CN116813829B - Composition for preparing super absorbent resin, super absorbent resin and preparation method of super absorbent resin - Google Patents
Composition for preparing super absorbent resin, super absorbent resin and preparation method of super absorbent resin Download PDFInfo
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- CN116813829B CN116813829B CN202310839869.4A CN202310839869A CN116813829B CN 116813829 B CN116813829 B CN 116813829B CN 202310839869 A CN202310839869 A CN 202310839869A CN 116813829 B CN116813829 B CN 116813829B
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- comonomer
- absorbent resin
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- super absorbent
- alkoxide
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- 239000011347 resin Substances 0.000 title claims abstract description 91
- 229920005989 resin Polymers 0.000 title claims abstract description 91
- 239000002250 absorbent Substances 0.000 title claims abstract description 58
- 230000002745 absorbent Effects 0.000 title claims abstract description 55
- 239000000203 mixture Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 29
- 239000003431 cross linking reagent Substances 0.000 claims description 27
- 150000004703 alkoxides Chemical class 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000000084 colloidal system Substances 0.000 claims description 20
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 19
- 238000004132 cross linking Methods 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 18
- CRZJPEIBPQWDGJ-UHFFFAOYSA-N 2-chloro-1,1-dimethoxyethane Chemical compound COC(CCl)OC CRZJPEIBPQWDGJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000003999 initiator Substances 0.000 claims description 17
- 239000003444 phase transfer catalyst Substances 0.000 claims description 17
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 238000006386 neutralization reaction Methods 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- -1 sodium alkoxide Chemical class 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 230000003472 neutralizing effect Effects 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 6
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229920000768 polyamine Polymers 0.000 claims description 6
- 150000005846 sugar alcohols Polymers 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 5
- 229940035437 1,3-propanediol Drugs 0.000 claims description 5
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical group NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 claims description 3
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 3
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-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
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 3
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 3
- 229940057847 polyethylene glycol 600 Drugs 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 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
- 239000000600 sorbitol Substances 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical group [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims 2
- 238000010521 absorption reaction Methods 0.000 abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 230000015556 catabolic process Effects 0.000 abstract description 12
- 238000006731 degradation reaction Methods 0.000 abstract description 12
- 230000014759 maintenance of location Effects 0.000 abstract description 9
- 229920001002 functional polymer Polymers 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 28
- 238000001816 cooling Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000012216 screening Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- 239000002689 soil Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004971 Cross linker Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 229940047670 sodium acrylate Drugs 0.000 description 2
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical group [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004383 yellowing 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a composition for preparing super absorbent resin, the super absorbent resin and a preparation method thereof, and belongs to the technical field of functional polymers. The super absorbent resin prepared by the composition has excellent water absorption and retention properties and degradation properties.
Description
Technical Field
The invention relates to the technical field of functional polymers, in particular to a composition for preparing super absorbent resin, the super absorbent resin and a preparation method thereof.
Background
The super absorbent resin is a novel functional polymer material and is commonly used as personal care products and water-retaining agents. At present, the super absorbent resin is mainly formed by cross-linking and polymerizing acrylic acid serving as a monomer, and the traditional cross-linked polyacrylic acid (salt) is prepared by taking a C-C bond as a main chain, is difficult to decompose by bacteria and microorganisms in soil, is a non-biodegradable polymer, and can bring huge environmental pollution after being abandoned in a large quantity; the preparation of biodegradable super absorbent resins is an important research topic for current super absorbent resins.
However, the existing degradable super absorbent resin is mainly prepared by graft copolymerization of natural polymers such as starch, cellulose, protein and the like and acrylic acid, and the prepared super absorbent resin has poor water absorption and retention properties, low gel strength after water absorption, easy deterioration and difficult storage.
Therefore, there is a need to provide a degradable super absorbent resin with good water absorption and retention properties.
Disclosure of Invention
Aiming at one or more technical problems in the prior art, the invention provides a composition for preparing a super absorbent resin, the super absorbent resin and a preparation method thereof.
In a first aspect, the present invention provides a composition for preparing a super absorbent resin, the composition comprising a comonomer, wherein the comonomer is prepared from chloroacetaldehyde dimethyl acetal, 1, 3-propanediol and alkoxide.
