CN115947947A - Functional finishing agent copolymer and preparation method thereof - Google Patents
Functional finishing agent copolymer and preparation method thereof Download PDFInfo
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- CN115947947A CN115947947A CN202211673298.3A CN202211673298A CN115947947A CN 115947947 A CN115947947 A CN 115947947A CN 202211673298 A CN202211673298 A CN 202211673298A CN 115947947 A CN115947947 A CN 115947947A
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 47
- 229920002635 polyurethane Polymers 0.000 claims abstract description 31
- 239000004814 polyurethane Substances 0.000 claims abstract description 31
- 239000005018 casein Substances 0.000 claims abstract description 28
- 235000021240 caseins Nutrition 0.000 claims abstract description 28
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims abstract description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 17
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000002202 Polyethylene glycol Substances 0.000 claims description 17
- 229920001223 polyethylene glycol Polymers 0.000 claims description 17
- 239000000839 emulsion Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 10
- -1 hydroxypropyl Chemical group 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 150000003254 radicals Chemical class 0.000 claims description 8
- 238000007334 copolymerization reaction Methods 0.000 claims description 7
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 7
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 7
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 5
- 229960003237 betaine Drugs 0.000 claims description 5
- 239000003995 emulsifying agent Substances 0.000 claims description 5
- 239000012875 nonionic emulsifier Substances 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 claims description 3
- 229940073507 cocamidopropyl betaine Drugs 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- WJYAJBDKANFOID-AWEZNQCLSA-N (2s)-2-(dodecylamino)propanoic acid Chemical compound CCCCCCCCCCCCN[C@@H](C)C(O)=O WJYAJBDKANFOID-AWEZNQCLSA-N 0.000 claims description 2
- UQTBADOQMIRHSO-FQEVSTJZSA-N (2s)-2-(octadecylamino)propanoic acid Chemical compound CCCCCCCCCCCCCCCCCCN[C@@H](C)C(O)=O UQTBADOQMIRHSO-FQEVSTJZSA-N 0.000 claims description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 2
- 235000010469 Glycine max Nutrition 0.000 claims description 2
- 244000068988 Glycine max Species 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 239000004744 fabric Substances 0.000 abstract description 22
- 229920001778 nylon Polymers 0.000 abstract description 13
- 239000004677 Nylon Substances 0.000 abstract description 12
- 238000000576 coating method Methods 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000007598 dipping method Methods 0.000 abstract description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 230000035699 permeability Effects 0.000 description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- KGNODGBRNMOQBA-UHFFFAOYSA-N CCO.OCCOC(=O)C=C Chemical compound CCO.OCCOC(=O)C=C KGNODGBRNMOQBA-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 235000018102 proteins Nutrition 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229940024463 silicone emollient and protective product Drugs 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a functional finishing agent copolymer and a preparation method thereof. The copolymer comprises the following copolymerized units: 1) 35-75% by mass of acrylate-modified polyurethane copolymerized units; 2) 15-35 mass% casein copolymerized units; 3) 5-35% by mass of aminopolyethylene glycol acrylate copolymerized units. The copolymer prepared by the invention is suitable for the processes of dipping, padding and coating, and endows the nylon fabric with excellent hydrophilic and moisture-permeable performances, good washability, soft hand feeling and good style.
Description
Technical Field
The invention relates to the field of textile auxiliary agents, in particular to a functional and hand feeling style finishing agent, and especially relates to a functional finishing agent copolymer suitable for nylon fabrics and a preparation method thereof.
Background
The nylon fiber has good strength and good wear resistance, is usually used for underwear, sports wear and the like, but the nylon fabric has poor hydrophilicity and sweat is not easy to discharge when the garment is worn. In order to improve the comfort of nylon fabrics, the nylon fabrics need to be subjected to functional finishing such as hydrophilicity and moisture permeability and hand feeling style finishing.
The functional finishing agents with good hydrophilicity, moisture permeability and washability which are commonly used in the market at present are all used on polyester fabrics. However, if the functional finishing agent is used for nylon fabrics, the good hydrophilic moisture-permeable effect cannot be achieved, or the effect is not durable, and the effect is reduced or ineffective after one household washing. Therefore, a hand feeling style finishing agent which has excellent washability and is suitable for nylon fabrics and has the functions of hydrophily, moisture permeability and the like is urgently needed in the market.
