and preparation method and application thereof

Also Published As

Publication number Publication date
CN117567714A (en) 2024-02-20

Similar Documents

Publication Publication Date Title
JP2717942B2 (en) Non-yellowing fabric soft finish using a composition comprising a polyorganosiloxane
US5100991A (en) Organosilicon compounds
CA1270990A (en) Aminofunctional polysiloxanes and emulsions thereof useful for treating textiles
JP2821037B2 (en) Processing method of fiber material
CN107474069B (en) A kind of silicon phosphorus Hybrid fire retardant and preparation method thereof and a kind of silicon phosphorus hybridisation emulsion
EP0342834A2 (en) Treatment of fibrous materials
CN114621281B (en) Dihydrocarbyl silicon acyl dimelamine compound of organic silicon nitrogen flame retardant and preparation method thereof
CN112921647B (en) Anti-dripping finishing method for terylene
CN110670351B (en) Synthesis and application of triazine derivative flame retardant
CN117567714B (en) Organosilicon hydrophilic flame-retardant finishing agent and preparation method thereof
CN102875816B (en) Organosilicone modified halogen-free intumescent flame retardant and preparation method thereof
CN108794751A (en) One kind resin fire retardant of structural silicone containing phosphonitrile and preparation method thereof
CN111235677A (en) Preparation method of high-strength polyester yarn with impact resistance
CN102558078B (en) Cyanuric chloride derivative as well as preparation method and application in anti-wrinkle finishing agent of cyanuric chloride derivative and finishing method of pure silk fabric
CN114182535B (en) Organic silicon finishing agent with thermal stability
CN111041591A (en) Modified polyester for labor protection fabric
CN114349947B (en) Fiber flame-retardant moisture-absorbing modifier and preparation method thereof
CN101086136A (en) Flame-resistant agent and its preparing process and usage
CN117265880B (en) Smooth and crease-resistant T/C fabric and preparation method thereof
CN117126366B (en) Synthesis process of flame-retardant polyurethane and application of flame-retardant polyurethane in fabric finishing
CN117661328A (en) Preparation process of hydrophilic crease-resistant polyester fabric
TWI837368B (en) Organopolysiloxanes and fiber treatment agents containing aminoalkyl groups
CN110105577B (en) Preparation method of reactive silicon-phosphorus-nitrogen synergistic flame-retardant water-repellent functional auxiliary for cotton
CN115322224A (en) Preparation method of novel flame retardant, product thereof and application of product in cotton fiber
CN114381820A (en) Flame-retardant acrylic fiber with high moisture absorption and production method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant