CN102226314A - Environmentally-friendly halogen-free reaction type soft and hard segment co-modified flame retardant waterborne polyurethane fabric coating agent and preparation method thereof - Google Patents
Environmentally-friendly halogen-free reaction type soft and hard segment co-modified flame retardant waterborne polyurethane fabric coating agent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an environmentally-friendly halogen-free reaction type soft and hard segment co-modified flame retardant waterborne polyurethane fabric coating agent and a preparation method thereof and belongs to the technical field of light industry. The method comprises the following steps: adding diisocyanate, non-flame retardant polyol, reaction type organic phosphorus flame retardant polyol, reaction type phosphorus-nitrogen system flame retardant polyol and a hydrophilic chain extender into a reaction kettle for reaction while stirring in the presence of N2, thus obtaining a prepolymer; cooling, and then utilizing a solvent to regulate the viscosity of the system; and adding the prepolymer a water solution containing a neutralizing agent, neutralizing, and removing the solvent, thus obtaining a target product. The synthesized inherent flame retardant waterborne polyurethane fabric coating agent has the advantages of environmental friendliness, no toxicity, low smoke, phosphorus-nitrogen synergistic flame retardant effect and significant flame retardant effect; after the coating agent is adopted for performing after-finishing on a fabric, a coating is transparent, the color change of the fabric is less, the fabric is not sticky, the hand feeling of the fabric is not affected, the fabric is resistant to soaping, and the fabric can simultaneously pass the B1 level in a GB/T5455-1997 textiles-burning behavior-vertical method.
Description
Technical field
What the present invention relates to is environment friendly non-halogen reacting soft or hard section modified flame-retardant aqueous polyurethane textile coating agent and preparation method thereof altogether, belongs to the light industry technical field.
Background technology
Aqueous polyurethane is mainly used in fabric, leather, construction material or the like, and these materials all are combustible material, generally all requires to carry out flame treatment.Aqueous polyurethane is a medium with water, has that nontoxic, environmental protection, execution conditions are good, production and application safety, a advantage that cost is low, helps the production of colored coating product, and coating hydrophilic is good.Chinese patent application number is the patent of 200510122057.X, it with consumption fire-retardant monomer dibromoneopentyl glycol adding system before polymerization of 15%, make to have fire-retardant halogen atom bromine in the polyurethane macromolecular chain that is generated, prepare the aqueous polyurethane that has from fire resistance.Number of patent application is 200410025154.2 patent, and adopting the polyalcohol that contains phosphorus, chlorine, bromine atoms in the structure simultaneously is flame-retardant composition, and it is synthesized in the aqueous polyurethane, makes case type extinguishing waterborn polyurethane.The patent No. is 200510030113.7 patent, adopt phosphorus antimony chlorine ternary phosphoric acid ester polyether Glycols, or the mixture of phosphoric acid ester polyether Glycols and dibromoneopentyl glycol, or the mixture of phosphoric acid ester polyether Glycols and chloro polyether polyol is flame-retardant composition, makes reacting fire-retardant aqueous polyurethane.The used flame-retardant composition of these patents is halogen or contains halogen, generates more cigarette, corrosive gas and toxic gas when burning, can work the mischief to environment and human body, does not reach the environmental requirement of Halogen.Along with environmental requirement is more and more higher, the non-halogen more and more important position that demonstrates of fire retardant.Therefore developing the environment friendly halogen-free fireproof aqueous polyurethane is that relevant industry institute is very expected.Number of patent application is 200810172238.7 patent, adopts organophosphor polyalcohol and oh type two piperazine mixtures to prepare non-halogen reacting phosphorus one phosphorus-nitrogen coordinated fire-retardant aqueous polyurethane; Number of patent application is 200810172239.1 patent, adopts organophosphor polyalcohol and organosilicon polyol blends preparation feedback type extinguishing waterborn polyurethane, has the characteristics of halogen-free environmental.Number of patent application is 200810204199.4 patent, adopts aqueous polyurethane dispersing liquid and phosphorous nitrogenous fire retardant to prepare flame retardant coating in composite mode and starches to be coated in and reach flame retardant effect on the dacron.Though being its combustibility of patent of 200810204199.4, number of patent application reaches national B1 level, but its fire retardant is to be coated on the dacron in composite mode with aqueous polyurethane dispersing liquid, have not water-fast washing, fire retardant consumption shortcoming big, that easily move.
