CN107740278B - Comb-shaped polyurethane flame-retardant water-repellent finishing agent and preparation method and application thereof - Google Patents
Comb-shaped polyurethane flame-retardant water-repellent finishing agent and preparation method and application thereof Download PDFInfo
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- CN107740278B CN107740278B CN201711058835.2A CN201711058835A CN107740278B CN 107740278 B CN107740278 B CN 107740278B CN 201711058835 A CN201711058835 A CN 201711058835A CN 107740278 B CN107740278 B CN 107740278B
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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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- 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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- 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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- 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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- 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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- 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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- 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
Abstract
The invention discloses a comb-shaped polyurethane flame-retardant water-repellent finishing agent, and a preparation method and application thereof. The structural formula of the comb-shaped polyurethane flame-retardant water-repellent finishing agent is shown as a formula I; a is any integer of 10-20; b is any integer of 5-15; c is any integer of 10-20; d is any integer of 1-5; r1Is a halogen-containing alcohol residue; r2is the residue of long-chain fatty alcohol C12-C22 fatty alcohol; a. the1Is the residue of a diisocyanate; a. the2Is the residue of a small molecule polyol; a3 is the residue of a soft segment polyol; a. the4Is the residue of a hydrophilic group or segment-containing polyol. The comb-shaped polyurethane flame-retardant water-repellent finishing agent provided by the invention enables the fabric to have the flame-retardant and water-repellent functions at the same time, and the flame-retardant and water-repellent finishing agent and the fabric do not influence each other(ii) a The raw materials are cheap and easy to obtain, the preparation processing technology is simple, and the finishing agent is safe and environment-friendly and is a green high-efficiency flame-retardant water-repellent finishing agent.
Description
Technical Field
The invention belongs to the technical field of textile chemical industry, and particularly relates to a comb-shaped polyurethane flame-retardant water-repellent finishing agent, and a preparation method and application thereof.
Background
Polyester cotton textiles are widely used in the fields of daily wear, home textiles and industrial protection due to excellent wearability, but the textiles are easy to burn and absorb water, so that the application of the textiles in certain special industries (fire-fighting clothing, forestry protective clothing and the like) is influenced, and meanwhile, the textiles with flame retardance, water repellency and multiple functions are more and more popular with people. The water repellent finishing of the fabric usually adopts fluorine-containing finishing agent, and the water repellent finishing agent is forbidden by European Union and American market due to containing harmful substances such as perfluorooctane sulfonate (PFOS). The waterborne polyurethane is a green and environment-friendly material, and compared with solvent type polyurethane, the waterborne polyurethane takes water as a dispersion medium, so that the environment cannot be polluted in the using process. The comb-shaped alkane long chains are introduced into the polyurethane chain segments, and the alkane long chains are orderly arranged on the surface of the fabric during baking, so that the effect of water repellency is achieved.
Patent 201610935976.7 discloses a flame-retardant water-repellent finishing agent for textiles, but fluorine element is introduced in the preparation process, so that the environment is easily polluted. Patent 201610796436.5 discloses a method for preparing a nano-composite flame retardant, but the compatibility of the flame retardant and a water repellent agent is not good. In the process of flame-retardant water-repellent finishing, the flame retardant and the water repellent agent hardly have a synergistic effect on the fabric. If water repellent finishing is carried out first and then flame retardant finishing is carried out, the liquid carrying rate of the flame retardant is lower, the flame retardant adsorbed on the fabric is less, the flame retardant effect is poorer, and the water repellent effect is reduced; if the flame retardant finishing is performed first and then the water repellent finishing is performed, the flame retardant effect is also deteriorated. Therefore, the development of a finishing agent which enables the fabric to have the functions of flame retardance and water repellency simultaneously and has no mutual influence on the fabric has important practical significance.
disclosure of Invention
Aiming at the defect of poor water resistance of the existing waterborne polyurethane, the comb-shaped long-chain alkane is introduced into the main chain of the polyurethane molecule, so that the water-repellent effect is achieved; meanwhile, halogen is introduced into the tail end of the molecular chain, so that the flame-retardant effect is achieved, the problem that the synergistic effect of flame-retardant water repellency on the fabric is poor is solved, and fluorine is not introduced into the polyurethane molecular chain, so that the flame-retardant water repellent fabric has the characteristics of safety and environmental protection.
the structural general formula of the comb-shaped polyurethane flame-retardant water-repellent finishing agent provided by the invention is shown as formula I:
Wherein:
a is any integer of 10-20;
b is any integer of 5-15;
c is any integer of 10-20;
d is any integer of 1-5;
R1Is a halogen-containing alcohol residue (free of hydroxyl groups);
The halogen-containing alcohol is preferably at least one selected from the group consisting of chlorobutanol, 2,2, 2-trichloroethanol, chlorobutanol, 1, 3-dichloropropanol, 2, 4-dichlorobenzyl alcohol, 3, 4-dichlorobenzyl alcohol, 2, 6-dichlorobenzyl alcohol, tribromoethanol, 2, 3-dibromo-1-propanol, 1, 3-dibromo-2-propanol and tribromoneopentanol;
R2is the residue of long-chain fatty alcohol C12-C22 fatty alcohol;
The long-chain fatty alcohol is preferably C12-C22 fatty alcohol, and is more preferably at least one of dodecanol, tetradecanol, hexadecanol, octadecanol and behenyl alcohol;
A1is the residue of a diisocyanate (free of-NCO groups);
the diisocyanate is preferably at least one selected from toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, 1, 12-dodecyl diisocyanate, xylylene diisocyanate and diphenylmethane diisocyanate;
A2Is the residue of a small molecule polyol;
The small molecular polyol is preferably at least one of trimethylolpropane, trimethylolethane, glycerol, hexanetriol and pentaerythritol;
A3is the residue of a soft segment polyol;
the soft segment polyol is preferably at least one of polyether diol, polyester diol, polycarbonate diol, polycaprolactone diol, polytetrahydrofuran ether diol, polybutylene diol, polybutadiene diol and hydroxyl-terminated polysiloxane;
A4is a residue of a hydrophilic group or segment-containing polyol;
The polyhydric alcohol containing the hydrophilic group or the segment is preferably at least one of dihydric alcohol containing a tertiary amine structure, dihydric alcohol containing a carboxylic acid structure, dihydric alcohol containing a sulfonic acid structure and polyethylene glycol.
