CN105484042A - After-chain-extension inflaming retarding waterborne polyurethane fabric coating with high resistance to static water pressure - Google Patents
After-chain-extension inflaming retarding waterborne polyurethane fabric coating with high resistance to static water pressure Download PDFInfo
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- CN105484042A CN105484042A CN201610012662.XA CN201610012662A CN105484042A CN 105484042 A CN105484042 A CN 105484042A CN 201610012662 A CN201610012662 A CN 201610012662A CN 105484042 A CN105484042 A CN 105484042A
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- D—TEXTILES; PAPER
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- 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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- C08G18/30—Low-molecular-weight compounds
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- C08G18/40—High-molecular-weight compounds
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- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
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- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
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- C08G18/6618—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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Abstract
The invention relates to an after-chain-extension inflaming retarding waterborne polyurethane fabric coating with high resistance to static water pressure and belongs to the technical field of textile chemical engineering. By using a macromolecule cross-linking agent and a phosphorus-containing diamine fire retardant to serve as the after-chain-extension agent, the after-chain-extension inflaming retarding waterborne polyurethane fabric coating with high resistance to static water pressure is prepared. When the prepared waterborne polyurethane is applied to polyester low elastic filament fabric, high resistance to static water pressure is realized (the static water pressure resistance value is between 20 kPa and 100 kPa), and flame retardancy is realized to a certain extent and can meet the requirement of the B1 grade of GB/T5455-1997 textile combustion performance normal beam testing. Furthermore, emulsion storage stability is high, the comprehensive performance of the coating is excellent, and when the coating is applied to textile finishing, the coating is transparent, good in hand feeling, high in cohesiveness, free of toxicity, and environmentally friendly.
Description
Technical field
The present invention relates to a kind of rear fire-retardant high hydrostatic pressure resistance Waterborne Polyurethane Fabric Coatings of chain extension, belong to technical field of textile chemical engineering.
Background technology
Aqueous polyurethane refers to that polyurethane is dissolved in water or is scattered in a kind of polyaminoester emulsion formed in water.It take water as decentralized medium, there is the advantages such as volatile organic content is low, film-forming temperature is low, ABRASION RESISTANCE is good, strong adhesion, production cost are low, pollution-free, therefore its research and production receives the extensive attention of countries in the world, widely applied in fields such as leather finishing agent, adhesive, coating, printing and dyeing at present, be there is good development prospect.But the textile coating agent prepared by aqueous polyurethane also exists some defects at aspect of performance, as not good in resistance to hydrostatic pressure ability, flame retardant effect, poor solvent resistance, not resistance to wet rubbing etc., can not meet the application requirement that the mankind are growing.Therefore, overcoming these defects, is the direction of various countries researcher effort in recent years.
In order to overcome the deficiency of above-mentioned aqueous polyurethane, improve by rear chain extension technology.In the production process of aqueous polyurethane, introduce amine after general emulsification and carry out chain extension and be rear chain extension.After utilizing, chain extension technology can improve its average molecular mass for the aqueous polyurethane of linear structure on the one hand, and effectively can improve its crosslink density for the aqueous polyurethane of cross-linking system, the urea bond structure of strong polarity can be introduced on the other hand, and then its performance can be made to be improved.The phosphorous Diamines fire retardant selected is not only using the phosphorus oxygen double bond as acid source, as the pentaerythrite construction unit in charcoal source with include same a part in as the amino of source of the gas, make it have more effective " inherent flame retardant " action effect; And it has reactive group-amino, can participate in rear chain extending reaction, effectively can improve the crosslink density etc. of cross-linking system aqueous polyurethane as rear chain extender, and then the performance such as the resistance to hydrostatic pressure improving aqueous polyurethane.
At present, in order to improve the resistance to hydrostatic pressure performance of aqueous polyurethane, scientific research personnel has dropped into certain experimental study.As Tian Tao etc. adopts self-emulsification to synthesize fabric use polyurethane, when R value is 1.4, emulsion property is stablized, and resistance to hydrostatic pressure value reaches 6kPa.The preparation method of publication number a kind of high hydrostatic pressure resistance anion aqueous polyurethane textile coating agent that has been the patent disclosure of CN102418274A, this polyurethane loomage coating agent is under the effect of emulsifying agent neopelex, adopt outer emulsion process to be prepared from.This kind of method needs additional emulsifying agent easily to cause Waterborne Polyurethane Fabric Coatings to store instability, affects its application performance (as feel, mechanical property etc.); And because this polyurethane loomage coating agent is linear structure, also there is larger problem in the lasting maintenance of its resistance to hydrostatic pressure.The waterborne polyurethane coatings for fabrics research that the people such as Li Haibei announces, prepared have waterborne polyurethane coatings for fabrics although have employed interior crosslinking technological, resistance to hydrostatic pressure is up to 21.6kPa.
