CN104610729A - Flame retardant waterborne polyurethane and preparation method thereof - Google Patents
Flame retardant waterborne polyurethane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses flame retardant waterborne polyurethane which is prepared from the following raw materials: toluene diisocyanate, 2, 2-dimethylolpropionic acid, polyether diol, a catalyst, triethylamine, a silane coupling agent, deionized water, a defoamer and a dispersed nano-silicon sol. According to the flame retardant waterborne polyurethane disclosed by the invention, a polyurethane emulsion is modified by using the silane coupling agent, so that polyurethane has excellent waterproofness, polyurethane, mechanical property and the like, and moreover, the dispersed nano-silicon sol is introduced by using an ultrasonic dispersion method to prepare the flame retardant waterborne polyurethane. As SiO2 has reinforcing and flame-retarding effects, a SiO2 covering matter is formed when the polyurethane is combusted so as to have dual functions of shielding and insulating heat, alleviating burning rate and inhibiting combustion reaction, so that the flame retardant effect is improved, and moreover, the preparation method is good in operability and has a good application prospect.
Description
Technical field
The present invention relates to field of high polymer material processing, particularly a kind of extinguishing waterborn polyurethane.
Technical background
Aqueous polyurethane (WPU) take water as dispersion medium, there is the advantages such as nontoxic, environmental protection, smell are little, safe and reliable, save energy, be a kind of novel green material, be widely used in the fields such as leather finish, synthetic leather covering with paint, fabric coating, coating, building thermal insulation material, foam.But urethane belongs to inflammable material, and combustionvelocity is fast, and releasing heat is high, also along with flammable molten drop during burning, makes flame bamboo telegraph.If do not carry out fire-retardant finish to it, the potential risk of initiation fire will be become.Therefore, under the prerequisite retaining aqueous polyurethane premium properties, improve its flame retardant properties, be one of important development direction of water-base polyurethane material functionalization.
Seo J W etc. passes through hybrid, prepare aqueous polyurethane/nano silicon composite emulsion, with silicon, thermostability modification is carried out to urethane, but silicon is not good as its flame retardant effect of simple ignition-proof element, to need with other fire retardant or compound, as collaborative uses such as dibasic lead phosphite, tribasic lead sulfate, calcium carbonate, aluminium hydroxide (or magnesium hydroxide), zinc borates, just can reach desirable flame retardant effect; Phosphorous, the halogen flame retardant polyether glycol such as the Wang Wei of Donghua University replace PART EPOXY propane condenses, react with isophorone diisocyanate, again with sodium bisulfite to isocyanate groups end-blocking, obtain the aqueous polyurethane of end-sealed type, but due to the toxicity and not environmentally of halogen, require not to be inconsistent with the environment-protecting asepsis of aqueous polyurethane.
The pressure of degraded product to environment of silicon based compound is little, is generally acknowledged eco-friendly fire retardant, gains great popularity in fire-retardant family.Wherein, the molecular formula of Nano silica sol can be expressed as mSiO
2nH
2o, internal structure is siloxane bond (-Si-O-Si-), and top layer covered by silicone hydroxyl (-Si-OH).The aqueous polyurethane bittern-free flame-proof material of the present invention's silane coupling agent/Nano silica sol modification that adopted ultrasonic dispersion to prepare, Nano silica sol is utilized to have good high thermal resistance, water-soluble, reactive and specific surface area is large, nontoxic, tasteless, Halogen, the feature such as fire-retardant, improve the flame retardant resistance of WPU, simultaneously with silane coupling agent to aqueous polyurethane emulsion modification, obtained coating has excellent water tolerance, sticking power and mechanical property etc., and this preparation method's good operability, have a good application prospect, for the research of halogen-free flameproof aqueous polyurethane and practical application provide new thinking.