The preparation method of the comb-shaped polyurethane flame-retardant water-repellent finishing agent provided by the invention comprises the following steps:
(1) under the protection of inert gas and in the presence of a catalyst, reacting diisocyanate with micromolecular polyol to prepare a-NCO-terminated prepolymer I; then adding metered long-chain fatty alcohol to carry out a branching reaction to prepare a prepolymer II containing two-NCO end-capped oligomers and having a long paraffin branched chain;
(2) preparation of polyurethane: uniformly mixing metered diisocyanate, prepolymer II and soft segment polyol, cooling to 30 ℃ when reacting for 1-2 h (enabling-NCO content to reach a set value) at 50-100 ℃, then adding polyol containing hydrophilic groups or hydrophilic chain segments, and reacting for 1-2 h (enabling-NCO content to reach a set value) at 35-60 ℃ to obtain prepolymer III;
(3) End capping with halogen-containing alcohols: and (3) carrying out end-capping reaction on the prepolymer III and halogen-containing alcohol until the-NCO content is zero, then cooling to below 40 ℃, adding a neutralizing agent for neutralization reaction, and finally emulsifying to obtain the comb-shaped polyurethane flame-retardant water-repellent finishing agent.
The catalyst in step (1) may be selected from at least one of the following: dibutyltin dilaurate, stannous octoate, potassium carboxylate and bismuth carboxylate.
adding the catalyst in the step (1) in the form of solution, wherein the solvent in the solution is a ketone solvent; the catalyst here is predominantly involved in the reaction of all-NCO groups with-OH groups throughout the process. The ketone solvent may be acetone, butanone, methyl isobutyl ketone, cyclohexanone or diisobutyl ketone, and is preferably butanone. In the catalyst solution, the dilution ratio (mass ratio) of the catalyst to the ketone solvent is preferably 1: 1-3.
The dosage of the catalyst solution is 0.02-0.1% of the total mass of all substances in the reaction system.
the molar ratio of the diisocyanate to the micromolecular polyol to the long-chain fatty alcohol in the step (1) is 3-4: 1: 1-2;
the molar ratio of the small molecular polyol in the step (1) to the soft segment polyol in the step (3) is 0.5-1.5: 1;
the molar ratio of-NCO in the diisocyanate in the step (2) to the sum of-OH in the soft segment polyol in the step (3), the hydrophilic group or segment-containing polyol in the step (3) and the small molecule polyol in the step (2) is 1.2-2.0: 1;
The using amount of the polyalcohol containing the hydrophilic group or the hydrophilic chain segment in the step (2) is 5 to 10 percent of the total mass of all substances in the reaction system.
the reaction temperature of the reaction for preparing the prepolymer I in the step (1) is 50-100 ℃, and the reaction time is 1-2 hours.
The reaction temperature of the branching reaction in the step (1) is 50-100 ℃, and the reaction time is 1-2 h.
in the step (2), the soft segment polyol needs to be dehydrated for 2 hours at 20 ℃ before being used.
in the step (3), the molar ratio of the halogen-containing alcohol to unreacted-NCO in the prepolymer III is 1.05-1.3: 1.
the mol ratio of the neutralizing agent in the step (3) to the polyhydric alcohol containing the hydrophilic group or the hydrophilic chain segment in the step (2) is 1.2-2: 1.
The reaction temperature of the end capping reaction in the step (3) is 50-100 ℃, and the reaction time is 1-4 h.
the reaction temperature of the neutralization reaction in the step (3) is 15-55 ℃, and the reaction time is 0.5-1 h.
The diisocyanate is preferably at least one selected from the group consisting of toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, 1, 12-dodecyl diisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate.
the small-molecule polyol is preferably at least one of trimethylolpropane, trimethylolethane, glycerol, hexanetriol and pentaerythritol.
The long-chain fatty alcohol is preferably a C12-C22 fatty alcohol, and more preferably at least one of dodecanol, tetradecanol, hexadecanol, octadecanol and behenyl alcohol.
the soft segment polyol is preferably at least one of polyether diol, polyester diol, polycarbonate diol, polycaprolactone diol, polytetrahydrofuran ether diol, polybutylene diol, polybutadiene diol and hydroxyl-terminated polysiloxane; the molecular weight of the soft segment polyol is 1000-3000.
The polyhydric alcohol containing the hydrophilic group or the chain segment is preferably at least one of dihydric alcohol containing a tertiary amine structure, dihydric alcohol containing a carboxylic acid structure, dihydric alcohol containing a sulfonic acid structure and polyethylene glycol;
The halogen-containing alcohol is preferably at least one selected from the group consisting of chlorobutanol, 2,2, 2-trichloroethanol, chlorobutanol, 1, 3-dichloropropanol, 2, 4-dichlorobenzyl alcohol, 3, 4-dichlorobenzyl alcohol, 2, 6-dichlorobenzyl alcohol, tribromoethanol, 2, 3-dibromo-1-propanol, 1, 3-dibromo-2-propanol and tribromoneopentanol;
The neutralizing agent is preferably at least one selected from potassium hydroxide, triethylamine, ammonia water, formic acid, acetic acid, phosphoric acid and hydrochloric acid.
