CN109503778A - A kind of preparation method of offal base composite hydrogel - Google Patents
A kind of preparation method of offal base composite hydrogel Download PDFInfo
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- CN109503778A CN109503778A CN201811430648.7A CN201811430648A CN109503778A CN 109503778 A CN109503778 A CN 109503778A CN 201811430648 A CN201811430648 A CN 201811430648A CN 109503778 A CN109503778 A CN 109503778A
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- Prior art keywords
- offal
- composite hydrogel
- acrylic acid
- preparation
- initiator
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 95
- 239000002131 composite material Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 42
- 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 37
- 239000003999 initiator Substances 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229940047670 sodium acrylate Drugs 0.000 claims abstract description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 235000019441 ethanol Nutrition 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 30
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 20
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 19
- 244000028419 Styrax benzoin Species 0.000 claims description 16
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 16
- 229960002130 benzoin Drugs 0.000 claims description 16
- 235000019382 gum benzoic Nutrition 0.000 claims description 16
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 10
- 239000012965 benzophenone Substances 0.000 claims description 10
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 10
- 238000006386 neutralization reaction Methods 0.000 claims description 10
- 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 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 6
- -1 alkylbenzene ketone Chemical class 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 4
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical class C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 150000001451 organic peroxides Chemical class 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 claims description 3
- BSZXAFXFTLXUFV-UHFFFAOYSA-N 1-phenylethylbenzene Chemical compound C=1C=CC=CC=1C(C)C1=CC=CC=C1 BSZXAFXFTLXUFV-UHFFFAOYSA-N 0.000 claims description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 3
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 claims description 3
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 235000015511 Liquidambar orientalis Nutrition 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 241000736148 Styrax Species 0.000 claims description 3
- 239000004870 Styrax Substances 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 239000000203 mixture 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
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims 2
- SEPPVOUBHWNCAW-FNORWQNLSA-N (E)-4-oxonon-2-enal Chemical compound CCCCCC(=O)\C=C\C=O SEPPVOUBHWNCAW-FNORWQNLSA-N 0.000 claims 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 claims 1
- MWKAGZWJHCTVJY-UHFFFAOYSA-N 3-hydroxyoctadecan-2-one Chemical compound CCCCCCCCCCCCCCCC(O)C(C)=O MWKAGZWJHCTVJY-UHFFFAOYSA-N 0.000 claims 1
- LLBZPESJRQGYMB-UHFFFAOYSA-N 4-one Natural products O1C(C(=O)CC)CC(C)C11C2(C)CCC(C3(C)C(C(C)(CO)C(OC4C(C(O)C(O)C(COC5C(C(O)C(O)CO5)OC5C(C(OC6C(C(O)C(O)C(CO)O6)O)C(O)C(CO)O5)OC5C(C(O)C(O)C(C)O5)O)O4)O)CC3)CC3)=C3C2(C)CC1 LLBZPESJRQGYMB-UHFFFAOYSA-N 0.000 claims 1
- 125000002252 acyl group Chemical group 0.000 claims 1
- WQPDQJCBHQPNCZ-UHFFFAOYSA-N cyclohexa-2,4-dien-1-one Chemical group O=C1CC=CC=C1 WQPDQJCBHQPNCZ-UHFFFAOYSA-N 0.000 claims 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 239000002689 soil Substances 0.000 description 25
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 8
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 7
- 235000011130 ammonium sulphate Nutrition 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005213 imbibition Methods 0.000 description 5
- 241000208125 Nicotiana Species 0.000 description 4
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 230000002285 radioactive effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000005406 washing 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
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
-
- 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
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
Abstract
The present invention discloses a kind of preparation method of offal base composite hydrogel; include the following steps: step 1: pretreated offal, acrylic acid and sodium acrylate neutralizer, initiator and crosslinking agent are mixed; mixed liquor is carried out to ultraviolet light irradiation 3-25min at room temperature, obtains composite hydrogel；Wherein, the power of the ultraviolet lamp is 50~500W, the ultraviolet lamp is 15~50cm at a distance from the mixed liquor, right in the acrylic acid and sodium acrylate neutralizer is 75%~85%, the quality of the initiator is the 0.85%~1.25% of the quality of the acrylic acid and sodium acrylate neutralizer, and the quality of the crosslinking agent is the 0.05~0.08% of the quality of the acrylic acid and sodium acrylate neutralizer；Step 2: the composite hydrogel is placed in methanol or ethyl alcohol and is impregnated, standing 12~for 24 hours, it removes unreacted monomer and reacts incomplete oligomer, and is dry；Wherein, drying temperature is 50~100 DEG C, 4~12h of drying time.The present invention can make the offal of lower utility value be converted into the composite hydrogel of high added value.
