CN104987493A - Waterborne polyurethane containing silicon and boron and preparation method thereof - Google Patents
Waterborne polyurethane containing silicon and boron and preparation method thereof Download PDFInfo
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Abstract
The invention primarily aims to provide waterborne polyurethane containing silicon and boron further aims to provide a preparation method thereof. The preparation method comprises the following steps: 1 weighing macromolecule dibasic alcohol for being mixed with TDI, raising the temperature to be within 70-90 DEG C under the protection of N2, conducting the reaction for 1-3 hours, firstly adding in DMPA for reacting for 1-2 hours, then adding in BDO for reacting for 1-3 hours, lowering the temperature to be within 60-70 DEG C, subsequently, dropwise adding siloxane with the end capped by amino for reacting for 0.5-1.5 hours, lowering the temperature to be within 30-50 DEG C, and obtaining polyurethane with the end capped by the siloxane; 2 conditioning the polyurethane with the end capped by the siloxane at the rotation speed of 1500-2000 rpm, firstly adding in TEA for conducting the emulsification and neutralization for 20-30 minutes, then adding in boric acid for conducting the emulsification continuously for 10-20 minutes, conducting the reduced pressure distillation, and obtaining the waterborne polyurethane which contains the silicon and the boron and is 25-35% in solid content. The waterborne polyurethane obtained through the preparation method has good dewatering, inflaming retarding and smoke suppressing performance, and in the practical application, the mechanical properties of materials can be effectively guaranteed.
Description
Technical field
The present invention relates to technical field of chemistry, be specifically related to a kind of siliceous boracic aqueous polyurethane and preparation method thereof.
Background technology
At present, aqueous polyurethane has been widely used in the processing of the products such as coating, tackiness agent and leather, but aqueous polyurethane conventional now contains hydrophilic radical, its film does not have hydrophobicity, in addition, the film of aqueous polyurethane easily burns, and not only flame retardant properties is poor, and also usually produce with more smog during burning, these defects limit the practical application of aqueous polyurethane undoubtedly.
As everyone knows, silicon-containing compound has excellent hydrophobic performance, such as, " synthesis of hydroxyethyl-terminapolydimethylsiloxanewaterborne polydimethylsiloxanewaterborne waterborne polyurethane " that the 26th volumes the 1st in 2012 of Chinese periodical " organosilicon material " are interim the article pointed out that the organic-silicon-modified aqueous polyurethane of anionic effectively can improve the hydrophobicity of material; " preparation of hydroxypropyl terminated polysiloxane modified aqueous polyurethane and the performance study thereof " one that 32nd volumes the 1st in 2015 of Chinese periodical " dyeing and printing auxiliary " are interim the article pointed out that hydroxypropyl terminated polysiloxane modified aqueous polyurethane emulsion can improve the hydrophobicity of material.Make researchist be not difficult to learn by these data informations, in theory silicon-containing compound is incorporated into the hydrophobicity of the glued membrane that can improve aqueous polyurethane in aqueous polyurethane segment, but how reliably to introduce silicon-containing compound, this or a technical barrier.In addition, boron be a kind of have fire-retardant, press down the element of hood, boron-containing compound is directly added to the flame retarding and smoke suppressing properties that can improve material in water-base polyurethane material, but during practical application, finds the mechanical property that can reduce water-base polyurethane material like this.In general, have not been reported the aqueous polyurethane simultaneously with good hydrophobic, fire-retardant and smoke suppressing in the market.
Summary of the invention
Primary and foremost purpose of the present invention is to provide a kind of siliceous boracic aqueous polyurethane simultaneously with good hydrophobic, fire-retardant and smoke suppressing.
For achieving the above object, the technical solution used in the present invention is: 1, a kind of siliceous boracic aqueous polyurethane, is characterized in that: the chemical structural formula of described aqueous polyurethane is as follows:
Wherein the structure of-R-is :-CH
2cH
2cH
2-,-CH
2cH
2nHCH
2cH
2cH
2-or-CH
2cH
2nHCH
2cH
2nHCH
2cH
2cH
2-;
-R
1-structure be:
-R
2-structure be:
N in structural formula be greater than zero arbitrary integer, m is the integer between 1 ~ 30.
