CN111321598B - Phosphate for textile refining agent, application thereof and textile refining agent - Google Patents
Phosphate for textile refining agent, application thereof and textile refining agent Download PDFInfo
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- CN111321598B CN111321598B CN201811545830.7A CN201811545830A CN111321598B CN 111321598 B CN111321598 B CN 111321598B CN 201811545830 A CN201811545830 A CN 201811545830A CN 111321598 B CN111321598 B CN 111321598B
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- phosphate
- refining agent
- textile
- polyether
- ester
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 55
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 48
- 239000010452 phosphate Substances 0.000 title claims abstract description 48
- 238000007670 refining Methods 0.000 title claims abstract description 40
- 239000004753 textile Substances 0.000 title claims abstract description 37
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 26
- -1 phosphate ester Chemical class 0.000 claims abstract description 62
- 229920000570 polyether Polymers 0.000 claims abstract description 43
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 41
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 29
- 239000000194 fatty acid Substances 0.000 claims abstract description 29
- 229930195729 fatty acid Natural products 0.000 claims abstract description 29
- 150000002148 esters Chemical class 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 43
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 26
- 150000002191 fatty alcohols Chemical class 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 7
- 230000000865 phosphorylative effect Effects 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 230000026731 phosphorylation Effects 0.000 claims description 3
- 238000006366 phosphorylation reaction Methods 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000003513 alkali Substances 0.000 abstract description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 19
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 10
- 238000004043 dyeing Methods 0.000 abstract description 5
- 230000035699 permeability Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 27
- 238000009991 scouring Methods 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 7
- 150000005690 diesters Chemical class 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 229960001545 hydrotalcite Drugs 0.000 description 7
- 229910001701 hydrotalcite Inorganic materials 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 description 5
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 4
- 150000003138 primary alcohols Chemical class 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- 229940106681 chloroacetic acid Drugs 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 2
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 2
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- SHBUUTHKGIVMJT-UHFFFAOYSA-N Hydroxystearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OO SHBUUTHKGIVMJT-UHFFFAOYSA-N 0.000 description 1
- CVXHBROPWMVEQO-UHFFFAOYSA-N Peroxyoctanoic acid Chemical compound CCCCCCCC(=O)OO CVXHBROPWMVEQO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- BRDYCNFHFWUBCZ-UHFFFAOYSA-N dodecaneperoxoic acid Chemical compound CCCCCCCCCCCC(=O)OO BRDYCNFHFWUBCZ-UHFFFAOYSA-N 0.000 description 1
- UQDUPQYQJKYHQI-UHFFFAOYSA-N dodecanoic acid methyl ester Natural products CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002193 fatty amides Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FHWBTAQRRDZDIY-UHFFFAOYSA-N methyl 3-hydroxyoctanoate Chemical compound CCCCCC(O)CC(=O)OC FHWBTAQRRDZDIY-UHFFFAOYSA-N 0.000 description 1
- CEQFOVLGLXCDCX-WUKNDPDISA-N methyl red Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-WUKNDPDISA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000001007 puffing effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- 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
- D06M15/53—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention provides a phosphate ester for a textile refining agent, which is a mixed ester formed by hydroxy fatty acid ester polyether shown in a formula (1) and phosphoric acid. The invention also provides the use of the phosphate and a textile refining agent containing the phosphate. The phosphate raw material provided by the invention has wide source and simple and convenient preparation method, and the variety and application field of the surfactant are expanded. The textile refining agent provided by the invention has the advantages of few components, simpler preparation process, lower cost, high safety and environmental friendliness, has the characteristics of strong permeability and good wettability under a high-alkali condition, has good alkali resistance, and has great application potential in the fields of textile and printing and dyeing. CH (CH) 3 (CH 2 ) n CH(OH)(CH 2 ) m CO(CH 2 CH 2 O) k OR(1)。
Description
Technical Field
The invention relates to the field of textile printing and dyeing auxiliaries, in particular to phosphate for a textile refining agent, application of the phosphate and the textile refining agent containing the phosphate.