Summary of the invention
The objective of the invention is to overcome in the prior art preparation extinguishing waterborn polyurethane and need add halogen flame retardant, and be attended by poisonous gas, the problem that the amount of being fuming is big provides environment friendly non-halogen reacting soft or hard section modified flame-retardant aqueous polyurethane textile coating agent and preparation method thereof altogether.
The objective of the invention is to be achieved through the following technical solutions.
Environment friendly non-halogen reacting soft or hard section of the present invention is modified flame-retardant aqueous polyurethane textile coating agent altogether, and in the gross mass of polyurethane loomage coating agent, the mass percent of each component is:
Described vulcabond is hexa-methylene two isocyanic acid HDI, 2,6-vulcabond methyl caproate LDI, isophorone diisocyanate IPDI, toluene di-isocyanate(TDI) TDI, methyl diphenylene diisocyanate MDI, xylylene diisocyanate XDI, naphthalene-1,5-vulcabond NDI, 4,4 '-methylene-dicyclohexyl vulcabond H
12MDI, 1,12-dodecyl vulcabond C
12The mixture of any one or a few among the DDI;
Described non-flame-proof polyol is any one or a few the mixture in polyester diol, polyether polyol, polybutene glycol, polybutadiene diol, PCDL, acrylate polyalcohol, polycaprolactone glycol, the PTMG;
The structural formula of described response type organophosphor flame-proof polyol is as the formula (1):
R in the formula
1Alkylidene or alkylene for C1～C4; R
2Alkyl, alkylene or aryl for C1～C6; R
3Alkylidene, alkylene or aryl for C1～C6; R
4Alkyl, alkylene or aryl for C1～C6; R
5Alkylidene or alkylene for C1～C4; K is 1,2,3 or 4;
The structural formula that described response type phosphorus-nitrogen is flame-proof polyol is as the formula (2):
R in the formula
1Alkyl, alkylene or aryl for C1～C4; R
2Alkyl, alkylene or aryl for C1～C4; R
3Alkylidene or aryl for C1～C5; R
4Alkylidene or alkylene for C1～C4; R
5Alkylidene or alkylene for C1～C4.
The mixture of any one or a few in the dihydroxylic alcohols that described hydrophilic chain extender is the dihydroxylic alcohols that contains carboxyl structure, contain the sulfonic group structure.
Described neutralizer is any one or a few the mixture in tri-n-butylamine, triethylamine, NaOH, the potassium hydroxide.
Environment friendly non-halogen reacting soft or hard section of the present invention is the preparation method of modified flame-retardant aqueous polyurethane textile coating agent altogether, and its concrete steps are:
1) at N
2Protection, stirring down, is that flame-proof polyol and hydrophilic chain extender join reaction kettle for reaction 2～5h with vulcabond, non-flame-proof polyol, response type organophosphor flame-proof polyol, response type phosphorus-nitrogen in the time of 60～95 ℃, obtains prepolymer;
2) prepolymer that obtains in the step 1) is cooled to below 50 ℃ or 50 ℃, use the solvent adjustment system viscosity then, then prepolymer is joined in the aqueous solution that contains neutralizer, in emulsifying device, carry out in the emulsification and more than the 3min, rotary evaporation removes to desolvate and promptly gets target product again.
Step 2) solvent described in is any one or a few the mixture in acetone, butanone, toluene, dimethylbenzene, ethyl acetate, butyl acetate, the oxolane;
The concentration of the aqueous solution of the neutralizer step 2) is 2%～10%.