The waterborne polyurethane has strong binding power, good flexibility, elasticity, wear resistance, stretchability and adhesive force, the molecular structure of the casein is similar to that of protein, the main chain is mainly composed of peptide bonds (-NH-CO-), the side chain is mainly composed of carboxyl (-COOH), amino (-NH), imino (-NH-), hydroxyl (-OH) and the like, the waterborne polyurethane has good hydrophilicity, internal crosslinking can be formed inside the copolymer, external crosslinking can be formed with fabric, a soft film is formed on the fabric and is attached to the fabric, and the durability is good.
Therefore, the functional and hand feeling style finishing agent with a special structure is designed to meet wide market demands.
Disclosure of Invention
One aspect of the present invention provides a functional finish copolymer comprising the following copolymerized units:
1) 35-75 mass% of acrylate modified polyurethane copolymerization units;
2) 15-35 mass% casein copolymer units;
3) 5-35% by mass of aminopolyethylene glycol acrylate copolymerized units.
Another aspect of the present invention is to provide a method for preparing the above-described functional finish copolymer, the method comprising the steps of:
1) Preparing acrylate modified polyurethane;
2) Preparing casein liquid;
3) Preparing amino polyethylene glycol acrylate aqueous solution;
4) Dissolving an amphoteric emulsifier and a nonionic emulsifier in water, adding 5-15% of the acrylate modified polyurethane prepared in 1), all the casein solution prepared in 2) and 5-15% of the amino polyethylene glycol acrylate aqueous solution prepared in 3), and stirring to prepare a pre-emulsion;
5) Heating the pre-emulsion prepared in the step 4) to 50-70 ℃, keeping the temperature, dripping 30-35% of the aqueous solution of the free radical initiator, and keeping the temperature for 10-50min after finishing dripping, preferably keeping the temperature for 20-40min;
6) Heating to 70-90 ℃, preferably to 75-85 ℃, keeping the temperature, simultaneously dripping the rest of the acrylate modified polyurethane prepared in the step 1), the rest of the amino polyethylene glycol acrylate aqueous solution prepared in the step 3) and the rest of the free radical initiator aqueous solution for 2-4 hours, and continuing the heat preservation reaction for 1-3 hours after the dripping is finished.
The functional finishing agent copolymer of the invention is introduced with acrylate modified polyurethane copolymerization unit, casein copolymerization unit and amino polyethylene glycol acrylate copolymerization unit. The waterborne polyurethane has strong binding power, good flexibility, elasticity, wear resistance, stretchability and adhesive force, the molecular structural formula of the casein is a structure similar to protein, a main chain is mainly formed by peptide bonds (-NH-CO-), and side chains are mainly formed by carboxyl (-COOH), amino (-NH), imino (-NH-), hydroxyl (-OH) and the like, so that the waterborne polyurethane has good hydrophilicity, can form internal crosslinking in a copolymer and external crosslinking with fabric, forms a soft film on the fabric and is attached to the fabric, and the durability is good.
Detailed Description
In a preferred embodiment, the functional finish copolymer of the present invention comprises the following copolymerized units:
1) 40-70 mass% of acrylate modified polyurethane copolymerization units;
2) 20-30 mass% of modified casein copolymerization units;
3) 10-30 mass% of aminopolyethylene glycol acrylate copolymerized units.
In a more preferred embodiment, in the functional finishing agent copolymer, the acrylate-modified polyurethane copolymerized unit is one or more selected from hydroxyl C2-3 alkyl (meth) acrylate-modified aqueous polyurethane copolymerized units. The hydroxy C2-3 alkyl (meth) acrylate is hydroxyethyl (meth) acrylate and/or hydroxypropyl (meth) acrylate.
In a more preferred embodiment, the aminopolyethylene glycol acrylate has a weight average molecular weight of 1000 to 10000, preferably 2000 to 8000.
In a preferred embodiment, the process for preparing the functional finish copolymer of the present invention comprises the steps of:
1) Preparing acrylate modified polyurethane;
2) Preparing casein liquid;
3) Preparing amino polyethylene glycol acrylate aqueous solution;
4) Dissolving an amphoteric emulsifier and a nonionic emulsifier in water, adding 5-15% of the acrylate modified polyurethane prepared in 1), all of the casein solution prepared in 2) and 5-15% of the amino polyethylene glycol acrylate aqueous solution prepared in 3), and stirring to prepare a pre-emulsion;
5) Heating the pre-emulsion prepared in the step 4) to 50-70 ℃, dripping 30-35% of the aqueous solution of the free radical initiator, keeping the temperature basically unchanged in the dripping process, and preserving the heat for 10-50min after finishing dripping;
6) Heating to 70-90 ℃, simultaneously dripping the rest 1), 3) and the free radical initiator aqueous solution, keeping the temperature basically unchanged in the dripping process, dripping for 2-4h, keeping the temperature for 1-3h after finishing dripping, and carrying out polymerization.
