CN107740278A - A kind of comb polyurethane flame-retardant water-repellent finishing agent and preparation method and application - Google Patents
A kind of comb polyurethane flame-retardant water-repellent finishing agent and preparation method and application Download PDFInfo
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- CN107740278A CN107740278A CN201711058835.2A CN201711058835A CN107740278A CN 107740278 A CN107740278 A CN 107740278A CN 201711058835 A CN201711058835 A CN 201711058835A CN 107740278 A CN107740278 A CN 107740278A
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- 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
- D06M15/568—Reaction products of isocyanates with polyethers
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- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- 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
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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- 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
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/653—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain modified by isocyanate compounds
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- 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
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- 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
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
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- 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
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
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- 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
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
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- 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
Abstract
The invention discloses a kind of comb polyurethane flame-retardant water-repellent finishing agent and preparation method and application.The comb polyurethane flame-retardant water-repellent finishing agent, structural formula is shown in formula I；A is 10~20 arbitrary integer；B is 5~15 arbitrary integer；C is 10~20 arbitrary integer；D is 1~5 arbitrary integer；R1For the residue of the alcohol containing halogen；R2For the residue of long-chain fatty alcohol C12~C22 fatty alcohols；A1For the residue of diisocyanate；A2For the residue of small molecule polyol；A3 is the residue of soft segment polyalcohol；A4For the residue containing hydrophilic radical or the polyalcohol of segment.Comb polyurethane flame-retardant water-repellent finishing agent provided by the invention makes fabric while has fire-retardant and waterproofing function, and both do not influence each other；Raw material is cheap and easy to get, prepares processing technology simply, safety and environmental protection, is a kind of green high-efficient flame-retardant water-repellent finishing agent.
Description
Technical field
The invention belongs to technical field of textile chemical engineering, and in particular to a kind of comb polyurethane flame-retardant water-repellent finishing agent and its system
Preparation Method and application.
Background technology
Polyester-cotton textiles are widely used in everyday general purpose, life home textile and industrial protection neck because of its excellent wearability
Domain, but textile because it is inflammable hygroscopic the shortcomings that, have impact on it at some special industries (fire-entry suit, forestry protective garment etc.)
Application, while the textile for having flame-retardant water-repellent multi-functional is more and more welcomed by the people.Usual fabric water repellent finish is adopted
It is fluorine-contained finishing agent, such water repellent finishing agent is because containing the harmful substances such as PFOS (PFOS), by European Union and U.S.
State's market disabling.Aqueous polyurethane is a kind of green material, and compared to solvent borne polyurethane, it is situated between using water as scattered
Matter, environment will not be polluted in use.By introducing the alkane long-chain of pectination in polyurethane segment, during baking
Alkane long-chain is in fabric face ordered arrangement, so as to play the effect of water repellent.
Patent 201610935976.7 discloses a kind of flame-retardant water-repellent finishing agent for textile, but in preparation process
In introduce fluorine element, easily environment is polluted.Patent 201610796436.5 discloses a kind of composite nanometer flame retardant
Preparation method, but the compatibility of this fire retardant and water repellent is bad.In flame-retardant water-repellent arranges process, fire retardant
With water repellent it is difficult to play synergy on fabric.If first do water repellent finish does flame-proof treatment again, then the band of fire retardant
Liquid rate is relatively low, and the fire retardant adsorbed on fabric is less, and flame retardant effect is poor, and can make the reduction of water repellent effect；If first do fire-retardant
Water repellent finish is done in arrangement again, then flame retardant effect can equally be deteriorated.Therefore, exploitation one kind makes fabric while has fire-retardant and water repellent
Function, and both not interactional finishing agents have important practical significance.
The content of the invention
The shortcomings that for existing Water-resistance of Waterborne Polyurethane difference, the present invention introduce pectination length on polyurethane molecular main chain
Alkane, so as to reach water repellent effect；Halogen is introduced in molecule chain end simultaneously, reaches flame retardant effect, solves flame-retardant water-repellent
The synergy difference on fabric the problem of, and fluorine element is not introduced in polyurethane molecular chain, there is the characteristics of safety and environmental protection.
Comb polyurethane flame-retardant water-repellent finishing agent provided by the invention, its general structure is shown in formula I：
Wherein：
A is 10~20 arbitrary integer；
B is 5~15 arbitrary integer；
C is 10~20 arbitrary integer；
D is 1~5 arbitrary integer；
R1For the residue (not hydroxyl) of the alcohol containing halogen；
Described alcohols containing halogen preferably be selected from anesin, 2,2,2- ethapons, methaform, 1,3- dichlorohydrins,
The bromo- 1- propyl alcohol of 2,4- dybenals, 3,4- dybenals, 2,6- dybenals, ethobrom, 2,3- bis-, the bromo- 2- third of 1,3- bis-
At least one of alcohol and tribromoneoamyl alcohol；
R2For the residue of long-chain fatty alcohol C12~C22 fatty alcohols；
Described long-chain fatty alcohol is preferably C12~C22 fatty alcohols, still more preferably from lauryl alcohol, tetradecyl alchohol, 16
At least one of alcohol, octadecyl alcolol and docosanol；
A1For the residue of diisocyanate (without-NCO group)；
It is different that described diisocyanate preferably is selected from toluene di-isocyanate(TDI), hexamethylene diisocyanate, isophorone two
Cyanate, methyl diphenylene diisocyanate, 1,5- naphthalene diisocyanates, 1,12- dodecane diisocyanates, the methylene of benzene two
At least one of diisocyanate and methyl diphenylene diisocyanate；
A2For the residue of small molecule polyol；
Described small molecule polyol preferably is selected from trimethylolpropane, trimethylolethane, glycerine, hexanetriol and season penta
At least one of tetrol；
A3For the residue of soft segment polyalcohol；
Described soft segment polyalcohol preferred, polyethers dihydric alcohol, polyester diol, PCDL, polycaprolactone glycol,
At least one of PTMG, polybutene glycol, polybutadiene diol and hydroxy-terminated polysiloxane；
A4For the residue containing hydrophilic radical or the polyalcohol of segment；
The described polyalcohol containing hydrophilic radical or the segment preferably dihydric alcohol containing tertiary amine structure, the binary containing carboxylic acid structure
At least one of alcohol, the dihydric alcohol containing Sulfonic acid structures and polyethylene glycol.