The emulsification is carried out in a high speed emulsification device. The emulsifying rotating speed is as follows: 2000 r/min-5000 r/min; the emulsifying time is 0.5 h-2.5 h.
the invention also aims to provide a method for finishing the fabric by adopting the comb-shaped polyurethane flame-retardant water-repellent finishing agent.
The method for finishing the fabric provided by the invention comprises the following steps: preparing the comb-shaped polyurethane flame-retardant water-repellent finishing agent into working solution with the concentration of 50-150 g/L (specifically 100g/L), and treating the fabric in a one-dipping-one-rolling mode; and then carrying out heat setting on the padded fabric.
Wherein, the liquid carrying rate of the first soaking and the first rolling is 50-80% (specifically 70%).
The heat setting temperature is 120-160 ℃, and the setting time is 60-120 s.
the fabric can be polyester, chinlon or cotton fabric.
The external conditions and equipment for preparing the comb-shaped polyurethane flame-retardant water-repellent finishing agent are basically the same as those for preparing the conventional synthetic waterborne polyurethane emulsion.
the comb-shaped polyurethane flame-retardant water-repellent finishing agent prepared by the invention has the following advantages and effects: (1) comb-shaped long-chain alkane is introduced into a main chain of a polyurethane molecule, and orderly arrangement is formed on the surface of the fabric during high-temperature baking, so that the water repellent effect is achieved; meanwhile, the water repellent agent does not contain fluorine element in the synthetic process, has no pollution to the environment, and is safe and environment-friendly; (2) the comb-shaped polyurethane is mainly determined by a main chain structure and a branched chain structure, and the designability of functions is achieved by changing the types, contents and molecular structures of synthetic raw materials; (3) the polyurethane molecular chain is blocked by cheap halogen-containing alcohols, so that an excellent flame-retardant effect is achieved; (4) the long alkane chain and the halogen are introduced into the main molecular chain, so that the defect of poor flame retardant and water repellent synergistic effect is overcome, and the fabric is endowed with excellent flame retardant and water repellent performance; (5) flame retardant with reactivity is prepared by introducing flame retardant elements such as chlorine, bromine, phosphorus and the like into a polyurethane molecular chain, and compared with an additive flame retardant, the fabric has a longer flame retardant property. The comb-shaped polyurethane flame-retardant water-repellent finishing agent has the advantages of cheap and easily-obtained raw materials, simple preparation and processing technology, safety and environmental protection; the fabric has the functions of flame retardance and water repellency, and the flame retardance and the water repellency are not influenced mutually.
Detailed Description
the method of the present invention is illustrated by the following specific examples, but the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included within the scope of the present invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
example 1
formula of comb-shaped polyurethane flame-retardant water-repellent finishing agent
firstly, preparation
The comb-shaped polyurethane flame-retardant water-repellent finishing agent is prepared from the raw materials in the formula according to the preparation method of the invention.
The preparation method comprises the following steps: diluting and dissolving 1 part of dibutyltin dilaurate catalyst by two parts of butanone, and uniformly stirring to obtain a catalyst solution; under the protection of inert gas nitrogen, 18mol of toluene diisocyanate, 6mol of trimethylolpropane and 2ml of catalyst solution react at 60 ℃ for 1.5h to prepare a-NCO group terminated prepolymer I, 6mol of octadecanol is added, and the reaction is carried out at 70 ℃ for 1h to carry out branching reaction to prepare a prepolymer II containing two-NCO groups; uniformly mixing 82mol of toluene diisocyanate, prepolymer II and 36mol of polyether glycol 1000 (dehydrated at 120 ℃ for 2 hours before use), reacting at 80 ℃ for 2 hours (-NCO group content reaches a set value), cooling to 30 ℃, adding 21mol of N-methyldiethanolamine, and reacting at 45 ℃ for 1.5 hours (-NCO group content reaches a set value), thus obtaining prepolymer III; and (3) uniformly mixing the prepolymer III with 58mol of tribromoethanol, reacting at 60 ℃ for 3h (-NCO group content is zero), cooling to below 40 ℃, adding 21mol of acetic acid for neutralization for 30min, and finally emulsifying in high-speed emulsification equipment at a rotating speed of 2000r/min for 2h to obtain the comb-shaped polyurethane flame-retardant water-repellent finishing agent. Second, application
preparing the prepared comb-shaped polyurethane flame-retardant water repellent finishing agent into 100g/L working solution, and respectively finishing terylene, chinlon and cotton fabrics, wherein the processing process comprises the following steps:
(1) padding treatment: the comb-shaped polyurethane flame-retardant water-repellent finishing agent working solution prepared by the embodiment is used for treating three fabrics in a one-dipping one-rolling mode, and the liquid carrying rate is about 70%.
(2) Heat setting treatment: the fabric padded with the flame-retardant water-repellent finishing agent of the embodiment is subjected to heat setting on a setting machine, wherein the setting temperature is 150 ℃ and the setting time is 90 s. The water repellency is tested according to the AATCC 22-2001 water spraying test method, the flame retardant property is tested according to the GB/T5455-1997 vertical combustion method, and the test results are shown in Table 1.
