CN114197212A - A kind of water-based polyurethane emulsification modified epoxy resin stiffener and preparation method thereof - Google Patents
A kind of water-based polyurethane emulsification modified epoxy resin stiffener and preparation method thereof Download PDFInfo
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- CN114197212A CN114197212A CN202210113406.5A CN202210113406A CN114197212A CN 114197212 A CN114197212 A CN 114197212A CN 202210113406 A CN202210113406 A CN 202210113406A CN 114197212 A CN114197212 A CN 114197212A
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- 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
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- 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
- D06M15/55—Epoxy resins
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- 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
- D06M15/572—Reaction products of isocyanates with polyesters or polyesteramides
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- 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/20—Treatment influencing the crease behaviour, the wrinkle resistance, the crease recovery or the ironing ease
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- Polyurethanes Or Polyureas (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a waterborne polyurethane emulsion modified epoxy resin stiffening agent and a preparation method thereof. Polyether diol or polyester diol, isophorone diisocyanate, 1, 2-hexadecanediol, bisphenol A, 2-dimethylolpropionic acid and triethylamine are used as raw materials to synthesize waterborne polyurethane, and the waterborne polyurethane is blocked by methyl ethyl ketoxime and subjected to high-speed shearing emulsification treatment to obtain waterborne polyurethane emulsion; and then sequentially adding epoxy resin and ethylenediamine to obtain the waterborne polyurethane emulsion modified epoxy resin stiffening agent. The waterborne polyurethane containing the long hydrophobic side chain and the bisphenol A chain segment synthesized by the invention has a good emulsifying effect on epoxy resin, and in the baking stage of finishing, the blocked isocyanate group in the waterborne polyurethane is deblocked and can perform a crosslinking reaction with hydroxyl groups in epoxy resin molecules or some active groups on fibers, so that the stiffening finishing effect of fabrics can be improved, and the water washing resistance of the finishing effect can be effectively improved.
Description
Technical Field
The invention relates to the technical field of synthesis of textile printing and dyeing auxiliaries, and particularly relates to an aqueous polyurethane emulsion modified epoxy resin stiffening agent and a preparation method thereof.
Technical Field
Stiffening finishing is widely applied to post-finishing of fabrics such as lining cloth, bag cloth, advertising cloth, tents and the like, and aims to form a film or generate cross-linking inside, among or on the surface of fibers by using a stiffening agent so as to endow the fabrics with stiff, smooth, full and thick styles. The fabrics finished by the melamine resin stiffening agent in the market at present have good stiffness, shrinkage, elasticity and hand feeling, but the finished fabrics release free formaldehyde and are restricted in use because the fabrics do not conform to environmental regulations; the widely used synthetic stiffening agents are polyvinyl alcohols, polyvinyl acetate and polyacrylates, the polyvinyl alcohol stiffening agents have good rheological property, can form films with higher strength, and have good stiffening finishing effect on cellulose fibers, but the finishing agents are easy to soften and seep out after being heated on fabrics, and the fabric stiffness has poor washing fastness; the stiffening agent of polyacrylic acid and polyvinyl acetate ester is inferior to the stiffening agent of polyvinyl alcohol, and the stiffening effect to synthetic fiber fabric is inferior to that of melamine resin, and the fabric lacks thick feeling and has poor rebound resilience after finishing. Therefore, the development of the stiffening agent which has a good stiffening effect on the fabric, can endow the fabric with certain resilience, and is safe, environment-friendly and pollution-free has very important significance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a stiffening agent which has a good stiffening effect on fabrics, can endow the fabrics with certain resilience, and is safe and environment-friendly, and a preparation method thereof.
