CN107793546B - Cation-nonionic mixed waterborne polyurethane and preparation method and application thereof - Google Patents
Cation-nonionic mixed waterborne polyurethane and preparation method and application thereof Download PDFInfo
- Publication number
- CN107793546B CN107793546B CN201711113992.9A CN201711113992A CN107793546B CN 107793546 B CN107793546 B CN 107793546B CN 201711113992 A CN201711113992 A CN 201711113992A CN 107793546 B CN107793546 B CN 107793546B
- Authority
- CN
- China
- Prior art keywords
- nonionic
- chain extender
- cationic
- waterborne polyurethane
- stirring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
-
- 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
- C08G18/4825—Polyethers containing two hydroxy 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
- C08G18/65—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
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/568—Reaction products of isocyanates with polyethers
Abstract
The invention discloses a cation-nonionic mixed waterborne polyurethane which is prepared from the following components in parts by weight: 18-30 parts of nonionic hydrophilic monomer, 30-50 parts of polyether diol, 20-35 parts of diisocyanate, 4-7 parts of chain extender and 2-6 parts of neutralizing acid. The modified starch can be used as one of components in textile size, can be stably dispersed in neutral or weakly acidic (pH 5-7) textile size under the condition of being diluted to 20-100 times, and has the function of enabling the textile size not to be prone to fluffing and yarn breaking in the spinning process.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to cation-nonionic mixed waterborne polyurethane and a preparation method and application thereof.
Background
The textile size is a general name of natural and artificially synthesized water-soluble or water-dispersible high polymer with viscosity used in the pretreatment process of textile fibers, the polymers can be uniformly mixed in water, can be stably dispersed after boiling, can be uniformly coated on the surface of the textile fibers in the spinning process, ensures that the fibers are not broken and fluffed in the spinning process, and is easy to be quickly desized in alkaline water after the spinning process is finished. The main components of the conventional textile sizing agent comprise starch and derivatives thereof, polyvinyl alcohol (PVA), acrylic acid or polyester adhesives, post-waxing auxiliaries, mildewproof agents, moisture absorbents and the like. At present, main stream products in the market, such as polyvinyl alcohol, water-based acrylic acid and the like, are poor in wear resistance and strength, are generally mixed with starch in a mass ratio of 1: 4-1: 2, are more in consumption, are high in raw material and transportation cost, and cause the problem of subsequent waste liquid treatment.
As a novel environment-friendly product with low VOC, the aqueous polyurethane has the advantages of high strength, good elasticity and good wear resistance compared with polyvinyl alcohol and aqueous acrylate dispersoids. However, the conventional anionic aqueous polyurethane has the following disadvantages: a. the textile size is sensitive to pH value, the stability is poor after the textile size is diluted by 20-100 times in water, modified starch, polyvinyl alcohol, part of filler auxiliaries and the like used in the textile size are weak in acidity, conventional anionic waterborne polyurethane is mixed with the textile size and is easy to break milk and aggregate to form floccules, and the dispersion effect and spinning efficiency of size boiling are seriously influenced; b. because the hydrophilicity of the aqueous polyurethane is poorer than that of the polyvinyl alcohol and the aqueous acrylate dispersoid, the post-treatment desizing efficiency is lower; c. the traditional anionic waterborne polyurethane is more expensive than polyvinyl alcohol and acrylic resin, and the spinning efficiency is not obviously improved compared with polyvinyl alcohol and the like at a lower dosage, so that the popularization scale of the waterborne polyurethane in the textile size industry is smaller.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a cation-nonionic mixed type waterborne polyurethane which can be used as one of components in textile size, can be stably dispersed in the neutral or weakly acidic (pH 5-7) textile size under the condition of being diluted to 20-100 times, and has the function of preventing the textile size from fluffing and breaking during the spinning process.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention comprises cation-nonionic mixed waterborne polyurethane which is prepared from the following components in parts by weight:
preferably, the non-ionic hydrophilic monomer is one or more of polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate and polyoxyethylene monostearate.
Preferably, the polyether diol is one or more of polyether N-205, polyether N-210, polyether N-220 and polyether N-330.
Preferably, the diisocyanate is one or more of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate and carbodiimide modified MDI.