In a more preferred embodiment, the incubation is continued for 20 to 40min after the end of the dropwise addition in step 5), and the temperature is raised to 75 to 85 ℃ in step 6).
In a more preferred embodiment, the amphoteric emulsifier includes, but is not limited to, one or more of C12-18 alkyl dihydroxyethyl betaine, cocamidopropyl betaine, soya amidopropyl betaine, N-dodecylalanine, N-octadecylalanine, N-dodecyl-N- (2-hydroxy-3-sulfopropylidene) dimethylammonium.
In a more preferred embodiment, the nonionic emulsifier comprises one or more of fatty alcohol polyoxyethylene ether (5-40 EO), isomeric alcohol polyoxyethylene ether (3-15 EO).
In a more preferred embodiment, the free radical initiator is one of ammonium sulfate and potassium persulfate, preferably potassium persulfate.
The functional finishing agent prepared by the invention has good stability, the moisture absorption and moisture permeability of the nylon fabric are obviously improved after the finishing agent is treated, and the nylon fabric has soft hand feeling and excellent washability.
Examples
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
In the present application,% means% by weight unless otherwise specified.
Raw materials used in the examples: the waterborne polyurethane prepolymer is Toluene Diisocyanate (TDI) polyester prepolymer (NCO content is 5.8-6.5%) and Tantawawa company; the fabric is nylon woven fabric and is sold in the market; the thickening agent is SeatexPT-20N of Shanghai Yayun science and technology, and the rest are common commercial products.
The performance measurement and the application effect in each example were measured and evaluated as follows:
1. fabric treatment process
The padding process comprises the following steps: first soaking and first rolling → 150 ℃ for 2min, dosage: 40g/L
The impregnation process comprises the following steps: impregnation (50 ℃ × 30 min) → dewatering and drying (105 ℃.) → setting (150 ℃ × 1 min), amount: 4% o.w.f
The coating process comprises the following steps:
printing a magnetic rod pressure of 40V, a speed of 30m/min and a size by adopting a flat screen magnetic rod printing small prototype:
120 meshes.
Knife coating → oven drying (150 ℃,2 min), functional finish copolymer amount: 2 percent of thickening agent and the balance of water.
2. Hydrophilicity
According to GB/T21655.1-2008. Expressed as drip diffusion time and wicking height. The shorter the drip diffusion time, the higher the wicking height indicating better hydrophilicity.
3. Moisture permeability
According to GB/T21655.1-2008. The moisture permeability is more than or equal to 8000 g/(m) 2 D) shows the moisture permeability effect, the greater the moisture permeability, the better the moisture permeability effect.
4. Washing method
Performed according to AATCC 135.
5. Hand feel evaluation
The hand feeling of the original cloth is taken as 1 point, and the average value is taken by integrating the hand feeling evaluation results of 5 persons (1-5 points, the worst point for 1 point and the best point for 5 points).
Example 1
Adding 16.5g of waterborne polyurethane prepolymer into a four-neck flask provided with a stirrer, a thermometer and a reflux condenser, heating to 65 ℃, dropwise adding 3.5g of hydroxyethyl acrylate ethanol solution, keeping the temperature for 1h after dropwise adding, adjusting the viscosity of the system by using acetone in the reaction process, cooling to 40 ℃, neutralizing by using triethylamine, reacting for 1h, and cooling to room temperature. And adding 60g of water, stirring at a high speed for water dispersion, and finally removing acetone under reduced pressure to obtain the acrylate modified waterborne polyurethane.
Adding 6.4g of casein and 25.6g of water into a four-neck flask provided with a stirrer, a thermometer and a reflux condenser, heating to 65 ℃, slowly stirring to swell the casein, adding a certain amount of triethanolamine to adjust the pH to be about =7.5, and continuously keeping the water temperature and stirring for 1h after the casein is fully swelled to be transparent liquid to obtain casein liquid.
An aqueous aminopolyethylene glycol acrylate solution was prepared by mixing 3.5g of aminopolyethylene glycol acrylate (weight average molecular weight: 8000) and 24.5g of water for subsequent use.
And adding 1.2g of dodecyl dihydroxy ethyl betaine, 1g of lauryl polyoxyethylene ether (15 EO) and 10g of deionized water into another four-neck flask, stirring for dissolving, adding 8g of the acrylic ester modified waterborne polyurethane, 32g of the casein solution and 2.8g of the amino polyethylene glycol acrylate aqueous solution, and stirring at a high speed for 30min to obtain a pre-emulsion.
