CN110776601A - Preparation method and application of anti-staining agent - Google Patents
Preparation method and application of anti-staining agent Download PDFInfo
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- CN110776601A CN110776601A CN201911081174.4A CN201911081174A CN110776601A CN 110776601 A CN110776601 A CN 110776601A CN 201911081174 A CN201911081174 A CN 201911081174A CN 110776601 A CN110776601 A CN 110776601A
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- maleic anhydride
- acrylic acid
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- 238000010186 staining Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 79
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims abstract description 42
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229920001577 copolymer Polymers 0.000 claims abstract description 30
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003999 initiator Substances 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 8
- 230000009471 action Effects 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 40
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000011261 inert gas Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 12
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 10
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 150000002191 fatty alcohols Chemical class 0.000 claims description 6
- 239000005871 repellent Substances 0.000 claims description 4
- 230000002940 repellent Effects 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000203 mixture Substances 0.000 description 12
- 239000004744 fabric Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 150000005215 alkyl ethers Chemical class 0.000 description 7
- -1 polyoxy Polymers 0.000 description 7
- 229920001897 terpolymer Polymers 0.000 description 7
- 239000001639 calcium acetate Substances 0.000 description 6
- 229960005147 calcium acetate Drugs 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000009920 chelation Effects 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- PSPOTRNUMVKPLL-UHFFFAOYSA-N C(=C)N1C(CCC1)=O.C(C=C)(=O)O.C1(C=C/C(=O)O1)=O Chemical compound C(=C)N1C(CCC1)=O.C(C=C)(=O)O.C1(C=C/C(=O)O1)=O PSPOTRNUMVKPLL-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 4
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 4
- 235000011092 calcium acetate Nutrition 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- JPZROSNLRWHSQQ-UHFFFAOYSA-N furan-2,5-dione;prop-2-enoic acid Chemical compound OC(=O)C=C.O=C1OC(=O)C=C1 JPZROSNLRWHSQQ-UHFFFAOYSA-N 0.000 description 4
- 239000000985 reactive dye Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- SGHZXLIDFTYFHQ-UHFFFAOYSA-L Brilliant Blue Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 SGHZXLIDFTYFHQ-UHFFFAOYSA-L 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/02—After-treatment
- D06P5/04—After-treatment with organic compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/02—After-treatment
- D06P5/04—After-treatment with organic compounds
- D06P5/08—After-treatment with organic compounds macromolecular
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method of an anti-staining agent, which comprises the following steps: under the action of an initiator, maleic anhydride, acrylic acid and allyl alcohol polyoxyalkyl ether as an active monomer are subjected to polymerization reaction, and the obtained water-soluble copolymer MA-AA-F6 is used as an anti-staining agent. The invention also discloses the application of the stain resistant agent, which is used for preparing a soaping agent, and the preparation method of the soaping agent comprises the following steps: and uniformly mixing the nonionic surfactant, the water-soluble copolymer MA-AA-F6 and water to obtain the soaping agent. The invention can solve the problem of serious staining of the common stain-resistant agent in the market due to poor dispersion and chelating performance on one hand, and can solve the problem of limited marketization application due to high cost on the other hand.
Description
Technical Field
The invention belongs to the technical field of textile printing and dyeing auxiliaries, and particularly relates to preparation and application of an anti-staining agent.
Background
It is known that reactive dye-printed fabrics are generally subjected to a soaping treatment, the main purpose of which is to remove the hydrolysed dyes, unfixed dyes and other impurities from the fibres and to prevent them from sticking back to the surface of the fabric, on the one hand to improve the wet crockfastness and washfastness of the dyed fabric and on the other hand to prevent the fabric from becoming stained again. Most common anti-staining agents in the current market have the problems of incomplete removal of floating color, serious staining and the like, namely, the problems of poor anti-staining effect and the like caused by poor dispersion and chelation performance; while the MA-AA-NVP anti-staining agent (maleic anhydride-acrylic acid-N-vinyl pyrrolidone terpolymer) can effectively solve the problems, the cost of raw materials is too high, and the marketable application is severely limited, so that an anti-staining agent with excellent anti-staining performance and low cost is urgently needed in the market.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method and application of an anti-staining agent, and by adopting the method, the cost can be reduced, and the problem of serious staining caused by poor dispersion and chelation performance can be avoided.