Description
Technical field
The present invention relates to hydrogel preparation technical fields, and more particularly, the present invention relates to a kind of offal base compound water congealings
Glue and preparation method thereof.
Background technique
Offal is the by-product of tobacco industry, is important nature renewable resource, abundance, and China is every year about at present
There is few hundred thousand tonnes of offal resource to be discarded, not only pollute environment, but also be the serious waste to existing resource, so research is discarded
The comprehensive utilization of offal has important practical significance.The main component of offal is cellulose, pectin, total reducing sugar, protein etc.,
In with content of cellulose maximum, contain great amount of hydroxy group in cellulose, these hydroxy chemical properties are active, are easily chemically modified to obtain
Composite polymer material, waste tobacco stem are the desirable feedstocks for synthesizing composite polymer material.The side of conventional synthesis composite hydrogel
Method such as solution polymerization process, the reaction time of suspension emulsion polymerization is long, and energy consumption is more, needs to add other reaction dissolvents, has secondary
Pollution, post-processing complex process are complicated.
Summary of the invention
The present invention has designed and developed a kind of preparation method of offal base composite hydrogel, causes method using ultraviolet radioactive, with
Waste tobacco stem is raw material, and acrylic acid and sodium acrylate are monomer, and it is compound that offal base is synthesized in the presence of photoinitiator and crosslinking agent
Hydrogel, the reaction time is short, less energy consumption, without secondary pollution without adding other reaction dissolvents, handles easier.
Technical solution provided by the invention are as follows:
A kind of preparation method of offal base composite hydrogel, includes the following steps:
Step 1: pretreated offal, acrylic acid and sodium acrylate neutralizer, initiator and crosslinking agent being mixed, will be mixed
It closes liquid and carries out ultraviolet light irradiation 3-25min at room temperature, obtain composite hydrogel；
Wherein, the power of the ultraviolet lamp be 50~500W, the ultraviolet lamp with the mixed liquor at a distance from be 15~
Right in 50cm, the acrylic acid and sodium acrylate neutralizer is 75%~85%, and the quality of the initiator is described third
The 0.85%~1.25% of the quality of olefin(e) acid and sodium acrylate neutralizer, the quality of the crosslinking agent are the acrylic acid and propylene
The 0.05~0.08% of the quality of sour sodium neutralizer；
Step 2: the composite hydrogel is placed in methanol or ethyl alcohol and is impregnated, standing 12~for 24 hours, remove unreacted list
Body and the incomplete oligomer of reaction, and it is dry；
Wherein, drying temperature is 50~100 DEG C, 4~12h of drying time.
Preferably, the pretreatment of the offal includes:
The offal is crushed, 40 meshes is crossed, is placed in 10%NaOH solution, 2h is stirred at 95 DEG C, abandons supernatant liquor, to
NaClO and H is added in residual mixed liquor2O2Mixed liquor stirs 2h in ice-water bath, filters and washs to neutrality, dry to constant weight,
Smash it through 120 meshes.
Preferably, the preparation of the acrylic acid and sodium acrylate neutralizer includes:
Acrylic monomers is added dropwise in 20%NaOH solution, it is stirring while adding, it obtains acrylic acid and sodium acrylate neutralizes
Liquid；
Wherein, the acrylic monomers and the ratio of NaOH are controlled, so that the acrylic acid and sodium acrylate neutralizer
Degree of neutralization is 75%~85%.
Preferably, the initiator is the mixing initiation of single photoinitiator or photoinitiator and thermal initiator composition
Agent.
Preferably, the photoinitiator is benzoin and derivative, benzil class, alkylbenzene ketone and benzophenone
One of.
Preferably, the thermal initiator is one of organic peroxide, azo-initiator and ammonium ceric nitrate.
Preferably, the benzoin and derivative are styrax, benzoin dimethylether, benzoin ethyl ether, benzoin isobutyl
One of propyl ether and benzoin isobutyl ether；The benzil class is diphenylethan and α, alpha, alpha-dimethyl oxygroup-α-phenyl acetophenone
One of；The alkylbenzene ketone is α, one in α-diethoxy acetophenone, alpha-hydroxyalkyl benzophenone and α-amine alkyl phenones
Kind；The benzophenone is one of benzophenone and 2,4 dihydroxyl benzophenone.
