CN105838232A - Method for preparing cowhair keratin modified polyurethane coating agent - Google Patents
Method for preparing cowhair keratin modified polyurethane coating agent Download PDFInfo
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- CN105838232A CN105838232A CN201610416992.5A CN201610416992A CN105838232A CN 105838232 A CN105838232 A CN 105838232A CN 201610416992 A CN201610416992 A CN 201610416992A CN 105838232 A CN105838232 A CN 105838232A
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- polyurethane
- finishing agent
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- polyurethane prepolymer
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 25
- 102000011782 Keratins Human genes 0.000 title claims abstract description 13
- 108010076876 Keratins Proteins 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title abstract description 7
- 239000011527 polyurethane coating Substances 0.000 title abstract 3
- 229920002635 polyurethane Polymers 0.000 claims abstract description 32
- 239000004814 polyurethane Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 10
- 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 10
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000004970 Chain extender Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 claims description 11
- 108091005658 Basic proteases Proteins 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- -1 2-phosphonobutane-1,2,4-tricarboxylic acids Sodium salt Chemical class 0.000 claims description 7
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 7
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 5
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- 238000004945 emulsification Methods 0.000 claims 1
- 239000010985 leather Substances 0.000 abstract description 15
- 230000007547 defect Effects 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract 1
- 229920000909 polytetrahydrofuran Polymers 0.000 abstract 1
- ALXDAYUOWUEKLS-UHFFFAOYSA-M sodium;3-(dimethylcarbamothioylsulfanyl)propane-1-sulfonate Chemical compound [Na+].CN(C)C(=S)SCCCS([O-])(=O)=O ALXDAYUOWUEKLS-UHFFFAOYSA-M 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 230000001804 emulsifying effect Effects 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- ZUFQODAHGAHPFQ-UHFFFAOYSA-N pyridoxine hydrochloride Chemical compound Cl.CC1=NC=C(CO)C(CO)=C1O ZUFQODAHGAHPFQ-UHFFFAOYSA-N 0.000 description 3
- 229960004172 pyridoxine hydrochloride Drugs 0.000 description 3
- 235000019171 pyridoxine hydrochloride Nutrition 0.000 description 3
- 239000011764 pyridoxine hydrochloride Substances 0.000 description 3
- GXVUZYLYWKWJIM-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanamine Chemical compound NCCOCCN GXVUZYLYWKWJIM-UHFFFAOYSA-N 0.000 description 2
- 108090000765 processed proteins & peptides Proteins 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- XADCESSVHJOZHK-UHFFFAOYSA-N Meperidine Chemical compound C=1C=CC=CC=1C1(C(=O)OCC)CCN(C)CC1 XADCESSVHJOZHK-UHFFFAOYSA-N 0.000 description 1
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- MQVMJSWYKLYFIG-UHFFFAOYSA-N propane-1-sulfonic acid;sodium Chemical compound [Na].CCCS(O)(=O)=O MQVMJSWYKLYFIG-UHFFFAOYSA-N 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
- C08G18/3825—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing amide groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Cosmetics (AREA)
Abstract
The invention discloses a method for preparing a cowhair keratin modified polyurethane coating agent. The method comprises the following steps: mixing polytetramethylene ether glycol with isophorone diisocyanate, and reacting for 2 to 4 hours at a temperature of 85 to 95 DEG C to obtain a polyurethane prepolymer A; adding a hydrophilic chain extender and an acetone solvent to the prepolymer A to react for 1.5 to 3.5 hours at a temperature of 65 to 85 DEG C, adding triethylamine to be subjected to a neutral reaction for 30 to 50min, adding a lower-layer liquid A obtained in a step (1) to react for 30 to 60 min at a temperature of 65 to 85 DEG C, adding 0.5% sodium 3-[[(dimethylamino)thioxomethyl]thio]propanesulphonate, and reacting at a temperature of 55 DEG C and stirring for 1 hour to obtain a polyurethane coating agent. The prepared waterborne polyurethane has good compatibility with leather, and the defect that the plasticity of the traditional polyurethane is too strong is avoided.
Description
Technical field
The present invention relates to the preparation method of the polyurethane used in a kind of leather making process, carry particularly to a kind of nano material
The preparation method of high aqueous polyurethane anti-flammability.