Beneficial effect
Soft section fire retardant that contains the phosphorus ignition-proof element in the molecular structure of the present invention, hard section contains the fire retardant of phosphorus, nitrogen ignition-proof element, and these two kinds of fire retardants all contain terminal hydroxy group, are response type; With this organophosphor flame-proof polyol, phosphorus-nitrogen is that flame-proof polyol and isocyanates radical reaction are introduced ignition-proof element in the polyurethane structural, synthesize intrinsically flame retarded aqueous polyurethane textile coating agent, have environmental protection, nontoxic, low cigarette, phosphorus-phosphorus-nitrogen coordinated fire-retardant, and the flame retardant effect outstanding feature; After adopting this extinguishing waterborn polyurethane textile coating agent that fabric is carried out the back arrangement, coating is transparent, and the fabric look diminishes, and is tack-free, do not influence fabric feeling, and anti-soaping simultaneously can be by the B1 level in the GB/T5455-1997 textile combustion performance test normal beam technique.
The specific embodiment
Further specify embodiment of the present invention below by embodiment, but embodiment of the present invention are not limited thereto.
Embodiment 1
Environment friendly non-halogen reacting soft or hard section is the prescription such as the table 1 of modified flame-retardant aqueous polyurethane textile coating agent altogether:
Table 1 embodiment 1 environment friendly non-halogen reacting soft or hard section is the prescription of modification sun combustion aqueous polyurethane textile coating agent altogether
| Raw material | Quality/g |
| Isophorone diisocyanate | 65 |
| Polyether polyol (hydroxyl value 110mgKOH/g) | 110 |
| Organophosphor flame-proof polyol (hydroxyl value 100mgKOH/g) | 12 |
| Phosphorus-nitrogen is flame-proof polyol (hydroxyl value 435mgKOH/g) | 8 |
| Dihydromethyl propionic acid | 6 |
| Tri-n-butylamine | 8.2 |
Organophosphor polyol structure formula is:
H-[-OCH
2OP(O)(OCH
3)]
2x-[-OCH
2OP(O)(CH
3)]
x-OCH
2-OH
Response type phosphorus-nitrogen is that flame-proof polyol is: N-methylol, N-hydroxyethylamino ethylphosphonic acid dimethyl esters.
1) adding isophorone diisocyanate, hydroxyl value in the four-hole boiling flask that agitator, reflux condensing tube and thermometer are housed is that the polyether polyol of 110mgKOH/g, the organophosphor polyalcohol that hydroxyl value is 100mgKOH/g, phosphorus-nitrogen that hydroxyl value is 435mgKOH/g are flame-proof polyol and dihydromethyl propionic acid, in 80 ℃ at N
2Protection is reaction 4h down, obtains prepolymer;
2) prepolymer that step 1) is obtained is cooled to 50 ℃, adds 35g acetone and regulates prepolymer viscosity;
3) tri-n-butylamine is dissolved in the deionized water, be made into concentration and be 4% the neutralizer aqueous solution, with step 2) prepolymer join in the neutralizer aqueous solution, with emulsify at a high speed equipment it is carried out the emulsification neutralization immediately, time is 5min, remove acetone with Rotary Evaporators then, obtain response type soft or hard section modified flame-retardant aqueous polyurethane altogether.
The fire resistance test: with terylene ox Feng tent cloth is test fabric, weightening finish 20.7g/m
2Fabrics feel soft after the flame-proof treatment is dry and comfortable, adopts the test of GB/T5455-1997 vertical combustion method to detect, and after flame time is 0s, and the time of glowing is 0s, and char length is 10.8cm.Soap by the AATCC standard and to take out cloth specimen after 5 times, GB/T-5455-1997 vertical combustion method test detection press in oven dry, and after flame time is 0s, and the time of glowing is 0s, and char length is 11.0cm.