The preparation method of comb polyurethane flame-retardant water-repellent finishing agent provided by the invention, comprises the steps：
(1) under inert gas shielding and in the presence of catalyst, make diisocyanate and small molecule polyol, carry out anti-
Should, the performed polymer I that-NCO is blocked is made；Then the long-chain fatty alcohol of metering is added, is branched reaction, is made and contains two-NCO
End-blocking and the performed polymer II with long chain alkane side chain；
(2) preparation of polyurethane：The diisocyanate of metering, performed polymer II, soft segment polyalcohol are well mixed, 50~
During 100 DEG C of 1~2h of reaction (make-NCO content reach setting value), 30 DEG C are cooled to, is then added containing hydrophilic radical or containing hydrophilic
The polyalcohol of segment, react 1~2h (make-NCO content reach setting value) at 35~60 DEG C, you can obtain performed polymer III；
(3) alcohol end capping containing halogen：Performed polymer III and alcohol containing halogen are subjected to end capping reaction, until-NCO content is zero,
Then less than 40 DEG C are cooled to and adds nertralizer progress neutralization reaction, is finally emulsified, you can it is fire-retardant to obtain comb polyurethane
Water repellent finishing agent.
Catalyst may be selected from following at least one described in step (1)：Dibutyl tin laurate, stannous octoate, carboxylic acid
Potassium, bismuth carboxylate.
Catalyst adds as a solution described in step (1), and the solvent in the solution is ketones solvent；Urge herein
Agent is mainly to participate in whole all-NCO and-OH reaction.The ketones solvent can be acetone, butanone, espeleton, methyl
Isobutyl ketone, cyclohexanone or diisobutyl ketone, preferably butanone.In catalyst solution, catalyst and ketones solvent thinner ratio (quality
Than) preferably 1:1~3.
The dosage of described catalyst solution is the 0.02~0.1% of reaction system total material gross mass.
The mol ratio 3~4 of diisocyanate, small molecule polyol, long-chain fatty alcohol described in step (1):1:1~2；
Small molecule polyol described in step (1) is 0.5~1.5 with soft segment polyol mole ratio described in step (3):1；
- NCO described in step (2) in diisocyanate and institute in soft segment polyalcohol, step (3) described in step (3)
State the mol ratio of the polyalcohol containing hydrophilic radical or segment and the-OH summations in step (2) small molecular polyalcohol for 1.2~
2.0:1；
The dosage of polyalcohol described in step (2) containing hydrophilic radical or containing hydrophilic segment is that reaction system total material is total
The 5%~10% of quality.
The reaction temperature that performed polymer I reaction is prepared in step (1) is 50~100 DEG C, and the reaction time is 1~2h.
The reaction temperature of branching reaction described in step (1) is 50~100 DEG C, and the reaction time is 1~2h.
Soft segment polyalcohol described in step (2) need to be dehydrated 2h at 20 DEG C before the use.
Alcohol containing halogen described in step (3) is 1.05~1.3 with unreacted-NCO mol ratios in performed polymer III:1.
Nertralizer described in step (3) rubs with the polyalcohol described in step (2) containing hydrophilic radical or containing hydrophilic segment
You are than being 1.2~2:1.
The reaction temperature of end capping reaction described in step (3) is 50~100 DEG C, and the reaction time is 1~4h.
The reaction temperature of neutralization reaction described in step (3) is 15~55 DEG C, and the reaction time is 0.5~1h.
It is different that described diisocyanate preferably is selected from toluene di-isocyanate(TDI), hexamethylene diisocyanate, isophorone two
Cyanate, methyl diphenylene diisocyanate, 1,5- naphthalene diisocyanates, 1,12- dodecane diisocyanates, the methylene of benzene two
At least one of diisocyanate and methyl diphenylene diisocyanate.
The preferred trimethylolpropane of described small molecule polyol, trimethylolethane, glycerine, hexanetriol and season penta 4
At least one in alcohol.
Described long-chain fatty alcohol is preferably C12~C22 fatty alcohols, still more preferably from dodecanol, tetradecanol,
At least one of hexadecanol, octadecanol and tadenan.
Described soft segment polyalcohol preferred, polyethers dihydric alcohol, polyester diol, PCDL, polycaprolactone glycol,
At least one of PTMG, polybutene glycol, polybutadiene diol and hydroxy-terminated polysiloxane；Described is soft
The molecular weight of section polyalcohol is 1000~3000.
The described polyalcohol containing hydrophilic radical or the segment preferably dihydric alcohol containing tertiary amine structure, the binary containing carboxylic acid structure
At least one of alcohol, the dihydric alcohol containing Sulfonic acid structures and polyethylene glycol；
Described alcohols containing halogen preferably be selected from anesin, 2,2,2- ethapons, methaform, 1,3- dichlorohydrins,
The bromo- 1- propyl alcohol of 2,4- dybenals, 3,4- dybenals, 2,6- dybenals, ethobrom, 2,3- bis-, the bromo- 2- third of 1,3- bis-
At least one of alcohol and tribromoneoamyl alcohol；
The nertralizer preferably is selected from least one in potassium hydroxide, triethylamine, ammoniacal liquor, formic acid, acetic acid, phosphoric acid and hydrochloric acid
Kind.
Described be emulsified in high speed emulsifying device is carried out.It is described emulsification rotating speed be：2000r/min~5000r/min；It is described
Emulsification times are 0.5h~2.5h.
Fabric is entered using above-mentioned comb polyurethane flame-retardant water-repellent finishing agent it is a further object to provide one kind
The method that row arranges.
The method provided by the present invention arranged to fabric, comprises the steps：Pectination provided by the invention is gathered
Urethane flame-retardant water-repellent finishing agent is configured to the working solution that concentration is 50g/L~150g/L (concretely 100g/L), using a leaching
One mode rolled handles fabric；Then the fabric after padding carries out thermal finalization.
Wherein, the liquid carrying rate of an immersing and rolling is in 50%~80% (concretely 70%).
The temperature of the thermal finalization is 120 DEG C~160 DEG C, and shaping time is 60s~120s.
The fabric can be terylene, polyamide fibre or bafta.
The comb polyurethane flame-retardant water-repellent finishing agent of the present invention prepares external condition and equipment and synthesizes water-based poly- ammonia at present
The preparation external condition and equipment of ester emulsion are essentially identical.