Preferably, the mole ratio of chloroacetaldehyde dimethyl acetal, 1, 3-propylene glycol and alkoxide in the preparation raw material of the comonomer is 1 (1.2-1.5): 1.2-1.5.
Preferably, the composition further comprises acrylic acid, a phase transfer catalyst, a crosslinker, an initiator, and a surface crosslinker.
Preferably, the composition comprises, in parts by weight, 5 to 40 parts of comonomer, 200 to 300 parts of acrylic acid, 1 to 3 parts of phase transfer catalyst, 0.5 to 3 parts of cross-linking agent, 0.1 to 2 parts of initiator and 10 to 20 parts of surface cross-linking agent.
Preferably, the alkoxide is sodium alkoxide or potassium alkoxide; preferably, the alkoxide is sodium or potassium tert-butoxide;
The phase transfer catalyst is tetrabutylammonium bromide;
The cross-linking agent is one or more of N, N-methylene bisacrylamide, N-methylolacrylamide, polyethylene glycol 600 acrylic ester, trimethylolpropane triacrylate and pentaerythritol triacrylate;
The initiator is sodium persulfate and sodium bisulfite;
The surface crosslinking is one or more of polyalcohol, polyamine compound and epoxy compound;
preferably, the polyalcohol is one or more of diol, butanediol, glycerol and triethylene glycol; the polyamine compound is one or more of ethylenediamine, diethylenediamine and triethylenediamine; the epoxy compound is one or more of 1, 4-butanediol diglycidyl ether, glycerol triglycidyl ether and sorbitol glycidyl ether.
In a second aspect, the present invention provides a super absorbent resin, the super absorbent resin being prepared from a raw material comprising the composition of the first aspect.
In a third aspect, the present invention provides a method for preparing the super absorbent resin according to the second aspect, the method comprising the steps of:
s1, neutralizing acrylic acid with a sodium hydroxide solution to a pH value of 6-6.5 to obtain a neutralization solution;
S2, mixing a comonomer, a neutralization solution and a phase transfer catalyst, introducing nitrogen to remove oxygen, and adding a cross-linking agent and an initiator to perform polymerization reaction to obtain a resin colloid;
s3, granulating the resin colloid, placing the granulated resin colloid into a surface cross-linking agent, and carrying out surface cross-linking to obtain the water-absorbent resin particles.
Preferably, the preparation method of the comonomer comprises the following steps: mixing chloroacetaldehyde dimethyl acetal and 1, 3-propylene glycol, and performing a first reaction by taking 4-dimethylaminopyridine as a catalyst, and distilling to obtain an intermediate;
mixing the intermediate with alkoxide, and obtaining the comonomer through a second reaction, washing, filtering and distilling.
Preferably, the temperature of the first reaction is 115-120 ℃ and the time is 5-6 h; and/or
The temperature of the second reaction is 105-110 ℃ and the time is 5-6 h.
Preferably, the temperature of the polymerization reaction is 80-90 ℃ and the time is 2-3 h; and/or
The surface cross-linking temperature is 120-200 ℃ and the time is 10-60 min.
Compared with the prior art, the invention has at least the following beneficial effects:
The comonomer of the invention takes chloroacetaldehyde dimethyl acetal, 1, 3-propylene glycol and alkoxide as raw materials, and the structure of the comonomer contains a six-membered ring containing two oxygen atoms, which belongs to an electron-rich vinyl monomer. The monomer can be subjected to ring-opening cross-linking copolymerization reaction with acrylic acid under the action of a catalyst to form the super absorbent resin with the three-dimensional network structure. The super absorbent resin prepared by the composition containing the comonomer has excellent water absorption and retention properties and degradation properties, and solves the problem that the existing degradable super absorbent resin has poor water absorption and retention properties.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the embodiments described below will be clearly and completely described in conjunction with the technical solutions of the embodiments of the present invention, and it is apparent that the described embodiments are some, but not all, embodiments of the present invention, and all other embodiments obtained by persons of ordinary skill in the art without making any inventive effort based on the embodiments of the present invention are within the scope of protection of the present invention.