Another object of the present invention is to provide a kind of preparation method of siliceous boracic aqueous polyurethane as above, comprises the following steps:
A, take macromolecule dihydric alcohol by the mol ratio of 1:2.2 ~ 3.0 and mix, at N with TDI (i.e. tolylene diisocyanate)
270 ~ 90 DEG C are warming up under protection, reaction 1 ~ 3h, then DMPA (namely 2 is first added, 2-dimethylol propionic acid) react 1 ~ 2h, add BDO (namely 1 again, 4-butyleneglycol) react 1 ~ 3h, be cooled to 60 ~ 70 DEG C, then amino-terminated siloxane reactions 0.5 ~ 1.5h is dripped, be cooled to 30 ~ 50 DEG C, obtain the urethane of siloxane blocking, acetone regulation system viscosity is dripped in reaction process, described DMPA, BDO, amino-terminated siloxanes and the mol ratio of TDI are respectively 0.2 ~ 0.4:0.1 ~ 0.5:0.03 ~ 0.23:1, described macromolecule dihydric alcohol is polyester diol or polyether Glycols, the quality addition of described acetone is the 50-150% of macromolecule dihydric alcohol quality,
B, the urethane of siloxane blocking is placed in 1500 ~ 2000rpm speed conditions under, first add TEA carry out emulsification, in and 20 ~ 30min, add boric acid again and continue emulsification 10 ~ 20min, underpressure distillation, obtain the siliceous boracic aqueous polyurethane that solid content is 25 ~ 35%, the mol ratio of described TEA and DMPA is 0.8 ~ 1:1, and the mol ratio of the element silicon in the boron in boric acid and amino-terminated siloxanes is 2 ~ 3:1.
Siliceous boracic aqueous polyurethane disclosed by the invention is the novel aqueous urethane of a class, compared with existing aqueous polyurethane, it has the advantage of the following aspects: the first, the surface tension of silicon-containing compound is little, and the tendency of the oriented film surface enrichment of silicon-containing group, thus make the water-base polyurethane material of hydrophobic performance higher than routine of siliceous boracic water-base polyurethane material; The second, boron be a kind of fire-retardant, press down the element of hood, melting can form the material of similar vitreous state and cover the surface of siliceous boracic water-base polyurethane material during boron-containing compound burning, material so not only can be avoided to degrade further generation inflammable gas, reduce the generation of flammable effusion thing, and the one-tenth carbon amounts of material can be increased, thus the oxygen in isolated air, and then effectively improve fire-retardant, the smoke suppressing of material.Compared with prior art, the present invention by chemical method by silicon, boron is incorporated in urethane segment, can not have hydrophobic after overcoming current aqueous polyurethane film forming simultaneously, the shortcoming of fire-retardant and smoke suppressing, in addition, prior art mainly adopts interpolation anti-flaming smoke-inhibiting agent in the material that material flame retarding and smoke suppressing properties is improved, but the mechanical properties decrease of material can be caused like this, by comparison, the siliceous boracic aqueous polyurethane adopting polymerization process disclosed by the invention to prepare, it is not only hydrophobic, flame retarding and smoke suppressing properties is good, and effectively can ensure the mechanical property of material in actual applications.
Concrete, the macromolecule dihydric alcohol in described step a is polyoxytrimethylene ether dibasic alcohol, PTMG dibasic alcohol or polyethylene glycol adipate glycol; Amino-terminated siloxanes in described step a is 3-aminopropyl triethoxysilane, N-(2-aminoethyl)-3-aminopropyl trimethoxysilane or diethylenetriamine base propyl trimethoxy silicane.