Embodiment 2
Environment friendly non-halogen reacting soft or hard section is the prescription such as the table 2 of modified flame-retardant aqueous polyurethane textile coating agent altogether:
Table 2 embodiment 2 environment friendly non-halogen reacting soft or hard sections are the prescription of modification sun combustion aqueous polyurethane textile coating agent altogether
| Raw material | Quality/g |
| 2,6-vulcabond methyl caproate | 63 |
| Polyester polyol (hydroxyl value 105mgKOH/g) | 100 |
| Organophosphor polyalcohol (hydroxyl value 135mgKOH/g) | 15.7 |
| Phosphorus-nitrogen is flame-proof polyol (hydroxyl value 450mgKOH/g) | 8 |
| The dihydroxy half ester | 14 |
| Triethylamine | 3.4 |
Organophosphor polyol structure formula is:
H-[-OCH
2CH
2OP(O)(OCH
3)]
2x-[-OCH
2OP(O)(CH
2CH
3)]
x-OCH
2-OH
Response type phosphorus-nitrogen is that flame-proof polyol is: N-methylol, N-hydroxypropyl aminomethylphosphonic acid diethyl ester.
1) in the four-hole boiling flask that agitator, reflux condensing tube and thermometer are housed, adds 2,6-vulcabond methyl caproate, hydroxyl value are that the polyester polyol of 105mgKOH/g, the organophosphor polyalcohol that hydroxyl value is 135mgKOH/g, phosphorus-nitrogen that hydroxyl value is 450mgKOH/g are flame-proof polyol and dihydroxy half ester, in 70 ℃ at N
2Protection is reaction 5h down, obtains prepolymer;
2) prepolymer that step 1) is obtained is cooled to 50 ℃, adds the 30g butanone and regulates prepolymer viscosity;
3) triethylamine is dissolved in the deionized water, be made into concentration and be 4% the neutralizer aqueous solution, with step 2) prepolymer join in the neutralizer aqueous solution, neutralize to wherein carrying out emulsification with emulsify at a high speed equipment immediately, time is 5min, remove butanone with Rotary Evaporators then, obtain response type soft or hard section modified flame-retardant aqueous polyurethane altogether.
The fire resistance test: with terylene ox Feng tent cloth is test fabric, weightening finish 21.4g/m
2Fabrics feel soft after the flame-proof treatment is dry and comfortable, adopts the test of GB/T5455-1997 vertical combustion method to detect, and after flame time is 0s, and the time of glowing is 0s, and char length is 10.5cm.Soap by the AATCC standard and to take out cloth specimen after 5 times, GB/T-5455-1997 vertical combustion method test detection press in oven dry, and after flame time is 0s, and the time of glowing is 0s, and char length is 10.6cm.
Embodiment 3
Environment friendly non-halogen reacting soft or hard section is the prescription such as the table 3 of modified flame-retardant aqueous polyurethane textile coating agent altogether:
Table 3 embodiment 3 environment friendly non-halogen reacting soft or hard sections are the prescription of modified flame-retardant aqueous polyurethane textile coating agent altogether
| Raw material | Quality/g |
| Hexamethylene diisocyanate | 50 |
| Polyester polyol (hydroxyl value 100mgKOH/g) | 90 |
| Organophosphor polyalcohol (hydroxyl value 110mgKOH/g) | 30.2 |
| Phosphorus-nitrogen is flame-proof polyol (hydroxyl value 410mgKOH/g) | 40 |
| Dihydromethyl propionic acid | 12 |
| Triethylamine | 9.6 |
Organophosphor polyol structure formula is:
H-[-OCH
2CH
2OP(O)(OCH
3)]
x-[-OCH
2OP(O)(CH
3)]
x-OCH
2CH
2-OH
Response type phosphorus-nitrogen is that flame-proof polyol is: two (methylol) amino-ethyl dimethyl phosphonate
1) adding hexamethylene diisocyanate, hydroxyl value in the four-hole boiling flask that agitator, reflux condensing tube and thermometer are housed is that the polyester polyol of 100mgKOH/g, the organophosphor polyalcohol that hydroxyl value is 110mgKOH/g, phosphorus-nitrogen that hydroxyl value is 410mgKOH/g are flame-proof polyol and dihydromethyl propionic acid, in 75 ℃ at N
2Protection reaction 5h down obtains prepolymer;
2) prepolymer that step 1) is obtained is cooled to 50 ℃, adds 28g acetone and regulates prepolymer viscosity;
3) triethylamine is dissolved in the deionized water, be made into concentration and be 5% the neutralizer aqueous solution, with step 2) prepolymer join in the neutralizer aqueous solution, neutralize to wherein carrying out emulsification with emulsify at a high speed equipment immediately, time is 5min, remove acetone with Rotary Evaporators then, obtain response type soft or hard section modified flame-retardant aqueous polyurethane altogether.
