CN115894851B - Preparation method of organosilicon modified waterborne polyurethane for leather finishing - Google Patents
Preparation method of organosilicon modified waterborne polyurethane for leather finishing Download PDFInfo
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- CN115894851B CN115894851B CN202211630212.9A CN202211630212A CN115894851B CN 115894851 B CN115894851 B CN 115894851B CN 202211630212 A CN202211630212 A CN 202211630212A CN 115894851 B CN115894851 B CN 115894851B
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 40
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 40
- 239000010985 leather Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000839 emulsion Substances 0.000 claims abstract description 37
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 29
- 229920000570 polyether Polymers 0.000 claims abstract description 29
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- -1 siloxane structure Chemical class 0.000 claims abstract description 12
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 9
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 150000002009 diols Chemical class 0.000 claims abstract description 7
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims abstract description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229920000728 polyester Polymers 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 229920002545 silicone oil Polymers 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 7
- 229920006264 polyurethane film Polymers 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000921 polyethylene adipate Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 238000011056 performance test Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920000616 Poly(1,4-butylene adipate) Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-butanediol Substances OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 239000013523 DOWSIL™ Substances 0.000 description 1
- 229920013731 Dowsil Polymers 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention aims to provide a preparation method of organosilicon modified waterborne polyurethane for leather finishing, and relates to the field of organic chemistry. The method comprises the following steps: mixing 5-10 parts by mass of dihydroxyl polyether modified siloxane and 20-30 parts by mass of polyester diol, dehydrating, cooling, adding isophorone diisocyanate, dropwise adding stannous octoate, and reacting at 65-75 ℃ for 1.5-2.5 hours; then adding 2-4 parts by mass of dimethylolpropionic acid, and continuously reacting for 1-3 hours at 65-75 ℃ to obtain a prepolymer; cooling to 40-50 ℃, adding 2-4 parts by mass of triethylamine, adding 35-45 parts by mass of water and 1-3 parts by mass of ethylenediamine under stirring, and reacting for 1-2 hours to obtain the organosilicon modified waterborne polyurethane emulsion. According to the invention, the dihydroxy polyether modified siloxane structure is introduced into polyurethane, so that the obtained organosilicon modified waterborne polyurethane emulsion is stable, and the prepared film has the characteristics of low water absorption and excellent mechanical property.
Description
Technical Field
The invention relates to the field of organic chemistry, in particular to a preparation method of organosilicon modified waterborne polyurethane for leather finishing.
Background
Finishing is an important process step in leather manufacturing. The coating can increase the beautiful appearance of the leather, protect the leather, prolong the service time and improve the grade of the leather. Among various finishing agents, the aqueous polyurethane leather finishing agent has the advantages of no toxicity, safety, environmental friendliness and the like, and has good leveling property, good film forming property and strong covering capacity during finishing. After the aqueous polyurethane is coated, the leather surface is smooth and bright, the hand feeling is comfortable, the grade of finished leather can be greatly improved, and the leather is widely applied. In the prior art, the mechanical property, the water resistance and the emulsion stability of the waterborne polyurethane are poor.
Disclosure of Invention
The invention aims to provide a preparation method of organosilicon modified waterborne polyurethane for leather finishing, which introduces a dihydroxyl polyether modified siloxane structure into polyurethane, and the prepared organosilicon modified waterborne polyurethane emulsion is stable, and a film prepared after coating has the characteristics of low water absorption and excellent mechanical property.
The invention adopts the following technical scheme:
the preparation method of the organosilicon modified waterborne polyurethane for leather finishing comprises the following steps:
mixing 5-10 parts by mass of dihydroxyl polyether modified siloxane and 20-30 parts by mass of polyester diol, and adding the mixture into N 2 Dehydrating under protection, cooling to 65-75 ℃, adding 10-20 parts by mass of isophorone diisocyanate, dropwise adding 0.2-0.4 part by mass of stannous octoate, and reacting for 1.5-2.5 hours at 65-75 ℃; then adding 2-4 parts by mass of dimethylolpropionic acid, and continuously reacting for 1-3 hours at 65-75 ℃ to obtain a prepolymer; cooling to 40-50 ℃, adding 2-4 parts by mass of triethylamine, adding 35-45 parts by mass of water and 1-3 parts by mass of ethylenediamine under stirring, and reacting for 1-2 hours to obtain organosilicon modified waterborne polyurethane emulsion;
the structural formula of the dihydroxyl polyether modified siloxane is as follows:
，
wherein a is more than or equal to 0 and less than or equal to 20, b is more than or equal to 1 and less than or equal to 20, m is more than or equal to 0 and less than or equal to 30, n is more than or equal to 1 and less than or equal to 30, a, b, m and n are integers, and Me is methyl.