Background
The scouring process is a complex process of the textile under the combined action of alkali and scouring agent at a certain temperature, and comprises the actions of permeation, cleaning, puffing, emulsification, saponification, dispersion, chelation, decoloration and the like, wherein the permeation and cleaning are important. The first step of the refining process is that under the action of a surfactant, alkali liquor permeates into the fibers to expand the fibers and impurities; the second step is cleaning action, i.e. after the fibre is fully wetted, its impurities are removed by the action of heat and chemicals of soaping, emulsifying, extracting and dispersing, etc. The scouring agent helps alkali liquor penetrate into fiber, promotes saponification of wax, decomposition of cotton seed hull, protein, pectin, etc., disperses impurities removed from fiber in scouring liquor, and prevents reattachment to fiber.
In the printing and dyeing process, the alkali dosage in different processes is greatly different, so the alkali resistance requirement of the refining agent is different. For example, some of the refining agents used in the pretreatment require a relatively high amount of alkali for scouring, and the highest alkali resistance is as high as 280g NaOH/L. Chinese patent CN 200710131367 discloses an environment-friendly high-efficiency scouring agent, which comprises surfactants such as fatty amide polyoxyethylene ether succinic acid monoester sodium sulfonate, C12-14 alkyl polyglycoside, isomeric C13 alcohol polyoxyethylene ether sodium carboxylate, secondary alkyl sodium sulfonate and the like, and other auxiliaries. Chinese patent CN 201310652898 discloses an environment-friendly alkali-resistant scouring agent, which comprises glycerol monostearate, sodium hydroxide, tetramethyl ammonium bromide, chloroacetic acid, isomeric alcohol ethers, bromoacetic acid, potassium hydroxide and the like.
The prior scouring agent formula usually contains a surfactant and a plurality of surfactants, so that the preparation of the scouring agent is complicated, the cost is high, and the problems of poor alkali resistance effect, unsatisfactory capillary effect and the like exist. Therefore, the development of a more efficient surfactant and a refining agent with fewer components, simple preparation and better alkali resistance is urgently needed to meet the requirements of textile printing and dyeing and more chemical fields.
Disclosure of Invention
In order to overcome the defects of the prior refining agent, the invention aims to provide a phosphate ester which can be used in a textile refining agent.
It is another object of the present invention to provide uses of the phosphate esters.
It is a further object of the present invention to provide a textile refining agent.
The phosphate ester used for the textile refining agent provided by the invention is a mixed ester formed by hydroxy fatty acid ester polyether shown in formula (1) and phosphoric acid,
CH 3 (CH 2 ) n CH(OH)(CH 2 ) m CO(CH 2 CH 2 O) k OR
(1)
in the formula (1), m + n represents an integer of 5-15, and k represents an integer of 3-10;
r represents an alkyl group having 1 to 6 carbon atoms.
The phosphate provided by the invention is prepared by reacting hydroxyl contained in hydroxyl fatty acid ester polyether with phosphoric acid, and the mixed ester can comprise phosphoric monoester, phosphoric diester, phosphoric triester or any component and any proportion of combination. Preferably, the mixed ester may contain a monoester phosphate in a molar content of 30% or more (for example, the molar content of the monoester phosphate may be 30% or more, 40% or more, 50% or more, or 60% or more), and the remainder may be a diester phosphate, a triester phosphate, or a combination of both esters in any ratio; more preferably, the mixed ester may be a phosphoric acid diester, except for the phosphoric acid monoester; more preferably, the mixed ester comprises the phosphoric monoester and the phosphoric diester at a molar ratio of 1-5: 1; most preferably, the mixed ester comprises the monoester phosphate and the diester phosphate at a molar ratio of 1-2: 1.
In the phosphate provided by the invention, m and n can be any integers respectively containing 0 under the condition that the sum of m and n is in a range of 5-15. For example, each may be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc. Preferably, m may represent an integer of 0 to 10; n represents an integer of 1 to 8. More preferably, m represents 10 and n represents 5; or m represents 0 and n represents 7; or m represents 1 and n represents 4. K can represent an integer of 3, 4, 5, 6, 7, 8, 9, 10, preferably K can represent an integer of 3-8.
In the phosphate provided by the invention, R can represent C1-C6 alkyl, including straight-chain or branched-chain alkyl; including but not limited to methyl, ethyl, n-propyl, isopropyl, 2-methyl-l-propyl, 2-methyl-2-propyl, 2-methyl-1-butyl, 3-methyl-l-butyl, 2-methyl-3-butyl, 2-dimethyl-1-propyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-l-pentyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, and the like. Preferably, R represents methyl, ethyl, n-propyl or isopropyl.