The fire resistance test: with terylene ox Feng tent cloth is test fabric, weightening finish 21.0g/m
2Fabrics feel soft after the flame-proof treatment is dry and comfortable, adopts the test of GB/T5455-1997 vertical combustion method to detect, and after flame time is 0s, and the time of glowing is 0s, and char length is 10.2cm.Soap by the AATCC standard and to take out cloth specimen after 5 times, GB/T-5455-1997 vertical combustion method test detection press in oven dry, and after flame time is 0s, and the time of glowing is 0s, and char length is 10.4cm.
Embodiment 4
Environment friendly non-halogen reacting soft or hard section is the prescription such as the table 4 of modified flame-retardant aqueous polyurethane textile coating agent altogether:
Table 4 embodiment 4 environment friendly non-halogen reacting soft or hard sections are the prescription of modified flame-retardant aqueous polyurethane textile coating agent altogether
| Raw material | Quality/g |
| Toluene di-isocyanate(TDI) | 62 |
| Polyether polyol (hydroxyl value 100mgKOH/g) | 75 |
| Organophosphor polyalcohol (hydroxyl value 150mgKOH/g) | 35.6 |
| Phosphorus-nitrogen is flame-proof polyol (hydroxyl value 450mgKOH/g) | 5 |
| Dihydromethyl propionic acid | 15 |
| Triethylamine | 7.7 |
Organophosphor polyol structure formula is:
H-[-OCH
2CH
2OP(O)(OCH
3)]
2x-[-OCH
2CH
2OP(O)(CH
3)]
x-OCH
2CH
2-OH
Response type phosphorus-nitrogen is that flame-proof polyol is: two (ethoxy) aminomethylphosphonic acid diethylester
1) adding toluene di-isocyanate(TDI), hydroxyl value in the four-hole boiling flask that agitator, reflux condensing tube and thermometer are housed is that the polyether polyol of 100mgKOH/g, the organophosphor polyalcohol that hydroxyl value is 150mgKOH/g, phosphorus-nitrogen that hydroxyl value is 450mgKOH/g are flame-proof polyol and dihydromethyl propionic acid, in 75 ℃ at N
2Protection reaction 4h down obtains prepolymer;
2) prepolymer that step 1) is obtained is cooled to 50 ℃, adds 35g acetone and regulates prepolymer viscosity;
3) triethylamine is dissolved in the deionized water, be made into concentration and be 5% the neutralizer aqueous solution, with step 2) prepolymer join in the neutralizer aqueous solution, neutralize to wherein carrying out emulsification with emulsify at a high speed equipment immediately, time is 5min, remove acetone with Rotary Evaporators then, obtain response type soft or hard section modified flame-retardant aqueous polyurethane altogether.
The fire resistance test: with terylene ox Feng tent cloth is test fabric, weightening finish 21.0g/m
2Fabrics feel soft after the flame-proof treatment is dry and comfortable, adopts the test of GB/T5455-1997 vertical combustion method to detect, and after flame time is 0s, and the time of glowing is 0s, and char length is 10.5cm.Soap by the AATCC standard and to take out cloth specimen after 5 times, GB/T-5455-1997 vertical combustion method test detection press in oven dry, and after flame time is 0s, and the time of glowing is 0s, and char length is 10.7cm.