In a first aspect, the present invention provides a composition for preparing a super absorbent resin, the composition comprising a comonomer, wherein the comonomer is prepared from chloroacetaldehyde dimethyl acetal, 1, 3-propanediol and alkoxide.
The comonomer of the invention takes chloroacetaldehyde dimethyl acetal, 1, 3-propylene glycol and alkoxide as raw materials, and the structure of the comonomer contains a six-membered ring containing two oxygen atoms, which belongs to an electron-rich vinyl monomer. The monomer can be subjected to ring-opening cross-linking copolymerization reaction with acrylic acid under the action of a catalyst to form the super absorbent resin with the three-dimensional network structure. The super absorbent resin prepared by the composition containing the comonomer has excellent water absorption and retention properties and degradation properties, and solves the problem that the existing degradable super absorbent resin has poor water absorption and retention properties.
In some preferred embodiments of the invention, the comonomer comprises 0.5 to 5% (e.g., may be 0.5%, 0.6%, 1%, 1.5%, 2%, 2.3%, 3%, 3.5%, 4%, 4.5% or 5%) of the total mass of the composition, preferably 1.5 to 4% (e.g., may be 1.5%, 1.8%, 2%, 2.3%, 2.5%, 3%, 3.5% or 4%). The invention ensures that the prepared super absorbent resin has more excellent water absorption and retention performance and degradation performance by using the comonomer of the composition in the above range.
According to some preferred embodiments, the comonomer is prepared from a starting material having a molar ratio of chloroacetaldehyde dimethyl acetal, 1, 3-propanediol, and alkoxide of 1 (1.2 to 1.5): 1.2 to 1.5.
According to some preferred embodiments, the composition further comprises acrylic acid, a phase transfer catalyst, a crosslinker, an initiator, and a surface crosslinker.
According to some preferred embodiments, the composition comprises 5 to 40 parts (e.g., may be 5 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts or 40 parts) of comonomer, preferably 10 to 30 parts (e.g., may be 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts or 30 parts), 200 to 300 parts (e.g., may be 200 parts, 210 parts, 220 parts, 230 parts, 240 parts, 250 parts, 260 parts, 270 parts, 280 parts, 290 parts or 300 parts) of acrylic acid, 1 to 3 parts of phase transfer catalyst, 0.5 to 3 parts of cross-linking agent, 0.1 to 2 parts of initiator, and 10 to 20 parts of surface cross-linking agent, in parts by weight.
According to some preferred embodiments, the alkoxide is sodium alkoxide or potassium alkoxide; preferably, the alkoxide is sodium or potassium tert-butoxide;
The phase transfer catalyst is tetrabutylammonium bromide;
The cross-linking agent is one or more of N, N-methylene bisacrylamide, N-methylolacrylamide, polyethylene glycol 600 acrylic ester, trimethylolpropane triacrylate and pentaerythritol triacrylate;
The initiator is sodium persulfate and sodium bisulfite;
The surface crosslinking is one or more of polyalcohol, polyamine compound and epoxy compound;
preferably, the polyalcohol is one or more of diol, butanediol, glycerol and triethylene glycol; the polyamine compound is one or more of ethylenediamine, diethylenediamine and triethylenediamine; the epoxy compound is one or more of 1, 4-butanediol diglycidyl ether, glycerol triglycidyl ether and sorbitol glycidyl ether.
In a second aspect, the present invention provides a super absorbent resin, the super absorbent resin being prepared from a raw material comprising the composition of the first aspect.
The main chain of the super absorbent resin prepared by adopting the self-made copolymer contains C-O bonds, so that the super absorbent resin is easy to decompose by microorganisms, and the degradation performance of the super absorbent resin can be effectively improved; meanwhile, the super absorbent resin prepared by adopting the composition containing the comonomer has excellent water absorption and retention properties.
In a third aspect, the present invention provides a method for preparing the super absorbent resin according to the second aspect, the method comprising the steps of:
s1, neutralizing acrylic acid with a sodium hydroxide solution to a pH value of 6-6.5 to obtain a neutralization solution;
S2, mixing a comonomer, a neutralization solution and a phase transfer catalyst, introducing nitrogen to remove oxygen, and adding a cross-linking agent and an initiator to perform polymerization reaction to obtain a resin colloid;
s3, granulating the resin colloid, placing the granulated resin colloid into a surface cross-linking agent, and carrying out surface cross-linking to obtain the water-absorbent resin particles.