Applicant is found, as further preferred version: described step a takes macromolecule dihydric alcohol by the mol ratio of 1:2.6 to mix with TDI, at N by a large amount of experimental studies checking
280 DEG C are warming up under protection; reaction 2h; then first add DMPA and react 1.5h; add BDO again and react 2h; be cooled to 65 DEG C; then drip amino-terminated siloxanes and continue reaction 1h; be cooled to 40 DEG C; obtain the urethane of siloxane blocking; the mol ratio of described DMPA, BDO, amino-terminated siloxanes and TDI is 0.28:0.23:0.21:1; adopt above-mentioned parameter condition to make hydrophobic, the fire-retardant and smoke suppressing of the siliceous boracic aqueous polyurethane prepared best, and during practical application, the mechanical property of material is good.
Method disclosed by the invention is adopted to prepare in siliceous boracic aqueous polyurethane process, in order to ensure preparation technology further, preferred version in reactant, drips acetone with regulation system viscosity in the whole reaction process of step a, and the dropping quality of acetone is 100% ~ 150% of macromolecule dihydric alcohol quality.The viscosity adding reactant in the whole reaction process that can reduce step a of acetone, and then ensure that reaction raw materials is able to abundant mixing, make to react completely.Further, the mol ratio of described TEA and DMPA is 0.9:1; The mol ratio of the element silicon in the boron in described boric acid and amino-terminated siloxanes is 2:1.
Embodiment
Below in conjunction with embodiment 1-4, technical scheme disclosed by the invention is further described:
Embodiment 1: the preparation of siliceous boracic aqueous polyurethane
1) take by the mol ratio of 1:2.2 polyethylene glycol adipate glycol and the TDI join in four dry neck round-bottomed flasks, at N that molecular-weight average is 1000
280 DEG C are warming up under protection, reaction 2h, then first add DMPA and react 1h, add BDO again and carry out chain extending reaction 2h, be cooled to 60 DEG C, then 3-aminopropyl triethoxysilane reaction 0.5h is dripped, be cooled to 40 DEG C, obtain the urethane of siloxane blocking, acetone regulation system viscosity is dripped in reaction process, the mol ratio of described DMPA, BDO, 3-aminopropyl triethoxysilane and TDI is 0.23:0.27:0.08:1, and the quality addition of described acetone is 150% of polyethylene glycol adipate glycol quality;
2) under the urethane of siloxane blocking step 1 synthesized is placed in the speed conditions of 1500rpm, first add TEA carry out emulsification, in and 20min, add boric acid again and continue emulsification 20min, underpressure distillation desolventizing, obtain the siliceous boracic aqueous polyurethane that solid content is 25%, the mol ratio of described TEA and DMPA is 0.8:1, and the mol ratio of the element silicon in the boron in boric acid and amino-terminated siloxanes is 2:1;
3) take the siliceous boracic aqueous polyurethane that appropriate step 2 prepares, pour in mould, then first leave standstill to the glued membrane on surface dry at ambient temperature, then put into baking oven under the condition of 120 DEG C and dry 2h, obtain sample 1, to be measured.
Embodiment 2: the preparation of siliceous boracic aqueous polyurethane
1) take by the mol ratio of 1:2.6 PTMG dibasic alcohol and the TDI join in four dry neck round-bottomed flasks, at N that molecular-weight average is 2000
290 DEG C are warming up under protection, reaction 1h, then first add DMPA and react 1.5h, add BDO again and carry out chain extending reaction 3h, be cooled to 70 DEG C, then N-(2-aminoethyl)-3-aminopropyl trimethoxysilane reaction 1.5h is dripped, be cooled to 50 DEG C, obtain the urethane of siloxane blocking, acetone regulation system viscosity is dripped in reaction process, described DMPA, BDO, the mol ratio of N-(2-aminoethyl)-3-aminopropyl trimethoxysilane and TDI is respectively 0.28:0.23:0.21:1, the quality addition of described acetone is 150% of PTMG dibasic alcohol quality,
2) under the urethane of siloxane blocking step 1 synthesized is placed in the speed conditions of 1700rpm, first add TEA carry out emulsification, in and 30min, add boric acid again and continue emulsification 10min, underpressure distillation desolventizing, obtain the siliceous boracic aqueous polyurethane that solid content is 30%, the mol ratio of described TEA and DMPA is 0.9:1, and the mol ratio of the element silicon in the boron in boric acid and amino-terminated siloxanes is 2.5:1;
3) take the siliceous boracic aqueous polyurethane that appropriate step 2 prepares, pour in mould, then first leave standstill to the glued membrane on surface dry at ambient temperature, then put into baking oven under the condition of 110 DEG C and dry 3h, obtain sample 2, to be measured.