The technical scheme for realizing the aim of the invention is to provide a preparation method of the waterborne polyurethane emulsion modified epoxy resin stiffening agent, which comprises the following steps:
1. a preparation method of an aqueous polyurethane emulsion modified epoxy resin stiffening agent is characterized by comprising the following steps:
(1) according to the mass parts, 20 parts of polyether diol or polyester diol and 10-20 parts of acetone are mixed and then added into a reaction container provided with a stirrer, a thermometer, a constant-pressure dropping funnel and a condensation reflux device, nitrogen is introduced, the stirring and condensation reflux device is started, the temperature is raised to 70-80 ℃, 5-15 parts of isophorone diisocyanate is dropwise added at a constant speed within 20-30 min, and the heat preservation reaction is carried out for 2-3 h at the temperature of 70-80 ℃; adjusting the temperature to 80-90 ℃, adding 0.27-1.14 parts of 1, 2-hexadecanediol into the reaction vessel, and carrying out heat preservation reaction for 1-1.5 h at the temperature of 80-90 ℃; adding 0.23 part of bisphenol A into a reaction container, and carrying out heat preservation reaction at the temperature of 80-90 ℃ for 1-1.5 h; mixing 1.32-2.89 parts of 2, 2-dimethylolpropionic acid and 3 parts of N, N-dimethylformamide, adding into a reaction container, and carrying out heat preservation reaction at the temperature of 80-90 ℃ for 1-1.5 h; cooling to 40-50 ℃, adding 0.99-2.18 parts of triethylamine into the reaction container, and carrying out heat preservation reaction at the temperature of 40-50 ℃ for 0.5-1 h; heating to 80-90 ℃, adding 0.91-6.19 parts of methyl ethyl ketoxime into the reaction vessel, and carrying out heat preservation reaction at 80-90 ℃ for 1-1.5 h. Adjusting the temperature to 110-120 ℃, the pressure to-0.09-0.1 Mpa, distilling under reduced pressure, and removing acetone and N, N-dimethylformamide to obtain waterborne polyurethane;
(2) adding 217-344 parts of deionized water into the waterborne polyurethane prepared in the step (1), and stirring and emulsifying at the rotating speed of 1000-1500 rpm to obtain a waterborne polyurethane emulsion;
(3) slowly adding 24-38 parts of epoxy resin into the aqueous polyurethane emulsion prepared in the step (2) at a constant speed, and stirring and emulsifying at a rotating speed of 1000-1500 rpm to obtain an epoxy resin-aqueous polyurethane emulsion;
(4) and (3) adding 1-3 parts of ethylenediamine into the epoxy resin-aqueous polyurethane emulsion prepared in the step (3), and stirring at a rotating speed of 200-500 rpm to obtain the aqueous polyurethane emulsion modified epoxy resin stiffening agent.
The invention provides a preparation method of an aqueous polyurethane emulsification modified epoxy resin stiffening agent, and a preferable scheme is as follows: the polyether diol or polyester diol used in the step (1) is one of polyethylene glycol 2000, polypropylene glycol 2000 and polycaprolactone diol 2000.
The technical scheme of the invention also comprises the waterborne polyurethane emulsion modified epoxy resin stiffening agent obtained by the preparation method.
The synthesis reaction formula of the waterborne polyurethane emulsion modified epoxy resin stiffening agent prepared by the technical scheme of the invention is as follows:
R1comprises the following steps:
R2comprises the following steps:
R3comprises the following steps:
wherein, when R is
When n = 34;
when R is
When n = 45;
when R is
When n = 35;
and a is more than or equal to 1 and less than or equal to 4, b =1, and c is more than or equal to 9 and less than or equal to 22.
Epoxy resin has excellent mechanical and thermal properties, such as high hardness, high strength, good thermal stability and the like, and has the defects of high brittleness, poor toughness, poor impact resistance and the like. The waterborne polyurethane has the advantages of good toughness, excellent rebound resilience, good wear resistance and the like after film forming. The waterborne polyurethane modified epoxy resin is adopted, the advantages of the waterborne polyurethane modified epoxy resin and the epoxy resin can be combined, and the synthesized stiffening agent can endow the fabric with good stiffness and certain resilience, and simultaneously meets the requirements of environmental protection regulations.