TABLE 1 flame retardance and Water repellency after finishing of Dacron, Chinlon, and Cotton fabrics
example 2
formula of comb-shaped polyurethane flame-retardant water-repellent finishing agent
Firstly, preparation
The comb-shaped polyurethane flame-retardant water-repellent finishing agent is prepared from the raw materials in the formula according to the preparation method of the invention. The preparation method comprises the following steps: diluting and dissolving 1 part of dibutyltin dilaurate catalyst by two parts of butanone, and uniformly stirring to obtain a catalyst solution; under the protection of inert gas nitrogen, 18mol of isophorone diisocyanate, 6mol of trimethylolpropane and 2ml of catalyst solution react for 1.5h at 60 ℃ to prepare a-NCO group terminated prepolymer I, 6mol of octadecanol is added, and the reaction is carried out for 1h at 70 ℃ for branching reaction to prepare a prepolymer II containing two-NCO groups; uniformly mixing 82mol of isophorone diisocyanate, a prepolymer II and 36mol of polyether glycol 1000 (dehydrated at 120 ℃ for 2h before use), cooling to 30 ℃ when reacting for 2h (-NCO group content reaches a set value) at 80 ℃, then adding 21mol of N-methyldiethanolamine, and reacting for 1.5h (-NCO group content reaches a set value) at 45 ℃ to obtain a prepolymer III; and (3) uniformly mixing the prepolymer III with 58mol of tribromoethanol, reacting at 60 ℃ for 3h (-NCO group content is zero), cooling to below 40 ℃, adding 21mol of acetic acid for neutralization for 30min, and finally emulsifying in high-speed emulsification equipment at a rotating speed of 2000r/min for 2h to obtain the comb-shaped polyurethane flame-retardant water-repellent finishing agent.
Second, application
Preparing the prepared comb-shaped polyurethane flame-retardant water repellent finishing agent into 100g/L working solution, and respectively finishing terylene, chinlon and cotton fabrics, wherein the processing process comprises the following steps:
(1) padding treatment: the comb-shaped polyurethane flame-retardant water-repellent finishing agent working solution prepared by the embodiment is used for treating three fabrics in a one-dipping one-rolling mode, and the liquid carrying rate is about 70%.
(2) heat setting treatment: the fabric padded with the flame-retardant water-repellent finishing agent of the embodiment is subjected to heat setting on a setting machine, wherein the setting temperature is 150 ℃ and the setting time is 90 s. The water repellency is tested according to the AATCC 22-2001 water spraying test method, the flame retardant property is tested according to the GB/T5455-1997 vertical combustion method, and the test results are shown in Table 2.
TABLE 2 flame retardancy and Water repellency after finishing of Dacron, Chinlon, and Cotton fabrics
Example 3
Formula of comb-shaped polyurethane flame-retardant water-repellent finishing agent
Firstly, preparation
The comb-shaped polyurethane flame-retardant water-repellent finishing agent is prepared from the raw materials in the formula according to the preparation method of the invention. The preparation method comprises the following steps: diluting and dissolving 1 part of dibutyltin dilaurate catalyst by two parts of butanone, and uniformly stirring to obtain a catalyst solution; under the protection of inert gas nitrogen, 18mol of toluene diisocyanate, 6mol of trimethylolpropane and 2ml of catalyst solution react at 60 ℃ for 1.5h to prepare a-NCO group terminated prepolymer I, 6mol of octadecanol is added, and the reaction is carried out at 70 ℃ for 1h to carry out branching reaction to prepare a prepolymer II containing two-NCO groups; uniformly mixing 82mol of isophorone diisocyanate, a prepolymer II and 36mol of polyether glycol 1000 (dehydrated at 120 ℃ for 2h before use), cooling to 30 ℃ when reacting for 2h (-NCO group content reaches a set value) at 80 ℃, then adding 21mol of N-methyldiethanolamine, and reacting for 1.5h (-NCO group content reaches a set value) at 45 ℃ to obtain a prepolymer III; and (3) uniformly mixing the prepolymer III with 58mol of tribromoethanol, reacting at 60 ℃ for 3h (-NCO group content is zero), cooling to below 40 ℃, adding 21mol of acetic acid for neutralization for 30min, and finally emulsifying in high-speed emulsification equipment at a rotating speed of 2000r/min for 2h to obtain the comb-shaped polyurethane flame-retardant water-repellent finishing agent. Second, application
preparing the prepared comb-shaped polyurethane flame-retardant water repellent finishing agent into 100g/L working solution, and respectively finishing terylene, chinlon and cotton fabrics, wherein the processing process comprises the following steps:
(1) Padding treatment: the comb-shaped polyurethane flame-retardant water-repellent finishing agent working solution prepared by the embodiment is used for treating three fabrics in a one-dipping one-rolling mode, and the liquid carrying rate is about 70%.
(2) heat setting treatment: the fabric padded with the flame-retardant water-repellent finishing agent of the embodiment is subjected to heat setting on a setting machine, wherein the setting temperature is 150 ℃ and the setting time is 90 s. The water repellency is tested according to the AATCC 22-2001 water spraying test method, the flame retardant property is tested according to the GB/T5455-1997 vertical combustion method, and the test results are shown in Table 3.
TABLE 3 flame retardancy and Water repellency after finishing of Dacron, Chinlon, and Cotton fabrics
Example 4
Formula of comb-shaped polyurethane flame-retardant water-repellent finishing agent
Firstly, preparation
the comb-shaped polyurethane flame-retardant water-repellent finishing agent is prepared from the raw materials in the formula according to the preparation method of the invention. The preparation method comprises the following steps: diluting and dissolving 1 part of dibutyltin dilaurate catalyst by two parts of butanone, and uniformly stirring to obtain a catalyst solution; under the protection of inert gas nitrogen, 24mol of toluene diisocyanate, 6mol of pentaerythritol and 2ml of catalyst solution react at 60 ℃ for 1.5h to prepare a prepolymer I with an end capped by-NCO group, then 12mol of octadecanol is added, and the reaction is carried out at 70 ℃ for 1h to carry out a branching reaction, so as to prepare a prepolymer II with two-NCO groups; uniformly mixing 82mol of isophorone diisocyanate, a prepolymer II and 33mol of polyether glycol 1000 (dehydrated at 120 ℃ for 2h before use), cooling to 30 ℃ when reacting for 2h (-NCO group content reaches a set value) at 80 ℃, then adding 24mol of N-methyldiethanolamine, and reacting for 1.5h (-NCO group content reaches a set value) at 45 ℃ to obtain a prepolymer III; and (3) uniformly mixing the prepolymer III with 58mol of tribromoethanol, reacting at 60 ℃ for 3h (-NCO group content is zero), cooling to below 40 ℃, adding 21mol of acetic acid for neutralization for 30min, and finally emulsifying in high-speed emulsification equipment at a rotating speed of 2000r/min for 2h to obtain the comb-shaped polyurethane flame-retardant water-repellent finishing agent.