Summary of the invention
In order to overcome, the flame retardant effect that prior art exists is poor, the problem such as not environmentally, expand the purposes of urethane, the invention provides a kind of extinguishing waterborn polyurethane, and preparation method thereof, the present invention utilizes the advantageous property of silane coupling agent and Nano silica sol to improve the flame retardant resistance of WPU, achieves the preparation of extinguishing waterborn polyurethane.
Of the present inventionly to be achieved through the following technical solutions:
A kind of extinguishing waterborn polyurethane, be made up of the raw material of following weight part: polyether glycol 55 ~ 65 parts, tolylene diisocyanate 30 ~ 40 parts, 2,2-dimethylol propionic acid 4 ~ 10 parts, catalyzer 1 ~ 3 part, silane coupling agent 0.5 ~ 2.0 part, triethylamine 3.5 ~ 9 parts, 8 ~ 15 parts, water, defoamer 0.5 ~ 2.0 part, Nano silica sol 5 ~ 10 parts.
Described silane coupling agent is selected from 3-aminopropyl Ethoxysilane, γ-(2,3-glycidoxy) propyl trimethoxy silicane or γ-aminopropyl triethoxysilane.
Described defoamer is selected from polydimethylsiloxane or polypropylene glycerol aether.
Described catalyzer is selected from dibutyl tin dilaurate or Dibutyltin oxide.
The solid content of described Nano silica sol is 30 ~ 40%.
The preferred deionized water of described water.
The preparation method of described extinguishing waterborn polyurethane, step is as follows:
(1) respectively by polyether glycol and 2,2-dimethylol propionic acid at 120 ~ 125 DEG C, vacuum hydro-extraction 2.0 ~ 3.0h under 4 ~ 4.5kPa condition, then sealing saves backup;
(2) in the closed reactor protected with high speed dispersor, thermometer and high pure nitrogen, tolylene diisocyanate is added, by 2, the mixture of 2-dimethylol propionic acid and polyether glycol is heated to 120 ~ 130 DEG C, make 2,2-dimethylol propionic acid dissolves, and joins in above-mentioned reactor, then add catalyzer after being cooled to room temperature, nitrogen protection atmosphere, at 70 ~ 75 DEG C with the speed stirring reaction 4.0 ~ 4.5h of 700 ~ 1000r/min, obtain base polyurethane prepolymer for use as;
(3) triethylamine and silane coupling agent are dissolved in the water of 5 ~ 10 DEG C, slowly add above-mentioned base polyurethane prepolymer for use as, with the spinner velocity high speed shear emulsification 30 ~ 40min of the shearing rate of 100 ~ 180rpm, 30 ~ 50m/s, add defoamer, after being uniformly dispersed, obtain silane coupler modified aqueous polyurethane emulsion;
(4) Nano silica sol is joined in above-mentioned polyaminoester emulsion, ultrasonic disperse 30 ~ 40min, obtain silane coupling agent/Nano silica sol modified aqueous polyurethane.
Beneficial effect of the present invention:
1, coating is obtained with silane coupler modified aqueous polyurethane emulsion in the present invention, because one end of silane coupling agent to connect with isocyanate-terminated base polyurethane prepolymer for use as molecular backbone (-NH
2react with-NCO), the Si-O chain of the other end is then stretched over substrate surface, thus shows organosilyl characteristic in silane coupler modified resin, as excellent water tolerance, sticking power and mechanical property etc., and this preparation method's good operability, there is good popularizing application prospect.
2, ultrasonic dispersion is adopted to introduce Nano silica sol in the present invention, because SiO
2have reinforcement and fire retardation concurrently, during urethane burning, form SiO
2coverture, plays shielding and adiabatic dual function, slow down rate of combustion, suppresses combustion reactions to be carried out, thus plays the flame retardant effect improving glued membrane.
Embodiment
In order to understand the present invention better, the preparation method of extinguishing waterborn polyurethane in the application is described below by way of specific embodiment, but is not limited only to these embodiments.