The principle of the invention is as follows: the waterborne polyurethane synthesized by using polyether diol or polyester diol, isophorone diisocyanate, 1, 2-hexadecanediol, bisphenol A, 2-dimethylolpropionic acid, triethylamine and methyl ethyl ketoxime as raw materials simultaneously contains a hydrophobic chain segment and a hydrophilic group, so that the waterborne polyurethane is a high molecular compound with surface activity. The hydrophobic epoxy resin is added into the aqueous polyurethane emulsion to obtain the epoxy resin-aqueous polyurethane emulsion, and the aqueous polyurethane can emulsify the epoxy resin. Meanwhile, the waterborne polyurethane contains chain segments with similar molecular structures with the epoxy resin, so that intermolecular force between the waterborne polyurethane and the epoxy resin is improved. Therefore, the epoxy resin has good stability in the aqueous polyurethane emulsion without coagulation. And then, adding ethylenediamine into the epoxy resin-waterborne polyurethane emulsion to obtain the waterborne polyurethane emulsion modified epoxy resin stiffening agent. Because the epoxy resin is emulsified by the waterborne polyurethane and is wrapped by the hydrophobic chain of the waterborne polyurethane, the ethylenediamine can not immediately carry out curing reaction with the epoxy resin and is remained in the water phase. In the baking stage of the textile finished by the stiffening agent, the epoxy resin is released along with the evaporation of moisture, and the epoxy resin film forming a cross-linked net structure is fixed on the surface of the textile when meeting the curing reaction of ethylene diamine, so that the textile is endowed with good stiffness. And then, the blocked isocyanate group in the waterborne polyurethane is deblocked, and the blocked isocyanate group and hydroxyl in the epoxy resin molecule or some active groups on the fiber are subjected to a crosslinking reaction, so that the stiffening effect is further improved, and meanwhile, the fabric is endowed with good resilience. In addition, the low-polarity long hydrophobic side chain in the waterborne polyurethane tends to be arranged on the surface of the stiffening agent film, so that the water washing resistance of the finishing effect is improved.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the waterborne polyurethane emulsion modified epoxy resin stiffening agent synthesized by the invention not only can endow the fabric with good stiffness, but also can endow the fabric with certain resilience, and is safe, environment-friendly and pollution-free.
2. The waterborne polyurethane synthesized by the invention can be used as an emulsifier of epoxy resin, and on one hand, no emulsifier is added, so that the adverse effect of the added emulsifier on the performance of a stiffening agent is avoided; on the other hand, the waterborne polyurethane can also play a role in modifying the epoxy resin.
3. According to the invention, a low-polarity long hydrophobic side chain is introduced during the synthesis of the waterborne polyurethane, so that on one hand, the emulsifying property of the waterborne polyurethane is improved by the long hydrophobic side chain; on the other hand, long hydrophobic side chains tend to align on the surface of the stiffener film during baking, improving the wash-resistance of the finish.
4. The invention introduces chain segments with similar molecular structures with the epoxy resin when synthesizing the waterborne polyurethane, improves intermolecular force between the waterborne polyurethane and the epoxy resin, and leads the epoxy resin to be more stable in the waterborne polyurethane emulsion.
Drawings
FIG. 1 is an infrared spectrum of an aqueous polyurethane emulsion modified epoxy resin stiffening agent provided in example 1 of the present invention;
FIG. 2 is an infrared spectrum of an aqueous polyurethane emulsion modified epoxy resin stiffening agent provided in example 2 of the present invention;
fig. 3 is an infrared spectrum of the waterborne polyurethane emulsion modified epoxy resin stiffening agent provided in embodiment 3 of the present invention.
Detailed Description
The technical solution of the present invention is further described with reference to the accompanying drawings and the detailed description.
Example 1
The embodiment provides a waterborne polyurethane emulsion modified epoxy resin stiffening agent, and a preparation method thereof comprises the following steps:
(1) mixing 20g of polycaprolactone diol 2000 and 10g of acetone, adding the mixture into a reaction vessel provided with a stirrer, a thermometer, a constant-pressure dropping funnel and a condensation reflux device, introducing nitrogen, starting the stirring and condensation reflux device, heating to 70 ℃, dropwise adding 5.38g of isophorone diisocyanate at a constant speed within 20min, and carrying out heat preservation reaction at the temperature of 70 ℃ for 2 h; adjusting the temperature to 80 ℃, adding 0.27g of 1, 2-hexadecanediol into a reaction vessel, and carrying out heat preservation reaction for 1h at the temperature of 80 ℃; adding 0.23g of bisphenol A into a reaction vessel, and carrying out heat preservation reaction for 1h at the temperature of 80 ℃; mixing 1.32g of 2, 2-dimethylolpropionic acid and 3g N, N-dimethylformamide, adding into a reaction vessel, and reacting at 80 ℃ for 1 h; cooling to 40 ℃, adding 0.99g of triethylamine into the reaction vessel, and carrying out heat preservation reaction for 0.5h at the temperature of 40 ℃; the temperature is increased to 80 ℃, 0.91g of methyl ethyl ketoxime is added into a reaction vessel, and the reaction is carried out for 1 hour under the temperature of 80 ℃. Adjusting the temperature to 110 ℃ and the pressure to-0.09 Mpa, and removing the acetone and the N, N-dimethylformamide by reduced pressure distillation to obtain the waterborne polyurethane.