Heating the pre-emulsion to 65 ℃, slowly dripping 1g of 10% potassium persulfate aqueous solution, keeping the temperature unchanged in the dripping process, finishing dripping, and keeping the temperature for 20min.
And (2) continuously heating to 78 ℃, respectively dripping 72g of acrylic acid modified waterborne polyurethane, 25.2g of amino polyethylene glycol acrylate aqueous solution and 2g of 10% potassium persulfate aqueous solution for 2 hours, keeping the temperature unchanged in the dripping process, and after the dripping is finished, carrying out heat preservation reaction for 1.5 hours to obtain the finishing agent 1.
Example 2
Adding 10.2g of waterborne polyurethane prepolymer into a four-neck flask provided with a stirrer, a thermometer and a reflux condenser, heating to 65 ℃, dropwise adding 2.5g of an ethanol solution of hydroxypropyl acrylate, keeping the temperature for 1h after dropwise adding, adjusting the viscosity of the system by using acetone in the reaction process, cooling to 40 ℃, neutralizing by using triethylamine, reacting for 1h, and cooling to room temperature. Adding 38g of water, stirring at a high speed for water dispersion, and finally removing acetone under reduced pressure to obtain the acrylate modified waterborne polyurethane.
Adding 8.5g of casein and 34g of water into a four-neck flask provided with a stirrer, a thermometer and a reflux condenser, heating to 65 ℃, slowly stirring to swell the casein, adding a certain amount of triethanolamine to adjust the pH to be about =7.5, and continuously keeping the water temperature to stir for 1h after the casein is fully swelled to be a transparent liquid to obtain a casein liquid.
9g of aminopolyethylene glycol acrylate (weight average molecular weight: 2000) and 63g of water were mixed to prepare an aminopolyethylene glycol acrylate aqueous solution for use.
And adding 1.4g of cocamidopropyl betaine, 0.9g of isomeric tridecanol polyoxyethylene ether (5 EO) and 10g of deionized water into another four-neck flask, stirring for dissolving, adding 5.07g of the acrylic ester modified waterborne polyurethane, 42.5g of the casein solution and 7.2g of the amino polyethylene glycol acrylate aqueous solution, and stirring at a high speed for 40min to obtain a pre-emulsion.
Heating the pre-emulsion to 65 ℃, slowly dripping 1g of 10% potassium persulfate aqueous solution, keeping the temperature unchanged in the dripping process, finishing dripping, and keeping the temperature for 40min.
And (3) continuously heating to 78 ℃, respectively dripping 45.63g of acrylic acid modified waterborne polyurethane, 64.8g of amino polyethylene glycol acrylate aqueous solution and 2g of 10% potassium persulfate aqueous solution for 2 hours, ensuring the temperature to be unchanged in the dripping process, and after the dripping is finished, carrying out heat preservation reaction for 2.5 hours to obtain the finishing agent 2.
Example 3
Adding 13.5g of waterborne polyurethane prepolymer into a four-neck flask provided with a stirrer, a thermometer and a reflux condenser, heating to 65 ℃, dropwise adding 2.8g of hydroxyethyl acrylate ethanol solution, keeping the temperature for 1h after dropwise adding, adjusting the viscosity of the system by using acetone in the reaction process, cooling to 40 ℃, neutralizing by using triethylamine, reacting for 1h, and cooling to room temperature. And adding 48.9g of water, stirring at a high speed for water dispersion, and finally decompressing to remove acetone to obtain the acrylate modified waterborne polyurethane.
Adding 7.5g of casein and 30g of water into a four-neck flask provided with a stirrer, a thermometer and a reflux condenser, heating to 65 ℃, slowly stirring to swell the casein, then adding a certain amount of triethanolamine to adjust the pH to be about =7.5, and continuously keeping the water temperature and stirring for 1h after the casein is fully swelled to be a transparent liquid to obtain a casein liquid.
6g of aminopolyethylene glycol acrylate (weight average molecular weight: 3400) and 42g of water were mixed to prepare an aminopolyethylene glycol acrylate aqueous solution for use.
And adding 1.4g N-dodecyl-N- (2-hydroxy-3-sulfopropylene) dimethylammonium, 1g of isomeric dodecyl polyoxyethylene ether (8 EO) and 10g of deionized water into another four-neck flask, stirring for dissolving, adding 6.52g of the acrylic modified waterborne polyurethane, 37.5g of the casein solution and 4.8g of the amino polyethylene glycol acrylate aqueous solution, and stirring at high speed for 30min to obtain a pre-emulsion.
Heating the pre-emulsion to 65 ℃, slowly dripping 1g of 10% potassium persulfate aqueous solution, keeping the temperature unchanged in the dripping process, finishing dripping, and keeping the temperature for 30min.