In order to solve the technical problems, the invention provides a preparation method of a staining resistant agent, which comprises the following steps:
under the action of an initiator (in an aqueous solution of the initiator), maleic anhydride, acrylic acid and allyl alcohol polyoxyalkyl ether (F6) serving as an active monomer are subjected to polymerization reaction at the temperature of 80 +/-5 ℃ for 2 +/-0.5 hours to obtain a water-soluble copolymer MA-AA-F6 (which is a water-soluble copolymer with good dispersion and chelating properties), and the water-soluble copolymer MA-AA-F6 is an anti-staining agent;
maleic anhydride: acrylic acid: allyl alcohol polyoxyalkyl ether is 2:6: 0.1-0.8 in mass ratio;
maleic anhydride, acrylic acid: the sum of the masses of the allyl alcohol polyoxyalkyl ethers is called the total mass of the monomers;
the initiator accounts for 3-6% (mass%) of the total mass of the monomers.
As an improvement of the method for preparing the anti-staining agent, the method comprises the following steps
① adding water into maleic anhydride, stirring until the maleic anhydride is dissolved, heating to 65 +/-5 ℃ under the protection of inert gas, adjusting the pH value to 6.0-6.5, and adding allyl alcohol polyoxyalkyl ether (F6);
under the protection of inert gas, heating to 80 +/-5 ℃, simultaneously dropwise adding acrylic acid and an initiator aqueous solution (namely, 2 simultaneously and respectively starting and finishing dropwise adding), wherein the dropwise adding time is (2 +/-0.2) h, and after dropwise adding, carrying out heat preservation reaction for (2 +/-0.5) h;
the mass concentration of the initiator in the initiator aqueous solution is 6-8%;
remarks explanation: when water is added to maleic anhydride, the amount of water is only required to ensure that the maleic anhydride can be dissolved, and the following maleic anhydride is preferred: water 1:3 (mass ratio).
The entire process ① is carried out under an inert gas blanket.
②, cooling the obtained reaction product to room temperature to obtain the water-soluble copolymer MA-AA-F6.
As a further improvement of the method for preparing the anti-staining agent of the present invention: the initiator is at least one of sodium persulfate, potassium persulfate and ammonium persulfate.
The invention also provides the application of the anti-staining agent: the method is used for preparing the soaping agent, and the preparation method of the soaping agent comprises the following steps:
uniformly mixing a nonionic surfactant, a water-soluble copolymer MA-AA-F6 and water to obtain a soaping agent;
the sum of the mass of the nonionic surfactant and the mass of the water-soluble copolymer MA-AA-F6 accounts for 18-22% of the total mass of the soaping agent (namely, the solid content is 18-22%).
Improvement as the use of the stain repellent of the present invention: the nonionic surfactant consists of fatty alcohol-polyoxyethylene ether AEO-7 and fatty alcohol-polyoxyethylene ether AEO-25;
fatty alcohol polyoxyethylene ether AEO-7: fatty alcohol polyoxyethylene ether AEO-25: the mass ratio of the water-soluble copolymer MA-AA-F6 to the copolymer is 1:0.5: 12.
In the invention, the allyl alcohol polyoxy alkyl ether as the active monomer has good solubilization, contains a large amount of O in the molecular structure, and can form a hydrogen bond with a hydrolytic dye; the carboxylate radical in the MA-AA-F6 ternary copolymer can provide electrostatic action and adsorption site, and can adsorb and disperse solid particles powerfully to prevent redeposition. Namely, the water-soluble copolymer MA-AA-F6 serving as the anti-staining agent prepared by the invention has the advantages of excellent anti-staining performance (namely, good dispersion and chelating performance), low price, easiness in popularization and application and the like.
The price of allyl alcohol polyoxyalkyl ether (F6) is only 30% of that of N-vinylpyrrolidone.
The water-soluble copolymer MA-AA-F6 can be compounded with a nonionic surfactant to prepare a soaping agent, is used for soaping reactive dyes, and has excellent floating and stain-proof removal capabilities. Namely, the soaping agent finally obtained by the invention has excellent cleaning function to the reactive dye, and has the characteristics of excellent performance and low price.
Therefore, the invention can solve the problem of serious staining of the common stain-resistant agent in the market due to poor dispersion and chelation performance on one hand, and can solve the problem of limited marketization application due to high cost on the other hand.