(2) 217.08g of deionized water is added into the waterborne polyurethane prepared in the step (1), and stirring and emulsification are carried out at the rotating speed of 1000 r/min, so as to obtain the waterborne polyurethane emulsion.
(3) And (3) slowly adding 24.12g of epoxy resin into the aqueous polyurethane emulsion prepared in the step (2) at a constant speed, and stirring and emulsifying at a rotating speed of 1000 revolutions per minute to obtain the epoxy resin-aqueous polyurethane emulsion.
(4) And (3) adding 1.19g of ethylenediamine into the epoxy resin-aqueous polyurethane emulsion prepared in the step (3), and stirring at the rotating speed of 200 revolutions per minute to obtain the aqueous polyurethane emulsion modified epoxy resin stiffening agent.
Referring to the attached figure 1, it is an infrared spectrogram of the waterborne polyurethane emulsion modified epoxy resin stiffening agent prepared in the embodiment; 3360 cm-1Is the stretching vibration peak of N-H, 2944cm-1、2865cm-1is-CH2and-CH31728cm of the stretching vibration peak-1Is the stretching vibration peak of C = O in carbamate and polyester dihydric alcohol, 1459cm-1、1557cm-1Is the stretching vibration peak of C = C in benzene ring, 1667cm-1Stretching vibration peak of 1235cm with C = N-1Is the stretching vibration peak of C-O, 1094cm-1Is the stretching vibration peak of C-O-C, 1042cm-1Is the stretching vibration peak of the aliphatic amine C-N at 740cm is- (CH)2）nPeak of rocking vibration of 2270cm-1The characteristic peak of the-NCO group does not appear, which indicates that the-NCO group is blocked by the methyl ethyl ketone oxime, and the target product is synthesized.
Example 2:
the embodiment provides a waterborne polyurethane emulsion modified epoxy resin stiffening agent, and a preparation method thereof comprises the following steps:
(1) mixing 20g of polypropylene glycol 2000 and 12g of acetone, adding the mixture into a reaction vessel provided with a stirrer, a thermometer, a constant-pressure dropping funnel and a condensation reflux device, introducing nitrogen, starting the stirring and condensation reflux device, heating to 75 ℃, dropwise adding 9.65g of isophorone diisocyanate at a constant speed within 25min, and carrying out heat preservation reaction for 2.5h at the temperature of 75 ℃; adjusting the temperature to 85 ℃, adding 0.64g of 1, 2-hexadecanediol into the reaction vessel, and carrying out heat preservation reaction for 1.3h at the temperature of 85 ℃; adding 0.23g of bisphenol A into a reaction vessel, and carrying out heat preservation reaction at the temperature of 85 ℃ for 1.3 h; mixing 1.83g of 2, 2-dimethylolpropionic acid and 3g N, N-dimethylformamide, adding into a reaction vessel, and reacting at 85 ℃ for 1.3h under heat preservation; cooling to 45 ℃, adding 1.52g of triethylamine into the reaction container, and carrying out heat preservation reaction for 0.5h at the temperature of 45 ℃; the temperature is increased to 85 ℃, 3.43g of methyl ethyl ketoxime is added into a reaction vessel, and the reaction is carried out for 1.3h under the temperature of 85 ℃. Adjusting the temperature to 115 ℃ and the pressure to-0.095 Mpa, and distilling under reduced pressure to remove acetone and N, N-dimethylformamide to obtain the waterborne polyurethane.
(2) 322.02g of deionized water is added into the waterborne polyurethane prepared in the step (1), and stirring and emulsification are carried out at the rotating speed of 1200 r/min, so as to obtain the waterborne polyurethane emulsion.
(3) And (3) slowly dripping 35.78g of epoxy resin into the aqueous polyurethane emulsion prepared in the step (2) at a constant speed, and stirring and emulsifying at a rotating speed of 1200 r/min to obtain the epoxy resin-aqueous polyurethane emulsion.
(4) And (3) adding 2.85g of ethylenediamine into the epoxy resin-aqueous polyurethane emulsion prepared in the step (3), and stirring at the rotating speed of 300 revolutions per minute to obtain the aqueous polyurethane emulsion modified epoxy resin stiffening agent.
