CN104047176A - Preparation method of blended emulsion of hyperbranched waterborne polyurethane/compound flame-retardant waterborne polyurethane - Google Patents
Preparation method of blended emulsion of hyperbranched waterborne polyurethane/compound flame-retardant waterborne polyurethane Download PDFInfo
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- CN104047176A CN104047176A CN201410286875.2A CN201410286875A CN104047176A CN 104047176 A CN104047176 A CN 104047176A CN 201410286875 A CN201410286875 A CN 201410286875A CN 104047176 A CN104047176 A CN 104047176A
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Abstract
The invention relates to a preparation method of a blended emulsion of hyperbranched waterborne polyurethane/compound flame-retardant waterborne polyurethane, belonging to the technical field of textile chemical engineering. By virtue of the preparation method, the hyperbranched waterborne polyurethane is added into the compound flame-retardant waterborne polyurethane and is stirred so as to obtain the blended emulsion of hyperbranched waterborne polyurethane/compound flame-retardant waterborne polyurethane at the room temperature. The hyperbranched waterborne polyurethane accounts for 2-15% of the total mass of the system. A coating agent prepared by the emulsion is good in flame-retardant property; meanwhile, by adding a hyperbranched polyurethane emulsion, a blended compound waterborne polyurethane coating agent has maximum tensile strength being 5.2MPa and maximum elongation at break being 751%; the coating agent is applied to a fabric coating agent, so that the coated fabric is good in flame-retardant property and good in hydrostatic pressure resistance reaching up to 14.7KPa, capable of maintaining good flame-retardant property after being subjected to soaping, and reaching the grade B1 in a normal beam method before and after soaping.
Description
Technical field
The preparation method who the present invention relates to hyperbranched aqueous polyurethane/compositional flame-retardant aqueous polyurethane blending emulsion, belongs to technical field of textile chemical engineering.
Background technology
Along with improving constantly that people require Fire-proof Finishing Agents for Textile, flame-retardant modified aqueous polyurethane has become an important kind of functional form aqueous polyurethane.Composite aqueous flame retardant polyurethane, mainly by adding relevant auxiliary agent and special preparation technology, makes aqueous polyurethane emulsion adsorb flame-retardant composition and be coated, thereby obtains stable extinguishing waterborn polyurethane emulsion.In composite aqueous polyurethane, contain a large amount of inorganic and organic fire-retardants, have good fire resistance, preparation method is simple in addition, is the flame-retardant modified usual way of aqueous polyurethane.
Flame retardant polyurethane textile coating agent TF680 is a kind of blend compositional flame-retardant aqueous polyurethane, is one of at present main flame retardant textiles coating agent kind.The people such as Lin Hongsheng have announced the synthetic method of a kind of flame retardant polyurethane WP TF680 and have applied, and result shows that TF680 has good flame retardant effect and has the effects such as waterproof and oilproof.
Dissaving polymer is the large molecule that a class has highly branched structure, because it contains a large amount of outside functional groups, and without features such as winding, amorphisms, aqueous hyperbranched polyurethane can improve aqueous polyurethane emulsion mobility and mechanical property, and being applied in extinguishing waterborn polyurethane is one of hyperbranched aqueous polyurethane developing direction.
Patent CN102924689B has announced a kind of hyperbranched aqueous polyurethane (SWHBPU) emulsion and preparation method thereof.That this emulsion has is stable, viscosity is low, the simple advantage of addition manner, solves hyperbranched aqueous polyurethane stability of emulsion poor, and the problem that viscosity is large, can be used for preparing high solid content aqueous polyurethane emulsion.This hyperbranched aqueous polyurethane coating is when TENSILE STRENGTH improves, and elongation at break also obtains lifting, has solved the problem that when hyperbranched aqueous polyurethane TENSILE STRENGTH improves, elongation at break declines, and can be used for preparing high-performance water-based polyurethane coating.
Patent CN102851987 has announced a kind of terminal hydroxy group sealing hyperbranched aqueous polyurethane (AWHBPU) emulsion and preparation method thereof.Thereby the crosslinked problem of avoiding terminal hydroxy group to bring.That this emulsion has is stable, viscosity is low, the simple advantage of addition manner, solves hyperbranched aqueous polyurethane stability of emulsion poor, and the problem that viscosity is large, can be used for preparing high solid content aqueous polyurethane emulsion.
Aqueous hyperbranched polyurethane can improve mechanical property and the resistance to water of textile coating agent, can also reduce emulsion viscosity, is conducive to further improve the solid content of emulsion.
Summary of the invention
The present invention seeks to, in order to solve existing blend compositional flame-retardant Aqueous Polyurethane Coating Agent mechanical property and the poor problem of water resistance, provides a kind of hyperbranched aqueous polyurethane/compositional flame-retardant aqueous polyurethane blending emulsion and preparation method thereof.
The present invention seeks to be achieved through the following technical solutions.