Preferably, the chain extender is methyldiethanolamine.
The neutralizing acid is one or more of acetic acid, 2-hydroxypropionic acid and butyric acid.
The invention also comprises a preparation method of the cation-nonionic mixed type waterborne polyurethane, which comprises the following steps:
1) heating the nonionic hydrophilic monomer and the polyether glycol to 100-125 ℃ and then carrying out vacuum dehydration treatment;
2) cooling the product subjected to vacuum dehydration treatment in the step 1) to 50-60 ℃, adding diisocyanate once, and carrying out heat preservation treatment;
3) cooling the product subjected to heat preservation treatment in the step 2) to 30-40 ℃, dropwise adding an acetone solution containing a chain extender, adding a neutralizing acid after dropwise adding, stirring, and then adding deionized water for emulsification treatment under high-speed dispersion;
4) heating the product emulsified in the step 3) to 60-75 ℃, and pumping out acetone under a vacuum condition to obtain the product.
Further, the temperature in the step 3) can be reduced to 30-40 ℃, an acetone solution containing the chain extender is dripped, and then the neutralization acid is added after the dripping is finished, and the mixture is stirred, and then is added into deionized water for emulsification treatment under high-speed dispersion; or, cooling to 30-40 ℃, dropwise adding an acetone solution containing a chain extender, and after dropwise adding, adding a deionized water solution containing a neutralizing acid under high-speed dispersion for emulsification treatment.
Further, in the step 1), the vacuum dehydration treatment is specifically vacuum dehydration for 1.5-2.5h, and the vacuum degree is between 0.08 and 1.0 MPa; in the step 2), the heat preservation treatment is specifically heat preservation for 2.5 to 3.5 hours at the temperature of between 50 and 70 ℃; in the step 3), the acetone solution containing the chain extender is an acetone solution containing the chain extender with the mass concentration of 7.5-15%, the dripping time of the acetone solution containing the chain extender is 30 min-1 h, and the stirring speed of high-speed dispersion is 500-2000 r/min; in the step 4), the vacuum condition is specifically that the vacuum degree is between 0.04 and 1.0 MPa.
The invention also comprises the application of the cation-nonionic mixed type waterborne polyurethane in textile sizing agent.
The invention also comprises a preparation method of the textile size, which comprises the following steps:
a) adding deionized water into a reaction bottle, and adding starch for textile sizing agent under a stirring state, wherein the stirring speed is 120-240 r/min, and the stirring time is 5-10 min;
b) adding the cation-nonionic waterborne polyurethane into a reaction bottle, heating to 95-100 ℃, and boiling for 20-40min to obtain the cationic-nonionic waterborne polyurethane.
Compared with the prior art, the invention has the beneficial effects that: the invention provides cation-nonionic mixed type waterborne polyurethane, which can be used as one of components in textile size, can be stably dispersed in neutral or weakly acidic (pH 5-7) textile size under the condition of being diluted to 20-100 times, and has the effect of preventing the textile size from fluffing and breaking in the spinning process. The textile size prepared from the cationic-nonionic waterborne polyurethane is relatively simple in preparation process and easy to operate. The cationic-nonionic waterborne polyurethane is viscous liquid and is very easy to disperse uniformly in water, and the whole pulp boiling process only needs 40 min-1 h, so that manpower and material resources are greatly saved; the slurry has low viscosity, is convenient to convey, and has relatively low requirements on equipment such as pipelines; meanwhile, the dosage of the cationic-nonionic waterborne polyurethane is lower than that of polyvinyl alcohol, so that the generated waste liquid is easy to treat, and the material belongs to an environment-friendly material.
Drawings
FIG. 1 shows the molecular formula of polyoxyethylene sorbitan monostearate (Tween 60);
FIG. 2 is a schematic view of the "core-shell structure" of the cationic-nonionic mixed aqueous polyurethane of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
The invention relates to cation-nonionic mixed waterborne polyurethane which is prepared from the following components in parts by weight: 18-30 parts of nonionic hydrophilic monomer, 30-50 parts of polyether diol, 20-35 parts of diisocyanate, 4-7 parts of chain extender and 2-6 parts of neutralizing acid.