In recent years, extinguishing waterborn polyurethane can significantly improve the fire resistance of fabric because of it, is also applied in fabric coating more and more.Number of patent application is the patent of 200810172239.1, adopts organophosphor polyalcohol and organosilicon polyol blends preparation feedback type extinguishing waterborn polyurethane.Number of patent application is the patent of 200810204199.4, adopts aqueous polyurethane dispersing liquid and phosphorous nitrogenous fire retardant to prepare flame retardant coating agent in composite mode and prepares flame retardant coating agent in composite mode and be coated on dacron and reach flame retardant effect.The people such as FundaCelebi, first by synthesis Diamines organophosphor halogen-free flame retardants (BPPO), then prepare intrinsically flame retarded rear chain extension extinguishing waterborn polyurethane by amino with isocyanates radical reaction.
Application number be 201510586967.7 patent prepared a kind of high hydrostatic pressure resistance extinguishing waterborn polyurethane textile coating agent by introducing macromolecules cross-linking agent and fire retardant.When it is coated on dacron, by the B1 level in GB/T5455-1997 textile combustion performance test normal beam technique, have certain resistance to hydrostatic pressure effect, resistance to hydrostatic pressure value, within the scope of 10 ~ 23kPa, has possessed good fire-retardant and resistance to hydrostatic pressure double action effect simultaneously.
Summary of the invention
The object of this invention is to provide a kind of rear fire-retardant high hydrostatic pressure resistance Waterborne Polyurethane Fabric Coatings of chain extension, make aqueous polyurethane possess resistance to hydrostatic pressure and fire-retardant two kinds of functions simultaneously, the functional modification of research aqueous polyurethane, with the living needs that the development and people that meet textiles are growing.
The object of the invention is to be achieved through the following technical solutions.
The fire-retardant high hydrostatic pressure resistance Waterborne Polyurethane Fabric Coatings of chain extension after a kind of, concrete preparation process is as follows:
Step one, polyether Glycols or polyester diol and polyether-tribasic alcohol to be dewatered at 100 ~ 120 DEG C; Described polyether Glycols (or polyester diol) is 4:1 ~ 9:1 with the mass ratio of polyether-tribasic alcohol;
Step 2, be cooled to 50 ~ 90 DEG C, under the protection of nitrogen, add solvent dilution, after dilution, add aromatic isocyanate; Until hydroxyl reaction is complete, obtain performed polymer; The isocyano of described aromatic isocyanate and the amount of substance ratio of hydroxyl are 1.2 ~ 3.0;
Step 3, in the performed polymer of step 2 gained, add lipophile chain extender, until the hydroxyl reaction in lipophile chain extender is complete, obtain solution A; The addition of lipophile chain extender is 1 ~ 2% of system gross mass; Described system gross mass refers to the summation of the quality of monomeric polyether dihydroxylic alcohols (or polyester diol), polyether-tribasic alcohol, aromatic isocyanate, lipophile chain extender, hydrophilic chain extender and triethylamine.
Step 4, in the solution A of step 3 gained, add hydrophilic chain extender, until the hydroxyl reaction in hydrophilic chain extender is complete, obtain solution B; The addition of hydrophilic chain extender is 3 ~ 6% of system gross mass;
Step 5, be down to room temperature, in the solution B of step 4 gained, add triethylamine neutralization, after reacting completely, obtain solution C;
The solution C of step 6, whipping step five gained, and add the deionized water emulsification of 0 ~ 10 DEG C, then add phosphorous Diamines fire retardant and carry out rear chain extending reaction, except desolventizing obtains aqueous polyurethane emulsion after reacting completely; Described phosphorous Diamines fire retardant amino with solution C in remain isocyano amount of substance ratio be 0.2 ~ 1.0.