Second, application
Preparing the prepared comb-shaped polyurethane flame-retardant water repellent finishing agent into 100g/L working solution, and respectively finishing terylene, chinlon and cotton fabrics, wherein the processing process comprises the following steps:
(1) padding treatment: the comb-shaped polyurethane flame-retardant water-repellent finishing agent working solution prepared by the embodiment is used for treating three fabrics in a one-dipping one-rolling mode, and the liquid carrying rate is about 70%.
(2) heat setting treatment: the fabric padded with the flame-retardant water-repellent finishing agent of the embodiment is subjected to heat setting on a setting machine, wherein the setting temperature is 150 ℃ and the setting time is 90 s. The water repellency is tested according to the AATCC 22-2001 water spraying test method, the flame retardant property is tested according to the GB/T5455-1997 vertical combustion method, and the test results are shown in Table 4.
TABLE 4 flame retardancy and Water repellency after finishing of Dacron, Chinlon, and Cotton fabrics
example 5
formula of comb-shaped polyurethane flame-retardant water-repellent finishing agent
Firstly, preparation
The comb-shaped polyurethane flame-retardant water-repellent finishing agent is prepared from the raw materials in the formula according to the preparation method of the invention.
The preparation method comprises the following steps: diluting and dissolving 1 part of dibutyltin dilaurate catalyst by two parts of butanone, and uniformly stirring to obtain a catalyst solution; under the protection of inert gas nitrogen, 18mol of toluene diisocyanate, 6mol of trimethylolpropane and 2ml of catalyst solution react at 60 ℃ for 1.5h to prepare a-NCO group terminated prepolymer I, 6mol of octadecanol is added, and the reaction is carried out at 70 ℃ for 1h to carry out branching reaction to prepare a prepolymer II containing two-NCO groups; uniformly mixing 82mol of isophorone diisocyanate, a prepolymer II and 36mol of polysiloxane diol 1000 (dehydrated at 120 ℃ for 2h before use), cooling to 30 ℃ when reacting for 2h (-NCO group content reaches a set value) at 80 ℃, then adding 21mol of N-methyldiethanolamine, and reacting for 1.5h (-NCO group content reaches a set value) at 45 ℃ to obtain a prepolymer III; and (3) uniformly mixing the prepolymer III with 58mol of tribromoethanol, reacting at 60 ℃ for 3h (-NCO group content is zero), cooling to below 40 ℃, adding 21mol of acetic acid for neutralization for 30min, and finally emulsifying in high-speed emulsification equipment at a rotating speed of 2000r/min for 2h to obtain the comb-shaped polyurethane flame-retardant water-repellent finishing agent.
Second, application
Preparing the prepared comb-shaped polyurethane flame-retardant water repellent finishing agent into 100g/L working solution, and respectively finishing terylene, chinlon and cotton fabrics, wherein the processing process comprises the following steps:
(1) Padding treatment: the comb-shaped polyurethane flame-retardant water-repellent finishing agent working solution prepared by the embodiment is used for treating three fabrics in a one-dipping one-rolling mode, and the liquid carrying rate is about 70%.
(2) Heat setting treatment: the fabric padded with the flame-retardant water-repellent finishing agent of the embodiment is subjected to heat setting on a setting machine, wherein the setting temperature is 150 ℃ and the setting time is 90 s. The water repellency of the flame retardant is tested according to the AATCC 22-2001 water spraying test method, the flame retardant is tested according to the GB/T5455-1997 vertical combustion method, and the test results are shown in Table 5.
TABLE 5 flame retardancy and Water repellency after finishing of Dacron, Chinlon, and Cotton fabrics
Example 6
Formula of comb-shaped polyurethane flame-retardant water-repellent finishing agent
firstly, preparation
The comb-shaped polyurethane flame-retardant water-repellent finishing agent is prepared from the raw materials in the formula according to the preparation method of the invention. The preparation method comprises the following steps: diluting and dissolving 1 part of dibutyltin dilaurate catalyst by two parts of butanone, and uniformly stirring to obtain a catalyst solution; under the protection of inert gas nitrogen, 18mol of toluene diisocyanate, 6mol of trimethylolpropane and 2ml of catalyst solution react at 60 ℃ for 1.5h to prepare a prepolymer I with an end capped by-NCO groups, 6mol of docosanol is added, and the reaction is carried out at 70 ℃ for 1h to carry out a branching reaction to prepare a prepolymer II with two-NCO groups; uniformly mixing 82mol of isophorone diisocyanate, a prepolymer II and 36mol of polysiloxane diol 1000 (dehydrated at 120 ℃ for 2h before use), cooling to 30 ℃ when reacting for 2h (-NCO group content reaches a set value) at 80 ℃, then adding 21mol of N-methyldiethanolamine, and reacting for 1.5h (-NCO group content reaches a set value) at 45 ℃ to obtain a prepolymer III; and (3) uniformly mixing the prepolymer III with 58mol of tribromoethanol, reacting at 60 ℃ for 3h (-NCO group content is zero), cooling to below 40 ℃, adding 21mol of acetic acid for neutralization for 30min, and finally emulsifying in high-speed emulsification equipment at a rotating speed of 2000r/min for 2h to obtain the comb-shaped polyurethane flame-retardant water-repellent finishing agent.