In the invention, the organosilicon modified aqueous polyurethane emulsion is poured into a mould, naturally dried for 70-80 hours at room temperature, and then dried for 5-10 hours at 55-65 ℃ to obtain the aqueous polyurethane film.
In the present invention, the polyester diol is polyethylene adipate, polybutylene adipate, polyhexamethylene adipate or polycarbonate diol.
In the invention, the preparation method of the dihydroxyl polyether modified siloxane comprises the following steps: and performing hydrosilylation reaction on the dihydroxyl polyether and hydrogen-containing silicone oil under the catalysis of chloroplatinic acid to obtain the dihydroxyl polyether modified siloxane.
In the invention, the molecular weight of the dihydroxyl polyether is 300-2500, and the structural formula is as follows:
,
wherein a is more than or equal to 0 and less than or equal to 20, b is more than or equal to 1 and less than or equal to 20, and a and b are integers.
In the invention, the hydrogen content of the hydrogen-containing silicone oil is 0.1-0.45%, the molecular weight is 200-4000, and the structural formula is as follows:
，
wherein: m is more than or equal to 0 and less than or equal to 30, n is more than or equal to 1 and less than or equal to 30, m and n are integers, and Me is methyl.
In the preferable technical scheme, in the hydrosilylation reaction, the molar ratio of the dihydroxyl polyether to the hydrogen-containing silicone oil is 1-1.5:1, the addition amount of the catalyst chloroplatinic acid in each kilogram of reactant is 3-20 mg, the reaction temperature is 80-120 ℃, and the reaction time is 1-5 min; the reactants are dihydroxyl polyether and hydrogen-containing silicone oil.
The beneficial effects are that: the waterborne polyurethane modified by the dihydroxyl polyether modified siloxane has excellent reactivity, obviously improves the compatibility of the organosilicon chain segment and the polyurethane chain segment, ensures that the prepared emulsion is stable, and the waterborne polyurethane leather finishing film prepared after the film coating has the characteristics of excellent water resistance and mechanical property.
Drawings
FIG. 1 is a Fourier infrared spectrum of dihydroxypolyether NS-6 of example 1, with the abscissa representing wave numbers and the unit name representing cm -1 The ordinate is transmittance, and the unit name is%.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of dihydroxypolyether NS-6 of example 1, with chemical shifts on the abscissa and unit names in ppm.
FIG. 3 is a Fourier infrared spectrum of the hydrogen-containing silicone oil and the dihydroxypolyether modified siloxane of example 1, whereinIs hydrogen-containing silicone oil>Is dihydroxyl polyether modified siloxane, the abscissa is wave number, and the unit name is cm -1 The ordinate is transmittance, and the unit name is%.
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of the dihydroxypolyether modified siloxane of example 1, with chemical shifts on the abscissa and unit names in ppm.
Detailed Description
Dihydroxypolyether NS-6: the structure is thatHydroxyl number: 234 mgKOH/g, double bond: 2.06 mmol/g, acid number: 0.05 mgKOH/g, moisture: 0.08%, available from Jiangsu clock mountain New Material Co. The infrared spectrum of the dihydroxyl polyether NS-6 is shown in figure 1, the nuclear magnetic resonance hydrogen spectrum is shown in figure 2, and the molecular weight of the dihydroxyl polyether NS-6 is shown in the specification 1 H NMR data (CDCl) 3 Solvent, TMS as internal standard): 5.92 to 5.89 (m, H, =ch), 5.29 to 5.13 (s, 2H, =ch) 2 ），4.07（s，2H，-OCH 2 -），3.69～3.49（m，12H，-OCH 2 -），3.49～3.44（m，6H，－CH－），2.9487（d，2H，-OH），1.21～1.28（q，2H，-CH 2 -），1.16～1.14（d，18H，-CH 3 ），0.83～0.86（t，3H，-CH 3 ）。
The present invention will be described in further detail by way of examples, but the scope of the invention is not limited to the examples.