In following embodiment, tolylene diisocyanate used is purchased from Shanghai Fan Na rising sun Import and Export Co., Ltd., and name of product is tolylene diisocyanate, and No. CAS is 2641-62-5.Nano silica sol used is purchased from Red Star spacious mansion chemical building material limited liability company of Beijing, and name of product is silicate hydrate, and the raw material of other not detailed description is raw material conventional in prior art, buys obtain by conventional market approach.
Embodiment 1
(1) respectively by polyether glycol and 2,2-dimethylol propionic acid at 120 DEG C, vacuum hydro-extraction 2.0h under 4kPa condition, then sealing saves backup;
(2) in the closed reactor protected with high speed dispersor, thermometer and high pure nitrogen, add the tolylene diisocyanate of 30 parts, by 4 parts 2, the mixture of the polyether glycol of 2-dimethylol propionic acid and 55 parts is heated to 120 DEG C, make 2,2-dimethylol propionic acid dissolves, and joins in above-mentioned reactor, then add the dibutyl tin dilaurate of 1 part after being cooled to room temperature, nitrogen protection atmosphere, at 70 DEG C with the speed stirring reaction 4.0h of 700r/min, obtain base polyurethane prepolymer for use as;
(3) the 3-aminopropyl Ethoxysilane of the triethylamine of 4.0 parts and 0.5 part is dissolved in 8 parts of deionized waters of 5 DEG C, slowly add above-mentioned performed polymer, with the spinner velocity high speed shear emulsification 30min of the shearing rate of 100rpm, 30m/s, add the polydimethylsiloxane of 0.5 part, after being uniformly dispersed, obtain silane coupler modified aqueous polyurethane emulsion;
(4) Nano silica sol of 5 parts is joined in above-mentioned polyaminoester emulsion, ultrasonic disperse 30min, obtain silane coupling agent/Nano silica sol modified aqueous polyurethane.
Embodiment 2
(1) respectively by polyether glycol and 2,2-dimethylol propionic acid at 125 DEG C, vacuum hydro-extraction 3.0h under 4.5kPa condition, then sealing saves backup;
(2) in the closed reactor protected with high speed dispersor, thermometer and high pure nitrogen, add the tolylene diisocyanate of 40 parts, by 10 parts 2, the mixture of the polyether glycol of 2-dimethylol propionic acid and 65 parts is heated to 130 DEG C, make 2,2-dimethylol propionic acid dissolves, and joins in above-mentioned reactor, then add the dibutyl tin dilaurate of 3 parts after being cooled to room temperature, nitrogen protection atmosphere, at 75 DEG C with the speed stirring reaction 4.5h of 1000r/min, obtain base polyurethane prepolymer for use as;
(3) the 3-aminopropyl Ethoxysilane of the triethylamine of 9 parts and 2.0 parts is dissolved in 14 parts of deionized waters of 10 DEG C, slowly add above-mentioned performed polymer, with the spinner velocity high speed shear emulsification 40min of the shearing rate of 180rpm, 50m/s, add the polydimethylsiloxane of 2.0 parts, after being uniformly dispersed, obtain silane coupler modified aqueous polyurethane emulsion;
(4) Nano silica sol of 10 parts is joined in above-mentioned polyaminoester emulsion, ultrasonic disperse 40min, obtain silane coupling agent/Nano silica sol modified aqueous polyurethane.