Second, application
Preparing the prepared comb-shaped polyurethane flame-retardant water repellent finishing agent into 100g/L working solution, and respectively finishing terylene, chinlon and cotton fabrics, wherein the processing process comprises the following steps:
(1) Padding treatment: the comb-shaped polyurethane flame-retardant water-repellent finishing agent working solution prepared by the embodiment is used for treating three fabrics in a one-dipping one-rolling mode, and the liquid carrying rate is about 70%.
(2) Heat setting treatment: the fabric padded with the flame-retardant water-repellent finishing agent of the embodiment is subjected to heat setting on a setting machine, wherein the setting temperature is 150 ℃ and the setting time is 90 s. The water repellency of the flame retardant is tested according to the AATCC 22-2001 water spraying test method, the flame retardant is tested according to the GB/T5455-1997 vertical combustion method, and the test results are shown in Table 6.
TABLE 6 flame retardance and water repellency of finished Dacron, Chinlon, and Cotton fabrics
Example 7
Formula of comb-shaped polyurethane flame-retardant water-repellent finishing agent
Firstly, preparation
The comb-shaped polyurethane flame-retardant water-repellent finishing agent is prepared from the raw materials in the formula according to the preparation method of the invention. The preparation method comprises the following steps: diluting and dissolving 1 part of dibutyltin dilaurate catalyst by two parts of butanone, and uniformly stirring to obtain a catalyst solution; under the protection of inert gas nitrogen, 18mol of toluene diisocyanate, 6mol of trimethylolpropane and 2ml of catalyst solution react at 60 ℃ for 1.5h to prepare a prepolymer I with an end capped by-NCO groups, 6mol of docosanol is added, and the reaction is carried out at 70 ℃ for 1h to carry out a branching reaction to prepare a prepolymer II with two-NCO groups; uniformly mixing 82mol of isophorone diisocyanate, prepolymer II and 36mol of polysiloxane diol 1000 (dehydrated for 2h at 120 ℃ before use), cooling to 30 ℃ when reacting for 2h (-NCO group content reaches a set value) at 80 ℃, then adding 21mol of dimethylolpropionic acid, and reacting for 1.5h (-NCO group content reaches a set value) at 45 ℃ to obtain prepolymer III; and (3) uniformly mixing the prepolymer III with 58mol of tribromoethanol, reacting at 60 ℃ for 3h (-NCO group content is zero), cooling to below 40 ℃, adding 21mol of triethylamine for neutralization for 30min, and finally emulsifying in high-speed emulsification equipment at a rotating speed of 2000r/min for 2h to obtain the comb-shaped polyurethane flame-retardant water-repellent finishing agent.
Second, application
preparing the prepared comb-shaped polyurethane flame-retardant water repellent finishing agent into 100g/L working solution, and respectively finishing terylene, chinlon and cotton fabrics, wherein the processing process comprises the following steps:
(1) padding treatment: the comb-shaped polyurethane flame-retardant water-repellent finishing agent working solution prepared by the embodiment is used for treating three fabrics in a one-dipping one-rolling mode, and the liquid carrying rate is about 70%.
(2) heat setting treatment: the fabric padded with the flame-retardant water-repellent finishing agent of the embodiment is subjected to heat setting on a setting machine, wherein the setting temperature is 150 ℃ and the setting time is 90 s. The water repellency was measured according to AATCC 22-2001 water spray test method, and the flame retardancy was measured according to GB/T5455-1997 vertical combustion method, the experimental results are shown in Table 7.
TABLE 7 flame retardance and Water repellency of finished Dacron, Chinlon, and Cotton fabrics
Example 8
formula of comb-shaped polyurethane flame-retardant water-repellent finishing agent
Firstly, preparation
the comb-shaped polyurethane flame-retardant water-repellent finishing agent is prepared from the raw materials in the formula according to the preparation method of the invention. The preparation method comprises the following steps: diluting and dissolving 1 part of dibutyltin dilaurate catalyst by two parts of butanone, and uniformly stirring to obtain a catalyst solution; under the protection of inert gas nitrogen, 18mol of toluene diisocyanate, 6mol of trimethylolpropane and 2ml of catalyst solution react at 60 ℃ for 1.5h to prepare a prepolymer I with an end capped by-NCO groups, 6mol of docosanol is added, and the reaction is carried out at 70 ℃ for 1h to carry out a branching reaction to prepare a prepolymer II with two-NCO groups; uniformly mixing 82mol of isophorone diisocyanate, a prepolymer II and 36mol of polysiloxane diol 1000 (dehydrated at 120 ℃ for 2h before use), cooling to 30 ℃ when reacting for 2h (-NCO group content reaches a set value) at 80 ℃, then adding 21mol of N-methyldiethanolamine, and reacting for 1.5h (-NCO group content reaches a set value) at 45 ℃ to obtain a prepolymer III; and (3) uniformly mixing the prepolymer III with 58mol of chlorobutanol, reacting at 60 ℃ for 3h (-NCO group content is zero), cooling to below 40 ℃, adding 21mol of acetic acid for neutralization for 30min, and finally emulsifying in high-speed emulsification equipment at a rotating speed of 2000r/min for 2h to obtain the comb-shaped polyurethane flame-retardant water-repellent finishing agent. Second, application
preparing the prepared comb-shaped polyurethane flame-retardant water repellent finishing agent into 100g/L working solution, and respectively finishing terylene, chinlon and cotton fabrics, wherein the processing process comprises the following steps:
(1) Padding treatment: the comb-shaped polyurethane flame-retardant water-repellent finishing agent working solution prepared by the embodiment is used for treating three fabrics in a one-dipping one-rolling mode, and the liquid carrying rate is about 70%.