In conclusion, the method has the advantages of simple process, low cost, convenient implementation and operation, contribution to industrial large-scale production, great economic significance and good practical performance, and wide application prospect in the soaping agent for the reactive dye.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
in the following cases:
maleic anhydride, acrylic acid and allyl alcohol polyoxyalkyl ether (F6) are used as raw materials; different initiators are selected; the sum of the masses of maleic anhydride, acrylic acid and allyl alcohol polyoxyalkyl ether (F6) is referred to as the total mass of the monomers.
O-7, i.e., fatty alcohol polyoxyethylene ether AEO-7; the EO number is 7 and,
o-25, i.e., fatty alcohol polyoxyethylene ether AEO-25, EO number is 25;
inert gas, preferably N
2。
Example 1, a method for preparing a soaping agent, comprising the following two major steps:
firstly, preparing an anti-staining agent:
m (maleic anhydride): m (acrylic acid): m (allyl alcohol polyoxyalkyl ether) is 2:6:0.2 (mass ratio); ammonium persulfate is used as an initiator, and accounts for 3 percent of the total mass of the monomers.
1) Adding 10g of maleic anhydride into 30g of water, dissolving at 30 ℃, then placing the mixture into a four-neck flask provided with a reflux device, heating the mixture to 65 ℃ under the protection of inert gas, adjusting the pH value to about 6.5 by using 30% NaOH aqueous solution, continuously stirring the mixture for 20min, and adding 1g of allyl alcohol polyoxyalkyl ether (F6);
and continuously raising the temperature to 80 ℃ under the protection of inert gas, respectively and simultaneously dropwise adding 30g of acrylic acid and 18g of ammonium persulfate aqueous solution (containing 1.23g of ammonium persulfate), controlling the dropwise adding within 1.8-2 h, and keeping the polymerization temperature for reacting for 2 h.
2) And after the reaction is finished, cooling to room temperature to obtain clear and transparent light yellow viscous liquid, namely the maleic anhydride-acrylic acid-allyl alcohol polyoxy alkyl ether (MA-AA-F6) water-soluble copolymer (serving as an anti-staining agent).
Secondly, preparing a soaping agent:
1.5g of O-7, 0.75g of 0.75g O-25 and a suitable amount of water (about 45ml) were added to a reaction vessel, stirred at 30 ℃ to dissolve, after 10min, 18g of a maleic anhydride-acrylic acid-allyl alcohol polyoxyalkyl ether (MA-AA-F6) water-soluble copolymer (terpolymer, as anti-staining agent) was added, water was added in an amount of 100g, and stirring was continued at this temperature for 30min to prepare a soaping agent having a solid content of about 20.25%.
Example 2, a method for preparing a soaping agent, comprising the following two major steps:
firstly, preparing an anti-staining agent:
m (maleic anhydride): m (acrylic acid): m (allyl alcohol polyoxyalkyl ether) ═ 2:6: 0.4; ammonium persulfate is used as an initiator, and accounts for 4% of the total mass of the monomers.
1) Adding 10g of maleic anhydride into 30g of water, dissolving at 30 ℃, then placing the mixture into a four-neck flask provided with a reflux device, heating the mixture to 65 ℃ under the protection of inert gas, adjusting the pH value to about 6.5 by using 30% NaOH aqueous solution, continuously stirring the mixture for 20min, and adding 2g of allyl alcohol polyoxyalkyl ether;
and continuously raising the temperature to the polymerization temperature of 80 ℃ under the protection of inert gas, respectively and simultaneously dropwise adding 30g of acrylic acid and 24g of ammonium persulfate aqueous solution (containing 1.68g of ammonium persulfate), controlling the dropwise adding within 1.8-2 h, and keeping the polymerization temperature for reacting for 2 h.
2) And after the reaction is finished, cooling to room temperature to obtain clear and transparent light yellow viscous liquid, namely the maleic anhydride-acrylic acid-allyl alcohol polyoxy alkyl ether (MA-AA-F6) water-soluble copolymer.