In the phosphate provided by the invention, the preparation process can be that a phosphorylation reagent is used for reacting with the hydroxy fatty acid ester polyether. Wherein the phosphorylating agent is phosphoric acid or a substance capable of reacting to form phosphoric acid, such as phosphorus pentoxide (P) 2 O 5 ) (ii) a The phosphorylating agent is preferably P 2 O 5 . The molar amount of the phosphorylating agent and the hydroxy fatty acid ester polyether can be adjusted according to the required component ratio of the mixed ester. Preferably, each mole of P in the phosphorylation reagent corresponds to 1-10 moles of hydroxy fatty acid ester polyether; more preferably, each mole of P in the phosphorylating agent mayCorresponding to 5-8 mol of hydroxy fatty acid ester polyether.
Using P 2 O 5 When used as a phosphorylating reagent, the reaction process may be: will P 2 O 5 Reacting with hydroxy fatty acid ester polyether at 50-80 ℃ for 2-8 hours, adding water, and hydrolyzing at 80-100 ℃ for 0.5-3 hours to obtain the phosphate. Further, hydroxy fatty acid ester polyether with P 2 O 5 The molar ratio of (3) to (2) to (5) to (1) and the molar ratio of water to the hydroxyfatty acid ester polyether is from 1 to 1.5: 1. Further, hydroxy fatty acid ester polyether and P 2 O 5 Can be 3: 1.
In the phosphate provided by the invention, the hydroxy fatty acid ester polyether can be prepared by alkoxylating hydroxy fatty acid ester shown in a formula (2) with ethylene oxide.
CH 3 (CH 2 ) n CH(OH)(CH 2 ) m COOR
(2)
In the formula (2), m, n and R are as defined in the formula (1).
The alkoxylation reaction can use a conventional alkoxylation reaction process and a catalyst, and the addition number (namely k value) of the ethylene oxide can be 3-10.
Further, the alkoxylation reaction process may be: taking hydroxy fatty acid ester shown in formula (3) as a starting material, taking commercial hydrotalcite (or hydrotalcite after surface modification or an analogue thereof) as a catalyst, introducing ethylene oxide for reaction, wherein the reaction temperature can be 130-150 ℃, the reaction pressure can be less than or equal to 0.5MPa, cooling to 70-80 ℃ after the reaction is finished, and discharging to obtain the catalyst.
The phosphate provided by the invention has good functions of emulsification, dispersion and the like, and can be used as a surfactant; furthermore, the anionic surfactant can be used as an anionic surfactant and can be used in various fields such as chemical auxiliaries and chemical production.
The invention also provides a textile refining agent, which comprises the following components in percentage by mass: 35-60% of the phosphate ester according to any one of the above technical schemes, 5-25% of fatty alcohol polyether and the balance of water.
In practical application, different composition ratios can be selected according to different types of fibers and dyes, and besides the components described in the invention, other additives such as wetting agents, antifoaming agents, chelating agents, dispersing agents and the like can be additionally added to achieve more excellent performance. Preferably, the textile refining agent comprises the following components in percentage by mass: 40-60% of the phosphate ester according to any one of the above technical schemes, 10-25% of fatty alcohol polyether and the balance of water.
In the textile refining agent provided by the invention, the fatty alcohol polyether can be prepared by alkoxylating C6-C20 linear fatty alcohol and ethylene oxide.
Wherein, the linear fatty alcohol can be preferably linear primary alcohol; the straight-chain fatty alcohol is preferably C8-C18 straight-chain fatty alcohol.
The alkoxylation reaction can use a conventional alkoxylation reaction process and a catalyst, and the addition number of the ethylene oxide can be 3-10.
Further, the alkoxylation reaction process may be: the method comprises the steps of taking C6-C20 straight-chain fatty alcohol as an initial raw material, taking commercially available hydrotalcite (or hydrotalcite after surface modification or an analogue thereof) as a catalyst, introducing ethylene oxide to react, wherein the reaction temperature can be 130-150 ℃, the reaction pressure can be less than or equal to 0.5MPa, cooling to 70-80 ℃ after the reaction is finished, and discharging to obtain the product.