Comb polyurethane flame-retardant water-repellent finishing agent prepared by the present invention, has the following advantages that and effect：(1) in polyurethane point
Pectination long chain alkane is introduced on sub- main chain, ordered arrangement is formed in fabric face when high temperature is baked and banked up with earth, so as to reach water repellent effect；Together
When the water repellent building-up process in be free of fluorine element, environmentally safe, safety and environmental protection；(2) comb polyurethane is mainly by main chain
Structure and branched structure determine, by changing the species, content and molecular structure of synthesis material, so as to reach designing for function
Property；(3) the cheap alcohol end capping containing halogen of polyurethane molecular chain, reaches fabulous flame retardant effect；(4) by by alkane long-chain
Introduce molecular backbone with halogen, overcome the shortcomings that fire-retardant and water repellent synergy is bad, impart excellent fire-retardant of fabric and
Water repellency；(5) by introducing the ignition-proof elements such as chlorine, bromine, phosphorus in polyurethane molecular chain, prepare fire-retardant with reactivity
Agent, compared to additive flame retardant, fabric can have more longlasting fire resistance.Comb polyurethane flame-retardant water-repellent finishing agent raw material
It is cheap and easy to get, prepare that processing technology is simple, safety and environmental protection；Make fabric while there is fire-retardant and waterproofing function, and both not phases
Mutually influence.
Embodiment
The method of the present invention is illustrated below by specific embodiment, but the invention is not limited in this, it is all at this
All any modification, equivalent and improvement done within the spirit and principle of invention etc., should be included in the protection model of the present invention
Within enclosing.
Experimental method used in following embodiments is conventional method unless otherwise specified.
Material used, reagent etc., unless otherwise specified, are commercially obtained in following embodiments.
Embodiment 1
Comb polyurethane flame-retardant water-repellent arranges agent prescription
First, prepare
Comb polyurethane flame-retardant water-repellent finishing agent is made by the preparation method of the present invention in each raw material in above-mentioned formula.
Specifically preparation method is：1 part of dibutyltin dilaurate catalyst is diluted into dissolving with two parts of butanone, stirring is equal
After even, catalyst solution is obtained；Under inert nitrogen gas protection, by 18mol toluene di-isocyanate(TDI)s and 6mol trihydroxy methyls
Propane and 2ml catalyst solutions react 1.5h at 60 DEG C and the-performed polymer I of NCO group end-blocking are made, and then add the 18 of 6mol
Alkanol, react 1h at 70 DEG C and be branched reaction, the performed polymer II containing two-NCO group is made；82mol toluene two is different
Cyanate, performed polymer II, 36mol polyether Glycols 1000 (being dehydrated 2h at 120 DEG C before use) are well mixed, in 80 DEG C of reactions
2h (- NCO group content reaches setting value), is cooled to 30 DEG C, then adds 21mol N methyldiethanol amine, anti-at 45 DEG C
Answer 1.5h (- NCO group content reaches setting value), you can obtain performed polymer III；Performed polymer III and 58mol ethobrom is mixed
Close uniform, react 3h (- NCO group content is zero) at 60 DEG C, be cooled in less than the 40 DEG C acetic acid for adding 21mol and 30min,
2h is finally emulsified with 2000r/min rotating speeds in high speed emulsifying device, you can obtain comb polyurethane flame-retardant water-repellent finishing agent.
2nd, apply
By the above-mentioned comb polyurethane flame-retardant water-repellent finishing agent being prepared, 100g/L working solution is configured to, it is whole respectively
Terylene, polyamide fibre, bafta are managed, process step is as follows：
(1) processing is padded：Using comb polyurethane flame-retardant water-repellent finishing agent working solution manufactured in the present embodiment, using a leaching
One mode rolled handles three kinds of fabrics, and liquid carrying rate is 70% or so.
(2) thermal finalization is handled：It is fixed that the fabric for padding the present embodiment flame-retardant water-repellent finishing agent is subjected to heat on forming machine
Type, setting temperature are 150 DEG C, shaping time 90s.Its water repellency is tested according to AATCC 22-2001 water drenching methods of testing, is pressed
Its fire resistance is tested according to GB/T 5455-1997 vertical combustions, experimental result is as shown in table 1.
Fire resistance and water repellency after the terylene of table 1, polyamide fibre, Cotton Fabric
Embodiment 2
Comb polyurethane flame-retardant water-repellent arranges agent prescription
First, prepare
Comb polyurethane flame-retardant water-repellent finishing agent is made by the preparation method of the present invention in each raw material in above-mentioned formula.Tool
Preparation is：1 part of dibutyltin dilaurate catalyst is diluted into dissolving with two parts of butanone, after stirring, obtained
Catalyst solution；Under inert nitrogen gas protection, by 18mol IPDIs and 6mol trimethylolpropanes and
2ml catalyst solutions 60 DEG C react 1.5h be made-NCO group end-blocking performed polymer I, then add 6mol octadecanol,
1h is reacted at 70 DEG C and is branched reaction, and the performed polymer II containing two-NCO group is made；By the 82mol isocyanide of isophorone two
Acid esters, performed polymer II, 36mol polyether Glycols 1000 (being dehydrated 2h at 120 DEG C before use) are well mixed, react 2h at 80 DEG C
(- NCO group content reaches setting value) when, 30 DEG C are cooled to, then adds 21mol N methyldiethanol amine, it is anti-at 45 DEG C
Answer 1.5h (- NCO group content reaches setting value), you can obtain performed polymer III；Performed polymer III and 58mol ethobrom is mixed
Close uniform, react 3h (- NCO group content is zero) at 60 DEG C, be cooled in less than the 40 DEG C acetic acid for adding 21mol and 30min,
2h is finally emulsified with 2000r/min rotating speeds in high speed emulsifying device, you can obtain comb polyurethane flame-retardant water-repellent finishing agent.
2nd, apply
By the above-mentioned comb polyurethane flame-retardant water-repellent finishing agent being prepared, 100g/L working solution is configured to, it is whole respectively
Terylene, polyamide fibre, bafta are managed, process step is as follows：
(1) processing is padded：Using comb polyurethane flame-retardant water-repellent finishing agent working solution manufactured in the present embodiment, using a leaching
One mode rolled handles three kinds of fabrics, and liquid carrying rate is 70% or so.
(2) thermal finalization is handled：It is fixed that the fabric for padding the present embodiment flame-retardant water-repellent finishing agent is subjected to heat on forming machine
Type, setting temperature are 150 DEG C, shaping time 90s.Its water repellency is tested according to AATCC 22-2001 water drenching methods of testing, is pressed
Its fire resistance is tested according to GB/T 5455-1997 vertical combustions, experimental result is as shown in table 2.