The mass fraction of the sodium hydroxide solution is not particularly limited in the present invention, and preferably 50% by mass of the sodium hydroxide solution.
In a specific embodiment of the present invention, a method for preparing a super absorbent resin comprises: firstly, neutralizing acrylic acid with a sodium hydroxide solution with the mass fraction of 50% until the pH value is 6-6.5, and cooling the neutralized acrylic acid solution to 23+/-2 ℃; then preparing self-made comonomer, neutralization solution and phase transfer catalyst into solution, introducing nitrogen to remove oxygen, adding cross-linking agent and initiator into the mixed solution to initiate polymerization, naturally heating to constant temperature, then preserving heat at 80-90 ℃ for 2 hours to obtain resin colloid, granulating, drying, crushing and screening the resin colloid to obtain 30-80 mesh resin particles; adding the resin particles into the surface crosslinking liquid, fully and uniformly stirring, and carrying out surface crosslinking at 120-200 ℃ for 10-60 min; and cooling to room temperature after the surface crosslinking is finished, and sieving to obtain the super absorbent resin particles.
According to some preferred embodiments, the method of preparing the comonomer comprises: mixing chloroacetaldehyde dimethyl acetal and 1, 3-propylene glycol, and performing a first reaction by taking 4-dimethylaminopyridine as a catalyst, and distilling to obtain an intermediate; the catalyst of the invention is used in an amount of 1 to 2% by weight, preferably 1% by weight, based on the total mass of chloroacetaldehyde dimethyl acetal and 1, 3-propanediol.
Mixing the intermediate with alkoxide, and obtaining the comonomer through a second reaction, washing, filtering and distilling.
In the process of mixing the intermediate and the alkoxide, an organic solvent is also required to be added, and preferably, the organic solvent is alcohol corresponding to the alkoxide. The intermediate reacts with alkoxide to form carbon-carbon double bond, corresponding alcohol can be generated in the reaction process, and the addition of solvent in the reaction process can be reduced; the alcohol corresponding to the alkoxide is used as a solvent, so that the introduction of impurities can be reduced, and the separation and purification process of the comonomer is simplified.
According to some preferred embodiments, the temperature of the first reaction is 115-120 ℃ (e.g., may be 115 ℃, 116 ℃, 117 ℃, 118 ℃, 119 ℃, or 120 ℃) for a period of time of 5-6 hours (e.g., may be 5 hours, 5.2 hours, 5.4 hours, 5.5 hours, 5.6 hours, 5.8 hours, or 6 hours); preferably, the temperature of the first reaction is 115 ℃ and the time is 5h.
The second reaction is carried out at a temperature of 105-110 ℃ (for example, 105 ℃, 106 ℃, 107 ℃, 108 ℃, 109 ℃ or 110 ℃) for a time of 5-6 hours (for example, 5 hours, 5.2 hours, 5.4 hours, 5.5 hours, 5.6 hours, 5.8 hours or 6 hours); preferably, the temperature of the second reaction is 105 ℃ and the time is 5h.
According to some preferred embodiments, the polymerization reaction is at a temperature of 80-90 ℃ (e.g., may be 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, 86 ℃, 88 ℃, or 90 ℃) for a time of 2-3 hours (e.g., may be 2 hours, 2.2 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.8 hours, or 3 hours);
the surface crosslinking temperature is 120 to 200 ℃ (for example, it may be 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃ or 200 ℃) and the time is 10 to 60 minutes (for example, it may be 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes or 40 minutes).