Background technology
Aqueous polyurethane is a kind of polyurethane resin in the strand of polyurethane containing hydrophilic radical, has with water
The strongest affinity, uses specific technique can be allowed to disperse and formed stable system in water.Aqueous polyurethane mainly should
For leather finish.But the plasticity of polyurethane institute film forming is too strong, is sprayed on leather surface, affects kishke feel, it is therefore necessary to
Modified polyurethane, reduces its plasticity, improves the kishke feel of leather.
Summary of the invention
Present invention employs techniques below scheme.
A kind of preparation method utilizing ox hair keratin modified polyurethane finishing agent, it is characterised in that:
(1) weigh the pretreated ox hair of 10g, be placed in three-necked bottle, be separately added into NaOH solution 60 mL of 0.5 mol/L,
Put in thermostat water bath at 90 DEG C, stirring reaction 1 h, add alkaline protease 0.2g, 2-phosphonobutane-1,2,4-tricarboxylic acids
Sodium salt 0.32g, at 35 DEG C, stirring reaction 1 h, with filtered on buchner funnel after having reacted, obtain lower floor's liquid A,
(2) under conditions of dibutyltin dilaurate catalyst exists, it is 1.5:1 ~ 4.5 by the mol ratio of NCO/OH: 1,
PTMG is mixed with isophorone diisocyanate, at 85 ~ 95 DEG C, reacts 2 ~ 4h, obtain polyurethane prepolymer
Body A；Described catalyst amount is the 0.3 ~ 0.6% of PTMG and isophorone diisocyanate gross weight；
(3) hydrophilic chain extender of performed polymer A weight 4.2 ~ 7.2% and the acetone of base polyurethane prepolymer for use as A weight 12 ~ 25% in A
Solvent, reacts 1.5 ~ 3.5h under the conditions of 65 ~ 85 DEG C, and the triethylamine adding base polyurethane prepolymer for use as A weight 6 ~ 8% is neutralized instead
Answer 30 ~ 50min, add and react 30min ~ 60min under the conditions of step (1) gained lower floor liquid A65 ~ 85 DEG C, add N, N-dimethyl-
Dithio Methanamide propane sulfonic acid sodium 0.5%, reaction temperature 55 DEG C, mixing time 1h, form polyurethane finishing agent, lower floor's liquid A
For the 3 ~ 5% of base polyurethane prepolymer for use as A weight, N, N-dimethyl-dithio Methanamide propane sulfonic acid sodium is base polyurethane prepolymer for use as A weight
Amount 0.5%.
The molecular weight of PTMG is 2000g/mol；Chain extender is dihydromethyl propionic acid, dimethylolpropionic acid
In any one；
The invention have the characteristics that:
(1) aqueous polyurethane prepared by is good with the leather compatibility, reduces the defect that conventional urethane plasticity is too strong.
(2) alkaline protease is to be produced by your foreign trade company limited of Weifang, Shandong Audi, and this enzymatic activity becomes to adhere to separately
In a kind of serine inscribe alkaline protease, it can generate polypeptide or aminoacid by aminosal molecule peptide chain, belongs to solid
100000u/g。
(3) 2-phosphonobutane-1,2,4-tricarboxylic acids sodium salts strengthen the enzymolysis of alkaline protease, promote hydrolysis by novo
To protein molecule segment.
(4) N, N-Methyl disulfide acute pyogenic infection of nails amide propane sulfonic acid sodium, ethylene glycol bis (2-amino-ethyl ether) tetraacethyl are permissible
Be combined with dibutyl tin laurate, reduce the harm to environment of such catalyst.
(5) ox hair selected by is the hair saving process gained ox hair using Dongming, Hebei tannery.
(6) alkaline protease is played potentiation by pyridoxine hydrochloride and Cyanuric Chloride, increases its hydrolysis degree, makes institute
The keratin hydrolysis liquid of preparation is good with the compatibility of polyurethane.
Ox hair pretreatment: by the water joining 10kg from tannery taken ox hair 5kg, adds 0.5g detergent, 30 degree
Stirring 2h, controls water, washes twice, each 10kg water, by gained ox hair 102 degree of bakings, time 2h in an oven, take out standby.
Detailed description of the invention
The present invention is further illustrated below in conjunction with example.