Embodiment 5
Environment friendly non-halogen reacting soft or hard section is the prescription such as the table 5 of modified flame-retardant aqueous polyurethane textile coating agent altogether:
Table 5 embodiment 5 environment friendly non-halogen reacting soft or hard sections are the prescription of modified flame-retardant aqueous polyurethane textile coating agent altogether
| Raw material | Quality/g |
| Methyl diphenylene diisocyanate | 71 |
| Polyester polyol (hydroxyl value 110mgKOH/g) | 50 |
| Organophosphor polyalcohol (hydroxyl value 180mgKOH/g) | 60 |
| Phosphorus-nitrogen is flame-proof polyol (hydroxyl value 500mgKOH/g) | 10 |
| Dihydromethyl propionic acid | 8 |
| Tri-n-butylamine | 11.5 |
Organophosphor polyol structure formula is:
H-[-OCH
2CH
2OP(O)(OCH
3)]
3x-[-OCH
2CH
2OP(O)(CH
3)]
x-OCH
2CH
2-OH
Response type phosphorus-nitrogen is that flame-proof polyol is: two (methylol) aminophenyl diethyl phosphonate
1) adding methyl diphenylene diisocyanate, hydroxyl value in the four-hole boiling flask that agitator, reflux condensing tube and thermometer are housed is that the polyester polyol of 110mgKOH/g, the organophosphor polyalcohol that hydroxyl value is 180mgKOH/g, phosphorus-nitrogen that hydroxyl value is 500mgKOH/g are flame-proof polyol and dihydromethyl propionic acid, in 75 ℃ at N
2Protection reaction 5h down obtains prepolymer;
2) prepolymer that step 1) is obtained is cooled to 50 ℃, adds 35g toluene and regulates prepolymer viscosity;
3) tri-n-butylamine is dissolved in the deionized water, be made into concentration and be 6% the neutralizer aqueous solution, with step 2) prepolymer join in the neutralizer aqueous solution, neutralize to wherein carrying out emulsification with emulsify at a high speed equipment immediately, time is 5min, remove toluene with Rotary Evaporators then, obtain response type soft or hard section modified flame-retardant aqueous polyurethane altogether.
The fire resistance test: with terylene ox Feng tent cloth is test fabric, weightening finish 21.4g/m
2Fabrics feel soft after the flame-proof treatment is dry and comfortable, adopts the test of GB/T5455-1997 vertical combustion method to detect, and after flame time is 0s, and the time of glowing is 0s, and char length is 11.0cm.Soap by the AATCC standard and to take out cloth specimen after 5 times, GB/T-5455-1997 vertical combustion method test detection press in oven dry, and after flame time is 0s, and the time of glowing is 0s, and char length is 11.3cm.
Embodiment 6
Environment friendly non-halogen reacting soft or hard section is the prescription such as the table 6 of modified flame-retardant aqueous polyurethane textile coating agent altogether:
Table 6 embodiment 6 environment friendly non-halogen reacting soft or hard sections are the prescription of modified flame-retardant aqueous polyurethane textile coating agent altogether
| Raw material | Quality/g |
| Isophorone diisocyanate | 83 |
| Polyester polyol (hydroxyl value 110mgKOH/g) | 60 |
| Organophosphor polyalcohol (hydroxyl value 120mgKOH/g) | 45 |
| Phosphorus-nitrogen is flame-proof polyol (hydroxyl value 450mgKOH/g) | 15 |
| Dihydromethyl propionic acid | 7 |
| Tri-n-butylamine | 10 |
Organophosphor polyol structure formula is:
H-[-OCH
2CH
2OP(O)(OCH
3)]
2x-[-OCH
2CH
2OP(O)(CH
3)]
x-OCH
2CH
2-OH
Response type phosphorus-nitrogen is that flame-proof polyol is: two (ethoxy) aminomethylphosphonic acid diethylester
1) adding isophorone diisocyanate, hydroxyl value in the four-hole boiling flask that agitator, reflux condensing tube and thermometer are housed is that the polyester polyol of 110mgKOH/g, the organophosphor polyalcohol that hydroxyl value is 120mgKOH/g, phosphorus-nitrogen that hydroxyl value is 450mgKOH/g are flame-proof polyol and dihydromethyl propionic acid, in 75 ℃ at N
2Protection reaction 5h down obtains prepolymer;
2) prepolymer that step 1) is obtained is cooled to 50 ℃, adds the 37g butanone and regulates prepolymer viscosity;
3) tri-n-butylamine is dissolved in the deionized water, be made into concentration and be 6% the neutralizer aqueous solution, with step 2) prepolymer join in the neutralizer aqueous solution, neutralize to wherein carrying out emulsification with emulsify at a high speed equipment immediately, time is 5min, remove butanone with Rotary Evaporators then, obtain response type soft or hard section modified flame-retardant aqueous polyurethane altogether.