And continuously heating to 78 ℃, respectively dripping 58.68g of the acrylic acid modified waterborne polyurethane, 43.2g of the amino polyethylene glycol acrylate aqueous solution and 2g of 10% potassium persulfate aqueous solution for 2 hours, ensuring the temperature to be unchanged in the dripping process, and after the dripping is finished, carrying out heat preservation reaction for 3 hours to obtain the finishing agent 3.
The commercially available nylon woven fabrics were subjected to each process using the finishing agents 1 to 3 prepared in examples, and then the properties were measured. The application properties are shown in tables 1, 2 and 3.
TABLE 1 comparison of hydrophilicity and washability
In addition, the blank sample is that the fabric is treated by only adopting clear water according to the process.
TABLE 2 comparison of moisture permeability and washability
In addition, the blank sample is that the fabric is treated by only adopting clear water according to the process.
TABLE 3 Style of hand feeling
In addition, the method is characterized in that: the examples were prepared by coating processes, commercial silicone products were padded according to their product specifications, and controls were prepared by coating processes using only thickeners
As can be seen from the data in tables 1, 2 and 3, the functional finishing agent copolymer prepared by the invention has good hydrophilicity and moisture permeability, good hand feeling, excellent washability and good style after finishing the nylon fabric, is suitable for the processes of dipping, padding and coating, and has wide market prospect.
Claims (10)
1. A functional finish copolymer comprising interpolymerized units of:
1) 35-75 mass% of acrylate modified polyurethane copolymerization units;
2) 15-35 mass% casein copolymer units;
3) 5-35% by mass of aminopolyethylene glycol acrylate copolymerized units.
2. The functional finish copolymer of claim 1, comprising interpolymerized units of:
1) 40-70 mass% of acrylate modified polyurethane copolymer unit;
2) 20-30 mass% casein copolymer units;
3) 10-30 mass% of aminopolyethylene glycol acrylate copolymerized units.
3. The functional finish copolymer of claim 1, wherein the acrylate-modified polyurethane interpolymerized units are hydroxyethyl (meth) acrylate and/or hydroxypropyl (meth) acrylate-modified aqueous polyurethane interpolymerized units.
4. The functional finish copolymer of claim 1, wherein the amino polyethylene glycol acrylate has a weight average molecular weight of 1000 to 10000.
5. The functional finish copolymer of claim 1, wherein the amino polyethylene glycol acrylate has a weight average molecular weight of 2000 to 8000.
6. A process for preparing the functional finish copolymer of any of claims 1 to 5, comprising the steps of:
1) Preparing acrylate modified polyurethane;
2) Preparing casein liquid;
3) Preparing amino polyethylene glycol acrylate aqueous solution;
4) Dissolving an amphoteric emulsifier and a nonionic emulsifier in water, adding 5-15% of the acrylate modified polyurethane prepared in 1), all the casein solution prepared in 2) and 5-15% of the amino polyethylene glycol acrylate aqueous solution prepared in 3), and stirring to prepare a pre-emulsion;
5) Heating the pre-emulsion prepared in the step 4) to 50-70 ℃, keeping the temperature, dripping 30-35% of the aqueous solution of the free radical initiator, and keeping the temperature for 10-50min after dripping;
6) Heating to 70-90 ℃, keeping the temperature, simultaneously dripping the rest of the acrylic ester modified polyurethane prepared in the step 1), the rest of the amino polyethylene glycol acrylic ester aqueous solution prepared in the step 3) and the rest of the free radical initiator aqueous solution for 2-4 hours, and continuing the heat preservation reaction for 1-3 hours after the dripping is finished.
7. The process for preparing a functional finishing agent copolymer according to claim 6, wherein the heat is maintained for 20 to 40min after the end of the dropwise addition in step 5), and the temperature is raised to 75 to 85 ℃ in step 6).
8. The method of preparing the functional finish copolymer according to claim 6, wherein the amphoteric emulsifier is one or more selected from the group consisting of C12-18 alkyl dihydroxyethyl betaine, cocamidopropyl betaine, soya amidopropyl betaine, N-dodecylalanine, N-octadecylalanine, and N-dodecyl-N- (2-hydroxy-3-sulfinic acid propylene) dimethylammonium.
9. The method for preparing the functional finishing agent copolymer according to claim 6, wherein the nonionic emulsifier is one or more selected from fatty alcohol polyoxyethylene ether (5-40 EO) and isomeric alcohol polyoxyethylene ether (3-15 EO).
10. The process of claim 6, wherein the free radical initiator is ammonium persulfate or potassium persulfate.
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