EXAMPLE 1 preparation of Silicone-modified waterborne polyurethane
1. Preparation of dihydroxyl polyether modified siloxane
70g of dihydroxyl polyether NS-6 and 30g of structural formula areHydrogen-containing silicone oil (Me is methyl) and 0.8mg of chloroplatinic acid (added in the form of a solution of 1% by mass of chloroplatinic acid in isopropanol) are added into a reactor, the temperature is raised to 100 ℃, hydrosilylation reaction is carried out at 100 ℃, after 2 minutes of reaction, the reaction system is changed from turbid liquid to colorless transparent liquid, the reaction is completely carried out at the moment, and then reduced pressure distillation is carried out for 30 minutes at 100 ℃ under the vacuum degree of 0.098MPa, so that low-boiling substances are removed, and the dihydroxy polyether modified siloxane is obtained.
As can be seen from FIG. 3, the hydrogen-containing silicone oil is at 2152cm -1 The Si-H bond characteristic absorption peak is very strong, and the Si-H bond characteristic absorption peak of the dihydroxyl polyether modified siloxane is completely disappeared, which indicates that the hydrogen-containing silicone oil and the dihydroxyl polyether completely react.
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of a dihydroxypolyether modified siloxane. 1 H NMR data (CDCl) 3 Solvent, TMS as internal standard): 4.06-3.77 (s, 2H, -OCH) 2 -）；3.68～3.48（m，12H，-OCH 2 -），3.48～3.42（m，6H，－OCH－），3.16～3.07（d，2H，-OH），1.4～1.27（q，4H，-CH 2 -），1.1293（d，18H，－CH 3 ），0.93～0.78（t，3H，－CH 3 ），0.41～0.45（m，2H，Si－CH 2 －）0.06～0.11（m，27H，Si－CH 3 ). Therefore, the structural formula of the dihydroxyl polyether modified siloxane was determined as follows:
wherein Me is methyl.
2. Preparation of organosilicon modified waterborne polyurethane
8g of the dihydroxypolyether modified siloxane obtained in example 1 and 28g of poly (1, 4-butylene adipate) (Mn=2000) were mixed and mixed in N 2 Vacuum dehydrating at 105 ℃ for 2 hours under protection, cooling to 70 ℃, adding 15g of IPDI (isophorone diisocyanate), dropwise adding 0.3g of stannous octoate, and reacting at 70 ℃ for 2 hours; then, 3g of dimethylolpropionic acid and 10g of acetone were added, and the reaction was continued for 2 hours to obtain a prepolymer. The temperature of the prepolymer is reduced to 49 ℃, 3g of triethylamine is added for neutralization for 30min, 40ml of deionized water and 2g of ethylenediamine are added under high-speed shearing (the stirring rotating speed is 3000 r/min) for chain extension reaction for 1.5h, and finally the solvent is distilled off under reduced pressure under the conditions of vacuum degree of-0.098 MPa and 50 ℃ to obtain the dihydroxy organosilicon modified aqueous polyurethane emulsion a (abbreviated as aqueous polyurethane emulsion a) with the solid content of 40 percent (mass percent concentration).
Pouring the aqueous polyurethane emulsion a into a polytetrafluoroethylene mould, naturally drying for 72h at room temperature, and then placing the aqueous polyurethane emulsion a into an oven to dry for 8h at 60 ℃ to obtain the aqueous polyurethane film A with the thickness of about 2 mm.