A preparation for aqueous hyperbranched polyurethane/compositional flame-retardant aqueous polyurethane blending emulsion, concrete preparation process is as follows:
Under room temperature, hyperbranched aqueous polyurethane is added in compositional flame-retardant aqueous polyurethane and obtains hyperbranched aqueous polyurethane/compositional flame-retardant aqueous polyurethane blending emulsion after stirring.Hyperbranched aqueous polyurethane accounts for 2～15% of system gross mass.Described aqueous hyperbranched polyurethane is a kind of or two kinds of mixtures of SWHBPU or AWHBPU, and compositional flame-retardant aqueous polyurethane is following one in listed, but be not limited to following listed, TF680, TF686, TH681, TF688, TF689 etc.
Beneficial effect
1, a kind of super branched polyurethane/compositional flame-retardant aqueous polyurethane blending emulsion of the present invention is compared with other extinguishing waterborn polyurethanes, coating agent prepared by emulsion of the present invention is except having good fire resistance, and owing to adding super branched polyurethane emulsion, make the TENSILE STRENGTH of the composite Aqueous Polyurethane Coating Agent of blend can reach 5.1MPa, elongation at break can be up to 751%.This coating agent is applied to textile coating agent, and coated fabric, except having good fire resistance, also has good resistance to hydrostatic pressure simultaneously, resistance to hydrostatic pressure is up to 14.7KPa, after soaping, also can keep good fire resistance, before and after soaping, all reach the B1 level in normal beam technique.
2, the preparation method of a kind of super branched polyurethane/compositional flame-retardant aqueous polyurethane blending emulsion coating agent of the present invention, utilize hyperbranched aqueous polyurethane can improve the features such as compositional flame-retardant aqueous polyurethane emulsion mobility and mechanical property, by after itself and the blend of compositional flame-retardant aqueous polyurethane, prepare the Aqueous Polyurethane Coating Agent of good mechanical properties, with after its coated fabric, except having good fire resistance, also there is resistance to hydrostatic pressure performance good, the resistance to advantage such as soap.This preparation method simply, easily implement.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described.
The preparation method of AWHBPU and SWHBPU is as follows:
(1) WHBPU's is synthetic
1. dihydromethyl propionic acid 1: 4 in mass ratio～5 is dissolved in DMF (DMF), then this mixed liquor is added drop-wise in the isophorone diisocyanate of 50～80 DEG C, reaction 5～15h;
2. above-mentioned reacting liquid temperature is down to-25～0 DEG C, adds diethanol amine (DEOA), reaction 2～6h;
3. above-mentioned reacting liquid temperature is raised to 80～110 DEG C, and be that 0.1～5% proportionate relationship is added drop-wise in this reaction system by dibutyl tin laurate or stannous octoate according to accounting for gross mass, continue reaction 1～5h, obtain WHBPU solution, decompression distillation sloughs solvent, after dry required WHBPU.
(2) AWHBPU's is synthetic
The WHBPU that (1) is obtained mixes with end-capping reagent, the mol ratio of WHBPU and end-capping reagent is 1:0.8～2, then catalyst drops is added in reaction system, catalyst accounts for and adds 0.5～5% of rear gross mass, again above-mentioned mixed liquor is joined to 4～5 times in the pyridine of mixed liquor quality, at 50～120 DEG C, react 0.5～5h, obtain AWHBPU crude product, decompression distillation sloughs solvent, after dry required AWHBPU.
Wherein said end-capping reagent is the one in formic acid, acetic acid, acetic anhydride;
Wherein said catalyst is the concentrated sulfuric acid or p-methyl benzenesulfonic acid.
(3) SWHBPU's is synthetic
The WHBPU that (1) is obtained mixes with end-capping reagent, hydroxyl in WHBPU and the mol ratio of end-capping reagent are 1:1～2, then catalyst A is added drop-wise in reaction system, catalyst A accounts for and adds 0.5～5% of rear gross mass, again above-mentioned mixed liquor is joined to 4～5 times in the pyridine of mixed liquor quality, at 80～120 DEG C, react 2～6h, obtain SWHBPU crude product, decompression distillation sloughs solvent, after dry required SWHBPU;
Wherein said end-capping reagent is the one in stearic acid, palmitic acid, myristic acid, laurate, oleic acid, linoleic acid;
Wherein said catalyst A is the concentrated sulfuric acid or p-methyl benzenesulfonic acid.
Embodiment 1
A preparation for hyperbranched aqueous polyurethane/compositional flame-retardant aqueous polyurethane blending emulsion, concrete preparation process is as follows:
Under room temperature, 4gSWHBPU is added to after stirring 15min in 76gTF680 and obtains hyperbranched aqueous polyurethane/compositional flame-retardant aqueous polyurethane blending emulsion.
Embodiment 2
A preparation for hyperbranched aqueous polyurethane/compositional flame-retardant aqueous polyurethane blending emulsion, concrete preparation process is as follows:
Under room temperature, 5gAWHBPU is added to after stirring 10min in 45gTF686 and obtains hyperbranched aqueous polyurethane/compositional flame-retardant aqueous polyurethane blending emulsion.