The fire resistance test: with terylene ox Feng tent cloth is test fabric, weightening finish 22.8g/m
2Fabrics feel soft after the flame-proof treatment is dry and comfortable, adopts the test of GB/T5455-1997 vertical combustion method to detect, and after flame time is 0s, and the time of glowing is 0s, and char length is 10.2cm.Soap by the AATCC standard and to take out cloth specimen after 5 times, GB/T-5455-1997 vertical combustion method test detection press in oven dry, and after flame time is 0s, and the time of glowing is 0s, and char length is 10.3cm.
Embodiment 7
Environment friendly non-halogen reacting soft or hard section is the prescription such as the table 7 of modified flame-retardant aqueous polyurethane textile coating agent altogether:
Table 7 embodiment 7 environment friendly non-halogen reacting soft or hard sections are the prescription of modified flame-retardant aqueous polyurethane textile coating agent altogether
| Raw material | Quality/g |
| 4,4 '-methylene-dicyclohexyl vulcabond | 71 |
| Polyether polyol (hydroxyl value 110mgKOH/g) | 90 |
| Organophosphor polyalcohol (hydroxyl value 165mgKOH/g) | 10.4 |
| Phosphorus-nitrogen is flame-proof polyol (hydroxyl value 465mgKOH/g) | 40 |
| The dihydroxy half ester | 14 |
| Tri-n-butylamine | 5.6 |
Organophosphor polyol structure formula is:
H-[-OCH
2CH
2OP(O)(OCH
2CH
3)]
2x-[-OCH
2CH
2OP(O)(CH
3)]
x-OCH
2CH
2-OH
Response type phosphorus-nitrogen is that flame-proof polyol is: two (ethoxy) aminomethylphosphonic acid dimethyl ester
1) in the four-hole boiling flask that agitator, reflux condensing tube and thermometer are housed, adds 4,4 '-methylene-dicyclohexyl vulcabond, hydroxyl value are that the polyether polyol of 110mgKOH/g, the organophosphor polyalcohol that hydroxyl value is 165mgKOH/g, phosphorus-nitrogen that hydroxyl value is 465mgKOH/g are flame-proof polyol and dihydroxy half ester, in 80 ℃ at N
2Protection reaction 5h down obtains prepolymer;
2) prepolymer that step 1) is obtained is cooled to 50 ℃, adds 40g acetone and regulates prepolymer viscosity;
3) tri-n-butylamine is dissolved in the deionized water, be made into concentration and be 6% the neutralizer aqueous solution, with step 2) prepolymer join in the neutralizer aqueous solution, neutralize to wherein carrying out emulsification with emulsify at a high speed equipment immediately, time is 5min, remove acetone with Rotary Evaporators then, obtain response type soft or hard section modified flame-retardant aqueous polyurethane altogether.
The fire resistance test: with terylene ox Feng tent cloth is test fabric, weightening finish 21.1g/m
2Fabrics feel soft after the flame-proof treatment is dry and comfortable, adopts the test of GB/T5455-1997 vertical combustion method to detect, and after flame time is 0s, and the time of glowing is 0s, and char length is 10.4cm.Soap by the AATCC standard and to take out cloth specimen after 5 times, GB/T-5455-1997 vertical combustion method test detection press in oven dry, and after flame time is 0s, and the time of glowing is 0s, and char length is 10.6cm.