(2) Heat setting treatment: the fabric padded with the flame-retardant water-repellent finishing agent of the embodiment is subjected to heat setting on a setting machine, wherein the setting temperature is 150 ℃ and the setting time is 90 s. The water repellency was measured according to AATCC 22-2001 water spray test method, and the flame retardancy was measured according to GB/T5455-1997 vertical combustion method, the experimental results are shown in Table 8.
TABLE 8 flame retardancy and Water repellency after finishing of Dacron, Chinlon, and Cotton fabrics
example 9
Formula of comb-shaped polyurethane flame-retardant water-repellent finishing agent
firstly, preparation
The comb-shaped polyurethane flame-retardant water-repellent finishing agent is prepared from the raw materials in the formula according to the preparation method of the invention. The preparation method comprises the following steps: diluting and dissolving 1 part of dibutyltin dilaurate catalyst by two parts of butanone, and uniformly stirring to obtain a catalyst solution; under the protection of inert gas nitrogen, 18mol of toluene diisocyanate, 6mol of trimethylolpropane and 2ml of catalyst solution react at 60 ℃ for 1.5h to prepare a prepolymer I with an end capped by-NCO groups, 6mol of docosanol is added, and the reaction is carried out at 70 ℃ for 1h to carry out a branching reaction to prepare a prepolymer II with two-NCO groups; uniformly mixing 82mol of isophorone diisocyanate, a prepolymer II, 18mol of polysiloxane diol 1000 and 18mol of polyether diol 1000 (dehydrated at 120 ℃ for 2 hours before use), cooling to 30 ℃ when reacting for 2 hours (-NCO group content reaches a set value) at 80 ℃, then adding 21mol of N-methyldiethanolamine, and reacting for 1.5 hours (-NCO group content reaches a set value) at 45 ℃ to obtain a prepolymer III; and (3) uniformly mixing the prepolymer III with 58mol of tribromoethanol, reacting at 60 ℃ for 3h (-NCO group content is zero), cooling to below 40 ℃, adding 21mol of acetic acid for neutralization for 30min, and finally emulsifying in high-speed emulsification equipment at a rotating speed of 2000r/min for 2h to obtain the comb-shaped polyurethane flame-retardant water-repellent finishing agent.
Second, application
preparing the prepared comb-shaped polyurethane flame-retardant water repellent finishing agent into 100g/L working solution, and respectively finishing terylene, chinlon and cotton fabrics, wherein the processing process comprises the following steps:
(1) padding treatment: the comb-shaped polyurethane flame-retardant water-repellent finishing agent working solution prepared by the embodiment is used for treating three fabrics in a one-dipping one-rolling mode, and the liquid carrying rate is about 70%.
(2) Heat setting treatment: the fabric padded with the flame-retardant water-repellent finishing agent of the embodiment is subjected to heat setting on a setting machine, wherein the setting temperature is 150 ℃ and the setting time is 90 s. The water repellency was measured according to AATCC 22-2001 water spray test method, and the flame retardancy was measured according to GB/T5455-1997 vertical combustion method, the experimental results are shown in Table 9.
TABLE 9 flame retardance and Water repellency after finishing of Dacron, Chinlon, and Cotton fabrics
Claims (10)
1. A comb-shaped polyurethane flame-retardant water-repellent finishing agent has a structural general formula shown as formula I:
Wherein:
a is any integer of 10-20;
b is any integer of 5-15;
c is any integer of 10-20;
d is any integer of 1-5;
R1Is a halogen-containing alcohol residue;
R2Is the residue of long-chain fatty alcohol C12-C22 fatty alcohol;
A1is the residue of a diisocyanate which does not contain-NCO groups;
A2Is the residue of a small molecule polyol;
a3 is the residue of a soft segment polyol;
A4Is a residue of a hydrophilic group or segment-containing polyol;
the polyalcohol containing the hydrophilic group or the chain segment is at least one of dihydric alcohol containing a tertiary amine structure, dihydric alcohol containing a carboxylic acid structure, dihydric alcohol containing a sulfonic acid structure and polyethylene glycol;
The halogen-containing alcohol is selected from at least one of chlorobutanol, 2,2, 2-trichloroethanol, chlorobutanol, 1, 3-dichloropropanol, 2, 4-dichlorobenzyl alcohol, 3, 4-dichlorobenzyl alcohol, 2, 6-dichlorobenzyl alcohol, tribromoethanol, 2, 3-dibromo-1-propanol, 1, 3-dibromo-2-propanol and tribromoneopentanol;
The micromolecular polyalcohol is at least one of trimethylolpropane, trimethylolethane, glycerol, hexanetriol and pentaerythritol;
The soft segment polyol is selected from at least one of polyether diol, polyester diol, polycarbonate diol, polycaprolactone diol, polytetrahydrofuran ether diol, polybutylene diol, polybutadiene diol and hydroxyl-terminated polysiloxane.
2. the comb-shaped polyurethane flame-retardant water-repellent finishing agent according to claim 1, characterized in that:
The long-chain fatty alcohol is selected from at least one of dodecanol, tetradecanol, hexadecanol, octadecanol and behenyl alcohol;
the diisocyanate is at least one selected from toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, 1, 12-dodecyl diisocyanate, xylylene diisocyanate and diphenylmethane diisocyanate.