Comparative example 1
30g of polyadipic acid-1, 4-butanediol ester (Mn=2000) were reacted with N 2 Vacuum dehydrating for 2h at 100-110 ℃ under protection, cooling to 70 ℃, adding 20g of IPDI (isophorone diisocyanate), dropwise adding 0.3g of stannous octoate, and reacting for 2h at 70 ℃; then, 3g of dimethylolpropionic acid and 10g of acetone were added, and the reaction was continued for 2 hours to obtain a prepolymer. The temperature of the prepolymer is reduced to 49 ℃, 3g of triethylamine is added for neutralization for 30min, 39ml of ionized water and 2g of ethylenediamine are added under high-speed shearing (the stirring rotating speed is 3000 r/min), chain extension reaction is carried out for 1.5h, and finally, the solvent is distilled off under reduced pressure under the conditions of vacuum degree of-0.098 MPa and 50 ℃ to obtain the aqueous polyurethane emulsion b with the solid content of 40% (mass percentage concentration).
Pouring the aqueous polyurethane emulsion B into a polytetrafluoroethylene mould, naturally drying for 72 hours at room temperature, and then placing the aqueous polyurethane emulsion B into an oven to dry for 8 hours at 60 ℃ to obtain the aqueous polyurethane film B with the thickness of about 2 mm.
Comparative example 2
Dihydroxysilicone oil (purchased from DOWSIL, model PMX0930, mn=2000, structural formula) 8g and 28g of poly (1, 4-butylene adipate) (Mn=2000) were mixed in N 2 Vacuum dehydrating at 105 ℃ for 2 hours under protection, cooling to 70 ℃, adding 15g of IPDI (isophorone diisocyanate), dropwise adding 0.3g of stannous octoate, and reacting at 70 ℃ for 2 hours; then, 3g of dimethylolpropionic acid and 10g of acetone were added, and the reaction was continued for 2 hours to obtain a prepolymer.
The temperature of the prepolymer is reduced to 49 ℃, 3g of triethylamine is added for neutralization for 30min, 39ml of deionized water and 2g of ethylenediamine are added under high-speed shearing (the stirring rotating speed is 3000 r/min) for chain extension reaction for 1.5h, and finally, the solvent is distilled off under reduced pressure under the conditions of vacuum degree of-0.098 MPa and 50 ℃ to obtain the aqueous polyurethane emulsion c with the solid content of 40% (mass percentage concentration).
Pouring the aqueous polyurethane emulsion C into a polytetrafluoroethylene mould, naturally drying for 72h at room temperature, and then placing the aqueous polyurethane emulsion C into an oven to dry for 8h at 60 ℃ to obtain the aqueous polyurethane film C with the thickness of about 2 mm.
Example 2 Performance test
1. Emulsion Performance test
The properties of the aqueous polyurethane emulsions a, b and c were measured separately using the following method:
1) Appearance of emulsion: visual observation of macroscopic phenomena such as color, transparency, stability, precipitation layering state and the like of the aqueous polyurethane emulsion;
2) Emulsion particle size and distribution testing: diluting the emulsion with distilled water by about 500 times, measuring the particle size and distribution of samples at 25 ℃ by using a dynamic light scattering laser particle sizer, measuring each sample for 3 times, and taking an average value;
3) Emulsion viscosity: the emulsion was subjected to viscosity testing at 25℃using a DV2TLVTJ0 digital viscometer (Brookfield);
4) Emulsion mechanical stability: placing the emulsion sample in a centrifuge, centrifuging for 15min at 3000r/min, and observing whether precipitation and layering occur;
5) Emulsion storage stability: the aqueous polyurethane emulsion is taken and sealed in a 50ml small sample bottle, and is placed in a constant temperature drying oven at 60 ℃, and the state change of the emulsion is observed and recorded regularly, such as whether gel, layering or precipitation occurs. The storage time of the emulsion was reduced in such a manner that the emulsion was stored for 2 weeks under the above conditions, which corresponds to 6 months at normal temperature.
2. Film Performance test
The properties of the aqueous polyurethane films A, B and C were measured separately using the following method:
1) Water absorption measurement of film: the film was cut into square 25mm x 25mm, and weighed (m 1 ) Soaking in tap water at room temperature for 24h. The surface moisture of the adhesive film was removed by suction with a water absorbing paper, and the film was weighed (m 2 ). The measurement was performed 3 times, and an average was taken. Its water absorption is as per (m) 2 -m 1 ）/m 1 Calculating a formula of x 100%;
2) Mechanical property test of the film: the tensile strength and elongation at break of the samples were tested according to GB/T1040.3 using an electronic tensile tester (Shenzhen Sansi scientific instrument). Repeating the test for three times for each sample, and taking an average value;
3) Film hardness test: the shore a durometer (guang lan tai instrument limited) was used to measure the shore hardness of the samples, and each sample was repeatedly tested three times to obtain an average value.