Preferably, the nonionic hydrophilic monomer is polyoxyethylene sorbitan monostearate (Tween 60), polyoxyethylene sorbitan tristearate (Tween 65) or polyoxyethylene monostearate. As shown in FIGS. 1 and 2, Tween 60 is a nonionic emulsifier containing nonionic polyoxyethylene group-CH2CH2-O-with stearic acid-C18H38A hydrophobic group and a hydroxyl-OH group capable of reacting with isocyanate. The structural characteristics of Tween 65, polyoxyethylene monostearate and Tween 60 are similar, and the both contain nonionic hydrophilic polyoxyethylene group-CH2CH2-O-and having a long chain alkane hydrophobic group. When the nonionic hydrophilic monomer participates in the synthesis of polyurethane, on one hand, polyoxyethylene-CH is introduced into a polyurethane molecular chain segment2CH2the-O-group improves the hydrophilicity of a molecular chain segment, so as to form one of the components of the shell structure in the core-shell structure of the nonionic waterborne polyurethane, and simultaneously, the chain extender methyldiethanolamine forms quaternary ammonium salt cations after being neutralized by acid, so as to form one of the components of the shell structure in the core-shell structure of the cationic waterborne polyurethane, and the two components form the hydrophilic phase of the nonionic-cationic mixed waterborne polyurethane and are dissolved in water; in another aspect, stearic acid-C18H38The hydrophobic groups and the same hydrophobic groups in the polyurethane main chain, such as urethane bonds, form a core structure component in a core-shell structure, and the core-shell structure component with the pH value of 5 is prepared7-cationic-nonionic hybrid aqueous polyurethane stably dispersed in the textile size.
In the weakly acidic to neutral textile size with the pH value of 5-7, the system contains more cationic H+The nonionic-cationic aqueous polyurethane contains quaternary ammonium salt type cations, the quaternary ammonium salt type cations and H in a slurry system+Like charges repel each other, thereby stably dispersing; while the hydrophilicity of the non-ionic hydrophilic groups is completely free of H+And pH value influence, so that the nonionic-cationic mixed waterborne polyurethane can be stably dispersed in neutral or weakly acidic textile slurry under the condition of being diluted to 20-100 times compared with common anionic waterborne polyurethane.
Preferably, the polyether diol is one or more of polyether N-205, polyether N-210, polyether N-220 and polyether N-330. The diisocyanate is one or more of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate and carbodiimide modified MDI. The chain extender is methyl diethanolamine. The neutralizing acid is one or more of acetic acid, 2-hydroxypropionic acid and butyric acid.
The invention also comprises a preparation method of the cation-nonionic mixed type waterborne polyurethane, which comprises the following steps:
1) heating the nonionic hydrophilic monomer and the polyether glycol to 100-125 ℃ and then carrying out vacuum dehydration treatment;
2) cooling the product subjected to vacuum dehydration treatment in the step 1) to 50-60 ℃, adding diisocyanate once, and carrying out heat preservation treatment;
3) cooling the product subjected to heat preservation treatment in the step 2) to 30-40 ℃, dropwise adding an acetone solution containing a chain extender, adding a neutralizing acid after dropwise adding, stirring, and then adding deionized water for emulsification treatment under high-speed dispersion;
4) heating the product emulsified in the step 3) to 60-75 ℃, and pumping out acetone under a vacuum condition to obtain the product.
Further, the temperature in the step 3) can be reduced to 30-40 ℃, an acetone solution containing the chain extender is dripped, and then the neutralization acid is added after the dripping is finished, and the mixture is stirred, and then is added into deionized water for emulsification treatment under high-speed dispersion; or, cooling to 30-40 ℃, dropwise adding an acetone solution containing a chain extender, and after dropwise adding, adding a deionized water solution containing a neutralizing acid under high-speed dispersion for emulsification treatment.
Further, in the step 1), the vacuum dehydration treatment is specifically vacuum dehydration for 1.5-2.5h, and the vacuum degree is between 0.08 and 1.0 MPa; in the step 2), the heat preservation treatment is specifically heat preservation for 2.5 to 3.5 hours at the temperature of between 50 and 70 ℃; in the step 3), the acetone solution containing the chain extender is an acetone solution containing the chain extender with the mass concentration of 7.5-15%, the dripping time of the acetone solution containing the chain extender is 30 min-1 h, and the stirring speed of high-speed dispersion is 500-2000 r/min; in the step 4), the vacuum condition is specifically that the vacuum degree is between 0.04 and 1.0 MPa.