Fire resistance and water repellency after the terylene of table 2, polyamide fibre, Cotton Fabric
Embodiment 3
Comb polyurethane flame-retardant water-repellent arranges agent prescription
First, prepare
Comb polyurethane flame-retardant water-repellent finishing agent is made by the preparation method of the present invention in each raw material in above-mentioned formula.Tool
Preparation is：1 part of dibutyltin dilaurate catalyst is diluted into dissolving with two parts of butanone, after stirring, obtained
Catalyst solution；Under inert nitrogen gas protection, by 18mol toluene di-isocyanate(TDI)s and 6mol trimethylolpropanes and 2ml
Catalyst solution 60 DEG C react 1.5h be made-NCO group end-blocking performed polymer I, then add 6mol octadecanol, 70
DEG C reaction 1h be branched reaction, be made contain two-NCO group performed polymer II；By 82mol isophorone diisocyanate
Ester, performed polymer II, 36mol polyether Glycols 1000 (before use 120 DEG C be dehydrated 2h) are well mixed, reacted at 80 DEG C 2h (-
NCO group content reaches setting value) when, 30 DEG C are cooled to, then adds 21mol N methyldiethanol amine, in 45 DEG C of reactions
1.5h (- NCO group content reaches setting value), you can obtain performed polymer III；Performed polymer III is mixed with 58mol ethobrom
Uniformly, 60 DEG C react 3h (- NCO group content is zero), be cooled to less than 40 DEG C add 21mol acetic acid in and 30min, most
2h is emulsified with 2000r/min rotating speeds in high speed emulsifying device afterwards, you can obtain comb polyurethane flame-retardant water-repellent finishing agent.2nd,
Using
By the above-mentioned comb polyurethane flame-retardant water-repellent finishing agent being prepared, 100g/L working solution is configured to, it is whole respectively
Terylene, polyamide fibre, bafta are managed, process step is as follows：
(1) processing is padded：Using comb polyurethane flame-retardant water-repellent finishing agent working solution manufactured in the present embodiment, using a leaching
One mode rolled handles three kinds of fabrics, and liquid carrying rate is 70% or so.
(2) thermal finalization is handled：It is fixed that the fabric for padding the present embodiment flame-retardant water-repellent finishing agent is subjected to heat on forming machine
Type, setting temperature are 150 DEG C, shaping time 90s.Its water repellency is tested according to AATCC 22-2001 water drenching methods of testing, is pressed
Its fire resistance is tested according to GB/T 5455-1997 vertical combustions, experimental result is as shown in table 3.
Fire resistance and water repellency after the terylene of table 3, polyamide fibre, Cotton Fabric
Embodiment 4
Comb polyurethane flame-retardant water-repellent arranges agent prescription
First, prepare
Comb polyurethane flame-retardant water-repellent finishing agent is made by the preparation method of the present invention in each raw material in above-mentioned formula.Tool
Preparation is：1 part of dibutyltin dilaurate catalyst is diluted into dissolving with two parts of butanone, after stirring, obtained
Catalyst solution；Under inert nitrogen gas protection, 24mol toluene di-isocyanate(TDI)s and 6mol pentaerythrites and 2ml are catalyzed
Agent solution 60 DEG C react 1.5h be made-NCO group end-blocking performed polymer I, then add 12mol octadecanol, at 70 DEG C
Reaction 1h is branched reaction, and the performed polymer II containing two-NCO group is made；By 82mol IPDI,
Performed polymer II, 33mol polyether Glycols 1000 (being dehydrated 2h at 120 DEG C before use) are well mixed, react 2h (- NCO at 80 DEG C
Group content reaches setting value) when, 30 DEG C are cooled to, then adds 24mol N methyldiethanol amine, reacts 1.5h at 45 DEG C
(- NCO group content reaches setting value), you can obtain performed polymer III；Performed polymer III is mixed with 58mol ethobrom
It is even, 60 DEG C react 3h (- NCO group content is zero), be cooled to less than 40 DEG C add 21mol acetic acid in and 30min, finally
2h is emulsified with 2000r/min rotating speeds in high speed emulsifying device, you can obtain comb polyurethane flame-retardant water-repellent finishing agent.
2nd, apply
By the above-mentioned comb polyurethane flame-retardant water-repellent finishing agent being prepared, 100g/L working solution is configured to, it is whole respectively
Terylene, polyamide fibre, bafta are managed, process step is as follows：
(1) processing is padded：Using comb polyurethane flame-retardant water-repellent finishing agent working solution manufactured in the present embodiment, using a leaching
One mode rolled handles three kinds of fabrics, and liquid carrying rate is 70% or so.
(2) thermal finalization is handled：It is fixed that the fabric for padding the present embodiment flame-retardant water-repellent finishing agent is subjected to heat on forming machine
Type, setting temperature are 150 DEG C, shaping time 90s.Its water repellency is tested according to AATCC 22-2001 water drenching methods of testing, is pressed
Its fire resistance is tested according to GB/T 5455-1997 vertical combustions, experimental result is as shown in table 4.
Fire resistance and water repellency after the terylene of table 4, polyamide fibre, Cotton Fabric
Embodiment 5
Comb polyurethane flame-retardant water-repellent arranges agent prescription
First, prepare
Comb polyurethane flame-retardant water-repellent finishing agent is made by the preparation method of the present invention in each raw material in above-mentioned formula.
Specifically preparation method is：1 part of dibutyltin dilaurate catalyst is diluted into dissolving with two parts of butanone, stirring is equal
After even, catalyst solution is obtained；Under inert nitrogen gas protection, by 18mol toluene di-isocyanate(TDI)s and 6mol trihydroxy methyls
Propane and 2ml catalyst solutions react 1.5h at 60 DEG C and the-performed polymer I of NCO group end-blocking are made, and then add the 18 of 6mol
Alkanol, react 1h at 70 DEG C and be branched reaction, the performed polymer II containing two-NCO group is made；By 82mol isophorone
Diisocyanate, performed polymer II, 36mol polysiloxane binary alcohol 1000 (being dehydrated 2h at 120 DEG C before use) are well mixed,
During 80 DEG C of reaction 2h (- NCO group content reaches setting value), 30 DEG C are cooled to, then adds 21mol N- methyl diethanols
Amine, react 1.5h at 45 DEG C (- NCO group content reaches setting value), you can obtain performed polymer III；By performed polymer III and 58mol
Ethobrom be well mixed, 60 DEG C react 3h (- NCO group content is zero), be cooled to less than 40 DEG C add 21mol vinegar
Acid neutralizes 30min, finally emulsifies 2h in high speed emulsifying device with 2000r/min rotating speeds, you can it is fire-retardant to obtain comb polyurethane
Water repellent finishing agent.