3. A process for preparing a comb-like polyurethane flame-retardant water-repellent finishing agent as claimed in claim 1 or 2, comprising the steps of:
(1) Under the protection of inert gas, reacting diisocyanate with micromolecular polyol to prepare-NCO-terminated prepolymer I; then adding metered long-chain fatty alcohol to carry out a branching reaction to prepare a prepolymer II containing two-NCO end-capped oligomers and having a long paraffin branched chain;
(2) Preparation of polyurethane: uniformly mixing diisocyanate, prepolymer II and soft segment polyol, reacting at 50-100 ℃ for 1-2 h, cooling to 30 ℃, adding polyol containing hydrophilic groups or hydrophilic chain segments, and reacting at 35-60 ℃ for 1-2 h to obtain prepolymer III;
(3) End capping with halogen-containing alcohols: and (3) carrying out end-capping reaction on the prepolymer III and metered halogen-containing alcohol until the-NCO content is zero, then cooling to below 40 ℃, adding a neutralizing agent for neutralization reaction, and finally emulsifying to obtain the comb-shaped polyurethane flame-retardant water-repellent finishing agent.
4. The method of claim 3, wherein:
In step (1), the catalyst is selected from at least one of the following: dibutyltin dilaurate, stannous octoate, potassium carboxylate, and bismuth carboxylate;
Adding the catalyst in the step (1) in the form of solution, wherein the solvent in the solution is a ketone solvent; the ketone solvent is selected from at least one of the following: acetone, butanone, methyl isobutyl ketone, cyclohexanone or diisobutyl ketone; in the catalyst solution, the mass ratio of the catalyst to the ketone solvent is 1: 1-3;
The dosage of the catalyst is 0.02-0.1% of the total mass of all substances in the reaction system.
5. The method of claim 3, wherein:
The molar ratio of the diisocyanate to the micromolecular polyol to the long-chain fatty alcohol in the step (2) is 3-4: 1: 1-2;
the reaction temperature of the reaction for preparing the prepolymer I in the step (2) is 50-100 ℃, and the reaction time is 1-2 h;
The reaction temperature of the branching reaction in the step (2) is 50-100 ℃, and the reaction time is 1-2 h.
6. the method of claim 3, wherein:
The molar ratio of the small molecular polyol in the step (2) to the soft segment polyol in the step (3) is 0.5-1.5: 1;
the molar ratio of-NCO in the diisocyanate in the step (3) to the sum of-OH in the soft segment polyol in the step (3), the hydrophilic group or segment-containing polyol in the step (3) and the small molecule polyol in the step (2) is 1.2-2.0: 1;
the using amount of the polyalcohol containing the hydrophilic group or the hydrophilic chain segment in the step (3) is 5 to 10 percent of the total mass of all substances in the reaction system;
The soft segment polyol in step (3) needs to be dehydrated for 2 hours at 20 ℃ before being used.
7. The method of claim 3, wherein: in the step (3), the molar ratio of the halogen-containing alcohol to unreacted-NCO in the prepolymer III is 1.05-1.3: 1;
The mol ratio of the neutralizing agent in the step (3) to the polyhydric alcohol containing the hydrophilic group or the hydrophilic chain segment in the step (2) is 1.2-2: 1;
The reaction temperature of the end-capping reaction in the step (3) is 50-100 ℃, and the reaction time is 1-4 h;
The reaction temperature of the neutralization reaction in the step (3) is 15-55 ℃, and the reaction time is 0.5-1 h;
the emulsification is carried out in a high-speed emulsification device; the emulsifying rotating speed is as follows: 2000 r/min-5000 r/min; the emulsifying time is 0.5 h-2.5 h.
8. the method of claim 3, wherein: the diisocyanate is selected from at least one of toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, 1, 12-dodecyl diisocyanate, xylylene diisocyanate and diphenylmethane diisocyanate;
The small molecular polyol is at least one selected from trimethylolpropane, trimethylolethane, glycerol, hexanetriol and pentaerythritol;
The long-chain fatty alcohol is selected from at least one of dodecanol, tetradecanol, hexadecanol, octadecanol and behenyl alcohol;
The soft segment polyol is selected from at least one of polyether diol, polyester diol, polycarbonate diol, polycaprolactone diol, polytetrahydrofuran ether diol, polybutylene diol, polybutadiene diol and hydroxyl-terminated polysiloxane;
The polyalcohol containing the hydrophilic group or the chain segment is selected from at least one of dihydric alcohol containing a tertiary amine structure, dihydric alcohol containing a carboxylic acid structure, dihydric alcohol containing a sulfonic acid structure and polyethylene glycol;
the halogen-containing alcohol is selected from at least one of chlorobutanol, 2,2, 2-trichloroethanol, chlorobutanol, 1, 3-dichloropropanol, 2, 4-dichlorobenzyl alcohol, 3, 4-dichlorobenzyl alcohol, 2, 6-dichlorobenzyl alcohol, tribromoethanol, 2, 3-dibromo-1-propanol, 1, 3-dibromo-2-propanol and tribromoneopentanol.
9. A method for finishing a fabric by using the comb-shaped polyurethane flame-retardant water-repellent finishing agent as defined in claim 1 or 2, which comprises the following steps: preparing the comb-shaped polyurethane flame-retardant water-repellent finishing agent treated fabric of claim 1 or 2 into working solution with the concentration of 50 g/L-150 g/L, and treating the fabric in a one-dip one-roll mode; and then carrying out heat setting on the padded fabric.
10. The method of claim 9, wherein:
The liquid carrying rate of the first soaking and the first rolling is 50 to 80 percent;
The heat setting temperature is 120-160 ℃, and the setting time is 60-120 s;
the fabric is polyester, chinlon or cotton fabric.
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|---|---|---|---|---|
| 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 |
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| CN115322530B (en) * | 2022-08-10 | 2023-07-11 | 江阴市龙山合成材料有限公司 | Halogen-free flame-retardant enhanced PBT (polybutylene terephthalate) and processing technology thereof |
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