Secondly, preparing a soaping agent:
1.5g of O-7, 0.75g O-25 and a proper amount of water (about 45ml) were added to a reaction vessel, stirred at 30 ℃ to dissolve, after 10min, 18g of a terpolymer of maleic anhydride-acrylic acid-allyl alcohol polyoxyalkyl ether (MA-AA-F6) (anti-staining agent) was added, water was added in an amount of 100g, and stirring was continued at this temperature for 30min to prepare a soaping agent having a solid content of about 20.25%.
Example 3, a method for preparing a soaping agent, comprising the following two major steps:
firstly, preparing an anti-staining agent:
m (maleic anhydride): m (acrylic acid): m (allyl alcohol polyoxyalkyl ether) ═ 2:6: 0.6; ammonium persulfate is used as an initiator, and accounts for 6 percent of the total mass of the monomers.
1) Adding 10g of maleic anhydride into 30g of water to dissolve at 30 ℃, then placing the mixture into a four-neck flask provided with a reflux device, heating the mixture to 65 ℃ under the protection of inert gas, adjusting the pH value to about 6.5 by using 30% NaOH aqueous solution, continuously stirring the mixture for 20min, and adding 3g of allyl alcohol polyoxyalkyl ether;
and continuously raising the temperature to 80 ℃ under the protection of inert gas, respectively and simultaneously dropwise adding 30g of acrylic acid and 36g of ammonium persulfate aqueous solution (containing 2.58g of ammonium persulfate), controlling the dropwise adding within 1.8-2 h, and keeping the polymerization temperature for reacting for 2 h.
2) And after the reaction is finished, cooling to room temperature to obtain clear and transparent light yellow viscous liquid, namely the maleic anhydride-acrylic acid-allyl alcohol polyoxy alkyl ether (MA-AA-F6) water-soluble copolymer.
Secondly, preparing a soaping agent:
1.5g O-7, 0.75g O-25 and a proper amount of water (about 45ml) are added into a reaction vessel, stirred at 30 ℃ to dissolve the components, 18g of terpolymer (anti-staining agent) of maleic anhydride-acrylic acid-allyl alcohol polyoxy alkyl ether (MA-AA-F6) is added after 10min, then water is added to 100g, and stirring is continued at the temperature for 30min to prepare the soaping agent with the solid content of about 20.25%.
Example 4, a method for preparing a soaping agent, comprising the following two major steps:
firstly, preparing an anti-staining agent:
m (maleic anhydride): m (acrylic acid): m (allyl alcohol polyoxyalkyl ether) ═ 2:6: 0.8; ammonium persulfate is used as an initiator, and accounts for 5 percent of the total mass of the monomers.
1) Adding 10g of maleic anhydride into 30g of water to dissolve at 30 ℃, then placing the mixture into a four-neck flask provided with a reflux device, heating the mixture to 65 ℃ under the protection of inert gas, adjusting the pH value to about 6.5 by using 30% NaOH aqueous solution, continuously stirring the mixture for 20min, and adding 4g of allyl alcohol polyoxyalkyl ether;
and continuously raising the temperature to 80 ℃ under the protection of inert gas, respectively and simultaneously dropwise adding 30g of acrylic acid and 31g of ammonium persulfate aqueous solution (containing 2.2g of ammonium persulfate), controlling the dropwise adding within 1.8-2 h, and keeping the polymerization temperature for reacting for 2 h.
2) And after the reaction is finished, cooling to room temperature to obtain clear and transparent light yellow viscous liquid, namely the maleic anhydride-acrylic acid-allyl alcohol polyoxy alkyl ether (MA-AA-F6) water-soluble copolymer.
Secondly, preparing a soaping agent:
1.5g O-7, 0.75g O-25 and a proper amount of water (about 45ml) are added into a reaction vessel, stirred at 30 ℃ to dissolve the components, 18g of terpolymer (anti-staining agent) of maleic anhydride-acrylic acid-allyl alcohol polyoxy alkyl ether (MA-AA-F6) is added after 10min, then water is added to 100g, and stirring is continued at the temperature for 30min to prepare the soaping agent with the solid content of about 20.25%.
Comparative example 1, a method for preparing a soaping agent, comprising the following two major steps:
firstly, preparing a stain-proofing agent by using a maleic anhydride-acrylic acid copolymer:
m (maleic anhydride): m (acrylic acid) ═ 2: 6; ammonium persulfate is used as an initiator, and the amount of the initiator is 4 percent of the sum of the mass of maleic anhydride and acrylic acid;
(1) 10g of maleic anhydride and 30g of water are put into a four-neck flask provided with a reflux device, stirred to be dissolved, heated to 65 ℃ under the protection of inert gas, and the pH value is adjusted to about 6.5 by using 30% NaOH aqueous solution.