Referring to the attached figure 2, it is an infrared spectrum of the waterborne polyurethane emulsion modified epoxy resin stiffening agent prepared in this example; 3326cm-1Is the stretching vibration peak of N-H, 2870cm-1-2989cm-1Peaks within the range of-CH2and-CH31713cm of stretching vibration peak-1Is the stretching vibration peak of C = O in carbamate, 1459cm-1、1518cm-1Is the stretching vibration peak of C = C in benzene ring，1238cm-1Is the stretching vibration peak of C-O, 1096cm-1Is the stretching vibration peak of C-O-C, 1015cm-1740cm is the stretching vibration peak of aliphatic amine C-N-1Is represented by- (CH)2）nPeak of rocking vibration of 2270cm-1The characteristic peak of the-NCO group does not appear, which indicates that the-NCO group is blocked by the acetophenone oxime, and the target product is synthesized.
Example 3:
the embodiment provides a waterborne polyurethane emulsion modified epoxy resin stiffening agent, and a preparation method thereof comprises the following steps:
(1) mixing 20g of polyethylene glycol 2000 and 20g of acetone, adding the mixture into a reaction container provided with a stirrer, a thermometer, a constant-pressure dropping funnel and a condensation reflux device, introducing nitrogen, starting the stirring and condensation reflux device, heating to 80 ℃, dropwise adding 14.78g of isophorone diisocyanate at a constant speed within 30min, and carrying out heat preservation reaction at the temperature of 80 ℃ for 3 h; adjusting the temperature to 90 ℃, adding 1.14g of 1, 2-hexadecanediol into a reaction vessel, and carrying out heat preservation reaction at the temperature of 90 ℃ for 1.5 h; adding 0.23g of bisphenol A into a reaction vessel, and carrying out heat preservation reaction at the temperature of 90 ℃ for 1.5 h; 2.89g of 2, 2-dimethylolpropionic acid and 3g N, N-dimethylformamide are mixed and then added into a reaction vessel, and the mixture is subjected to heat preservation reaction at the temperature of 90 ℃ for 1.5 h; cooling to 50 ℃, adding 2.18g of triethylamine into the reaction container, and carrying out heat preservation reaction for 0.5h at the temperature of 50 ℃; the temperature is increased to 90 ℃, 6.19g of methyl ethyl ketoxime is added into a reaction vessel, and the reaction is carried out for 1.5h under the temperature of 90 ℃. Adjusting the temperature to 120 ℃ and the pressure to-0.1 Mpa, and removing acetone and N, N-dimethylformamide by reduced pressure distillation to obtain the waterborne polyurethane.
(2) 343.80g of deionized water is added into the waterborne polyurethane prepared in the step (1), and the mixture is stirred and emulsified at the rotating speed of 1500 rpm to obtain the waterborne polyurethane emulsion.
(3) 38.20g of epoxy resin is slowly added into the aqueous polyurethane emulsion prepared in the step (2) at a constant speed, and the mixture is emulsified at a rotating speed of 1500 revolutions per minute to obtain the epoxy resin-aqueous polyurethane emulsion.
(4) And (3) adding 3.03g of ethylenediamine into the epoxy resin-aqueous polyurethane emulsion prepared in the step (3), and stirring at the rotating speed of 500 revolutions per minute to obtain the aqueous polyurethane emulsion modified epoxy resin stiffening agent.
Referring to the attached figure 3, it is an infrared spectrum of the waterborne polyurethane emulsion modified epoxy resin stiffening agent prepared in this example. 3325cm-1Is the stretching vibration peak of N-H, 2882cm-1is-CH2and-CH31713cm of stretching vibration peak-1Is the stretching vibration peak of C = O in carbamate, 1465cm-1、1537cm-1Is the stretching vibration peak of C = C in benzene ring, 1667cm-1Peak of stretching vibration at C = N, 1240cm-1The stretching vibration peak of C-O is 1106cm-1Is the stretching vibration peak of C-O-C, 1060cm-1Is the stretching vibration peak of the aliphatic amine C-N, 745cm-1Is- (CH)2）nPeak of rocking vibration of 2270cm-1The characteristic peak of the-NCO group does not appear, which indicates that the-NCO group is blocked by the acetophenone oxime, and the target product is synthesized.