The preparation process of the textile refining agent provided by the invention can comprise the following steps: and uniformly mixing the phosphate, the fatty alcohol polyether and water at 30-40 ℃, and adjusting the pH value of the mixed material to 6-9 to obtain the product.
All components of the textile refining agent have better water solubility, and can be uniformly mixed at a temperature close to normal temperature compared with a conventional heating and mixing mode, so that energy consumption and components can be saved, the operation is simpler and easier, and the requirement on using equipment is lower; after all the components are uniformly mixed, the pH value of the obtained refining agent is controlled to be 6-9, and the final product is milder and more stable and is easy to store, transport and other subsequent links.
The phosphate ester provided by the invention has wide raw material source, simple and convenient preparation method, and easy adjustment of the components of the mixed ester, and enlarges the types and application fields of the surfactant. The textile refining agent provided by the invention contains the phosphate ester, only two components are needed to be compounded, and the components are few, so that the preparation process is simpler and more convenient, the cost is lower, the safety is high, and the environment is friendly. The textile refining agent has the characteristics of strong permeability and good wettability under the high-alkali condition (for example, 300g/L NaOH solution), and has good alkali resistance, and the textile using the refining agent has the advantages of high capillary effect, good whiteness and the like. Therefore, the textile refining agent has great application potential in the fields of textile and printing and dyeing.
Detailed Description
The present invention will be described in detail below with reference to examples to make the features and advantages of the present invention more apparent. It should be noted that the examples are for understanding the concept of the present invention and the scope of the present invention is not limited to only the examples listed herein.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The method for measuring the content of the monoester and the diester comprises the following steps:
accurately weighing 1-2 g of phosphate ester sample into a 250mL conical flask, adding 50mL of absolute ethyl alcohol, fully oscillating to dissolve the phosphate ester sample, dropwise adding 2-3 drops of methyl red indicator, titrating with 0.5mol/L potassium hydroxide standard solution, changing the solution from red to orange yellow, and recording the volume V1 of the consumed potassium hydroxide standard solution. And (4) dropwise adding 6-8 drops of phenolphthalein indicator, continuing titration, changing the solution from yellow to orange red, and recording the volume V2 of the consumed potassium hydroxide standard solution. 10mL of 10% aqueous calcium chloride solution was added and titration continued with the solution changing from red to orange-yellow, and the volume of potassium hydroxide standard solution consumed V3 was recorded.
The calculation formula is shown as follows:
diester% (V1-V2)/V1X 100%
Monoester% (V2-V3)/V1X 100%
Percent free phosphoric acid-V3/V1X 100%
Example 1
1. Synthesis of hydroxy fatty acid ester polyether
Adding 790Kg of 12-methyl hydroxystearate and 1Kg of hydrotalcite catalyst into a high-pressure reaction kettle, heating to 80 ℃, then adding 210Kg of ethylene oxide, controlling the reaction temperature at 130-150 ℃, and controlling the reaction pressure at less than or equal to 0.5 MPa. After the ethylene oxide feeding is finished, the reaction is continued until the reaction pressure is not reduced any more, the heating is stopped, the temperature of the materials is reduced to 70-80 ℃, and the materials are discharged, thus obtaining the final hydroxyl stearate polyether product with the ethylene oxide addition number of 3.
2. Synthesis of phosphate esters
900Kg of hydroxy fatty acid ester polyether prepared in the step 1 and P 2 O 5 100Kg react at 60-70 ℃ for 4 hours, wherein, the hydroxy fatty acid ester polyether and P 2 O 5 At a molar ratio of 1: 0.33. Keeping the temperature for 1 hour, adding 45.6Kg of water at a molar ratio of 1.2: 1 to the hydroxy fatty acid ester polyether, and hydrolyzing at 90 deg.C for 1 hour to obtain the phosphate ester.
The molar content of the monoester, the molar content of the diester and the molar content of the free phosphoric acid in the obtained product were respectively tested to be 57.33%, 39.01% and 3.66%.
3. Synthesis of fatty alcohol polyethers
Adding C into a high-pressure reaction kettle 8 425Kg of linear primary alcohol and 1Kg of KOH catalyst are heated to 80 ℃, 575Kg of ethylene oxide is added, the reaction temperature is controlled to be 120-130 ℃, and the reaction pressure is not more than 0.4 MPa. After the feeding of the ethylene oxide is finished, continuously reacting until the reaction pressure is not reduced any more, stopping heating, cooling the materials to 70-80 ℃, and discharging to obtain the final fatty alcohol-polyoxyethylene ether product with the ethylene oxide addition number of 4.
4. Compounding of scouring agent
And (3) mixing the phosphate synthesized in the step (2), the fatty alcohol polyether synthesized in the step (3) and water according to the weight ratio of 55: 15: 30, uniformly stirring at the temperature of 30-40 ℃, and adjusting the pH value of the material to 6-9.
Example 2
1. Synthesis of hydroxy fatty acid ester polyether
530Kg of 2-hydroxy methyl laurate and 1Kg of hydrotalcite catalyst are added into a high-pressure reaction kettle, the temperature is raised to 80 ℃, then 470Kg of ethylene oxide is added, the reaction temperature is controlled to be 130-ammonia-150 ℃, and the reaction pressure is not more than 0.5 MPa. After the feed of the ethylene oxide is finished, the reaction is continued until the reaction pressure is not reduced any more, the heating is stopped, the temperature of the materials is reduced to 70-80 ℃, and the materials are discharged, thus obtaining the final hydroxyl laurate polyether product with 5 ethylene oxide addition numbers.
2. Synthesis of phosphate esters
910Kg of hydroxy fatty acid ester polyether prepared in the step 1 and P 2 O 5 90Kg reacted at 60-70 ℃ for 4 hours, wherein the hydroxy fatty acid ester polyether and P 2 O 5 At a molar ratio of 1: 0.33. Keeping the temperature for 1 hour, adding 78.6Kg of water at a molar ratio of 1.2: 1 to the hydroxy fatty acid ester polyether, and hydrolyzing at 90 deg.C for 1 hour to obtain the phosphate ester.
The molar content of the monoester in the obtained product was determined to be 57.55%, the molar content of the diester was determined to be 38.20%, and the molar content of the free phosphoric acid was determined to be 4.25%.
3. Synthesis of fatty alcohol polyethers
Adding C into a high-pressure reaction kettle 12 414Kg of straight-chain primary alcohol and 1Kg of KOH catalyst are heated to 80 ℃, 586Kg of ethylene oxide is added, the reaction temperature is controlled at 120 ℃ and 130 ℃, and the reaction pressure is less than or equal to 0.4 MPa. After the feeding of the ethylene oxide is finished, continuously reacting until the reaction pressure is not reduced any more, stopping heating, cooling the materials to 70-80 ℃, and discharging to obtain the final fatty alcohol-polyoxyethylene ether product with the ethylene oxide addition number of 6.
4. Compounding of scouring agent
And (3) mixing the phosphate synthesized in the step 2, the fatty alcohol polyether synthesized in the step 3 and water according to the weight ratio of 40: 25: 35, uniformly stirring at the temperature of 30-40 ℃, and adjusting the pH value of the material to 6-9.
Example 3
1. Synthesis of hydroxy fatty acid ester polyether
315Kg of methyl 3-hydroxyoctanoate and 1Kg of hydrotalcite catalyst are added into a high-pressure reaction kettle, the temperature is raised to 80 ℃, 685Kg of ethylene oxide is added, the reaction temperature is controlled to be 130-150 ℃, and the reaction pressure is less than or equal to 0.5 MPa. After the ethylene oxide feeding is finished, the reaction is continued until the reaction pressure is not reduced any more, the heating is stopped, the temperature of the materials is reduced to 70-80 ℃, and the materials are discharged, thus obtaining the final hydroxyl caprylate polyether product with 8 ethylene oxide addition numbers.
2. Synthesis of phosphate esters
916Kg of hydroxy fatty acid ester polyether prepared in the step 1 is mixed with P 2 O 5 Reacting 84Kg at 60-70 ℃ for 4 hours, wherein, the hydroxy fatty acid ester polyether and P 2 O 5 At a molar ratio of 1: 0.33. Keeping the temperature for 1 hour, adding 38.5Kg of water at a molar ratio of 1.2: 1 to the hydroxy fatty acid ester polyether, and hydrolyzing at 90 deg.C for 1 hour to obtain the phosphate ester.
The molar content of the monoester in the obtained product was determined to be 56.33%, the molar content of the diester was determined to be 39.16%, and the molar content of the free phosphoric acid was determined to be 4.51%.
3. Synthesis of fatty alcohol ethers
Adding C into a high-pressure reaction kettle 18 406Kg of straight-chain primary alcohol and 1Kg of KOH catalyst are heated to 80 ℃, 594Kg of ethylene oxide is added, the reaction temperature is controlled to be 120 ℃ and 130 ℃, and the reaction pressure is less than or equal to 0.4 MPa. After the ethylene oxide feeding is finished, continuing to react until the reaction pressure is not reduced any more, stopping heating, cooling the materials to 70-80 ℃, and discharging to obtain the final fatty alcohol-polyoxyethylene ether product with the ethylene oxide addition number of 9.
4. Compounding of scouring agent
And (3) mixing the phosphate ester synthesized in the step (2), the fatty alcohol polyether synthesized in the step (3) and water according to the weight ratio of 60: 10: 30, uniformly stirring at the temperature of 30-40 ℃, and adjusting the pH value of the material to 6-9.
Comparative example 1
The environment-friendly alkali-resistant scouring agent used in the embodiment 3 of Chinese patent CN 201310652898 comprises the following components:
1.2 parts by mass of glycerol monostearate;
4.5 parts by mass of sodium hydroxide;
1.2 parts by mass of tetramethylammonium bromide;
4.5 parts by mass of chloroacetic acid;
8.9 parts by mass of isomeric alcohol ether;
3.4 parts by mass of bromoacetic acid;
2.4 parts by mass of potassium hydroxide.
Comparative example 2
The environment-friendly scouring agent in the embodiment 2 of Chinese patent CN 200710131367 is prepared by mixing and stirring the following components in percentage by weight:
comparative example 3
The phosphorus-free scouring agent of example 1 in Chinese patent CN 101498101A is composed of the following components:
the refining agents obtained in examples 1 to 3 and comparative examples 1 to 3 were subjected to performance tests in accordance with the following criteria. The results are shown in tables 1 to 3, respectively.
Alkali permeability resistance: GB/T11983-1989.
Alkali resistance stability: GB/T5556-2003.
Emulsibility: 40 g of 0.1% refining agent aqueous solution and 40 g of white oil are mixed uniformly and placed, and the time required for separating 10mL of water is observed, and the longer the time is, the better the emulsification effect is.
TABLE 1 alkali penetration resistance
TABLE 2 stability against alkali
TABLE 3 emulsifying Properties
As can be seen from tables 1-3, the textile refining agent provided by the invention is obviously superior to the comparative examples in the aspects of alkali resistance, emulsibility and the like, especially has alkali resistance, and has good stability even under 300g/L of strong alkali.
The refining agents prepared in examples 1-3 and comparative examples 1-3 were applied to the refining of textiles, and the procedure was as follows:
textile: cotton and cotton yarn fabrics;
working fluid: 2g/L of the refining agents obtained in examples 1 to 3 and comparative examples 1 to 3; 2g/L of NaOH; 6g/L of hydrogen peroxide (the content of the hydrogen peroxide is 30.5 percent in the market); 2g/L hydrogen peroxide stabilizer (commercially available);
the bath ratio is 1:20, and the boiling is carried out for 60 minutes at the temperature of 100 ℃.
After the scouring, the obtained textile fabric is washed with water and dried, and the capillary effect and the whiteness of the textile fabric are tested according to the following processes. The results are shown in tables 4 and 5.
Hair effect: the method comprises the steps of cutting a refined sample into cloth strips with the radial length of 30cm and the latitudinal length of 5cm, using a pencil as a parallel line at a position 1cm away from one end along the latitudinal direction, fixing a short glass rod weighing about 3 g at the tail end along the latitudinal direction as a heavy load, fixing one end of the sample on a frame to enable the sample to be vertically suspended, enabling the lower end of the sample to penetrate into 5g/L potassium dichromate solution, enabling the liquid level to be exactly aligned with the pencil line, measuring the height of the potassium dichromate solution rising along the radial direction within 30 minutes, and expressing that the refining effect is better when the numerical value is larger as expressed in cm.
Whiteness: GB/T8424.2-2001.
TABLE 4 hair effects
| Item | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Hair effect | 12.8cm | 13.5cm | 12.1cm | 9.6cm | 10.5cm | 8.3cm |
TABLE 5 whiteness
| Item | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Whiteness degree | 81.5 | 82.3 | 82.6 | 75.3 | 76.8 | 78.6 |
As can be seen from tables 4-5, the capillary effect and whiteness of the textile treated by the refining agent of the invention are also obviously superior to those of the comparative examples.
Unless otherwise defined, all terms used herein have the meanings commonly understood by those skilled in the art.
The described embodiments of the present invention are for illustrative purposes only and are not intended to limit the scope of the present invention, and those skilled in the art may make various other substitutions, alterations, and modifications within the scope of the present invention, and thus, the present invention is not limited to the above-described embodiments but only by the claims.
Claims (9)
1. A phosphate ester used for a textile refining agent, which is characterized in that the phosphate ester is a mixed ester formed by the reaction of hydroxy fatty acid ester polyether shown in formula (1) and a phosphorylation agent,
CH 3 (CH 2 ) n CH(OH)(CH 2 ) m CO(CH 2 CH 2 O) k OR
（1）
in the formula (1), m + n represents an integer of 5-15, and k represents an integer of 3-10;
r represents an alkyl group having 1 to 6 carbon atoms;
the phosphorylating agent is P 2 O 5 From P to P 2 O 5 Reacting with the hydroxy fatty acid ester polyether at 50-80 ℃ for 2-8 hours, adding water, and hydrolyzing at 80-100 ℃ for 0.5-3 hours to obtain the phosphate;the P is 2 O 5 The molar ratio of the hydroxy fatty acid ester polyether to the hydroxy fatty acid ester polyether is 1: 2-5.
2. The phosphate ester of claim 1, wherein the mixed ester comprises monoester phosphate and diester phosphate at a molar ratio of 1: 5: 1.
3. The phosphate according to claim 1 or 2, wherein m represents an integer of 0 to 10, and n represents an integer of 1 to 8.
4. Phosphate according to claim 1 or 2, characterized in that R represents a methyl, ethyl, n-propyl or isopropyl group.
5. Use of a phosphate ester according to any one of claims 1 to 4 as a surfactant.
6. Use according to claim 5, characterized in that the surfactant is an anionic surfactant.
7. A textile refining agent is characterized by comprising the following components in percentage by mass: 35 to 60% of the phosphate ester according to any one of claims 1 to 4, 5 to 25% of a fatty alcohol polyether and the balance water.
8. The textile refining agent according to claim 7, wherein the fatty alcohol polyether is prepared by alkoxylation reaction of C6-C20 linear fatty alcohol and ethylene oxide, and the addition number of the ethylene oxide is 3-10.
9. The textile refining agent according to claim 7 or 8, wherein the preparation process of the textile refining agent comprises: and uniformly mixing the phosphate, the fatty alcohol polyether and water at 30-40 ℃, and adjusting the pH value of the mixed material to 6-9 to obtain the product.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5414103A (en) * | 1992-01-10 | 1995-05-09 | Oceanfloor Limited | Polyether phosphate esters |
| CN108071012A (en) * | 2016-11-17 | 2018-05-25 | 哈尔滨市恒源麻纺机械有限公司 | A kind of weaving scouring agent |
| CN108611850A (en) * | 2018-06-22 | 2018-10-02 | 淄博鲁瑞精细化工有限公司 | The preparation method of the low bubble concise bleeding agent of phosphate |
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2018
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5414103A (en) * | 1992-01-10 | 1995-05-09 | Oceanfloor Limited | Polyether phosphate esters |
| CN108071012A (en) * | 2016-11-17 | 2018-05-25 | 哈尔滨市恒源麻纺机械有限公司 | A kind of weaving scouring agent |
| CN108611850A (en) * | 2018-06-22 | 2018-10-02 | 淄博鲁瑞精细化工有限公司 | The preparation method of the low bubble concise bleeding agent of phosphate |
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