2nd, apply
By the above-mentioned comb polyurethane flame-retardant water-repellent finishing agent being prepared, 100g/L working solution is configured to, it is whole respectively
Terylene, polyamide fibre, bafta are managed, process step is as follows：
(1) processing is padded：Using comb polyurethane flame-retardant water-repellent finishing agent working solution manufactured in the present embodiment, using a leaching
One mode rolled handles three kinds of fabrics, and liquid carrying rate is 70% or so.
(2) thermal finalization is handled：It is fixed that the fabric for padding the present embodiment flame-retardant water-repellent finishing agent is subjected to heat on forming machine
Type, setting temperature are 150 DEG C, shaping time 90s.Its water repellency is tested according to AATCC 22-2001 water drenching methods of testing, is pressed
Its fire resistance is tested according to GB/T 5455-1997 vertical combustions, experimental result is as shown in table 5.
Fire resistance and water repellency after the terylene of table 5, polyamide fibre, Cotton Fabric
Embodiment 6
Comb polyurethane flame-retardant water-repellent arranges agent prescription
First, prepare
Comb polyurethane flame-retardant water-repellent finishing agent is made by the preparation method of the present invention in each raw material in above-mentioned formula.Tool
Preparation is：1 part of dibutyltin dilaurate catalyst is diluted into dissolving with two parts of butanone, after stirring, obtained
Catalyst solution；Under inert nitrogen gas protection, by 18mol toluene di-isocyanate(TDI)s and 6mol trimethylolpropanes and 2ml
Catalyst solution 60 DEG C react 1.5h be made-NCO group end-blocking performed polymer I, then add 6mol tadenan,
70 DEG C of reaction 1h are branched reaction, and the performed polymer II containing two-NCO group is made；By 82mol isophorone diisocyanate
Ester, performed polymer II, 36mol polysiloxane binary alcohol 1000 (being dehydrated 2h at 120 DEG C before use) are well mixed, in 80 DEG C of reactions
During 2h (- NCO group content reaches setting value), 30 DEG C are cooled to, 21mol N methyldiethanol amine is then added, at 45 DEG C
React 1.5h (- NCO group content reaches setting value), you can obtain performed polymer III；By performed polymer III and 58mol ethobrom
It is well mixed, 3h (- NCO group content is zero) is reacted at 60 DEG C, the acetic acid for being cooled to less than 40 DEG C addition 21mol neutralizes
30min, 2h is finally emulsified with 2000r/min rotating speeds in high speed emulsifying device, you can it is whole to obtain comb polyurethane flame-retardant water-repellent
Manage agent.
2nd, apply
By the above-mentioned comb polyurethane flame-retardant water-repellent finishing agent being prepared, 100g/L working solution is configured to, it is whole respectively
Terylene, polyamide fibre, bafta are managed, process step is as follows：
(1) processing is padded：Using comb polyurethane flame-retardant water-repellent finishing agent working solution manufactured in the present embodiment, using a leaching
One mode rolled handles three kinds of fabrics, and liquid carrying rate is 70% or so.
(2) thermal finalization is handled：It is fixed that the fabric for padding the present embodiment flame-retardant water-repellent finishing agent is subjected to heat on forming machine
Type, setting temperature are 150 DEG C, shaping time 90s.Its water repellency is tested according to AATCC 22-2001 water drenching methods of testing, is pressed
Its fire resistance is tested according to GB/T 5455-1997 vertical combustions, experimental result is as shown in table 6.
Fire resistance and water repellency after the terylene of table 6, polyamide fibre, Cotton Fabric
Embodiment 7
Comb polyurethane flame-retardant water-repellent arranges agent prescription
First, prepare
Comb polyurethane flame-retardant water-repellent finishing agent is made by the preparation method of the present invention in each raw material in above-mentioned formula.Tool
Preparation is：1 part of dibutyltin dilaurate catalyst is diluted into dissolving with two parts of butanone, after stirring, obtained
Catalyst solution；Under inert nitrogen gas protection, by 18mol toluene di-isocyanate(TDI)s and 6mol trimethylolpropanes and 2ml
Catalyst solution 60 DEG C react 1.5h be made-NCO group end-blocking performed polymer I, then add 6mol tadenan,
70 DEG C of reaction 1h are branched reaction, and the performed polymer II containing two-NCO group is made；By 82mol isophorone diisocyanate
Ester, performed polymer II, 36mol polysiloxane binary alcohol 1000 (being dehydrated 2h at 120 DEG C before use) are well mixed, in 80 DEG C of reactions
During 2h (- NCO group content reaches setting value), 30 DEG C are cooled to, then adds 21mol dihydromethyl propionic acid, it is anti-at 45 DEG C
Answer 1.5h (- NCO group content reaches setting value), you can obtain performed polymer III；Performed polymer III and 58mol ethobrom is mixed
Close uniformly, react 3h (- NCO group content is zero) at 60 DEG C, the triethylamines for being cooled to less than 40 DEG C addition 21mol neutralize
30min, 2h is finally emulsified with 2000r/min rotating speeds in high speed emulsifying device, you can it is whole to obtain comb polyurethane flame-retardant water-repellent
Manage agent.
2nd, apply
By the above-mentioned comb polyurethane flame-retardant water-repellent finishing agent being prepared, 100g/L working solution is configured to, it is whole respectively
Terylene, polyamide fibre, bafta are managed, process step is as follows：
(1) processing is padded：Using comb polyurethane flame-retardant water-repellent finishing agent working solution manufactured in the present embodiment, using a leaching
One mode rolled handles three kinds of fabrics, and liquid carrying rate is 70% or so.
(2) thermal finalization is handled：It is fixed that the fabric for padding the present embodiment flame-retardant water-repellent finishing agent is subjected to heat on forming machine
Type, setting temperature are 150 DEG C, shaping time 90s.Its water repellency is tested according to AATCC 22-2001 water drenching methods of testing, is pressed
Its fire resistance is tested according to GB/T 5455-1997 vertical combustions, experimental result is as shown in table 7.