The pure cotton fabric is taken as a sample to be treated, and the waterborne polyurethane emulsified and modified epoxy resin stiffening agent, the commercially available polyacrylate stiffening agent and the commercially available melamine resin stiffening agent provided by the embodiments 1, 2 and 3 of the invention are respectively adopted as finishing liquids (the use amounts of the stiffening agents are the same), so that the sample is treated.
The polyester fabric is used as a sample to be treated, and the waterborne polyurethane emulsified and modified epoxy resin stiffening agent, the commercially available polyacrylate stiffening agent and the commercially available melamine resin stiffening agent provided by the embodiments 1, 2 and 3 of the invention are respectively used as finishing liquids (the use amounts of the stiffening agents are the same), so that the sample is treated.
1. Finishing process
The fabric used was: pure cotton fabric, polyester fabric;
the finishing process comprises the following steps: the dip finishing liquid (the stiffening agent content is 120 g/L) is 1min → the two-dipping and two-rolling (the rolling retention rate is 70%) → the pre-baking (100 ℃, 2 min) → the baking (120 ℃, 30 min) → the baking (160 ℃, 2 min) → the water washing (40 ℃, 10 min) → the baking → the performance testing.
2. Test methods and standards
The method for testing the stiffness of the fabric is as follows GB/T7689.4-2013 part 4 of test method of reinforcing material woven fabric: measurement of flexural stiffness method. The stiffness of the fabric is expressed in terms of the bending length, and the higher the measured value, the better the stiffening effect.
The warp breaking strength of the pure cotton fabric is determined according to GB/T3923.1-2013 part 1 of the tensile property of textile fabrics: determination of breaking Strength and elongation at Break (bar method).
The weft breaking strength of the polyester fabric is determined according to GB/T3923.1-2013 part 1 of the tensile property of textile fabrics: determination of breaking Strength and elongation at Break (bar method).
Fabric whiteness was measured on an UltraScan XE computer color measuring and matching instrument.
The fastness to washing of the stiffness of the fabric is tested in a color fastness to washing tester model SW-12A with reference to GB/T8629-. Soaking the fabric in soap solution (2 g/L of soaping agent), oscillating and washing for 10min at 40 ℃, and then washing for 2min with clear water, namely completing one-time washing for 5 times.
The total crease recovery angle test of the warp direction and the weft direction of the pure cotton fabric is carried out according to the horizontal method in GB/T3819-1997 method for measuring the crease recovery of the textile fabric. The results were averaged for 5 samples in each of the warp and weft directions.
The free formaldehyde on the cloth surface of the fabric is measured according to the method of GB/T5543-2006 determination of the total formaldehyde content, the free formaldehyde content and the hydroxymethyl formaldehyde content of the resin finishing agent.
The results of the application performance test comparison of the waterborne polyurethane emulsion modified epoxy resin stiffening agent, the commercially available polyacrylate stiffening agent and the commercially available melamine resin stiffening agent prepared in examples 1, 2 and 3 of the present invention before and after the treatment of the pure cotton fabric are shown in table 1.
The comparative results of the performance tests of the waterborne polyurethane emulsion modified epoxy resin stiffening agent, the commercially available polyacrylate stiffening agent and the commercially available melamine resin stiffening agent after polyester fabric stiffening finishing prepared in the embodiments 1, 2 and 3 of the invention are shown in table 2.
TABLE 1 comparison of performance test results before and after stiffening finishing of pure cotton fabric
TABLE 2 comparison of performance test results before and after stiffening finishing of polyester fabrics
Claims (4)
1. A preparation method of an aqueous polyurethane emulsion modified epoxy resin stiffening agent is characterized by comprising the following steps:
(1) according to the mass parts, 20 parts of polyether diol or polyester diol and 10-20 parts of acetone are mixed and then added into a reaction container provided with a stirrer, a thermometer, a constant-pressure dropping funnel and a condensation reflux device, nitrogen is introduced, the stirring and condensation reflux device is started, the temperature is raised to 70-80 ℃, 5-15 parts of isophorone diisocyanate is dropwise added at a constant speed within 20-30 min, and the heat preservation reaction is carried out for 2-3 h at the temperature of 70-80 ℃; adjusting the temperature to 80-90 ℃, adding 0.27-1.14 parts of 1, 2-hexadecanediol into the reaction vessel, and carrying out heat preservation reaction for 1-1.5 h at the temperature of 80-90 ℃; adding 0.23 part of bisphenol A into a reaction container, and carrying out heat preservation reaction at the temperature of 80-90 ℃ for 1-1.5 h; mixing 1.32-2.89 parts of 2, 2-dimethylolpropionic acid and 3 parts of N, N-dimethylformamide, adding into a reaction container, and carrying out heat preservation reaction at the temperature of 80-90 ℃ for 1-1.5 h; cooling to 40-50 ℃, adding 0.99-2.18 parts of triethylamine into the reaction container, and carrying out heat preservation reaction at the temperature of 40-50 ℃ for 0.5-1 h; heating to 80-90 ℃, adding 0.91-6.19 parts of methyl ethyl ketoxime into the reaction vessel, and carrying out heat preservation reaction at 80-90 ℃ for 1-1.5 h.