Example one
(1) weigh the pretreated ox hair of 10g, be placed in 250ml there-necked flask, be separately added into the NaOH solution 60 of 0.5 mol/L
ML, puts in thermostat water bath at 90 DEG C, stirring reaction 1 h, addition alkaline protease 0.2g, 2-phosphonobutane-1, and 2,4-tri-
Carboxylic acid sodium salt 0.32g and Cyanuric Chloride 0.5g, at 35 DEG C, stirring reaction 1 h, with filtered on buchner funnel after having reacted, obtain down
Layer liquid A, standby；
(2) in the four-hole boiling flask equipped with the 500ml stirring slurry, thermometer, condensing tube, at dibutyl tin laurate 0.21g
Under conditions of catalyst exists, PTMG 60g is mixed with isophorone diisocyanate 9.99g, in 85 DEG C
Lower reaction 2h, obtains base polyurethane prepolymer for use as A70g；
(3) in base polyurethane prepolymer for use as A, add dihydromethyl propionic acid 2.94g and acetone solvent 8.4g, react under the conditions of 65 DEG C
1.5h, adds triethylamine 4.2g and is neutralized reaction 30min, add step (1) gained 2.1g lower floor liquid A anti-under the conditions of 65 DEG C
Answer 30min, add N, N-dimethyl-dithio Methanamide propane sulfonic acid sodium 0.35g and water 120g emulsifying, reaction temperature 55 DEG C,
Mixing time 1h, forms polyurethane finishing agent.
Example two
((1) weighs the pretreated ox hair of 10g, is placed in three-necked bottle, is separately added into NaOH solution 60 mL of 0.5 mol/L,
Put in thermostat water bath at 90 DEG C, stirring reaction 1 h, add alkaline protease 0.2g, 2-phosphonobutane-1,2,4-tricarboxylic acids
Sodium salt 0.32g and Cyanuric Chloride 0.5g, at 35 DEG C, stirring reaction 1 h, with filtered on buchner funnel after having reacted, obtain subnatant
Body A,
(2) in the four-hole boiling flask equipped with the 500ml stirring slurry, thermometer, condensing tube, at dibutyl tin laurate 0.54g
Under conditions of catalyst exists, PTMG 60g is mixed with isophorone diisocyanate 30g, at 95 DEG C
Reaction 4h, obtains base polyurethane prepolymer for use as A90g；
(3) in base polyurethane prepolymer for use as A, add dimethylolpropionic acid 6.4g and acetone solvent 22.5g, react under the conditions of 85 DEG C
3.5h, adds triethylamine 7.2g and is neutralized reaction 50min, add step (1) gained 4.5g lower floor liquid A anti-under the conditions of 85 DEG C
Answer 60min, add N, N-dimethyl-dithio Methanamide propane sulfonic acid sodium 0.45g and 160g emulsifying, reaction temperature 55 DEG C, stir
Mix time 1h, form polyurethane finishing agent.
Example three
(1) weigh the pretreated ox hair of 10g, be placed in three-necked bottle, be separately added into NaOH solution 60 mL of 0.5 mol/L,
Put in thermostat water bath at 90 DEG C, stirring reaction 1 h, add alkaline protease 0.2g, 2-phosphonobutane-1,2,4-tricarboxylic acids
Sodium salt 0.32g and Cyanuric Chloride 0.5g, at 35 DEG C, stirring reaction 1 h, with filtered on buchner funnel after having reacted, obtain subnatant
Body A.
(2) in the four-hole boiling flask equipped with the 500ml stirring slurry, thermometer, condensing tube, at dibutyl tin laurate
Under conditions of 0.36g catalyst exists, PTMG 60g is mixed with isophorone diisocyanate 20g, in 90
React 3h at DEG C, obtain base polyurethane prepolymer for use as A80g；
(3) dihydromethyl propionic acid 4.6g and the acetone solvent of base polyurethane prepolymer for use as A weight 14.8g in base polyurethane prepolymer for use as A, in
React 2.5h under the conditions of 75 DEG C, add triethylamine 5.6g and be neutralized reaction 40min, add step (1) 3.2g gained lower floor liquid A
Under the conditions of 75 DEG C, react 45min, add N, N-dimethyl-dithio Methanamide propane sulfonic acid sodium 0.4g and water 130g emulsifying,
Reaction temperature 55 DEG C, mixing time 1h, form polyurethane finishing agent.