The invention also comprises the application of the cation-nonionic mixed type waterborne polyurethane in textile sizing agent.
The invention also comprises a preparation method of the textile size, which comprises the following steps:
a) adding deionized water into a reaction bottle, and adding starch for textile sizing agent under a stirring state, wherein the stirring speed is 120-240 r/min, and the stirring time is 5-10 min;
b) adding the cation-nonionic waterborne polyurethane into a reaction bottle, heating to 95-100 ℃, and boiling for 20-40min to obtain the cationic-nonionic waterborne polyurethane.
Example 1
1.1, preparing cation-nonionic mixed waterborne polyurethane WPU-1
Adding 100g of polyether N-210 and 50g of polyoxyethylene sorbitan monostearate (Tween 60) into a reaction bottle, heating to 120 ℃, and dehydrating in vacuum for 2h at the vacuum degree of 0.09 MPa; cooling to 50 ℃, adding 88.8g of IPDI, slowly heating to 70 ℃, and keeping the temperature for 3 h; cooling to 35 ℃, slowly dropwise adding 150g of mixed solution (15 g of methyldiethanolamine and 135g of acetone), adding 11.3g of lactic acid after dropwise adding is finished for 1h, neutralizing and stirring; 492g of deionized water is added under high-speed dispersion for emulsification, the stirring speed is 1000r/min, and the high-speed dispersion is carried out for 1 h; heating to 50 ℃, vacuumizing to remove acetone, and discharging to obtain the WPU-1. The WPU-1 has a solid content of 35%, a translucent appearance, a viscosity of 8160mPa · s, and a pH value of 6.0.
1.2 preparation of WPU-1-containing textile size JL-1
Adding 88g of deionized water into a reaction bottle, adding 9g of acidic starch under the stirring state, stirring at the speed of 120r/min, and stirring for 5 min; adding 3g WPU-1, heating to 95 deg.C, decocting for 30min, cooling, and discharging to obtain JB-1. The JB-1 has a solid content of 10%, milky turbid appearance, a pH value of 6.2, and a viscosity of 22S.
Example 2
2.1, preparing cation-nonionic mixed waterborne polyurethane WPU-2
100g of polyether N-220 and 60g of polyoxyethylene sorbitan tristearate are added into a reaction flask
(Tween 65) heating to 115 ℃, dehydrating for 2h in vacuum with the vacuum degree of 0.15 MPa; cooling to 55 deg.C, adding 55.9g TDI-80, slowly heating to 65 deg.C, and keeping the temperature for 3 h; cooling to 30 ℃, slowly dropwise adding 150g of mixed solution (17.9 g of methyldiethanolamine and 132.1g of acetone), adding 12.15g of lactic acid after dropwise adding for 1h, neutralizing and stirring; adding 568g of deionized water into the mixture for emulsification under high-speed dispersion, stirring at the speed of 1000r/min, and dispersing at a high speed for 1 h; heating to 50 ℃, vacuumizing to remove acetone, and discharging to obtain the WPU-2. WPU-2 has a solid content of 35%, yellowish and translucent appearance, viscosity of 4712mPa "s, and pH of 6.5.
2.2 preparation of WPU-2 containing textile size JL-2
Adding 88g of deionized water into a reaction bottle, adding 9g of acidic starch under the stirring state, stirring at the speed of 120r/min, and stirring for 5 min; adding 3g WPU-2, heating to 95 deg.C, decocting for 30min, cooling, and discharging to obtain JB-2. The JB-2 has a solid content of 10%, milky turbid appearance, a pH value of 6.3 and a viscosity of 22S.