Embodiment 3
(1) respectively by polyether glycol and 2,2-dimethylol propionic acid at 122 DEG C, vacuum hydro-extraction 2.5h under 4.5kPa condition, then sealing saves backup;
(2) in the closed reactor protected with high speed dispersor, thermometer and high pure nitrogen, add the tolylene diisocyanate of 35 parts, by 6 parts 2, the mixture of the polyether glycol of 2-dimethylol propionic acid and 60 parts is heated to 125 DEG C, make 2,2-dimethylol propionic acid dissolves, and joins in above-mentioned reactor, then add the dibutyl tin dilaurate of 2 parts after being cooled to room temperature, nitrogen protection atmosphere, at 70 DEG C with the speed stirring reaction 4.5h of 800r/min, obtain base polyurethane prepolymer for use as;
(3) the 3-aminopropyl Ethoxysilane of the triethylamine of 6 parts and 1.3 parts is dissolved in 10 parts of deionized waters of 6 DEG C, slowly add above-mentioned performed polymer, with the spinner velocity high speed shear emulsification 35min of the shearing rate of 150rpm, 40m/s, add the polydimethylsiloxane of 1.4 parts, after being uniformly dispersed, obtain silane coupler modified aqueous polyurethane emulsion;
(4) Nano silica sol of 7.6 parts is joined in above-mentioned polyaminoester emulsion, ultrasonic disperse 35min, obtain silane coupling agent/Nano silica sol modified aqueous polyurethane.
Embodiment 4
(1) respectively by polyether glycol and 2,2-dimethylol propionic acid at 120 DEG C, vacuum hydro-extraction 2.0h under 4kPa condition, then sealing saves backup;
(2) in the closed reactor protected with high speed dispersor, thermometer and high pure nitrogen, add the tolylene diisocyanate of 30 parts, by 4 parts 2, the mixture of the polyether glycol of 2-dimethylol propionic acid and 55 parts is heated to 120 DEG C, make 2,2-dimethylol propionic acid dissolves, and joins in above-mentioned reactor, then add the Dibutyltin oxide of 2.1 parts after being cooled to room temperature, nitrogen protection atmosphere, at 70 DEG C with the speed stirring reaction 4.0h of 750r/min, obtain base polyurethane prepolymer for use as;
(3) by the γ-(2 of the triethylamine of 3.2 parts and 0.9 part, 3-glycidoxy) propyl trimethoxy silicane is dissolved in 8 parts of deionized waters of 5 DEG C, slowly add above-mentioned performed polymer, with the spinner velocity high speed shear emulsification 30min of the shearing rate of 110rpm, 35m/s, add the polydimethylsiloxane of 0.8 part, after being uniformly dispersed, obtain silane coupler modified aqueous polyurethane emulsion;
(4) Nano silica sol of 5 parts is joined in above-mentioned polyaminoester emulsion, ultrasonic disperse 30min, obtain silane coupling agent/Nano silica sol modified aqueous polyurethane.
Embodiment 5
(1) respectively by polyether glycol and 2,2-dimethylol propionic acid at 125 DEG C, vacuum hydro-extraction 3.0h under 4.5kPa condition, then sealing saves backup;
(2) in the closed reactor protected with high speed dispersor, thermometer and high pure nitrogen, add the tolylene diisocyanate of 40 parts, by 10 parts 2, the mixture of the polyether glycol of 2-dimethylol propionic acid and 65 parts is heated to 130 DEG C, make 2,2-dimethylol propionic acid dissolves, and joins in above-mentioned reactor, then add the Dibutyltin oxide of 3.0 parts after being cooled to room temperature, nitrogen protection atmosphere, at 75 DEG C with the speed stirring reaction 4.5h of 950r/min, obtain base polyurethane prepolymer for use as;
(3) by the γ-(2 of the triethylamine of 8.4 parts and 2.0 parts, 3-glycidoxy) propyl trimethoxy silicane is dissolved in 15 parts of deionized waters of 10 DEG C, slowly add above-mentioned performed polymer, with the spinner velocity high speed shear emulsification 40min of the shearing rate of 180rpm, 50m/s, add the polydimethylsiloxane of 2.0 parts, after being uniformly dispersed, obtain silane coupler modified aqueous polyurethane emulsion;
(4) Nano silica sol of 10 parts is joined in above-mentioned polyaminoester emulsion, ultrasonic disperse 40min, obtain silane coupling agent/Nano silica sol modified aqueous polyurethane.