Example four
(1) weigh the pretreated ox hair of 10g, be placed in 250ml there-necked flask, be separately added into the NaOH solution 60 of 0.5 mol/L
ML, puts in thermostat water bath at 90 DEG C, stirring reaction 1 h, adds alkaline protease 0.2g, pyridoxine hydrochloride 0.1g, 2-
Phosphonobutane-1,2,4-tricarboxylic acids sodium salt 0.32g and Cyanuric Chloride 0.5g, at 35 DEG C, stirring reaction 1 h, uses after having reacted
Filtered on buchner funnel, obtains lower floor's liquid A, standby；
(2) in the four-hole boiling flask equipped with the 500ml stirring slurry, thermometer, condensing tube, at dibutyl tin laurate 0.21g
Under conditions of catalyst exists, PTMG 60g is mixed with isophorone diisocyanate 9.99g, in 85 DEG C
Lower reaction 2h, obtains base polyurethane prepolymer for use as A70g；
(3) in base polyurethane prepolymer for use as A, add dihydromethyl propionic acid 2.94g and acetone solvent 8.4g, react under the conditions of 65 DEG C
1.5h, adds triethylamine 3.2g and is neutralized reaction 30min, add step (1) gained 2.1g lower floor liquid A anti-under the conditions of 65 DEG C
Answer 30min, add N, N-dimethyl-dithio Methanamide propane sulfonic acid sodium 0.35g and water 120g emulsifying, reaction temperature 55 DEG C,
Mixing time 1h, forms polyurethane finishing agent.
Example five
(1) weigh the pretreated ox hair of 10g, be placed in three-necked bottle, be separately added into NaOH solution 60 mL of 0.5 mol/L,
Put in thermostat water bath at 90 DEG C, stirring reaction 1 h, add alkaline protease 0.2g, 2-phosphonobutane-1,2,4-tricarboxylic acids
Sodium salt 0.32g, pyridoxine hydrochloride 0.5g and Cyanuric Chloride 0.5g, at 35 DEG C, stirring reaction 1 h, uses Bu Shi after having reacted
Funnel filters, and obtains lower floor's liquid A,
(2) in the four-hole boiling flask equipped with the 500ml stirring slurry, thermometer, condensing tube, at dibutyl tin laurate 0.54g
Under conditions of catalyst exists, PTMG 60g is mixed with isophorone diisocyanate 30g, at 85 DEG C
Reaction 2h, obtains base polyurethane prepolymer for use as A90g；
(3) in base polyurethane prepolymer for use as A, add dimethylolpropionic acid 6.4g and acetone solvent 22.5g, react under the conditions of 85 DEG C
3.5h, adds triethylamine 6.2g and is neutralized reaction 50min, add step (1) gained 4.5g lower floor liquid A anti-under the conditions of 85 DEG C
Answer 60min, add N, N-dimethyl-dithio Methanamide propane sulfonic acid sodium 0.45g, ethylene glycol bis (2-amino-ethyl ether) tetrem
Acid 0.32g and 160g emulsifying, reaction temperature 55 DEG C, mixing time 1h, form polyurethane finishing agent.
Beneficial effects of the present invention is further illustrated below by relevant experimental data:
Ox hair keratin modified polyurethane finishing agent prepared by the specific embodiment of the invention is examined after being applied to leather finish spraying
Survey Leather Properties.Feel weighs its plasticity, is divided into that kishke feel is good, kishke feel is preferable, kishke feel is poor looks for three engineers to carry out hands
Touching (industry commonly uses experience), elongation at break characterizes its mechanical property, and conventional polyurethanes finishing agent comes from dolantin chemical industry.
Table 1 ox hair of the present invention keratin modified polyurethane finishing agent is applied to the sensory effects index of leather
| Experimental group | Conventional polyurethanes finishing agent | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Feel | Kishke feel is poor | Kishke feel is good | Kishke feel is good | Kishke feel is preferable | Kishke feel is good | Kishke feel is good |
As shown in Table 1, conventional poly-ammonia compared by the ox hair keratin modified polyurethane finishing agent that leather employs prepared by the present invention
Ester finishing agent gained leather can appear the kishke feel of leather suddenly.
The ox hair keratin modified polyurethane finishing agent of table 2 present invention is applied to the gained elongation at break of leather
| Experimental group | Conventional polyurethanes finishing agent | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Elongation at break/% | 136.21 | 137.67 | 122.5 | 212.69 | 201.4 | 232.45 |
Table 2 middle finger object detection method reference: Jiang Weiqi. leather finish physical and chemical inspection [M]. China Light Industry Press, 1999,
82-96, employs ox hair keratin modified polyurethane finishing agent of the present invention, leather elongation at break be improved significantly.
Testing discovery, in the present invention, the content of free stannum reduces by 32% than common books finishing agent simultaneously.