Example 3
3.1, preparing cation-nonionic mixed waterborne polyurethane WPU-3
Adding 100g of polyether N-205 and 50g of polyoxyethylene monostearate into a reaction bottle, heating to 125 ℃, and dehydrating in vacuum for 2h with the vacuum degree of 0.3 MPa; cooling to 50 ℃, adding 78.3g of TDI-80, slowly heating to 65 ℃, and keeping the temperature for 3 hours; cooling to 30 ℃, slowly dropwise adding 150g of mixed solution (15 g of methyldiethanolamine and 135g of acetone), adding 10.2g of lactic acid after dropwise adding for 1h, neutralizing and stirring; 470.8g of deionized water is added under high-speed dispersion for emulsification, the stirring speed is 1000r/min, and the high-speed dispersion is carried out for 1 h; heating to 50 ℃, vacuumizing to remove acetone, discharging and discharging to obtain the WPU-3. The WPU-3 had a solid content of 35%, a yellowish translucent appearance, a viscosity of 5280mPa "s, and a pH of 6.5.
3.2 preparation of WPU-3 containing textile size JL-3
Adding 88g of deionized water into a reaction bottle, adding 9g of acidic starch under the stirring state, stirring at the speed of 120r/min, and stirring for 5 min; adding 3g WPU-3, heating to 95 deg.C, decocting for 30min, cooling, and discharging to obtain JB-3. The solid content of JB-3 is 10%, the appearance is milky turbid, the pH value is 6.3, and the viscosity is 22S.
Example 4
4.1, preparing cation-nonionic mixed waterborne polyurethane WPU-4
Adding 90g of polyether N-210 and 50g of polyoxyethylene sorbitan monostearate (Tween 60) into a reaction bottle, heating to 120 ℃, and dehydrating in vacuum for 2h at the vacuum degree of 0.09 MPa; cooling to 50 ℃, adding 80.8g of IPDI, slowly heating to 70 ℃, and keeping the temperature for 3 h; cooling to 35 ℃, slowly dropwise adding 150g of mixed solution (15 g of methyldiethanolamine and 135g of acetone), adding 12g of lactic acid after dropwise adding is finished for 1h, neutralizing and stirring; 492g of deionized water is added under high-speed dispersion for emulsification, the stirring speed is 1500r/min, and the high-speed dispersion is carried out for 1 h; heating to 50 ℃, vacuumizing to remove acetone, and discharging to obtain the WPU-4. The WPU-4 has a solid content of 35%, a translucent appearance, a viscosity of 7560mPa · s, and a pH of 6.0.
4.2 preparation of WPU-4 containing textile size JL-4
Adding 102.3g of deionized water into a reaction bottle, adding 10g of acidic starch under the stirring state, stirring at the speed of 120r/min, and stirring for 5 min; adding 4g WPU-4, heating to 95 deg.C, decocting for 30min, cooling, and discharging to obtain JB-4. The solid content of JB-4 is 10%, the appearance is milky turbid, the pH value is 6.2, and the viscosity is 23S.
Example 5
5.1, preparing cation-nonionic mixed waterborne polyurethane WPU-2
Adding 85g of polyether N-220 and 60g of polyoxyethylene sorbitan tristearate (Tween 65) into a reaction bottle, heating to 125 ℃, and dehydrating in vacuum for 2h at the vacuum degree of 0.15 MPa; cooling to 55 ℃, adding 65.8g of TDI-80, slowly heating to 65 ℃, and keeping the temperature for 3 h; cooling to 30 ℃, slowly dropwise adding 150g of mixed solution (15.7 g of methyldiethanolamine and 134.3g of acetone), adding 12.15g of lactic acid after dropwise adding for 1h, neutralizing and stirring; adding 568g of deionized water into the mixture for emulsification under high-speed dispersion, stirring at the speed of 1000r/min, and dispersing at a high speed for 1 h; heating to 50 ℃, vacuumizing to remove acetone, and discharging to obtain the WPU-4. WPU-4 has a solid content of 35%, yellowish and translucent appearance, viscosity of 5312mPa "s, and pH of 6.5.
5.2 preparation of WPU-4-containing textile size JL-5
Adding 102.3g of deionized water into a reaction bottle, adding 10g of acidic starch under the stirring state, stirring at the speed of 120r/min, and stirring for 5 min; adding 5g WPU-5, heating to 95 deg.C, decocting for 30min, cooling, and discharging to obtain JB-5. The solid content of JB-5 is 10%, the appearance is milky turbid, the pH value is 6.3, and the viscosity is 23S.