Embodiment 3: the preparation of siliceous boracic aqueous polyurethane
1) take by the mol ratio of 1:3 polyoxytrimethylene ether dibasic alcohol and the TDI join in four dry neck round-bottomed flasks, at N that molecular-weight average is 1750
270 DEG C are warming up under protection, reaction 3h, then first add DMPA and react 2h, add BDO again and carry out chain extending reaction 1h, be cooled to 65 DEG C, then diethylenetriamine base propyl trimethoxy silicane reaction 0.5h is dripped, be cooled to 40 DEG C, obtain the urethane of siloxane blocking, acetone regulation system viscosity is dripped in reaction process, the mol ratio of described DMPA, diethylenetriamine base propyl trimethoxy silicane and TDI is 0.34:0.25:0.15:1, and the quality addition of described acetone is 100% of polyoxytrimethylene ether dibasic alcohol quality;
2) under the urethane of siloxane blocking step 1 synthesized is placed in the speed conditions of 2000rpm, first add TEA carry out emulsification, in and 25min, add boric acid again and continue emulsification 15min, underpressure distillation desolventizing, obtain the siliceous boracic aqueous polyurethane that solid content is 35%, the mol ratio of described TEA and DMPA is 1:1, and the mol ratio of the element silicon in the boron in boric acid and amino-terminated siloxanes is 3:1;
3) take the siliceous boracic aqueous polyurethane that appropriate step 2 prepares, pour in mould, then first leave standstill to the glued membrane on surface dry at ambient temperature, then put into baking oven under the condition of 130 DEG C and dry 1h, obtain sample 3, to be measured.
Embodiment 4: the Performance Detection of siliceous boracic aqueous polyurethane
The sample 1-3 prepared by embodiment 1-3 carries out hydrophobic respectively, fire-retardant, press down the detection of cigarette and mechanical property, and the detected result of sample 1-3 does not introduce silicon to corresponding separately, the performance of the Water-based polyurethane elastomer contrast sample of boron compares, concrete examination criteria and detected result refer to as shown in following table 1-4, wherein, the sample recorded in table 1-4 with the increase per-cent of the contact angle of water, the decline per-cent of maximum heat rate of release, the increase per-cent of decline per-cent tensile strength of maximum smoke density and the increase per-cent of elongation at break refer to the decline Comparatively speaking of the corresponding detect parameters of corresponding contrast sample respectively or increase per-cent.Here so-called corresponding contrast sample that is, such as sample 1, its corresponding contrast sample be adopt equally molecular-weight average be 1000 the Water-based polyurethane elastomer not introducing silicon, boron for preparing of polyethylene glycol adipate glycol, same reason, for sample 2, its corresponding contrast sample be adopt equally molecular-weight average be 2000 PTMG dibasic alcohol prepare do not introduce silicon, boron Water-based polyurethane elastomer, sample 3 is as the same.Can obviously find out from the data table 1-4: compared with not introducing the Water-based polyurethane elastomer of silicon, boron, use siliceous boracic aqueous polyurethane disclosed by the invention can make the increase by more than 40.6% of the contact angle of sample and water, the maximum heat rate of release decline more than 39.7% of sample, maximum smoke density decline more than 36.8%, tensile strength increase by more than 7.4%, and elongation at break increases by more than 9.7%.Above data analysis shows, uses siliceous boracic aqueous polyurethane disclosed by the invention in actual application, can effectively improve material hydrophobic, fire-retardant, press down cigarette and mechanical property.
The hydrophobic performance test of table 1 sample
The flame retardant properties test of table 2 sample
The smoke suppressing test of table 3 sample
The Mechanics Performance Testing of table 4 sample
Claims (8)
1. a siliceous boracic aqueous polyurethane, is characterized in that: the chemical structural formula of described aqueous polyurethane is as follows:
Wherein the structure of-R-is :-CH
2cH
2cH
2-,-CH
2cH
2nHCH
2cH
2cH
2-or-CH
2cH
2nHCH
2cH
2nHCH
2cH
2cH
2-;
-R
1-structure be:
-R
2-structure be:
N in structural formula be greater than zero arbitrary integer, m is the integer between 1 ~ 30.