Described in step one, polyether Glycols comprises: polytetrahydrofuran diol (PTMG), polypropylene glycol (PPG) or the mixture of the two; Described polyester diol comprises: polycaprolactone glycol (PCL), polybutylene glyool adipate (PBA) or the mixture of the two;
Described in step one, polyether-tribasic alcohol comprises N330 and N303
Described in step 2, solvent comprises: butanone, acetone or oxolane;
Described in step 2, aromatic isocyanate comprises: liquefied mdi, MDI or TDI;
Described in step 3, lipophile chain extender comprises: BDO, diglycol, TMP or pentaerythrite;
Described in step 4, hydrophilic chain extender comprises: dihydromethyl propionic acid or hydroxy sulfonate;
The amount of substance ratio of triethylamine described in step 5 and hydrophilic chain extender is 1:1;
The time of phosphorous Diamines fire retardant is added for after beginning emulsification 1 ~ 3min described in step 6;
Phosphorous Diamines fire retardant described in step 6 is 3,9-bis-(3-aminophenyl)-2,4,8,10-tetra-oxygen-3,9-hosphospiro [5.5] hendecane-3,9-dioxy;
Beneficial effect
Compared with traditional Waterborne Polyurethane Fabric Coatings, the fire-retardant high hydrostatic pressure resistance Waterborne Polyurethane Fabric Coatings of chain extension after one provided by the invention, when being applied to low elastic polyester filament cloth, not only there is the performance (resistance to hydrostatic pressure value is within the scope of 20 ~ 100kPa) of high hydrostatic pressure resistance, also there is certain flame retardant effect (the B1 level by GB/T5455-1997 textile combustion performance test normal beam technique).And the excellent storage stability of its emulsion, the excellent combination property of glued membrane, after textile finishing, coating transparent, good hand touch, caking property are good, asepsis environment-protecting.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.Scope of the present invention is not limited to this detailed description of the invention.
Embodiment 1
Get polyether Glycols PTMG (48g), polyether-tribasic alcohol N330 (12g) in the container with tetrafluoro paddle, 120 DEG C of vacuum dehydration 1h, be cooled to 70 DEG C, logical nitrogen, installs condensing reflux pipe, add the butanone of 40g, treat temperature stabilization, drip 26.25g liquefied mdi, control rate, about 0.5h adds, remove nitrogen, be warming up to 85 DEG C, reaction 2h.Add 0.97g1,4-butanediol (BDO), reaction 1h.Add 4.59g dihydromethyl propionic acid (DMPA) again and react 2h.Be down to room temperature, add in 3.46g triethylamine (TEA) and obtain performed polymer with 30s; Performed polymer is stirred under the rotating speed of 2300r/min, adds the deionized water that 176g temperature is 0 ~ 10 DEG C, after 1min, add the phosphorous Diamines fire retardant of 7.1g, then stir 19min and obtain emulsion, add 3 defoamers, place a night.Evaporating organic solvent, aqueous polyurethane emulsion is formed.Get emulsion 40g, mass fraction is the 601H thickener of about 2.5%, stirs, and coating arranges.Testing its resistance to hydrostatic pressure mean value is 36872Pa, and by the test of GB/T5455-1997 textile combustion performance test normal beam technique, it is B1 level.
Phosphorous Diamines fire retardant is 3,9-bis-(3-aminophenyl)-2,4,8,10-tetra-oxygen-3,9-hosphospiro [5.5] hendecane-3,9-dioxy;
Preparation method is: with pentaerythrite and diphenylphosphoryl dichloro for intermediate product 2,4,8,10-tetra-oxa--3,9-bis-phospha volution-3,9-dioxy-3,9-hexichol (BPPB) prepared by primary raw materials; Then phosphorus-containing compound 2,4,8,10-tetra-oxa--3,9-bis-phospha volution-3,9-dioxy-3,9-bis-(3-nitrobenzophenone) (BPPN) of method preparation containing two nitros of fuming nitric aicd reduction is adopted; Finally by method of reducing, BPPN is reduced into end product 2,4,8,10-tetra-oxa--3,9-bis-phospha volution-3,9-dioxy-3,9-bis-(3-aminophenyl) (BPPA).