Embodiment 6
(1) respectively by polyether glycol and 2,2-dimethylol propionic acid at 120 DEG C, vacuum hydro-extraction 2.5h under 4.5kPa condition, then sealing saves backup;
(2) in the closed reactor protected with high speed dispersor, thermometer and high pure nitrogen, add the tolylene diisocyanate of 37 parts, by 6 parts 2, the mixture of the polyether glycol of 2-dimethylol propionic acid and 60 parts is heated to 125 DEG C, make 2,2-dimethylol propionic acid dissolves, and joins in above-mentioned reactor, then add the Dibutyltin oxide of 3.2 parts after being cooled to room temperature, nitrogen protection atmosphere, at 73 DEG C with the speed stirring reaction 4.5h of 850r/min, obtain base polyurethane prepolymer for use as;
(3) by the γ-(2 of the triethylamine of 6.8 parts and 1.5 parts, 3-glycidoxy) propyl trimethoxy silicane is dissolved in 10 parts of deionized waters of 6 DEG C, slowly add above-mentioned performed polymer, with the spinner velocity high speed shear emulsification 35min of the shearing rate of 160rpm, 35m/s, add the polydimethylsiloxane of 1.6 parts, after being uniformly dispersed, obtain silane coupler modified aqueous polyurethane emulsion;
(4) Nano silica sol of 7.4 parts is joined in above-mentioned polyaminoester emulsion, ultrasonic disperse 35min, obtain silane coupling agent/Nano silica sol modified aqueous polyurethane.
Test with reference to method in following test example 1 ~ 4 extinguishing waterborn polyurethane obtained in embodiment 1 ~ 6, test result is as shown in table 1 ~ 4:
Test example 1
Stability of emulsion is tested: under room temperature condition, and emulsion, with after the centrifugal 15min of rotating speed 3000r/min, is observed precipitation capacity and judged its stability.If without sedimentation, the shelf stable for periods having 6 months can be thought.
The each embodiment of table 1 is on the impact of the emulsion appearance of aqueous polyurethane, stability and glued membrane state
| Sample number into spectrum | Emulsion appearance | Stability in storage (6 months) | Glued membrane state |
| Embodiment 1 | Translucent blue light | Centrifugal rear a little precipitation | Smooth, slightly hard |
| Embodiment 2 | Transparent blue light | Stable | Smooth, softer |
| Embodiment 3 | Transparent blue light | Stable | Smooth, soft |
| Embodiment 4 | Translucent blue light | Centrifugal rear a little precipitation | Smooth, slightly hard |
| Embodiment 5 | Transparent blue light | Stable | Smooth, softer |
| Embodiment 6 | Transparent blue light | Stable | Smooth, soft |
Test example 2
By QB/T2415-1998 standard, glued membrane compressing tablet is become 60 × 10mm dumbbell shaped, electronic universal tester measures tensile strength and the elongation at break of glued membrane, rate of extension is 100mm/min.
The elongation at break profit tensile strength of table 2 each experimental example aqueous polyurethane glued membrane
| Sample number into spectrum | Elongation at break/% | Fracture tensile strength/MPa |
| Embodiment 1 | 345 | 19.5 |
| Embodiment 2 | 370 | 21.2 |
| Embodiment 3 | 395 | 22.8 |
| Embodiment 4 | 350 | 20.1 |
| Embodiment 5 | 375 | 22.5 |
| Embodiment 6 | 390 | 23.4 |
Test example 3
According to the regulation about film or film sample in ASTM D2863 standard, glued membrane is made the shape of 140 × 52 × 1.5mm, determination limit oxygen index (LOI).
The oxygen index of table 3 each embodiment aqueous polyurethane glued membrane
| Sample number into spectrum | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| LOI/％ | 28 | 28 | 30 | 27 | 28 | 29 |
As can be seen from upper table 3, under each embodiment, the oxygen index of aqueous polyurethane glued membrane is all more than or equal to 27, belongs to nonflammable material.