TABLE 1 emulsion Performance test results
TABLE 2 film Performance test results
It can be seen from tables 1 and 2 that both aqueous polyurethane emulsions a and b have excellent stability. However, the aqueous polyurethane film a has extremely low water absorption and excellent mechanical properties. The aqueous polyurethane prepared by the dihydroxy polyether modified siloxane has the characteristics of water resistance and excellent mechanical property while ensuring the stability of emulsion.
Claims (7)
1. The preparation method of the organosilicon modified waterborne polyurethane for leather finishing is characterized by comprising the following steps:
mixing 5-10 parts by mass of dihydroxyl polyether modified siloxane and 20-30 parts by mass of polyester diol, and adding the mixture into N 2 Dehydrating under protection, cooling to 65-75 ℃, adding 10-20 parts by mass of isophorone diisocyanate, dropwise adding 0.2-0.4 part by mass of stannous octoate, and reacting for 1.5-2.5 hours at 65-75 ℃; then adding 2-4 parts by mass of dimethylolpropionic acid, and continuously reacting for 1-3 hours at 65-75 ℃ to obtain a prepolymer; cooling to 40-50 ℃, adding 2-4 parts by mass of triethylamine, adding 35-45 parts by mass of water and 1-3 parts by mass of ethylenediamine under stirring, and reacting for 1-2 hours to obtain organosilicon modified waterborne polyurethane emulsion;
the structural formula of the dihydroxyl polyether modified siloxane is as follows:
，
wherein a is more than or equal to 0 and less than or equal to 20, b is more than or equal to 1 and less than or equal to 20, m is more than or equal to 0 and less than or equal to 30, n is more than or equal to 1 and less than or equal to 30, a, b, m and n are integers, and Me is methyl.
2. The method for preparing the organosilicon modified waterborne polyurethane for leather finishing according to claim 1, wherein the organosilicon modified waterborne polyurethane emulsion is poured into a mould, naturally dried for 70-80 hours at room temperature, and then dried for 5-10 hours at 55-65 ℃ to obtain the waterborne polyurethane film.
3. The process according to claim 1 or 2, characterized in that the polyester diol is polyethylene adipate, polybutylene adipate, polyhexamethylene adipate or polycarbonate diol.
4. The method of preparing the dihydroxypolyether modified siloxane according to claim 3, wherein the method of preparing the dihydroxypolyether modified siloxane comprises the steps of: and performing hydrosilylation reaction on the dihydroxyl polyether and hydrogen-containing silicone oil under the catalysis of chloroplatinic acid to obtain the dihydroxyl polyether modified siloxane.
5. The method of claim 4, wherein: the molecular weight of the dihydroxy polyether is 300-2500, and the structural formula is as follows:
,
wherein a is more than or equal to 0 and less than or equal to 20, b is more than or equal to 1 and less than or equal to 20, and a and b are integers.
6. The method of manufacturing according to claim 5, wherein: the hydrogen content of the hydrogen-containing silicone oil is 0.1% -0.45%, the molecular weight is 200-4000, and the structural formula is as follows:
，
wherein: m is more than or equal to 0 and less than or equal to 30, n is more than or equal to 1 and less than or equal to 30, m and n are integers, and Me is methyl.
7. The preparation method according to claim 6, wherein in the hydrosilylation reaction, the molar ratio of the dihydroxyl polyether to the hydrogen-containing silicone oil is 1-1.5:1, the addition amount of the catalyst chloroplatinic acid in each kilogram of reactants is 3-20 mg, the reaction temperature is 80-120 ℃, and the reaction time is 1-5 min; the reactants are dihydroxyl polyether and hydrogen-containing silicone oil.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3954824A (en) * | 1974-04-03 | 1976-05-04 | Union Carbide Corporation | Organosilicone polymers and polyester urethane foam produced therewith |
| EP0811650A1 (en) * | 1996-05-31 | 1997-12-10 | Jeffrey A. Cooke | Polyether modified fluoroalkyl siloxanes |
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