Fire resistance and water repellency after the terylene of table 7, polyamide fibre, Cotton Fabric
Embodiment 8
Comb polyurethane flame-retardant water-repellent arranges agent prescription
First, prepare
Comb polyurethane flame-retardant water-repellent finishing agent is made by the preparation method of the present invention in each raw material in above-mentioned formula.Tool
Preparation is：1 part of dibutyltin dilaurate catalyst is diluted into dissolving with two parts of butanone, after stirring, obtained
Catalyst solution；Under inert nitrogen gas protection, by 18mol toluene di-isocyanate(TDI)s and 6mol trimethylolpropanes and 2ml
Catalyst solution 60 DEG C react 1.5h be made-NCO group end-blocking performed polymer I, then add 6mol tadenan,
70 DEG C of reaction 1h are branched reaction, and the performed polymer II containing two-NCO group is made；By 82mol isophorone diisocyanate
Ester, performed polymer II, 36mol polysiloxane binary alcohol 1000 (being dehydrated 2h at 120 DEG C before use) are well mixed, in 80 DEG C of reactions
During 2h (- NCO group content reaches setting value), 30 DEG C are cooled to, 21mol N methyldiethanol amine is then added, at 45 DEG C
React 1.5h (- NCO group content reaches setting value), you can obtain performed polymer III；Performed polymer III and 58mol methaform is mixed
Close uniform, react 3h (- NCO group content is zero) at 60 DEG C, be cooled in less than the 40 DEG C acetic acid for adding 21mol and 30min,
2h is finally emulsified with 2000r/min rotating speeds in high speed emulsifying device, you can obtain comb polyurethane flame-retardant water-repellent finishing agent.
2nd, apply
By the above-mentioned comb polyurethane flame-retardant water-repellent finishing agent being prepared, 100g/L working solution is configured to, it is whole respectively
Terylene, polyamide fibre, bafta are managed, process step is as follows：
(1) processing is padded：Using comb polyurethane flame-retardant water-repellent finishing agent working solution manufactured in the present embodiment, using a leaching
One mode rolled handles three kinds of fabrics, and liquid carrying rate is 70% or so.
(2) thermal finalization is handled：It is fixed that the fabric for padding the present embodiment flame-retardant water-repellent finishing agent is subjected to heat on forming machine
Type, setting temperature are 150 DEG C, shaping time 90s.Its water repellency is tested according to AATCC 22-2001 water drenching methods of testing, is pressed
Its fire resistance is tested according to GB/T 5455-1997 vertical combustions, experimental result is as shown in table 8.
Fire resistance and water repellency after the terylene of table 8, polyamide fibre, Cotton Fabric
Embodiment 9
Comb polyurethane flame-retardant water-repellent arranges agent prescription
First, prepare
Comb polyurethane flame-retardant water-repellent finishing agent is made by the preparation method of the present invention in each raw material in above-mentioned formula.Tool
Preparation is：1 part of dibutyltin dilaurate catalyst is diluted into dissolving with two parts of butanone, after stirring, obtained
Catalyst solution；Under inert nitrogen gas protection, by 18mol toluene di-isocyanate(TDI)s and 6mol trimethylolpropanes and 2ml
Catalyst solution 60 DEG C react 1.5h be made-NCO group end-blocking performed polymer I, then add 6mol tadenan,
70 DEG C of reaction 1h are branched reaction, and the performed polymer II containing two-NCO group is made；By 82mol isophorone diisocyanate
Ester, performed polymer II, 18mol polysiloxane binary alcohol 1000,18mol polyether Glycols 1000 are (in 120 DEG C of dehydrations before use
2h) it is well mixed, when reacting 2h (- NCO group content reaches setting value) for 80 DEG C, is cooled to 30 DEG C, then adds 21mol's
N methyldiethanol amine, react 1.5h at 45 DEG C (- NCO group content reaches setting value), you can obtain performed polymer III；By pre-polymerization
Body III is well mixed with 58mol ethobrom, reacts 3h (- NCO group content is zero) at 60 DEG C, is cooled to less than 40 DEG C and is added
Enter in 21mol acetic acid and 30min, 2h is finally emulsified with 2000r/min rotating speeds in high speed emulsifying device, you can obtain pectination
Polyurethane flame-proof water repellent finishing agent.
2nd, apply
By the above-mentioned comb polyurethane flame-retardant water-repellent finishing agent being prepared, 100g/L working solution is configured to, it is whole respectively
Terylene, polyamide fibre, bafta are managed, process step is as follows：
(1) processing is padded：Using comb polyurethane flame-retardant water-repellent finishing agent working solution manufactured in the present embodiment, using a leaching
One mode rolled handles three kinds of fabrics, and liquid carrying rate is 70% or so.
(2) thermal finalization is handled：It is fixed that the fabric for padding the present embodiment flame-retardant water-repellent finishing agent is subjected to heat on forming machine
Type, setting temperature are 150 DEG C, shaping time 90s.Its water repellency is tested according to AATCC 22-2001 water drenching methods of testing, is pressed
Its fire resistance is tested according to GB/T 5455-1997 vertical combustions, experimental result is as shown in table 9.
Fire resistance and water repellency after the terylene of table 9, polyamide fibre, Cotton Fabric
Claims (10)
1. a kind of comb polyurethane flame-retardant water-repellent finishing agent, its general structure is shown in formula I：
Wherein：
A is 10~20 arbitrary integer；
B is 5~15 arbitrary integer；
C is 10~20 arbitrary integer；
D is 1~5 arbitrary integer；
R1For the residue of the alcohol containing halogen；
R2For the residue of long-chain fatty alcohol C12~C22 fatty alcohols；
A1For the residue of diisocyanate, it is without-NCO group；
A2For the residue of small molecule polyol；
A3 is the residue of soft segment polyalcohol；
A4For the residue containing hydrophilic radical or the polyalcohol of segment；
The described polyalcohol containing hydrophilic radical or segment preferably the dihydric alcohol containing tertiary amine structure, the dihydric alcohol containing carboxylic acid structure,
At least one of dihydric alcohol and polyethylene glycol containing Sulfonic acid structures.