Claims (3)
1. the preparation method utilizing ox hair keratin modified polyurethane finishing agent, it is characterised in that:
(1) weigh the pretreated ox hair of 10g, be placed in three-necked bottle, be separately added into NaOH solution 60 mL of 0.5 mol/L,
Put in thermostat water bath at 90 DEG C, stirring reaction 1 h, add alkaline protease 0.2g, 2-phosphonobutane-1,2,4-tricarboxylic acids
Sodium salt 0.32g and Cyanuric Chloride 0.5g, at 35 DEG C, stirring reaction 1 h, with filtered on buchner funnel after having reacted, obtain subnatant
Body A,
(2) under conditions of dibutyltin dilaurate catalyst exists, it is 1.5:1 ~ 4.5 by the mol ratio of NCO/OH: 1,
PTMG is mixed with isophorone diisocyanate, at 85 ~ 95 DEG C, reacts 2 ~ 4h, obtain polyurethane prepolymer
Body A；Described catalyst amount is the 0.3 ~ 0.6% of PTMG and isophorone diisocyanate gross weight；
(3) hydrophilic chain extender of performed polymer A weight 4.2 ~ 7.2% and the acetone of base polyurethane prepolymer for use as A weight 12 ~ 25% in A
Solvent, reacts 1.5 ~ 3.5h under the conditions of 65 ~ 85 DEG C, and the triethylamine adding base polyurethane prepolymer for use as A weight 6 ~ 8% is neutralized instead
Answer 30 ~ 50min, add and react 30min ~ 60min under the conditions of step (1) gained lower floor liquid A65 ~ 85 DEG C, add N, N-dimethyl-
Dithio Methanamide propane sulfonic acid sodium 0.5% and water emulsification, reaction temperature 55 DEG C, mixing time 1h, form polyurethane finishing agent,
Lower floor's liquid A is the 3 ~ 5% of base polyurethane prepolymer for use as A weight, and N, N-dimethyl-dithio Methanamide propane sulfonic acid sodium is polyurethane
Performed polymer A weight 0.5%.
A kind of preparation method utilizing ox hair keratin modified polyurethane finishing agent, its feature exists
In: the molecular weight of PTMG is 2000g/mol.
A kind of preparation method utilizing ox hair keratin modified polyurethane finishing agent, its feature exists
In: chain extender is any one in dihydromethyl propionic acid, dimethylolpropionic acid.
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| CN108409935A (en) * | 2018-03-28 | 2018-08-17 | 齐鲁工业大学 | A kind of ox hair keratin is modified the preparation method of oiliness polyurethane film |
| CN108586692A (en) * | 2018-01-23 | 2018-09-28 | 陕西科技大学 | A kind of use for synthetic leather can polish the preparation method and application of aqueous polyurethane |
| CN110204679A (en) * | 2019-05-20 | 2019-09-06 | 齐鲁工业大学 | A kind of preparation method of modified environment-friendly aqueous polyurethane and its polyurethane of preparation |
| CN115815094A (en) * | 2022-12-10 | 2023-03-21 | 浙江南龙皮业有限公司 | Anti-cracking coating agent for leather and leather coating method |
| CN116589847A (en) * | 2023-05-19 | 2023-08-15 | 广东中鼎科技发展有限公司 | Modified TPU resin film forming agent, preparation method thereof and TPU composite film |
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| CN108586692A (en) * | 2018-01-23 | 2018-09-28 | 陕西科技大学 | A kind of use for synthetic leather can polish the preparation method and application of aqueous polyurethane |
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| CN108409935B (en) * | 2018-03-28 | 2020-08-04 | 齐鲁工业大学 | Preparation method of cow hair keratin modified oily polyurethane film |
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| CN110204679B (en) * | 2019-05-20 | 2021-08-31 | 齐鲁工业大学 | Preparation method of modified environment-friendly waterborne polyurethane and polyurethane prepared by same |
| CN115815094A (en) * | 2022-12-10 | 2023-03-21 | 浙江南龙皮业有限公司 | Anti-cracking coating agent for leather and leather coating method |
| CN116589847A (en) * | 2023-05-19 | 2023-08-15 | 广东中鼎科技发展有限公司 | Modified TPU resin film forming agent, preparation method thereof and TPU composite film |
| CN116589847B (en) * | 2023-05-19 | 2024-06-11 | 广东中鼎科技发展有限公司 | Modified TPU resin film forming agent, preparation method thereof and TPU composite film |
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