In one embodiment of the invention, the method of making the comonomer comprises:
(1) Using chloroacetaldehyde dimethyl acetal, 1, 3-propylene glycol and alkoxide with a molar ratio of 1:1.2 as initial raw materials, and using 4-dimethylaminopyridine as a catalyst, wherein the dosage is 1% of the mass of a comonomer; adding chloroacetaldehyde dimethyl acetal, 1, 3-propylene glycol, alkoxide and 4-dimethylaminopyridine into a three-neck flask, installing a stirring device, a thermometer and a collecting device of reaction byproducts, heating to 115 ℃ and stirring for 5 hours, stopping the reaction, and collecting fractions at 105 ℃ and 55mmHg through reduced pressure distillation to obtain an intermediate;
(2) Adding 1.2mol of tertiary butanol and 1mol of tertiary sodium butoxide into a three-neck flask, mounting a stirring device, a thermometer and a reflux condenser, heating to 80 ℃, slowly dropwise adding 1mol of intermediate, heating to 105 ℃ after the dropwise adding is finished, reacting for 5 hours, cooling after the reaction is finished, fully washing with tetrahydrofuran, pressurizing and suction filtering, distilling filtrate under reduced pressure, and collecting fractions at 78 ℃ and 63mmHg to obtain the comonomer.
The reaction formula for preparing the comonomer is as follows:
(1)
(2)
In order to more clearly illustrate the technical scheme and advantages of the present invention, the present invention will be further described below with reference to examples.
Test of absorption properties: the water absorption rate, the water retention rate, the absorption rate under pressure of 0.7psi and the absorption speed are all measured according to the national standard GB/T22905-2008 of the high-absorbency resin of paper diapers.
The soil burying degradation experimental method comprises the following steps: collecting green belt soil, placing the green belt soil in a beaker through 30 meshes for standby, shearing a super absorbent resin colloid into sheets with the thickness of 5cm and the thickness of 0.5cm, drying and recording the weight of m 1, inserting the super absorbent resin sheets into the position of 3cm below the soil surface layer, placing 5 sheets, placing the soil into a constant temperature and humidity box with the temperature of 30 ℃ and the humidity of 50, taking out one sheet every 15 days, drying after blowing the soil by a blower, recording the weight of m 2, and recording the degradation rate by the following formula:
Degradation rate= (m 1-m2)/m1
Wherein: m 1 is the weight of the super absorbent resin before degradation, and m 2 is the weight of the super absorbent resin after degradation.
Example 1
Preparation of comonomer:
(1) Using chloroacetaldehyde dimethyl acetal, 1, 3-propylene glycol and alkoxide with a molar ratio of 1:1.2 as initial raw materials, and using 4-dimethylaminopyridine as a catalyst, wherein the dosage is 1% of the mass of a comonomer; adding chloroacetaldehyde dimethyl acetal, 1, 3-propylene glycol, alkoxide and 4-dimethylaminopyridine into a three-neck flask, installing a stirring device, a thermometer and a collecting device of reaction byproducts, heating to 115 ℃ and stirring for 5 hours, stopping the reaction, and collecting fractions at 105 ℃ and 55mmHg through reduced pressure distillation to obtain an intermediate;
(2) Adding 1.2mol of tertiary butanol and 1mol of tertiary sodium butoxide into a three-neck flask, mounting a stirring device, a thermometer and a reflux condenser, heating to 80 ℃, slowly dropwise adding 1mol of intermediate, heating to 105 ℃ after the dropwise adding is finished, reacting for 5 hours, cooling after the reaction is finished, fully washing with tetrahydrofuran, pressurizing and suction filtering, distilling filtrate under reduced pressure, and collecting fractions at 78 ℃ and 63mmHg to obtain the comonomer.
Example 2
S1, neutralizing acrylic acid with a 50% sodium hydroxide solution to a pH value of 6.5, and cooling to 25 ℃ to obtain a neutralization solution;
S2, mixing a comonomer, a neutralization solution and a phase transfer catalyst, introducing nitrogen to remove oxygen, adding a cross-linking agent and an initiator to initiate polymerization reaction, naturally heating to a constant temperature, then preserving the temperature at 83 ℃ for 2 hours to obtain a resin colloid, and granulating, drying, crushing and screening the resin colloid to obtain 30-80-mesh resin particles;
S3, adding the resin particles into a surface cross-linking agent, fully and uniformly stirring, carrying out surface cross-linking at 150 ℃ for 60min, cooling to room temperature after heat preservation, and screening to obtain the super absorbent resin particles.