Under the protection of inert gas, when the temperature is raised to 85 ℃ of polymerization temperature, respectively and simultaneously dropping 30g of acrylic acid and 23g of ammonium persulfate aqueous solution (containing 1.6g of ammonium persulfate), controlling the dropping to be finished within 4h (2 dropping simultaneously, the dropping time is about 4h respectively), and keeping the polymerization temperature for reaction for 6 h.
(2) After the reaction is finished, cooling to room temperature to obtain clear, light, transparent and yellow viscous liquid, namely maleic anhydride-acrylic acid copolymer MA-AA (which is a conventional anti-staining agent).
Secondly, preparing a soaping agent:
1.5g O-7, 0.75g O-25 and a proper amount of water (about 45ml) are added into a reaction vessel, stirred at 30 ℃ to be dissolved, 18g of maleic anhydride-acrylic acid copolymer (MA-AA) is added after 10min, then the water is added to reach 100g, and stirring is continued for 30min at the temperature to prepare a soaping agent with the solid content of about 20.25%.
Comparative example 2, a method of preparing a soaping agent:
firstly, preparing an anti-staining soaping agent by using a maleic anhydride-acrylic acid-N-vinyl pyrrolidone copolymer:
m (maleic anhydride): m (acrylic acid): m (N-vinylpyrrolidone) ═ 2:6: 0.8; ammonium persulfate is used as an initiator, and the amount of the initiator is 4 percent of the sum of the mass of (maleic anhydride and + acrylic acid + N-vinyl pyrrolidone).
(1) 10g of maleic anhydride and 30g of water are placed in a four-neck flask provided with a reflux device, stirred to be dissolved, and introduced with N
2Raising the temperature to 65 ℃ under protection, and adjusting the pH value to about 6.5 by using a 30% NaOH aqueous solution.
In N
2Under protection, when the temperature is continuously raised to the polymerization temperature of 85 ℃, 30g of acrylic acid, 25g of ammonium persulfate aqueous solution (containing 1.76g of ammonium persulfate) and 4g of N-vinyl pyrrolidone are respectively and simultaneously dripped, the dripping is finished within 1.5h, and the polymerization temperature is kept for reaction for 6 h.
(2) And after the reaction is finished, cooling to room temperature to obtain clear and transparent yellow-brown viscous liquid, namely the maleic anhydride-acrylic acid-N-vinyl pyrrolidone (MA-AA-NVP) ternary water-soluble copolymer (MA-AA-NVP type anti-staining agent).
Secondly, preparing a soaping agent:
1.5g O-7, 0.75g O-25 and a proper amount of water (about 45ml) are added into a reaction vessel, stirred at 30 ℃ to dissolve the components, 18g of maleic anhydride-acrylic acid-N-vinyl pyrrolidone (MA-AA-NVP) ternary water-soluble copolymer (MA-AA-NVP type anti-staining agent) is added after 10min, then the water is added to 100g, and stirring is continued for 30min at the temperature to prepare the soaping agent with the solid content of about 20.25%.
Comparative example 3-1, the "1.5 gO-7, 0.75g O-25" in step two of example 2 was changed to "1.5 g O-7, 1.5 gO-25", and the remainder was identical to example 2.
Comparative example 3-2, the "1.5 gO-7, 0.75g O-25" in step two of example 2 was changed to "1.5 gO-7, 2.25 gO-25", and the remainder was identical to example 2.
Comparative examples 3 to 3, wherein "1.5 gO-7 and 0.75g O-25" in step two of example 2 were changed to "3 g O-7 and 0.75 gO-25", and the remainder was the same as in example 2.
Experiment I,
1. The dispersibility and the chelatability are measured under the condition of the same solid content, and the method for testing the dispersing force and the chelating force comprises the following steps:
(1) dispersibility test
Accurately weigh 4g of copolymer (antisticking agent) (accurate to 0.01g) to make 100ml of solution, transfer 25ml of sample into an Erlenmeyer flask, add 10ml of 10% Na
2CO
3The pH of the solution and 30ml of deionized water is adjusted to about 11 by 30 percent NaOH, and the solution is titrated by 0.1mol/L calcium acetate standard solution until white precipitate is generated at the beginning and the solution does not fade after 30 seconds, namely the end point.