Example 6
Preparation of a textile size JL-0 containing polyvinyl alcohol PVA17-99
153g of deionized water is added into a reaction bottle, 10g of acidic starch is added under the stirring state, the stirring speed is 240r/min, and the stirring is carried out for 30 min; adding 7g of PVA17-99, heating to 100 ℃, boiling for 3h, cooling and discharging to obtain JB-0. The JB-0 solid content is 10%, the appearance is milky turbid, the pH value is 6.0, and the viscosity is 31S.
In the above examples, the viscosities of WPU-1 to WPU-5 were rotational viscosities measured at 25 ℃ according to the national standard GB/T2794-2013; the solid content of the sample is measured by weighing 1.0g of sample according to the national standard GB/T1725-2007 and placing the sample in an oven at 105 ℃ for 2 h; the pH values of the WPU-1-WPU-5 and the JL-1-JL-5 are measured at 25 ℃ by using a pH meter according to the national standard GB/T-6920-; the viscosities of JL-0 to JL-5 are 4 cup-coating viscosities, which are determined at 25 ℃ according to the national standard GB/T1723-1993.
And (3) performance comparison:
the textile slurry samples of the above examples and comparative examples were sent to the mortar textile center of the textile institute of east China university for testing, and the performance results after testing are shown in Table 1 below.
TABLE 1 comparison of properties of textile size prepared from cationic-nonionic aqueous polyurethane and polyvinyl alcohol
| JL-1 | JL-2 | JL-3 | JL-4 | JL-5 | JL-0 | |
| Sizing rate/% | 10.7 | 10.2 | 10.4 | 10.9 | 10.8 | 10.8 |
| Wear resistance/time | 44.9 | 42.7 | 43.6 | 51.6 | 50.9 | 43.5 |
| Elongation reduction/%) | 9.7 | 9.2 | 9.3 | 10.5 | 10.2 | 10.7 |
| Elongation/percent | 6.1 | 5.9 | 5.4 | 7.6 | 7.8 | 5.8 |
| strength/CN | 271.4 | 272.4 | 270.3 | 281.0 | 278.2 | 275.7 |
| Number of regenerated hairs (1mm/10m) | 48.3 | 48.1 | 48.7 | 47.1 | 46.2 | 50.0 |
As can be seen from Table 1, the textile size JL-1 to JL-5 prepared from the cationic-nonionic aqueous polyurethane has detection performances close to or better than those of JL-0. The number of regenerated hairiness of one particularly important performance parameter in the textile size is lower than that of JL-0, which indicates that the fuzzing degree of the textile size is relatively low in the spinning process and the spinning efficiency is relatively high, and the dosage of the cationic-nonionic aqueous polyurethane in JL-1-JL-5 is lower than that of the polyvinyl alcohol in JL-0, so that the cationic-nonionic mixed aqueous polyurethane can be completely used for replacing the polyvinyl alcohol to be applied to the textile size.
Various other modifications and changes may be made by those skilled in the art based on the above-described technical solutions and concepts, and all such modifications and changes should fall within the scope of the claims of the present invention.
Claims (8)
1. The cation-nonionic mixed waterborne polyurethane is characterized by being prepared from the following components in parts by weight:
18-30 parts of non-ionic hydrophilic monomer,
30-50 parts of polyether glycol,
18-45 parts of diisocyanate,
4-8 parts of a chain extender,
2-6 parts of a neutralizing acid,
the non-ionic hydrophilic monomer is one or more of polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate and polyoxyethylene monostearate,
the cation-nonionic mixed waterborne polyurethane is prepared by a preparation method comprising the following steps:
1) heating the nonionic hydrophilic monomer and the polyether glycol to 100-125 ℃, and then carrying out vacuum dehydration treatment;
2) cooling the product subjected to vacuum dehydration treatment in the step 1) to 50-60 ℃, and carrying out heat preservation treatment after adding diisocyanate at one time;
3) cooling the product subjected to heat preservation treatment in the step 2) to 30-40 ℃, dropwise adding an acetone solution containing a chain extender, adding a neutralizing acid after dropwise adding, stirring, and then adding deionized water under high-speed dispersion for emulsification treatment;
4) heating the product emulsified in the step 3) to 60-75 ℃, and pumping out acetone under a vacuum condition to obtain the emulsified product;
the chain extender is methyl diethanol amine, and the neutralized acid is one or more of acetic acid, 2-hydroxypropionic acid and butyric acid.