2. a preparation method for siliceous boracic aqueous polyurethane as claimed in claim 1, comprises the following steps:
A, take macromolecule dihydric alcohol by the mol ratio of 1:2.2 ~ 3.0 and mix with TDI, at N
270 ~ 90 DEG C are warming up under protection, reaction 1 ~ 3h, then first add DMPA and react 1 ~ 2h, add BDO again and react 1 ~ 3h, be cooled to 60 ~ 70 DEG C, then amino-terminated siloxane reactions 0.5 ~ 1.5h is dripped, be cooled to 30 ~ 50 DEG C, obtain the urethane of siloxane blocking, acetone regulation system viscosity is dripped in reaction process, described DMPA, BDO, amino-terminated siloxanes and the mol ratio of TDI are 0.2 ~ 0.4:0.1 ~ 0.5:0.03 ~ 0.23:1, described macromolecule dihydric alcohol is polyester diol or polyether Glycols, the quality addition of described acetone is the 50-150% of macromolecule dihydric alcohol quality,
B, the urethane of siloxane blocking is placed in 1500 ~ 2000rpm speed conditions under, first add TEA carry out emulsification, in and 20 ~ 30min, add boric acid again and continue emulsification 10 ~ 20min, underpressure distillation, obtain the siliceous boracic aqueous polyurethane that solid content is 25 ~ 35%, the mol ratio of described TEA and DMPA is 0.8 ~ 1:1, and the mol ratio of the element silicon in the boron in boric acid and amino-terminated siloxanes is 2 ~ 3:1.
3. the preparation method of the siliceous boracic aqueous polyurethane according to right 2, is characterized in that: the macromolecule dihydric alcohol in described step a is polyoxytrimethylene ether dibasic alcohol, PTMG dibasic alcohol or polyethylene glycol adipate glycol.
4. the preparation method of the siliceous boracic aqueous polyurethane according to right 2, is characterized in that: the amino-terminated siloxanes in described step a is 3-aminopropyl triethoxysilane, N-(2-aminoethyl)-3-aminopropyl trimethoxysilane or diethylenetriamine base propyl trimethoxy silicane.
5. the preparation method of the siliceous boracic aqueous polyurethane according to right 2, is characterized in that: described step a takes macromolecule dihydric alcohol by the mol ratio of 1:2.6 to mix with TDI, at N
280 DEG C are warming up under protection; reaction 2h; then first add DMPA and react 1.5h; add BDO again and react 2h; be cooled to 65 DEG C, then drip amino-terminated siloxanes and continue reaction 1h, be cooled to 40 DEG C; the urethane of siloxane blocking, the mol ratio of described DMPA, BDO, amino-terminated siloxanes and TDI is 0.28:0.23:0.21:1.
6. the preparation method of the siliceous boracic aqueous polyurethane according to right 2, is characterized in that: the quality addition of described step a, middle acetone is 100% ~ 150% of macromolecule dihydric alcohol quality.
7. the preparation method of the siliceous boracic aqueous polyurethane according to right 2, is characterized in that: the mol ratio of described TEA and DMPA is 0.9:1.
8. the preparation method of the siliceous boracic aqueous polyurethane according to right 2, is characterized in that: the mol ratio of the element silicon in the boron in described boric acid and amino-terminated siloxanes is 2:1.
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| CN110373057A (en) * | 2019-08-05 | 2019-10-25 | 黄向云 | A kind of manufacture craft of jewelry protecting film |
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| CN112143470A (en) * | 2019-06-28 | 2020-12-29 | 中国石油化工股份有限公司 | Plugging material, preparation method thereof and plugging agent |
| CN110373057A (en) * | 2019-08-05 | 2019-10-25 | 黄向云 | A kind of manufacture craft of jewelry protecting film |
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