Structural formula is:
Embodiment 2
Polytetrahydrofuran diol (PTMG) (25g), polypropylene glycol (PPG) (25g), polyether-tribasic alcohol N303 (10g) in the container with tetrafluoro paddle, 120 DEG C of vacuum dehydration 40min, be cooled to 60 DEG C, logical nitrogen, installs condensing reflux pipe, add the acetone of about 40g, treat temperature stabilization, drip 18.30gTDI, control rate, about 0.5h adds, remove nitrogen, be warming up to 75 DEG C, reaction 2h.Add 1.14g diglycol, reaction 1h.Add 4.59g dihydromethyl propionic acid (DMPA) again and react 2h.Be down to room temperature, add in 3.46g triethylamine (TEA) and 30s, performed polymer is stirred under the rotating speed of 2500r/min, add the deionized water that 180g temperature is 0 ~ 10 DEG C, the phosphorous Diamines fire retardant of 5.1g is added after 3min, stir 15min again and obtain emulsion, add 3 defoamers, place a night.Evaporating organic solvent, aqueous polyurethane emulsion is formed.Get emulsion 40g, mass fraction is the 601H thickener of about 2.5%, stirs, and coating arranges.Testing its resistance to hydrostatic pressure mean value is 28979Pa, and by the test of GB/T5455-1997 textile combustion performance test normal beam technique, it is B1 level.
Embodiment 3
Get polycaprolactone glycol (PCL) (45g), polyether-tribasic alcohol N303 (15g) in the container with tetrafluoro paddle, 100 DEG C of vacuum dehydration 1.5h, be cooled to 60 DEG C, logical nitrogen, installs condensing reflux pipe, add the acetone of about 40g, treat temperature stabilization, add 26.25gMDI, control rate, about 0.5h adds, remove nitrogen, be warming up to 80 DEG C, reaction 2h.Add 0.97g1,4-butanediol (BDO), reaction 40min.Add 4.59g dihydromethyl propionic acid (DMPA) again and react 2h.Be down to room temperature, add in 3.46g triethylamine (TEA) and 30s, performed polymer is stirred under the rotating speed of 2400r/min, add the deionized water that 180g temperature is 0 ~ 10 DEG C, the phosphorous Diamines fire retardant of 9.3g is added after 1min, stir 18min again and obtain emulsion, add 3 defoamers, place a night.Evaporating organic solvent, aqueous polyurethane emulsion is formed.Get emulsion 40g, mass fraction is the 601H thickener of about 2.5%, stirs, and coating arranges.Testing its resistance to hydrostatic pressure mean value is 98197Pa, and by the test of GB/T5455-1997 textile combustion performance test normal beam technique, it is B1 level.
Embodiment 4
Get polycaprolactone glycol (PCL) (30g), polybutylene glyool adipate (PBA) (20g), polyether-tribasic alcohol N330 (10g) in the container with tetrafluoro paddle, 110 DEG C of vacuum dehydration 1h, be cooled to 80 DEG C, logical nitrogen, installs condensing reflux pipe, add the oxolane of about 40g, treat temperature stabilization, drip 26.25g liquefied mdi, control rate, about 0.5h adds, remove nitrogen, be warming up to 83 DEG C, reaction 2h.Add 0.73g pentaerythrite, reaction 30min.Add 4.59g dihydromethyl propionic acid (DMPA) again and react 2h.Be down to room temperature, add in 3.46g triethylamine (TEA) and 30s, performed polymer is stirred under the rotating speed of 2500r/min, add the deionized water that 180g temperature is 0 ~ 10 DEG C, the phosphorous Diamines fire retardant of 6.5g is added after 3min, stir 15min again and obtain emulsion, add 3 defoamers, place a night.Evaporating organic solvent, aqueous polyurethane emulsion is formed.Get emulsion 40g, mass fraction is the 601H thickener of about 2.5%, stirs, and coating arranges.Testing its resistance to hydrostatic pressure mean value is 78926Pa, and by the test of GB/T5455-1997 textile combustion performance test normal beam technique, it is B1 level.