2. Adjusting the temperature to 110-120 ℃, the pressure to-0.09-0.1 Mpa, distilling under reduced pressure, and removing acetone and N, N-dimethylformamide to obtain waterborne polyurethane;
(2) adding 217-344 parts of deionized water into the waterborne polyurethane prepared in the step (1), and stirring and emulsifying at the rotating speed of 1000-1500 rpm to obtain a waterborne polyurethane emulsion;
(3) slowly adding 24-38 parts of epoxy resin into the aqueous polyurethane emulsion prepared in the step (2) at a constant speed, and stirring and emulsifying at a rotating speed of 1000-1500 rpm to obtain an epoxy resin-aqueous polyurethane emulsion;
(4) and (3) adding 1-3 parts of ethylenediamine into the epoxy resin-aqueous polyurethane emulsion prepared in the step (3), and stirring at a rotating speed of 200-500 rpm to obtain the aqueous polyurethane emulsion modified epoxy resin stiffening agent.
3. The preparation method of the waterborne polyurethane emulsion modified epoxy resin stiffening agent according to claim 1, characterized in that: the polyether diol or polyester diol in the step (1) is one of polyethylene glycol 2000, polypropylene glycol 2000 and polycaprolactone diol 2000.
4. The waterborne polyurethane emulsion modified epoxy resin stiffening agent obtained by the preparation method of claim 1.
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| CN202210113406.5A CN114197212B (en) | 2022-01-30 | 2022-01-30 | A kind of water-based polyurethane emulsion modified epoxy resin stiffener and preparation method thereof |
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| CN116119948A (en) * | 2023-02-01 | 2023-05-16 | 巨石集团有限公司 | Glass fiber impregnating compound and preparation method and application thereof |
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| CN103608371A (en) * | 2011-08-22 | 2014-02-26 | 巴斯夫日本股份有限公司 | Water-based coating composition and method for forming multilayer coating film using said composition |
| CN105175679A (en) * | 2015-09-25 | 2015-12-23 | 三棵树涂料股份有限公司 | Waterborne polyurethane emulsion modified by epoxy resin and preparation method thereof |
| CN106317374A (en) * | 2016-08-18 | 2017-01-11 | 上海闵轩钢结构工程有限公司 | Method for preparing blocked polyurethane-epoxy resin composite emulsifier |
| CN110156953A (en) * | 2019-05-29 | 2019-08-23 | 苏州大学 | A color-fixing agent for reactive dyes and its preparation method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103608371A (en) * | 2011-08-22 | 2014-02-26 | 巴斯夫日本股份有限公司 | Water-based coating composition and method for forming multilayer coating film using said composition |
| CN105175679A (en) * | 2015-09-25 | 2015-12-23 | 三棵树涂料股份有限公司 | Waterborne polyurethane emulsion modified by epoxy resin and preparation method thereof |
| CN106317374A (en) * | 2016-08-18 | 2017-01-11 | 上海闵轩钢结构工程有限公司 | Method for preparing blocked polyurethane-epoxy resin composite emulsifier |
| CN110156953A (en) * | 2019-05-29 | 2019-08-23 | 苏州大学 | A color-fixing agent for reactive dyes and its preparation method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116119948A (en) * | 2023-02-01 | 2023-05-16 | 巨石集团有限公司 | Glass fiber impregnating compound and preparation method and application thereof |
| CN116119948B (en) * | 2023-02-01 | 2024-09-27 | 巨石集团有限公司 | Glass fiber impregnating compound and preparation method and application thereof |
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