Calculating the dispersion force:
dispersion value (mg/G) ═ V C100.1/G (1)
In the formula: v-volume of sample consumed calcium acetate standard solution, ml;
concentration of C-calcium acetate, mol/L;
g-weight of sample, G;
100.1 molecular weight of calcium carbonate
(2) Chelatability test
Accurately weighing 2g of copolymer (anti-staining agent) (accurate to 0.01g) to prepare 100ml of solution, transferring 25ml of sample solution into a conical flask, and adding 5ml of 2% Na
2C
2O
4Solution of NH
4Cl-NH
3(pH 10) the pH of the buffer was adjusted to 10-10.5, titrated with 0.1mol/L calcium acetate standard and the end point was reached when a white precipitate began to form and did not fade after 30 s.
Calculating the chelating force:
chelation value (mg/G) ═ V × C100.1/G (2)
In the formula: v-volume of sample consumed calcium acetate standard solution, ml;
concentration of C-calcium acetate, mol/L;
g-weight of sample, G;
100.1 molecular weight of calcium carbonate
The dispersibility and the chelatability of the stain repellents of example 1, example 2, example 3, example 4, comparative example 1 and comparative example 2 were all measured by the above-mentioned test method after the treatments under the same conditions; the test results are shown in table 1 below.
TABLE 1 comparison of the various properties of the copolymers (antisticking agents)
| Sample (I) | Dispersion number (mg/g) | Chelate number (mg/g) |
| Example 1 | 283.181 | 325.799 |
| Example 2 | 312.954 | 372.233 |
| Example 3 | 263.914 | 320.022 |
| Example 4 | 286.045 | 322.584 |
| Comparative example 1 | 188.417 | 194.526 |
| Comparative example 2 | 311.845 | 303.761 |
As can be seen from Table 1, the MA-AA-F6 terpolymer (anti-staining agent) has good dispersion and chelation performance and performance equivalent to that of the MA-AA-NVP terpolymer under the condition of containing the same mass of active ingredients by the same test method, but the cost price of F6 is far lower than that of NVP, and the MA-AA-F6 has good practicability and great economic significance.
Experiment two,
The soaping agents obtained in examples 1 to 4 were applied to soaping of reactive dye dyed fabrics (reactive brilliant blue KN-R type dye dyed cotton fabrics) at a soaping temperature of 95 ℃ for 30min at a bath ratio of 1:50 with a soaping agent amount of 3g/L, and the results are shown in Table 2.
TABLE 2 soaping agent Performance comparison
The K/S value is used for representing the staining resistance of the soaping agent, the lower the K/S value of the white cloth for the lining is, the better the staining resistance is, and otherwise, the worse the staining resistance is; the absorbance A value of the residual liquid is used for representing the content of the dye in the soap boiling residual liquid, the larger the absorbance A value of the residual liquid is, the better the cleaning capacity of the soaping agent is, and the worse the washing capacity is otherwise.
Comparative experiment, the maleic anhydride-acrylic acid soaping agent obtained in comparative example 1, the maleic anhydride-acrylic acid-N-vinylpyrrolidone soaping agent obtained in comparative example 2, and the soaping agents obtained in comparative example 3 were examined according to the method described in experiment two, and the K/S values obtained were as shown in Table 3 below.
TABLE 3
| Soaping agent | Anti-staining white cloth K/S |
| Comparative example 1 | 1.1608 |
| Comparative example 2 | 0.9106 |
| Comparative example 3-1 | 0.9703 |
| Comparative examples 3 to 2 | 0.9418 |
| Comparative examples 3 to 3 | 0.9856 |
As can be seen from tables 2 and 3, the stain resistant agent prepared by the invention has excellent stain resistant capability and cleaning capability, and the fabric after soaping has good dry and wet rubbing fastness.
Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (5)
1. The preparation method of the anti-staining agent is characterized by comprising the following steps:
under the action of an initiator, maleic anhydride, acrylic acid and allyl alcohol polyoxyalkyl ether as an active monomer are subjected to polymerization reaction (2 +/-0.5) at the temperature of (80 +/-5) ℃ for hours to obtain a water-soluble copolymer MA-AA-F6, wherein the water-soluble copolymer MA-AA-F6 is an anti-staining agent;
maleic anhydride: acrylic acid: allyl alcohol polyoxyalkyl ether is 2:6: 0.1-0.8 in mass ratio;
maleic anhydride, acrylic acid: the sum of the masses of the allyl alcohol polyoxyalkyl ethers is called the total mass of the monomers;
the initiator accounts for 3-6% of the total mass of the monomer.
2. The method of claim 1, comprising the step of
①, adding water into maleic anhydride, stirring until the maleic anhydride is dissolved, heating to 65 +/-5 ℃ under the protection of inert gas, adjusting the pH value to 6.0-6.5, and adding allyl alcohol polyoxyalkyl ether;
under the protection of inert gas, heating to 80 +/-5 ℃, simultaneously dropwise adding acrylic acid and an initiator aqueous solution (namely, 2 simultaneously and respectively starting and finishing dropwise adding), wherein the dropwise adding time is (2 +/-0.2) h, and after dropwise adding, carrying out heat preservation reaction for (2 +/-0.5) h;
the mass concentration of the initiator in the initiator aqueous solution is 6-8%;
②, cooling the obtained reaction product to room temperature to obtain the water-soluble copolymer MA-AA-F6.
3. The method for producing a stain inhibitor according to claim 1 or 2, characterized in that: the initiator is at least one of sodium persulfate, potassium persulfate and ammonium persulfate.
4. The use of the stain repellent according to any one of claims 1 to 3, wherein: the method is used for preparing the soaping agent, and the preparation method of the soaping agent comprises the following steps:
uniformly mixing a nonionic surfactant, a water-soluble copolymer MA-AA-F6 and water to obtain a soaping agent;
the sum of the mass of the nonionic surfactant and the mass of the water-soluble copolymer MA-AA-F6 accounts for 18-22% of the total mass of the soaping agent.
5. The use of the stain repellent according to claim 4, wherein: the nonionic surfactant consists of fatty alcohol-polyoxyethylene ether AEO-7 and fatty alcohol-polyoxyethylene ether AEO-25;
fatty alcohol polyoxyethylene ether AEO-7: fatty alcohol polyoxyethylene ether AEO-25: the mass ratio of the water-soluble copolymer MA-AA-F6 to the copolymer is 1:0.5: 12.
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| CN113637153A (en) * | 2021-10-18 | 2021-11-12 | 常熟耐素生物材料科技有限公司 | Multi-block polyether type high-molecular surfactant and preparation method and application thereof |
| CN114196483A (en) * | 2021-12-06 | 2022-03-18 | 浙江天浩新材料股份有限公司 | Laundry detergent with stain removal and prevention functions and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0364399A2 (en) * | 1988-10-03 | 1990-04-18 | Ciba-Geigy Ag | Water soluble or water dispersible copolymers, their preparation and use |
| CN108264617A (en) * | 2017-12-30 | 2018-07-10 | 绍兴市津工科技有限公司 | A kind of chelated dispersants and preparation method thereof |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0364399A2 (en) * | 1988-10-03 | 1990-04-18 | Ciba-Geigy Ag | Water soluble or water dispersible copolymers, their preparation and use |
| CN108264617A (en) * | 2017-12-30 | 2018-07-10 | 绍兴市津工科技有限公司 | A kind of chelated dispersants and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 严瑞瑄: "《水溶性高分子》", 30 June 1998, 化学工业出版社 * |
| 赖亚琴等: "MA-AA-NVP三元共聚物的合成及性能", 《浙江理工大学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113637153A (en) * | 2021-10-18 | 2021-11-12 | 常熟耐素生物材料科技有限公司 | Multi-block polyether type high-molecular surfactant and preparation method and application thereof |
| CN113637153B (en) * | 2021-10-18 | 2022-03-22 | 常熟耐素生物材料科技有限公司 | Multi-block polyether type high-molecular surfactant and preparation method and application thereof |
| CN114196483A (en) * | 2021-12-06 | 2022-03-18 | 浙江天浩新材料股份有限公司 | Laundry detergent with stain removal and prevention functions and preparation method thereof |
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