2. comb polyurethane flame-retardant water-repellent finishing agent according to claim 1, it is characterised in that：
Described alcohol containing halogen is selected from anesin, 2,2,2- ethapons, methaform, 1,3- dichlorohydrins, 2,4- dichloros
The bromo- 1- propyl alcohol of benzylalcohol, 3,4- dybenals, 2,6- dybenals, ethobrom, 2,3- bis-, the bromo- 2- propyl alcohol of 1,3- bis- and tribromo
At least one of neopentyl alcohol；
Described long-chain fatty alcohol is C12~C22 fatty alcohols, still more preferably from lauryl alcohol, tetradecyl alchohol, hexadecanol, 18
At least one of alcohol and docosanol；
Described diisocyanate be selected from toluene di-isocyanate(TDI), hexamethylene diisocyanate, IPDI,
Methyl diphenylene diisocyanate, 1,5- naphthalene diisocyanates, 1,12- dodecane diisocyanates, the isocyanide of two methylene of benzene two
At least one of acid esters and methyl diphenylene diisocyanate；
Described small molecule polyol is in trimethylolpropane, trimethylolethane, glycerine, hexanetriol and pentaerythrite
At least one；
Described soft segment polyalcohol is selected from polyether Glycols, polyester diol, PCDL, polycaprolactone glycol, poly- four
At least one of hydrogen furans ether glycol, polybutene glycol, polybutadiene diol and hydroxy-terminated polysiloxane；
The described polyalcohol containing hydrophilic radical or segment preferably the dihydric alcohol containing tertiary amine structure, the dihydric alcohol containing carboxylic acid structure,
At least one of dihydric alcohol and polyethylene glycol containing Sulfonic acid structures.
3. preparing the preparation method of the comb polyurethane flame-retardant water-repellent finishing agent described in claim 1 or 2, comprise the steps：
(1) under inert gas shielding, diisocyanate and small molecule polyol are reacted, the pre-polymerization of-NCO end-blockings is made
Body I；Then the long-chain fatty alcohol of metering is added, is branched reaction, is made containing two-NCO end-blockings and with long chain alkane branch
The performed polymer II of chain；
(2) preparation of polyurethane：Diisocyanate, performed polymer II, soft segment polyalcohol are well mixed, react 1 at 50~100 DEG C
~2h, is cooled to 30 DEG C, then adds the polyalcohol containing hydrophilic radical or containing hydrophilic segment, reacts 1~2h at 35~60 DEG C, i.e.,
Obtain performed polymer III；
(3) alcohol end capping containing halogen：Performed polymer III and the alcohol containing halogen of metering are subjected to end capping reaction, until-NCO content is
Zero, then it is cooled to less than 40 DEG C and adds nertralizer progress neutralization reaction, is finally emulsified, that is, it is fire-retardant to obtain comb polyurethane
Water repellent finishing agent.
4. according to the method for claim 3, it is characterised in that：
Catalyst described in step (1) is selected from following at least one：Dibutyl tin laurate, stannous octoate, carboxylic acid potassium and carboxylic
Sour bismuth；
Catalyst adds as a solution described in step (1), and the solvent in the solution is ketones solvent；The ketone is molten
Agent is selected from following at least one：Acetone, butanone, espeleton, methylisobutylketone, cyclohexanone or diisobutyl ketone；Catalyst solution
In, the mass ratio preferably 1 of catalyst and ketones solvent:1~3；
The dosage of described catalyst is the 0.02~0.1% of reaction system total material gross mass.
5. the method according to claim 3 or 4, it is characterised in that：
The mol ratio 3~4 of diisocyanate, small molecule polyol, long-chain fatty alcohol described in step (2):1:1~2；
The reaction temperature that performed polymer I reaction is prepared in step (2) is 50~100 DEG C, and the reaction time is 1~2h；
The reaction temperature of branching reaction described in step (2) is 50~100 DEG C, and the reaction time is 1~2h.
6. according to the method any one of claim 3-5, it is characterised in that：
Small molecule polyol described in step (2) is 0.5~1.5 with soft segment polyol mole ratio described in step (3):1；
- NCO described in step (3) in diisocyanate contains with soft segment polyalcohol described in step (3), step described in (3)
The mol ratio of-OH summations in polyalcohol and step (2) small molecular polyalcohol of hydrophilic radical or segment is 1.2~2.0:
1；
The dosage of polyalcohol described in step (3) containing hydrophilic radical or containing hydrophilic segment is reaction system total material gross mass
5%~10%；
Soft segment polyalcohol described in step (3) need to be dehydrated 2h at 20 DEG C before the use.
7. according to the method any one of claim 3-6, it is characterised in that：In the step (4), the alcohol containing halogen
Mol ratio with unreacted-NCO in performed polymer III is 1.05~1.3:1；
Nertralizer described in step (4) and the polyol mole ratio described in step (3) containing hydrophilic radical or containing hydrophilic segment
For 1.2~2:1；
The reaction temperature of end capping reaction described in step (4) is 50~100 DEG C, and the reaction time is 1~4h；
The reaction temperature of neutralization reaction described in step (4) is 15~55 DEG C, and the reaction time is 0.5~1h；
Described be emulsified in high speed emulsifying device is carried out；It is described emulsification rotating speed be for：2000r/min~5000r/min；The breast
The change time is 0.5h~2.5h.
8. according to the method any one of claim 3-7, it is characterised in that：Described diisocyanate is selected from toluene two
Isocyanates, hexamethylene diisocyanate, IPDI, methyl diphenylene diisocyanate, 1,5- naphthalenes two
In isocyanates, 1,12- dodecane diisocyanates, xylylene diisocyanate and methyl diphenylene diisocyanate
It is at least one；
Described small molecule polyol is in trimethylolpropane, trimethylolethane, glycerine, hexanetriol and pentaerythrite
At least one；
Described long-chain fatty alcohol is C12~C22 fatty alcohols, preferably is selected from lauryl alcohol, tetradecyl alchohol, hexadecanol, octadecyl alcolol and 20
At least one of glycol；
Described soft segment polyalcohol is selected from polyether Glycols, polyester diol, PCDL, polycaprolactone glycol, poly- four
At least one of hydrogen furans ether glycol, polybutene glycol, polybutadiene diol and hydroxy-terminated polysiloxane；
The described polyalcohol containing hydrophilic radical or segment be selected from the dihydric alcohol containing tertiary amine structure, the dihydric alcohol containing carboxylic acid structure,
At least one of dihydric alcohol and polyethylene glycol containing Sulfonic acid structures；
Described alcohols containing halogen is selected from anesin, 2,2,2- ethapons, methaform, 1,3- dichlorohydrins, 2,4- bis-
The bromo- 1- propyl alcohol of chlorobenzyl alcohol, 3,4- dybenals, 2,6- dybenals, ethobrom, 2,3- bis-, the bromo- 2- propyl alcohol of 1,3- bis- and three
At least one of bromine neopentyl alcohol.