Example 3
S1, neutralizing acrylic acid with a 50% sodium hydroxide solution to a pH value of 6, and cooling to 25 ℃ to obtain a neutralization solution;
S2, mixing a comonomer, a neutralization solution and a phase transfer catalyst, introducing nitrogen to remove oxygen, adding a cross-linking agent and an initiator to initiate polymerization reaction, naturally heating to a constant temperature, then preserving the temperature at 85 ℃ for 2 hours to obtain a resin colloid, and granulating, drying, crushing and screening the resin colloid to obtain 30-80-mesh resin particles;
S3, adding the resin particles into a surface cross-linking agent, fully and uniformly stirring, carrying out surface cross-linking at 150 ℃ for 60min, cooling to room temperature after heat preservation, and screening to obtain the super absorbent resin particles.
Example 4
S1, neutralizing acrylic acid with a 50% sodium hydroxide solution to a pH value of 6.5, and cooling to 25 ℃ to obtain a neutralization solution;
s2, mixing a comonomer, a neutralization solution and a phase transfer catalyst, introducing nitrogen to remove oxygen, adding a cross-linking agent and an initiator to initiate polymerization reaction, naturally heating to a constant temperature, then preserving the temperature at 87 ℃ for 2 hours to obtain a resin colloid, and granulating, drying, crushing and screening the resin colloid to obtain 30-80 mesh resin particles;
S3, adding the resin particles into a surface cross-linking agent, fully and uniformly stirring, carrying out surface cross-linking at 150 ℃ for 60min, cooling to room temperature after heat preservation, and screening to obtain the super absorbent resin particles.
Example 5
S1, neutralizing acrylic acid with a 50% sodium hydroxide solution to a pH value of 6.5, and cooling to 25 ℃ to obtain a neutralization solution;
S2, mixing a comonomer, a neutralization solution and a phase transfer catalyst, introducing nitrogen to remove oxygen, adding a cross-linking agent and an initiator to initiate polymerization reaction, naturally heating to a constant temperature, then preserving heat at 90 ℃ for 2 hours to obtain a resin colloid, and granulating, drying, crushing and screening the resin colloid to obtain 30-80-mesh resin particles;
S3, adding the resin particles into a surface cross-linking agent, fully and uniformly stirring, carrying out surface cross-linking at 150 ℃ for 60min, cooling to room temperature after heat preservation, and screening to obtain the super absorbent resin particles.
Example 6
Substantially the same as in example 2, except that: in step S2, the weight part of the comonomer is 5 parts.
Example 7
Substantially the same as in example 2, except that: in step S2, the weight part of the comonomer is 40 parts.
Comparative example 1
Substantially the same as in example 2, except that: in step S2, no comonomer is added.
Comparative example 2
Substantially the same as in example 2, except that: in step S2, the comonomer is cellulose.
TABLE 1 Performance data of the super absorbent resins prepared in examples and comparative examples
In Table 1, the pressure of the absorption under pressure was 0.7psi; as can be seen from Table 1, the high water-absorbing resin prepared by adopting the self-made copolymer monomer in the embodiment of the invention has excellent degradation performance and water-absorbing performance, and is suitable for the field of disposable sanitary products. In comparative example 1, no comonomer is added, sodium acrylate is used as a raw material to synthesize the super absorbent resin, the main chain is C-C bond, and the super absorbent resin has good water absorption performance, but poor degradation performance, and is easy to cause serious pollution to the environment after being used and abandoned in a large amount. Comparative example 2 is a cellulose grafted sodium acrylate binary copolymerized super absorbent resin which is degradable, but has poor water absorption performance, is easy to generate yellowing when placed for a long time, and is not suitable for being applied to the field of sanitary products.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. A composition for preparing a super absorbent resin, the composition comprising a comonomer, wherein the comonomer is prepared from chloroacetaldehyde dimethyl acetal, 1, 3-propanediol and alkoxide;
the molar ratio of chloroacetaldehyde dimethyl acetal, 1, 3-propylene glycol and alkoxide in the preparation raw materials of the comonomer is 1 (1.2-1.5): 1.2-1.5;
The composition further comprises acrylic acid, a phase transfer catalyst, a crosslinking agent, an initiator, and a surface crosslinking agent;
The composition comprises, by weight, 5-40 parts of comonomer, 200-300 parts of acrylic acid, 1-3 parts of a phase transfer catalyst, 0.5-3 parts of a crosslinking agent, 0.1-2 parts of an initiator and 10-20 parts of a surface crosslinking agent;
the preparation method of the comonomer comprises the following steps: mixing chloroacetaldehyde dimethyl acetal and 1, 3-propylene glycol, and performing a first reaction by taking 4-dimethylaminopyridine as a catalyst, and distilling to obtain an intermediate;
mixing the intermediate with alkoxide, and obtaining the comonomer through a second reaction, washing, filtering and distilling.