Claims (10)
1. environment friendly non-halogen reacting soft or hard section is total to modified flame-retardant aqueous polyurethane textile coating agent, and it is characterized in that: in the gross mass of polyurethane loomage coating agent, the mass percent of each component is:
2. environment friendly non-halogen reacting soft or hard section according to claim 1 is modified flame-retardant aqueous polyurethane textile coating agent altogether, it is characterized in that: vulcabond is hexa-methylene two isocyanic acid HDI, 2,6-vulcabond methyl caproate LDI, isophorone diisocyanate IPDI, toluene di-isocyanate(TDI) TDI, methyl diphenylene diisocyanate MDI, xylylene diisocyanate XDI, naphthalene-1,5-vulcabond NDI, 4,4 '-methylene-dicyclohexyl vulcabond H
12MDI, 1,12-dodecyl vulcabond C
12The mixture of any one or a few among the DDI.
3. environment friendly non-halogen reacting soft or hard section according to claim 1 is modified flame-retardant aqueous polyurethane textile coating agent altogether, it is characterized in that: non-flame-proof polyol is any one or a few the mixture in polyester diol, polyether polyol, polybutene glycol, polybutadiene diol, PCDL, acrylate polyalcohol, polycaprolactone glycol, the PTMG.
4. environment friendly non-halogen reacting soft or hard section according to claim 1 is modified flame-retardant aqueous polyurethane textile coating agent altogether, it is characterized in that: the structural formula of response type organophosphor flame-proof polyol as the formula (1):
R in the formula
1Alkylidene or alkylene for C1～C4; R
2Alkyl, alkylene or aryl for C1～C6; R
3Alkylidene, alkylene or aryl for C1～C6; R
4Alkyl, alkylene or aryl for C1～C6; R
5Alkylidene or alkylene for C1～C4; K is 1,2,3 or 4.
5. environment friendly non-halogen reacting soft or hard section according to claim 1 is modified flame-retardant aqueous polyurethane textile coating agent altogether, it is characterized in that: response type phosphorus-nitrogen be flame-proof polyol structural formula as the formula (2):
R in the formula
1Alkyl, alkylene or aryl for C1～C4; R
2Alkyl, alkylene or aryl for C1～C4; R
3Alkylidene or aryl for C1～C5; R
4Alkylidene or alkylene for C1～C4; R
5Alkylidene or alkylene for C1～C4.
6. environment friendly non-halogen reacting soft or hard section according to claim 1 is modified flame-retardant aqueous polyurethane textile coating agent altogether, it is characterized in that: the mixture of any one or a few in the dihydroxylic alcohols that hydrophilic chain extender is the dihydroxylic alcohols that contains carboxyl structure, contain the sulfonic group structure.
7. environment friendly non-halogen reacting soft or hard section according to claim 1 is modified flame-retardant aqueous polyurethane textile coating agent altogether, it is characterized in that: neutralizer is any one or a few the mixture in tri-n-butylamine, triethylamine, NaOH, the potassium hydroxide.
8. environment friendly non-halogen reacting soft or hard section is total to the preparation method of modified flame-retardant aqueous polyurethane textile coating agent, it is characterized in that concrete steps are:
1) at N
2Protection, stirring down, is that flame-proof polyol and hydrophilic chain extender join reaction kettle for reaction 2～5h with vulcabond, non-flame-proof polyol, response type organophosphor flame-proof polyol, response type phosphorus-nitrogen in the time of 60～95 ℃, obtains prepolymer;
2) prepolymer that obtains in the step 1) is cooled to below 50 ℃ or 50 ℃, use the solvent adjustment system viscosity then, then prepolymer is joined in the aqueous solution that contains neutralizer, in emulsifying device, carry out in the emulsification and more than the 3min, rotary evaporation removes to desolvate and promptly gets target product again.
9. environment friendly non-halogen reacting soft or hard section according to claim 8 is the preparation method of modified flame-retardant aqueous polyurethane textile coating agent altogether, it is characterized in that: step 2) described in solvent be any one or a few mixture in acetone, butanone, toluene, dimethylbenzene, ethyl acetate, butyl acetate, the oxolane.
10. environment friendly non-halogen reacting soft or hard section according to claim 8 is the preparation method of modified flame-retardant aqueous polyurethane textile coating agent altogether, it is characterized in that: step 2) described in the concentration of the aqueous solution of neutralizer be 2%～10%.
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