Test example 4
With level bar, adjustable horizontal stand is adjusted to level, clean after template as on horizontal stand, sample is poured in template, and makes it be uniformly distributed, drying at room temperature.When the transparent shape of emulsion film forming outward appearance, put into vacuum drying oven, vacuum tightness 0.933KPa, temperature rises to 60 ~ 62 DEG C, dry 4h, then temperature is risen to 90 ~ 92 DEG C, continue dry 2h after template cooling, mould is taken off gently, puts into loft drier for subsequent use, film is cut into 2 × 2cm square, weigh, immerse 25 DEG C of deionized waters, after 24 hours, weigh again, calculate:
M
1for proper mass, m
2for soaking rear quality.
The rate of body weight gain of table 4 each embodiment aqueous polyurethane glued membrane
| Sample number into spectrum | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Rate of body weight gain/% | 27.4 | 20.3 | 18.8 | 26.8 | 20.7 | 19.1 |
Claims (9)
1. an extinguishing waterborn polyurethane, it is characterized in that: be made up of the raw material of following weight part: polyether glycol 55 ~ 65 parts, tolylene diisocyanate 30 ~ 40 parts, 2,2-dimethylol propionic acid 4 ~ 10 parts, catalyzer 1 ~ 3 part, silane coupling agent 0.5 ~ 2.0 part, triethylamine 3.5 ~ 9 parts, 8 ~ 15 parts, water, defoamer 0.5 ~ 2.0 part, Nano silica sol 5 ~ 10 parts.
2. extinguishing waterborn polyurethane according to claim 1, is characterized in that: described silane coupling agent is selected from 3-aminopropyl Ethoxysilane, γ-(2,3-glycidoxy) propyl trimethoxy silicane or γ-aminopropyl triethoxysilane.
3. extinguishing waterborn polyurethane according to claim 1, is characterized in that: described defoamer is selected from polydimethylsiloxane or polypropylene glycerol aether.
4. extinguishing waterborn polyurethane according to claim 1, is characterized in that: described catalyzer is selected from dibutyl tin dilaurate or Dibutyltin oxide.
5. extinguishing waterborn polyurethane according to claim 1, is characterized in that: the solid content of described Nano silica sol is 30 ~ 40%.
6. the preparation method of the extinguishing waterborn polyurethane described in any one in Claims 1 to 5, is characterized in that: comprise the following steps:
(1) respectively by polyether glycol and the vacuum hydro-extraction of 2,2-dimethylol propionic acid, then sealing saves backup;
(2) in the closed reactor protected with high speed dispersor, thermometer and high pure nitrogen, tolylene diisocyanate is added, by 2, the mixture heating of 2-dimethylol propionic acid and polyether glycol, make 2,2-dimethylol propionic acid dissolves, join after cooling in above-mentioned reactor, then add catalyzer, stir and obtain base polyurethane prepolymer for use as;
(3) triethylamine and silane coupling agent are dissolved in deionized water, slowly add above-mentioned performed polymer high speed emulsification pretreatment, add defoamer, after being uniformly dispersed, obtain aqueous polyurethane emulsion;
(4) joined in above-mentioned polyaminoester emulsion by nanometer silica gel, ultrasonic disperse evenly obtains modified aqueous polyurethane.
7. the preparation method of extinguishing waterborn polyurethane according to claim 6, is characterized in that: in described step (3), and the temperature of deionized water is 5 ~ 10 DEG C.
8. the preparation method of extinguishing waterborn polyurethane according to claim 6, is characterized in that: in described step (3), and performed polymer high speed shear emulsification times is 30 ~ 40min.
9. the preparation method of extinguishing waterborn polyurethane according to claim 6, is characterized in that: in described step (4), and the ultrasonic disperse time is 30 ~ 40min.
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Application publication date: 20150513 |