Claims (10)
1. the fire-retardant high hydrostatic pressure resistance Waterborne Polyurethane Fabric Coatings of chain extension after, is characterized in that: concrete preparation process is as follows:
Step one, polyether Glycols or polyester diol and polyether-tribasic alcohol to be dewatered at 100 ~ 120 DEG C; The mass ratio of described polyether Glycols or polyester diol and polyether-tribasic alcohol is 4:1 ~ 9:1;
Step 2, be cooled to 50 ~ 90 DEG C, under the protection of nitrogen, add solvent dilution, after dilution, add aromatic isocyanate; Until hydroxyl reaction is complete, obtain performed polymer; The isocyano of described aromatic isocyanate and the amount of substance ratio of hydroxyl are 1.2 ~ 3.0;
Step 3, in the performed polymer of step 2 gained, add lipophile chain extender, until the hydroxyl reaction in lipophile chain extender is complete, obtain solution A; The addition of lipophile chain extender is 1 ~ 2% of system gross mass; Described system gross mass refers to the summation of the quality of monomeric polyether dihydroxylic alcohols or polyester diol, polyether-tribasic alcohol, aromatic isocyanate, lipophile chain extender, hydrophilic chain extender and triethylamine;
Step 4, in the solution A of step 3 gained, add hydrophilic chain extender, until the hydroxyl reaction in hydrophilic chain extender is complete, obtain solution B; The addition of hydrophilic chain extender is 3 ~ 6% of system gross mass;
Step 5, be down to room temperature, in the solution B of step 4 gained, add triethylamine neutralization, after reacting completely, obtain solution C;
The solution C of step 6, whipping step five gained, and add the deionized water emulsification of 0 ~ 10 DEG C, then add phosphorous Diamines fire retardant and carry out rear chain extending reaction, except desolventizing obtains aqueous polyurethane emulsion after reacting completely; Described phosphorous Diamines fire retardant amino with solution C in remain isocyano amount of substance ratio be 0.2 ~ 1.0.
2. a kind of rear fire-retardant high hydrostatic pressure resistance Waterborne Polyurethane Fabric Coatings of chain extension as claimed in claim 1, is characterized in that: described in step one, polyether Glycols comprises: polytetrahydrofuran diol, polypropylene glycol or the mixture of the two; Described polyester diol comprises: polycaprolactone glycol, polybutylene glyool adipate or the mixture of the two.
3. a kind of rear fire-retardant high hydrostatic pressure resistance Waterborne Polyurethane Fabric Coatings of chain extension as claimed in claim 1, is characterized in that: described in step one, polyether-tribasic alcohol comprises N330 and N303.
4. a kind of rear fire-retardant high hydrostatic pressure resistance Waterborne Polyurethane Fabric Coatings of chain extension as claimed in claim 1, is characterized in that: described in step 2, solvent comprises: butanone, acetone or oxolane.
5. a kind of rear fire-retardant high hydrostatic pressure resistance Waterborne Polyurethane Fabric Coatings of chain extension as claimed in claim 1, is characterized in that: described in step 2, aromatic isocyanate comprises: liquefied mdi, MDI or TDI.
6. a kind of rear fire-retardant high hydrostatic pressure resistance Waterborne Polyurethane Fabric Coatings of chain extension as claimed in claim 1, is characterized in that: described in step 3, lipophile chain extender comprises: BDO, diglycol, TMP or pentaerythrite.
7. a kind of rear fire-retardant high hydrostatic pressure resistance Waterborne Polyurethane Fabric Coatings of chain extension as claimed in claim 1, is characterized in that: described in step 4, hydrophilic chain extender comprises: dihydromethyl propionic acid or hydroxy sulfonate.
8. a kind of rear fire-retardant high hydrostatic pressure resistance Waterborne Polyurethane Fabric Coatings of chain extension as claimed in claim 1, is characterized in that: the amount of substance ratio of triethylamine described in step 5 and hydrophilic chain extender is 1:1.
9. a kind of rear fire-retardant high hydrostatic pressure resistance Waterborne Polyurethane Fabric Coatings of chain extension as claimed in claim 1, is characterized in that: add the time of phosphorous Diamines fire retardant described in step 6 for after beginning emulsification 1 ~ 3min.
10. a kind of rear fire-retardant high hydrostatic pressure resistance Waterborne Polyurethane Fabric Coatings of chain extension as claimed in claim 1, it is characterized in that: described in step 6, phosphorous Diamines fire retardant is 3,9-bis-(3-aminophenyl)-2,4,8,10-tetra-oxygen-3,9-hosphospiro [5.5] hendecane-3,9-dioxy.
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