2. The cationic-nonionic hybrid aqueous polyurethane as claimed in claim 1, wherein the polyether glycol is one or more of polyether N-205, polyether N-210, and polyether N-220.
3. The cationic-nonionic hybrid aqueous polyurethane according to claim 1, wherein the diisocyanate is one or more of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, and carbodiimide-modified MDI.
4. A method for preparing the cationic-nonionic mixed aqueous polyurethane as described in any one of claims 1 to 3, comprising:
1) heating the nonionic hydrophilic monomer and the polyether glycol to 100-125 ℃, and then carrying out vacuum dehydration treatment;
2) cooling the product subjected to vacuum dehydration treatment in the step 1) to 50-60 ℃, and carrying out heat preservation treatment after adding diisocyanate at one time;
3) cooling the product subjected to heat preservation treatment in the step 2) to 30-40 ℃, dropwise adding an acetone solution containing a chain extender, adding a neutralizing acid after dropwise adding, stirring, and then adding deionized water under high-speed dispersion for emulsification treatment;
4) heating the product emulsified in the step 3) to 60-75 ℃, and pumping out acetone under a vacuum condition to obtain the product,
the non-ionic hydrophilic monomer is one or more of polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate and polyoxyethylene monostearate.
5. The preparation method of the cationic-nonionic mixed waterborne polyurethane as claimed in claim 4, wherein the temperature in step 3) is reduced to 30 ℃ to 40 ℃, an acetone solution containing a chain extender is added dropwise, and after the dropwise addition, the acetone solution containing a chain extender is added into a deionized water solution containing a neutralizing acid under high-speed dispersion for emulsification treatment.
6. The method for preparing the cationic-nonionic mixed waterborne polyurethane as claimed in claim 4 or 5, wherein in the step 1), the vacuum dehydration treatment is specifically vacuum dehydration for 1.5-2.5h, and the vacuum degree is between 0.08-1.0 MPa; in the step 2), the heat preservation treatment is specifically heat preservation for 2.5-3.5h at 50-70 ℃; in the step 3), the acetone solution containing the chain extender is an acetone solution containing the chain extender with the mass concentration of 7.5-15%, the dripping time of the acetone solution containing the chain extender is 30 min-1 h, and the stirring speed of high-speed dispersion is 500-2000 r/min; in the step 4), the vacuum condition is specifically that the vacuum degree is between 0.04 and 1.0 MPa.
7. Use of the cationic-nonionic mixed aqueous polyurethane according to any one of claims 1 to 3 in textile sizing.
8. The use of the cationic-nonionic hybrid aqueous polyurethane of claim 7 in a textile size, wherein the textile size is prepared by a method comprising:
a) adding deionized water into a reaction bottle, and adding starch for textile sizing agent under a stirring state, wherein the stirring speed is 120-240 r/min, and the stirring time is 5-10 min;
b) adding the cation-nonionic waterborne polyurethane into a reaction bottle, heating to 95-100 ℃, and boiling for 20-40min to obtain the cationic-nonionic waterborne polyurethane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711113992.9A CN107793546B (en) | 2017-11-13 | 2017-11-13 | Cation-nonionic mixed waterborne polyurethane and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711113992.9A CN107793546B (en) | 2017-11-13 | 2017-11-13 | Cation-nonionic mixed waterborne polyurethane and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107793546A CN107793546A (en) | 2018-03-13 |
| CN107793546B true CN107793546B (en) | 2020-10-16 |
Family
ID=61534984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711113992.9A Active CN107793546B (en) | 2017-11-13 | 2017-11-13 | Cation-nonionic mixed waterborne polyurethane and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107793546B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109822039B (en) * | 2019-04-01 | 2020-08-04 | 西南大学 | Biological adhesive binder based on waterborne polyurethane modification and preparation method thereof |