2. The composition according to claim 1, wherein the alkoxide is sodium alkoxide or potassium alkoxide;
The phase transfer catalyst is tetrabutylammonium bromide;
the cross-linking agent is one or more of N, N-methylene bisacrylamide, N-methylol acrylamide, polyethylene glycol 600 acrylic ester, trimethylolpropane triacrylate and pentaerythritol triacrylate;
The initiator is sodium persulfate and sodium bisulfite;
the surface cross-linking agent is one or more of polyalcohol, polyamine compound and epoxy compound.
3. The composition according to claim 2, wherein the alkoxide is sodium tert-butoxide or potassium tert-butoxide;
The polyalcohol is one or more of butanediol, glycerol and triethylene glycol; the polyamine compound is one or more of ethylenediamine, diethylenediamine and triethylenediamine; the epoxy compound is one or more of 1, 4-butanediol diglycidyl ether, glycerol triglycidyl ether and sorbitol glycidyl ether.
4. A superabsorbent resin, characterized in that the superabsorbent resin is prepared from a starting material comprising the composition of any one of claims 1-3.
5. A method for producing a super absorbent resin as set forth in claim 4, comprising the steps of:
s1, neutralizing acrylic acid with a sodium hydroxide solution to a pH value of 6-6.5 to obtain a neutralization solution;
S2, mixing a comonomer, a neutralization solution and a phase transfer catalyst, introducing nitrogen to remove oxygen, and adding a cross-linking agent and an initiator to perform polymerization reaction to obtain a resin colloid;
s3, granulating the resin colloid, placing the granulated resin colloid into a surface cross-linking agent, and carrying out surface cross-linking to obtain the water-absorbent resin particles.
6. The method of claim 5, wherein the method of preparing the comonomer comprises: mixing chloroacetaldehyde dimethyl acetal and 1, 3-propylene glycol, and performing a first reaction by taking 4-dimethylaminopyridine as a catalyst, and distilling to obtain an intermediate;
mixing the intermediate with alkoxide, and obtaining the comonomer through a second reaction, washing, filtering and distilling.
7. The method according to claim 6, wherein the temperature of the first reaction is 115-120 ℃ for 5-6 hours; and/or
The temperature of the second reaction is 105-110 ℃ and the time is 5-6 h.
8. The preparation method according to claim 5, wherein the polymerization reaction is carried out at a temperature of 80-90 ℃ for 2-3 hours; and/or
The surface crosslinking temperature is 120-200 ℃ and the surface crosslinking time is 10-60 min.
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| CN101765435A (en) * | 2007-07-27 | 2010-06-30 | 巴斯夫欧洲公司 | Water-absorbing polymeric particles and method for the production thereof |
| CN103154043A (en) * | 2010-10-18 | 2013-06-12 | 住友精化株式会社 | Method for producing water-absorbent resin particles and water-absorbent resin particles |
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| CN107778398B (en) * | 2016-08-26 | 2020-02-21 | 北京超纳生物科技研究院 | Super absorbent resin and preparation method thereof |
| CN107474170B (en) * | 2017-08-15 | 2019-08-23 | 山东诺尔生物科技有限公司 | A kind of preparation method of the high hydroscopic resin of anti-moisture absorption conglomeration |
| CN112552468B (en) * | 2020-12-10 | 2022-12-06 | 山东诺尔生物科技有限公司 | Super absorbent resin and preparation method thereof |
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| CN103154043A (en) * | 2010-10-18 | 2013-06-12 | 住友精化株式会社 | Method for producing water-absorbent resin particles and water-absorbent resin particles |
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