9. a kind of method that comb polyurethane flame-retardant water-repellent finishing agent using described in claim 1 or 2 is arranged to fabric,
Comprise the steps：Comb polyurethane flame-retardant water-repellent finishing agent processing fabric described in claim 1 or 2 is configured into concentration is
50g/L~150g/L working solution, fabric is handled by the way of an immersing and rolling；Then it is fixed that the fabric after padding carries out heat
Type.
10. according to the method for claim 9, it is characterised in that：
The liquid carrying rate of one immersing and rolling is 50%~80%；
The temperature of the thermal finalization is 120 DEG C~160 DEG C, and shaping time is 60s~120s；
The fabric is terylene, polyamide fibre or bafta.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711058835.2A CN107740278B (en) | 2017-11-01 | 2017-11-01 | Comb-shaped polyurethane flame-retardant water-repellent finishing agent and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711058835.2A CN107740278B (en) | 2017-11-01 | 2017-11-01 | Comb-shaped polyurethane flame-retardant water-repellent finishing agent and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107740278A true CN107740278A (en) | 2018-02-27 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108467471A (en) * | 2018-04-04 | 2018-08-31 | 优美特（北京）环境材料科技股份公司 | A kind of hyper-branched aqueous polyurethane dispersion of pectination and its preparation and application |
| CN108951164A (en) * | 2018-06-06 | 2018-12-07 | 苏州印丝特纺织数码科技有限公司 | A kind of pure cotton fabric antiflaming finishing agent and preparation method thereof |
| CN108978225A (en) * | 2018-08-02 | 2018-12-11 | 北京中纺化工股份有限公司 | A kind of super branched polyurethane water repellent finishing agent and the preparation method and application thereof |
| CN110128615A (en) * | 2019-05-10 | 2019-08-16 | 江苏奥斯佳材料科技股份有限公司 | A kind of aqueous polyurethane and its preparation method and application |
| CN110452347A (en) * | 2019-07-10 | 2019-11-15 | 广东德美精细化工集团股份有限公司 | A kind of urethane intermediates and preparation method thereof with waterproof performance |
| CN110467717A (en) * | 2019-07-09 | 2019-11-19 | 广东德美精细化工集团股份有限公司 | A kind of not fluorine-containing waterproof polymer intermediate and preparation method thereof |
| CN111004361A (en) * | 2019-01-28 | 2020-04-14 | 江南大学 | Polyurethane-acrylate water repellent agent prepared by utilizing side chain double bonds |
| CN115322530A (en) * | 2022-08-10 | 2022-11-11 | 江阴市龙山合成材料有限公司 | Halogen-free flame-retardant enhanced PBT and processing technology thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1749291A (en) * | 2005-09-29 | 2006-03-22 | 上海申真企业发展有限公司 | Flame-retardant polyurethane water dispersion and its preparing method |
| CN101633718A (en) * | 2009-08-26 | 2010-01-27 | 中国科学院广州化学研究所 | Comb polyurethane associated thickener and preparation method and application thereof |
-
2017
- 2017-11-01 CN CN201711058835.2A patent/CN107740278B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1749291A (en) * | 2005-09-29 | 2006-03-22 | 上海申真企业发展有限公司 | Flame-retardant polyurethane water dispersion and its preparing method |
| CN101633718A (en) * | 2009-08-26 | 2010-01-27 | 中国科学院广州化学研究所 | Comb polyurethane associated thickener and preparation method and application thereof |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108467471A (en) * | 2018-04-04 | 2018-08-31 | 优美特（北京）环境材料科技股份公司 | A kind of hyper-branched aqueous polyurethane dispersion of pectination and its preparation and application |
| CN108467471B (en) * | 2018-04-04 | 2020-10-30 | 优美特（北京）环境材料科技股份公司 | Comb-shaped multi-branched aqueous polyurethane dispersion and preparation and application thereof |
| CN108951164A (en) * | 2018-06-06 | 2018-12-07 | 苏州印丝特纺织数码科技有限公司 | A kind of pure cotton fabric antiflaming finishing agent and preparation method thereof |
| CN108951164B (en) * | 2018-06-06 | 2021-03-19 | 苏州印丝特纺织数码科技有限公司 | Flame-retardant finishing agent for pure cotton fabric and preparation method thereof |
| CN108978225A (en) * | 2018-08-02 | 2018-12-11 | 北京中纺化工股份有限公司 | A kind of super branched polyurethane water repellent finishing agent and the preparation method and application thereof |
| CN108978225B (en) * | 2018-08-02 | 2020-10-27 | 北京中纺化工股份有限公司 | Hyperbranched polyurethane water repellent finishing agent and preparation method and application thereof |
| CN111004361A (en) * | 2019-01-28 | 2020-04-14 | 江南大学 | Polyurethane-acrylate water repellent agent prepared by utilizing side chain double bonds |
| CN111004361B (en) * | 2019-01-28 | 2021-04-30 | 高青如意纺织有限公司 | Polyurethane-acrylate water repellent agent prepared by utilizing side chain double bonds |
| CN110128615A (en) * | 2019-05-10 | 2019-08-16 | 江苏奥斯佳材料科技股份有限公司 | A kind of aqueous polyurethane and its preparation method and application |
| CN110128615B (en) * | 2019-05-10 | 2022-04-15 | 江苏奥斯佳材料科技股份有限公司 | Waterborne polyurethane and preparation method and application thereof |
| CN110467717A (en) * | 2019-07-09 | 2019-11-19 | 广东德美精细化工集团股份有限公司 | A kind of not fluorine-containing waterproof polymer intermediate and preparation method thereof |
| CN110452347A (en) * | 2019-07-10 | 2019-11-15 | 广东德美精细化工集团股份有限公司 | A kind of urethane intermediates and preparation method thereof with waterproof performance |
| CN115322530A (en) * | 2022-08-10 | 2022-11-11 | 江阴市龙山合成材料有限公司 | Halogen-free flame-retardant enhanced PBT and processing technology thereof |
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