Embodiment 3
A preparation for hyperbranched aqueous polyurethane/compositional flame-retardant aqueous polyurethane blending emulsion, concrete preparation process is as follows:
Under room temperature, 2gSWHBPU is added to after stirring 8min in 98gTF681 and obtains hyperbranched aqueous polyurethane/compositional flame-retardant aqueous polyurethane blending emulsion.
Embodiment 4
A preparation for hyperbranched aqueous polyurethane/compositional flame-retardant aqueous polyurethane blending emulsion, concrete preparation process is as follows:
Under room temperature, 5gSWHBPU is added to after stirring 10min in 28gTF689 and obtains hyperbranched aqueous polyurethane/compositional flame-retardant aqueous polyurethane blending emulsion.
Embodiment 5
A preparation for hyperbranched aqueous polyurethane/compositional flame-retardant aqueous polyurethane blending emulsion, concrete preparation process is as follows:
Under room temperature, 4gAWHBPU is added to after stirring 20min in 46gTF688 and obtains hyperbranched aqueous polyurethane/compositional flame-retardant aqueous polyurethane blending emulsion.
Embodiment 6
A preparation for hyperbranched aqueous polyurethane/compositional flame-retardant aqueous polyurethane blending emulsion, concrete preparation process is as follows:
Under room temperature, 3gAWHBPU and 3gSWHBPU are added to after stirring 15min in 44gTF680 and obtain hyperbranched aqueous polyurethane/compositional flame-retardant aqueous polyurethane blending emulsion.
The blending emulsion of embodiment 1 to embodiment 6 gained is prepared to film forming, and it is detected.
The preparation of glued membrane: by hyperbranched aqueous polyurethane/compositional flame-retardant aqueous polyurethane blending emulsion casting film-forming in mould of preparation, the about 0.5mm of thickness, air dry one week, is placed in vacuum drying oven interior in 60 DEG C of vacuumizes to constant weight, and taking-up is placed in drier for subsequent use.
The preparation of coated fabric sample: above-mentioned blending emulsion is added to appropriate thickener TF-601 thickening, use coating machine coating, coated baking temperature is 170 DEG C of left and right, and the coated baking time is 40s, two are coated with two dries, and final cloth cover coating thickness is 70～90 μ m.
Table 1 glue film performance test result
Table 2 coated fabric the performance test results
Claims (3)
1. a preparation for aqueous hyperbranched polyurethane/compositional flame-retardant aqueous polyurethane blending emulsion, is characterized in that: concrete preparation process is as follows:
Under room temperature, hyperbranched aqueous polyurethane is added in compositional flame-retardant aqueous polyurethane and obtains hyperbranched aqueous polyurethane/compositional flame-retardant aqueous polyurethane blending emulsion after stirring; Hyperbranched aqueous polyurethane accounts for 2～15% of system gross mass.
2. the preparation of a kind of aqueous hyperbranched polyurethane/compositional flame-retardant aqueous polyurethane blending emulsion as claimed in claim 1, is characterized in that: described aqueous hyperbranched polyurethane is a kind of or two kinds of mixtures of SWHBPU or AWHBPU.
3. the preparation of a kind of aqueous hyperbranched polyurethane/compositional flame-retardant aqueous polyurethane blending emulsion as claimed in claim 1, is characterized in that: described compositional flame-retardant aqueous polyurethane comprises TF680, TF686, TH681, TF688, TF689.
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| CN201410286875.2A CN104047176A (en) | 2014-06-24 | 2014-06-24 | Preparation method of blended emulsion of hyperbranched waterborne polyurethane/compound flame-retardant waterborne polyurethane |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105544215A (en) * | 2016-02-25 | 2016-05-04 | 陈东东 | Foaming flame-retardant coating for curtain |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1511907A (en) * | 2002-12-30 | 2004-07-14 | 罗运军 | Double component anion water polyurethane dispersion |
| US20110257284A1 (en) * | 2010-04-15 | 2011-10-20 | Basf Se | Process for producing flame-retardant pu foams |
| CN102851987A (en) * | 2012-10-11 | 2013-01-02 | 北京理工大学 | Hyperbranched waterborne polyurethane coating agent |
| CN102924689A (en) * | 2012-11-14 | 2013-02-13 | 北京理工大学 | Waterborne hyper-branched polyurethane coating agent |
-
2014
- 2014-06-24 CN CN201410286875.2A patent/CN104047176A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1511907A (en) * | 2002-12-30 | 2004-07-14 | 罗运军 | Double component anion water polyurethane dispersion |
| US20110257284A1 (en) * | 2010-04-15 | 2011-10-20 | Basf Se | Process for producing flame-retardant pu foams |
| CN102851987A (en) * | 2012-10-11 | 2013-01-02 | 北京理工大学 | Hyperbranched waterborne polyurethane coating agent |
| CN102924689A (en) * | 2012-11-14 | 2013-02-13 | 北京理工大学 | Waterborne hyper-branched polyurethane coating agent |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105544215A (en) * | 2016-02-25 | 2016-05-04 | 陈东东 | Foaming flame-retardant coating for curtain |
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Application publication date: 20140917 |