| CN113801286B (en) * | 2021-09-03 | 2022-07-08 | 华南农业大学 | Modified anionic vegetable oil-based waterborne polyurethane emulsion and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775578A (en) * | 2012-08-15 | 2012-11-14 | 中国海洋石油总公司 | Cation-nonionic mixed aqueous polyurethane emulsion and preparation method thereof |
| CN104592850A (en) * | 2014-12-31 | 2015-05-06 | 三棵树涂料股份有限公司 | Preparation method of super hydrophilic transparent anti-fog coating |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7465764B2 (en) * | 2004-06-18 | 2008-12-16 | Ocv Intellectual Captial, Llc | Epoxy sizing composition for filament winding |
| CN102153720B (en) * | 2011-02-10 | 2012-09-26 | 中国科学院过程工程研究所 | Method for preparing plant oil-based polyurethane material microspheres |
| CN103571164A (en) * | 2012-08-03 | 2014-02-12 | 上海载和实业投资有限公司 | Polylactic acid/core-shell structure composite material and preparation method thereof |
| CN104004142B (en) * | 2014-05-22 | 2016-05-18 | 浙江传化股份有限公司 | A kind of cation-non-ion aqueous polyurethane-poly acrylate composite emulsion and preparation method thereof |
| CN105273153A (en) * | 2014-07-24 | 2016-01-27 | 允友成(宿迁)复合新材料有限公司 | Degradable biological-based waterborne emulsion and preparation method thereof |
-
2017
- 2017-11-13 CN CN201711113992.9A patent/CN107793546B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775578A (en) * | 2012-08-15 | 2012-11-14 | 中国海洋石油总公司 | Cation-nonionic mixed aqueous polyurethane emulsion and preparation method thereof |
| CN104592850A (en) * | 2014-12-31 | 2015-05-06 | 三棵树涂料股份有限公司 | Preparation method of super hydrophilic transparent anti-fog coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107793546A (en) | 2018-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107793546B (en) | Cation-nonionic mixed waterborne polyurethane and preparation method and application thereof | |
| CN109868654B (en) | Water-based epoxy sizing agent and preparation method thereof | |
| CN101886336B (en) | Polyalcohol modified epoxy resin carbon fiber emulsion sizing agent component and preparation method thereof | |
| CN113897708B (en) | Oiling agent for polyacrylonitrile carbon fiber precursor and preparation method thereof | |
| CN102691207A (en) | Preparation method for ultraviolet resistant and damp-heat aging resistant PBO (polybenzoxazole) fiber | |
| CN111328827A (en) | Quaternized polysilsesquioxane nanosphere hybrid antibacterial material and preparation method thereof | |
| CN107760189A (en) | A kind of preparation method of environment-friendlywater-based water-based paint | |
| CN110219182B (en) | Method for quickly dyeing polyester textiles | |
| CN104278379B (en) | A kind of glass fiber reinforcement polyester composite filament and preparation method thereof | |
| CN113699796B (en) | Water-based modified resin sizing agent for carbon fibers and preparation and application thereof | |
| CN101880967A (en) | Method for preparing self-emulsifying carbon fiber sizing agent component | |
| CN114030250A (en) | High-elasticity-modulus high-strength glass fiber laminated board and preparation method thereof | |
| CN112160169A (en) | Environment-friendly fiber dipping solution, preparation method and application | |
| CN113480200B (en) | Dyeing process of glass fiber and colored glass fiber | |
| CN112760984B (en) | Method for preparing carbon fiber for composite material | |
| CN111978474B (en) | Preparation method of low-viscosity high-hydroxyl-value polymer surface reinforcing agent for paper | |
| CN103882710A (en) | Preparation method for environment-friendly type textile sizing agent | |
| CN103898754A (en) | Preparation method of textile size applicable to polyester fabrics | |
| CN115748009B (en) | Preparation method of water-repellent carpet non-woven fabric | |
| CN103924447A (en) | Preparation method of low-pollution textile sizing agent | |
| CN104278354A (en) | Preparation method of flesh-colored spandex | |
| CN113831494B (en) | Cardanol biological anti-wrinkle cross-linking agent and preparation method and application thereof | |
| CN109722901A (en) | A kind of polysulfone resin base carbon fibre suspension sizing agent and preparation method thereof | |
| CN111335039B (en) | Application of aliphatic polyurethane dispersion liquid | |
| CN113774716A (en) | Multifunctional auxiliary agent for improving paper strength and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |