CN113698549B - Hyperbranched polymer, preparation method, application and washing product thereof - Google Patents
Hyperbranched polymer, preparation method, application and washing product thereof Download PDFInfo
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- CN113698549B CN113698549B CN202111032597.4A CN202111032597A CN113698549B CN 113698549 B CN113698549 B CN 113698549B CN 202111032597 A CN202111032597 A CN 202111032597A CN 113698549 B CN113698549 B CN 113698549B
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- hyperbranched polymer
- hyperbranched
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- 229920000587 hyperbranched polymer Polymers 0.000 title claims abstract description 42
- 238000005406 washing Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000003999 initiator Substances 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 27
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
- 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 22
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 12
- 229920000570 polyether Polymers 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 9
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 7
- -1 acrylic ester Chemical class 0.000 claims abstract description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 claims abstract description 3
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 10
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 10
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 6
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 claims description 6
- CZXGXYBOQYQXQD-UHFFFAOYSA-N methyl benzenesulfonate Chemical compound COS(=O)(=O)C1=CC=CC=C1 CZXGXYBOQYQXQD-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 4
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 4
- 235000010262 sodium metabisulphite Nutrition 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 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- LBLYYCQCTBFVLH-UHFFFAOYSA-M 2-methylbenzenesulfonate Chemical compound CC1=CC=CC=C1S([O-])(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-M 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 125000005394 methallyl group Chemical group 0.000 claims description 2
- KPAMAVPLAHLEQE-UHFFFAOYSA-N methyl benzenesulfonate;potassium Chemical compound [K].COS(=O)(=O)C1=CC=CC=C1 KPAMAVPLAHLEQE-UHFFFAOYSA-N 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- 230000003139 buffering effect Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract description 3
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical class CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 5
- 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 5
- 238000003756 stirring Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 3
- 235000011092 calcium acetate Nutrition 0.000 description 3
- 239000001639 calcium acetate Substances 0.000 description 3
- 229960005147 calcium acetate Drugs 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 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
- 239000000843 powder Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910017917 NH4 Cl Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012490 blank solution Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000008096 xylene Substances 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3788—Graft polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Detergent Compositions (AREA)
Abstract
The invention discloses a hyperbranched polymer, a preparation method, application and a washing product thereof. The preparation method of the hyperbranched polymer comprises the following steps: s1: under the existence of a protective gas and the catalysis of a catalyst, acrylic ester, trimethylolpropane and allylamine react to generate a hyperbranched functional monomer A, wherein the catalyst is p-toluenesulfonic acid and/or toluenesulfonic acid salt; the reaction temperature is 70-100 ℃; s2: in the presence of an initiator and a reducing agent, carrying out polymerization reaction on the mixed monomer dispersed in the water phase to obtain the catalyst; the mixed monomer comprises a hyperbranched functional monomer A, unsaturated polyether and acrylic acid; the temperature of the polymerization reaction is 60-90 ℃. The hyperbranched polymer provided by the invention has strong chelating force, strong dispersing force and strong alkali buffering force, better washing assisting performance, environment-friendly preparation process, low-cost and easily obtained raw materials, no use of organic solvents, short process flow, low equipment investment and low production cost.
Description
Technical Field
The invention relates to a hyperbranched polymer, a preparation method, application and a washing product thereof.
Background
The polycarboxylic acid polymer has excellent chelating and dispersing effects, and is widely applied to the fields of detergents and water treatment, and mainly has dispersing effects in the washing field. When used as a washing auxiliary agent, the detergent has the following characteristics: the alkaline buffer effect is that even if a small amount of acidic substances exist, the pH value of the washing liquid is not changed obviously due to the action of the auxiliary agent, and the detergent has strong decontamination effect; has the functions of dispersing dirt into water and preventing the dirt from reattaching and depositing to fabrics; the polycarboxylic acid polymer has a large number of carboxylate groups on the side chains, and thus has a strong ability to chelate particles and a strong ability to soften hard water. In view of the excellent builder property of polycarboxylic acid type high molecular polymer, sodium tripolyphosphate can be completely or partially replaced, and the polycarboxylic acid type high molecular polymer can be used as a detergent builder.
The most studied at present are the sodium salts of acrylic acid-maleic anhydride copolymers, which are also the only copolymers that have found practical use. In the conventional acrylic acid-maleic anhydride copolymer synthesis process (for example, chinese patent document CN1099764 a), benzoyl peroxide is used as an initiator, and solution polymerization is performed in a toxic organic solvent (for example, toluene, xylene, etc.), and then neutralization hydrolysis is performed to obtain the acrylic acid-maleic anhydride copolymer. The disadvantage of this process is the high price and high amounts of initiator; the solvent adopted is toxic and harmful, and needs to be recycled after distillation, so that the process is complex, the equipment investment is large, the time and the energy consumption are long, and the production cost is high. In addition, the production process (such as China patent document CN 101921359A) that acrylic acid is not neutralized in advance and is directly added into solution for polymerization reaction has the defects of low efficiency of grafting maleic anhydride onto the copolymer, poor dispersion of the synthesized acrylic acid-maleic anhydride copolymer product, influence on washing-assisting performance and the like.
Disclosure of Invention
The invention aims to overcome the defects of high cost of an initiator, use of a toxic solvent, complex process, high equipment investment, long time consumption, poor product dispersion and poor washing assisting effect in the preparation of acrylic acid-maleic anhydride copolymer sodium salt in the prior art, and provides a hyperbranched polymer and a preparation method, application and washing products thereof. The hyperbranched polymer provided by the invention has strong chelating force, strong dispersing force and strong alkali buffering force, better washing assisting performance, environment-friendly preparation process, low-cost and easily obtained raw materials, no use of organic solvents, short process flow, low equipment investment and low production cost.
The invention adopts the following technical scheme to solve the technical problems:
the invention provides a preparation method of a hyperbranched polymer, which comprises the following steps:
S1: under the existence of a protective gas and the catalysis of a catalyst, acrylic ester, trimethylolpropane and allylamine react to generate a hyperbranched functional monomer A, wherein the catalyst is p-toluenesulfonic acid and/or toluenesulfonate; the reaction temperature is 70-100 ℃;
s2: in the presence of an initiator and a reducing agent, carrying out polymerization reaction on the mixed monomer dispersed in the water phase to obtain the catalyst; the mixed monomer comprises the hyperbranched functional monomer A, unsaturated polyether and acrylic acid; the initiator is persulfate and/or hydrogen peroxide; the reducing agent is one or more of sodium bisulphite, sodium sulfite and sodium metabisulfite; the temperature of the polymerization reaction is 60-90 ℃.
In S1, the acrylate may be conventional in the art, preferably one or more of methyl acrylate, methyl methacrylate, ethyl acrylate and ethyl methacrylate, more preferably methyl acrylate and/or methyl methacrylate.
In S1, the molar ratio of the acrylate, trimethylolpropane and allylamine may be conventional in the art, preferably 1 (0.3 to 0.7): (0.8 to 1.2), for example 1:0.56:1.11.
In S1, the temperature of the reaction is preferably 80 to 90 ℃.
In S1, the reaction time may be conventional in the art, preferably 2 to 4 hours, for example 3 hours.
In S1, the reaction is generally carried out with stirring. Wherein the stirring is typically magnetic stirring.
In S1, the reaction is preferably carried out under reflux. Wherein the reflux is generally carried out in a condensing reflux unit.
In S1, the shielding gas may be conventional in the art, and may be generally an inert gas and/or nitrogen, preferably nitrogen.
In S1, the methylbenzenesulfonate may be conventional in the art, and may be generally sodium and/or potassium methylbenzenesulfonate, preferably sodium methylbenzenesulfonate, and more preferably sodium p-methylbenzenesulfonate.
In S1, the methylbenzenesulfonate is preferably p-methylbenzenesulfonate.
In S1, the catalyst may be used in an amount conventional in the art, preferably in a molar ratio of the catalyst to the acrylate of (0.004-0.01): 1, more preferably 0.005-0.007:1, for example 0.006:1.
In S1, the reaction preferably further includes a purification and filtration step after the completion of the reaction.
Wherein the purification can be carried out by methods conventional in the art, and can be generally rectification.
In S2, the unsaturated polyether may be conventional in the art, preferably one or more of allyl alcohol polyoxyethylene ether, isopentenyl alcohol polyoxyethylene ether, and methallyl polyoxyethylene ether.
In S2, the mass ratio of the mixed monomer to the water may be conventional in the art, and generally the mixed monomer may be dispersed in the water.
In S2, the persulfate may be conventional in the art, preferably one or more of ammonium persulfate, potassium persulfate, and sodium persulfate.
In S2, the initiator is preferably used in the form of an aqueous initiator solution.
Wherein the concentration of the aqueous initiator solution may be conventional in the art, preferably 1 to 5%, for example 2%, 3% or 4%, by mass of the initiator based on the aqueous initiator solution.
In S2, the initiator may be added in an amount conventional in the art, preferably 0.1 to 10%, more preferably 0.1 to 2%, based on the mass of the acrylic acid.
In S2, the reducing agent is preferably used in the form of an aqueous reducing agent solution.
Wherein the concentration of the aqueous reducing agent solution may be conventional in the art, preferably 2 to 10%, more preferably 4 to 6%, for example 5%, by mass of the reducing agent based on the aqueous reducing agent solution.
In S2, the reducing agent may be added in an amount conventional in the art, preferably 0.2 to 20%, more preferably 0.8 to 3%, for example 1%, 1.47% or 2%, of the acrylic acid, all percentages being mass%.
In S2, before the polymerization reaction, the addition sequence of the materials can be conventional in the art. Preferably, the acrylic acid, the initiator and the reducing agent are added after the hyperbranched functional monomer A and the unsaturated polyether are dispersed in water.
More preferably, the hyperbranched functional monomer A and the unsaturated polyether are dispersed in water, then heated to the temperature of the polymerization reaction, and then the acrylic acid, the initiator and the reducing agent are added simultaneously.
Wherein, preferably, the acrylic acid, the initiator and the reducing agent are added in a dropwise manner.
Wherein, the time of the dripping can be conventional in the field, and is preferably 2-3 h.
In S2, the polymerization reaction temperature is preferably 70 to 80 ℃.
In S2, the polymerization time may be conventional in the art, preferably 0.5 to 4 hours.
In certain preferred embodiments, the hyperbranched functional monomer A and the unsaturated polyether are dispersed in water, heated to the temperature of the polymerization reaction, and then the acrylic acid, the initiator and the reducing agent are added dropwise at the same time; the dropwise adding time is 2-3 h, the polymerization reaction temperature is 70-80 ℃, and the polymerization reaction time is 1-2 h.
In S2, after the polymerization reaction is completed, a base neutralization step is preferably further included.
Wherein the base may be conventional in the art, preferably one or more of sodium hydroxide, potassium hydroxide, ammonia, liquid ammonia and organic amines.
The invention also provides the hyperbranched polymer prepared by the preparation method.
The invention also provides the use of a hyperbranched polymer as described above as a builder in a washing product. The invention also provides a washing product comprising a hyperbranched polymer as described above.
In the present invention, the washing product may be a washing liquid.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that:
1. The hyperbranched polymer has strong chelating force, and the chelating force on CaCO 3 can be higher than 360mg/g, even up to 378mg/g; the dispersion force is strong, and the dispersion force to CaCO 3 can be close to or higher than 300mg/g; the alkali buffering power is high and can be higher than 13g, and in certain preferred embodiments, can be as high as 14.42g;
2. the raw materials used in the preparation process are cheap and easy to obtain, and the cost of the raw materials is low;
3. The method does not use toxic solvents, is environment-friendly and safe in process, does not need a distillation recovery process of the solvents, shortens the process flow, reduces the equipment investment and reduces the production cost.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
The raw materials used in the following examples and comparative examples are all commercially available.
Example 1
S1: preparation of hyperbranched functional monomer A
Nitrogen is introduced into a three-neck flask for 5min, 80g of methyl acrylate, 70g of trimethylolpropane and 60g of allylamine are put into the three-neck flask, 1g of p-toluenesulfonic acid is added as a catalyst, reflux reaction is carried out for 3h under the condition of magnetic stirring at 80 ℃, and hyperbranched functional monomer A is obtained after purification and filtration.
S2: preparation of hyperbranched polymers
Adding the hyperbranched functional monomer A prepared in the step S1, 90g of deionized water and 10g of allyl alcohol polyoxyethylene ether into a reaction kettle, stirring and heating to 70-80 ℃, simultaneously dropwise adding 170g of acrylic acid, 50g of sodium persulfate aqueous solution (mass fraction is 2%) and 50g of sodium bisulfite aqueous solution (mass fraction is 5%), wherein the dropwise adding time is 3h, and reacting at constant temperature for 1h after the dropwise adding is finished. After the reaction is finished, the temperature is reduced to about 50 ℃, and the mixture is neutralized to be neutral by liquid alkali, so that the hyperbranched polymer is obtained.
Example 2
S1: preparation of hyperbranched functional monomer A
S1 is the same as in example 1.
S2: preparation of hyperbranched polymers
Adding the hyperbranched functional monomer A prepared in the step S1, 90g of deionized water and 10g of isopentenyl alcohol polyoxyethylene ether into a reaction kettle, stirring and heating to 70-80 ℃, simultaneously dropwise adding 170g of acrylic acid, 50g of potassium persulfate aqueous solution (mass fraction is 2%) and 50g of sodium metabisulfite aqueous solution (mass fraction is 5%), wherein the dropwise adding time is 2 hours, and reacting at constant temperature for 2 hours after the dropwise adding is finished. After the reaction is finished, the temperature is reduced to about 50 ℃, and the mixture is neutralized to be neutral by potassium hydroxide solution, thus obtaining the hyperbranched polymer.
Example 3
S1: preparation of hyperbranched functional monomer A
S1 is the same as in example 1.
S2: preparation of hyperbranched polymers
Adding the hyperbranched functional monomer A prepared in the step S1, 90g of deionized water and 10g of methyl allyl polyoxyethylene ether into a reaction kettle, stirring and heating to 70-80 ℃, simultaneously dropwise adding 170g of acrylic acid, 50g of ammonium persulfate aqueous solution (mass fraction is 2%) and 50g of sodium metabisulfite aqueous solution (mass fraction is 5%), wherein the dropwise adding time is 3h, and reacting at constant temperature for 1h after the dropwise adding is finished. After the reaction is finished, the temperature is reduced to about 50 ℃, and the reaction product is neutralized to be neutral by liquid ammonia, so that the hyperbranched polymer is obtained.
Comparative example 1
90G of deionized water and 10g of methyl allyl polyoxyethylene ether are added into a reaction kettle, stirred and heated to 70-80 ℃, 170g of acrylic acid, 50g of ammonium persulfate aqueous solution (mass fraction is 2%), 50g of sodium sulfite solution (mass fraction is 5%) are added dropwise, and the adding time is 3h; and after the dripping is finished, the reaction is carried out for 1h at constant temperature. After the reaction is finished, the temperature is reduced to about 50 ℃, and the polymer is obtained by neutralizing the reaction product with liquid ammonia to be neutral.
Comparative example 2
Maleic anhydride-acrylic acid copolymer produced by Shanghai chemical Co., ltd.
Effect examples
1. Chelating force test
The hyperbranched polymers obtained in examples 1 to 3, the polymer of comparative example 1 and the maleic anhydride-acrylic acid copolymer of comparative example 2 were each subjected to chelation force test by direct titration. About 5g of the sample is weighed to prepare 100mL of solution, 25mL of the solution is removed in a 250mL triangular flask, 5mL of 0.1mol/L sodium oxalate is added, the pH value is adjusted to 10-10.5 by using a NH 3-NH4 Cl buffer solution with the pH value of 10, then the solution is titrated by using a 0.1mol/L calcium acetate standard solution to generate permanent white sediment as an end point, and the chelating force for Ca 2+ is calculated according to the following formula:
F＝4VCM/m
wherein F is chelating force, mg/g; v is the volume of consumed calcium acetate, mL; c is the concentration of the calcium acetate solution and mol/L; m is the mass of the sample, g; m is the relative molecular weight of CaCO 3. The test results are shown in Table 1.
2. Dispersion force test
The hyperbranched polymers obtained in examples 1 to 3, the polymer of comparative example 1 and the maleic anhydride-acrylic acid copolymer of comparative example 2 were each subjected to a dispersion force test. The test procedure was as follows:
Two 50mL color comparison tubes are respectively filled with 50mL distilled water and 50mL water solution containing 0.5g sample to be tested, 1.00g CaCO 3 powder which is dried is respectively added, and the mixture is vigorously vibrated up and down for 100 times. After standing at room temperature for 30min, accurately transferring 10mL of the solution into a conical flask at 25mL of a colorimetric tube, adding 35mL of distilled water for dilution, then adding 10mL of 0.5mol/L hydrochloric acid solution and 2 drops of phenolphthalein indicator, and titrating to red by using 0.2mol/L NaOH standard solution. The dispersion force was calculated as follows:
f＝c(V0-V1)×100.09/2m
Wherein f is the dispersing force, mg/g; c is the concentration of NaOH standard solution and mol/L; v 0 and V 1 are respectively the volume of a titration blank solution (without a sample to be detected) and the volume of NaOH standard solution consumed by the sample to be detected, and mL; m is the mass of CaCO 3 powder and g. The test results are shown in Table 1.
3. Alkali buffering power test
The hyperbranched polymers obtained in examples 1 to 3, the polymer of comparative example 1 and the maleic anhydride-acrylic acid copolymer of comparative example 2 were each subjected to a base buffer force test. The test procedure was as follows:
100mL of the aqueous solution of the sample to be tested was adjusted to pH 10 with 0.1mol/L NaOH solution. Then, 0.1mol/L HCl solution was added dropwise, and the gram number of 0.1mol/L HCl consumed when the pH of the solution was changed from 10 to 8 was measured to obtain the alkali buffering capacity. The test results are shown in Table 1.
TABLE 1 washing aid Performance index test results for samples to be tested
As shown in Table 1, the hyperbranched polymers obtained in examples 1 to 3 were better in chelating force, dispersing force and slow impulse force than the maleic anhydride-acrylic acid copolymer of comparative example 2 and also better than that obtained in comparative example 1. The chelating forces of the hyperbranched polymers obtained in examples 1 to 3 are all higher than 360mg/g, and the chelating forces of the hyperbranched polymers obtained in example 1 are as high as 378.55mg/g; the dispersion force is equal to or close to 300mg/g; the alkali buffering force is higher than 13g, and the example 2 reaches 14.42g, which shows that the hyperbranched polymer prepared by the invention has excellent washing-assisting effect.
Claims (17)
1. A method for preparing a hyperbranched polymer, characterized in that it comprises the following steps:
S1: under the existence of protective gas and the catalysis of a catalyst, acrylic ester, trimethylolpropane and allylamine react to generate a hyperbranched functional monomer A;
The catalyst is p-toluenesulfonic acid and/or toluenesulfonate; the reaction temperature is 70-100 ℃;
S2: in the presence of an initiator and a reducing agent, carrying out polymerization reaction on the mixed monomer dispersed in the water phase to obtain the catalyst;
the mixed monomer comprises the hyperbranched functional monomer A, unsaturated polyether and acrylic acid; the initiator is persulfate and/or hydrogen peroxide; the reducing agent is one or more of sodium bisulphite, sodium sulfite and sodium metabisulfite; the temperature of the polymerization reaction is 60-90 ℃;
the mass of the initiator is 0.1-2% of that of the acrylic acid;
The mass of the reducing agent is 0.8-3% of that of the acrylic acid;
the mass of the unsaturated polyether is 5.9% of that of the acrylic acid.
2. The method of preparing a hyperbranched polymer according to claim 1 wherein the acrylate in S1 is one or more of methyl acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate;
And/or the molar ratio of the acrylic ester, the trimethylolpropane and the allylamine is 1 (0.3-0.7): 0.8-1.2);
and/or the temperature of the reaction in the step S1 is 80-90 ℃;
And/or the reaction time in the step S1 is 2-4 hours;
And/or, the reaction in S1 is carried out in reflux;
And/or, the methylbenzenesulfonate in the step S1 is p-methylbenzenesulfonate.
3. The method of preparing a hyperbranched polymer according to claim 2 wherein the acrylate is methyl acrylate and/or methyl methacrylate;
and/or the molar ratio of the acrylic ester, the trimethylolpropane and the allylamine is 1:0.56:1.11;
And/or the reaction time is 3h.
4. The method of preparing a hyperbranched polymer according to claim 1 wherein the shielding gas in S1 is an inert gas and/or nitrogen;
And/or, the methylbenzenesulfonate in the S1 is sodium methylbenzenesulfonate and/or potassium methylbenzenesulfonate;
and/or the molar ratio of the catalyst to the acrylic ester in the S1 is (0.004-0.01): 1;
and/or, the reaction in S1 is finished and further comprises purification and filtration steps.
5. The method of preparing a hyperbranched polymer according to claim 4 wherein the shielding gas is nitrogen;
and/or, the methylbenzenesulfonate is sodium methylbenzenesulfonate;
And/or the molar ratio of the catalyst to the acrylic ester is 0.005-0.007:1.
6. The method of preparing the hyperbranched polymer of claim 5, wherein the methylbenzenesulfonate is sodium p-methylbenzenesulfonate;
and/or the molar ratio of the catalyst to the acrylate is 0.006:1.
7. The method of preparing the hyperbranched polymer of claim 1, wherein the unsaturated polyether in S2 is one or more of allyl alcohol polyoxyethylene ether, isopentenyl alcohol polyoxyethylene ether, and methallyl polyoxyethylene ether;
And/or, the persulfate in S2 is one or more of ammonium persulfate, potassium persulfate and sodium persulfate;
And/or, the initiator in S2 is used in the form of an aqueous initiator solution;
and/or, the reducing agent in S2 is used in the form of an aqueous reducing agent solution;
And/or the mass of the reducing agent in S2 is 1%, 1.47% or 2% of the acrylic acid.
8. The method for preparing the hyperbranched polymer according to claim 7, wherein the concentration of the aqueous initiator solution is 1-5%, and the percentages are mass percentages;
and/or the concentration of the reducer aqueous solution is 2-10%, and the percentages are mass percentages.
9. The method of preparing a hyperbranched polymer according to claim 8 wherein the concentration of the aqueous initiator solution is 2%, 3%, or 4%;
and/or the concentration of the reducing agent aqueous solution is 4-6%.
10. The method of preparing a hyperbranched polymer according to claim 9 wherein the concentration of the aqueous solution of the reducing agent is 5%.
11. The method of claim 1, wherein in S2, the order of addition of the materials is to disperse the hyperbranched functional monomer a and the unsaturated polyether in water before adding the acrylic acid, the initiator and the reducing agent;
and/or the temperature of the polymerization reaction in the step S2 is 70-80 ℃;
and/or the polymerization reaction time in the step S2 is 0.5-4 h;
and/or, after the polymerization reaction in the step S2 is finished, a step of neutralizing alkali is further included.
12. The method of preparing a hyperbranched polymer according to claim 11 wherein the acrylic acid, the initiator, and the reducing agent are added in a dropwise manner.
13. The method of preparing the hyperbranched polymer according to claim 11, wherein the hyperbranched functional monomer a and the unsaturated polyether are dispersed in water, heated to the temperature of the polymerization reaction, and then the acrylic acid, the initiator, and the reducing agent are added;
and/or the alkali is one or more of sodium hydroxide, potassium hydroxide, ammonia water, liquid ammonia and organic amine.
14. The method for preparing hyperbranched polymer according to claim 1, wherein the hyperbranched functional monomer a and the unsaturated polyether are dispersed in water, heated to the polymerization temperature, and then the acrylic acid, the initiator and the reducing agent are added dropwise at the same time; the dropwise adding time is 2-3 h, the polymerization reaction temperature is 70-80 ℃, and the polymerization reaction time is 1-2 h.
15. A hyperbranched polymer obtainable by the process of any one of claims 1 to 14.
16. Use of the hyperbranched polymer of claim 15 as a builder in a washing product.
17. A washing product comprising the hyperbranched polymer of claim 15.
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