Preferably, the organic peroxide is benzoyl peroxide, methyl ethyl ketone peroxide, inorganic peroxide such as mistake
One of ammonium sulfate, potassium peroxydisulfate and sodium peroxydisulfate；The azo-initiator is azodiisobutyronitrile.
Preferably, the crosslinking agent is N, N- methylene-bisacrylamide.
It is of the present invention the utility model has the advantages that
(1) preparation method of offal base composite hydrogel provided by the invention causes method using ultraviolet radioactive, to discard cigarette
Stalk is raw material, and acrylic acid and sodium acrylate are monomer, and offal base composite hydrogel is synthesized in the presence of photoinitiator and crosslinking agent,
With the method such as solution polymerization process of conventional synthesis composite hydrogel, suspension emulsion polymerization, which is compared, has the reaction time short, energy consumption
It is few, it is without secondary pollution without adding other reaction dissolvents, handle the advantages that easy.
(2) present invention provides a kind of new way for the recycling of offal, and the offal of lower utility value can be made to be converted into
The composite hydrogel of high added value.And composite hydrogel water suction with higher and water retention property, it can be used as water-retaining agent and answer
For agricultural, the fields such as industry.
Detailed description of the invention
Fig. 1 is the water absorbent rate versus time curve of TS-PAA-1 described in the embodiment of the present invention 1.
Fig. 2 is water conservation linearity curve of TS-PAA-1 swollen hydrogel under the conditions of 60 DEG C described in the embodiment of the present invention 1.
Fig. 3 is the water conservation linearity curve of TS-PAA-1 swollen hydrogel under normal temperature conditions described in the embodiment of the present invention 1.
Fig. 4 is influence column analysis chart of the TS-PAA-1 hydrogel to specific retesion of soil described in the embodiment of the present invention 1.
Fig. 5 is influence column analysis chart of the TS-PAA-1 hydrogel to soil ph described in the embodiment of the present invention 1.
Specific embodiment
Present invention will be described in further detail below with reference to the accompanying drawings, to enable those skilled in the art referring to specification text
Word can be implemented accordingly.
The present invention provides a kind of preparation method of offal base composite hydrogel, includes the following steps:
Step 1: offal pretreatment,
A certain amount of offal is weighed, crushed 40 meshes, is subsequently placed in appropriate 10%NaOH solution, 95 DEG C, stirring condition
Under boil 2 hours, stand, abandon supernatant liquor, NaClO and H2O2 mixed liquor are added into residual mixed liquor, stirring 2 is small in ice-water bath
When, it filters, washing filter cake to pH value is in neutrality, and dry to constant weight, 120 meshes are crossed in crushing, spare.
Step 2: acrylic acid and sodium acrylate neutralizer are prepared,
Weigh a certain amount of acrylic monomers, be added dropwise in appropriate 20%NaOH solution, it is stirring while adding, obtain acrylic acid and
Sodium acrylate neutralizer, spare, according to the ratio of monomer and NaOH difference, the degree of neutralization of acrylic acid and sodium acrylate neutralizer is
75%~85%.
Step 3: pretreated offal, acrylic acid and sodium acrylate neutralizer, initiator and crosslinking agent being mixed, will be mixed
It closes liquid and carries out ultraviolet light irradiation 3-25min at room temperature, obtain composite hydrogel；
Wherein, the power of the ultraviolet lamp be 50~500W, the ultraviolet lamp with the mixed liquor at a distance from be 15~
Right in 50cm, the acrylic acid and sodium acrylate neutralizer is 75%~85%, and the quality of the initiator is described third
The 0.85%~1.25% of the quality of olefin(e) acid and sodium acrylate neutralizer, the quality of the crosslinking agent are the acrylic acid and propylene
The 0.05~0.08% of the quality of sour sodium neutralizer；
Step 4: the composite hydrogel is placed in methanol or ethyl alcohol and is impregnated, standing 12~for 24 hours, remove unreacted list
Body and react incomplete oligomer (unreacted monomer and react incomplete oligomer and can be dissolved into methanol or ethyl alcohol,
The purpose that methanol and ethyl alcohol is added is exactly to dissolve this moieties.Prepared composite hydrogel does not dissolve in methanol or second
Alcohol), and it is dry；
Wherein, drying temperature is 50~100 DEG C, 4~12h of drying time.
The initiator is the mixed initiator of single photoinitiator or photoinitiator and thermal initiator composition.
The photoinitiator is benzoin and derivative (styrax, benzoin dimethylether, benzoin ethyl ether, benzoin isobutyl
One of propyl ether and benzoin isobutyl ether), benzil class (diphenylethan and α, in alpha, alpha-dimethyl oxygroup-α-phenyl acetophenone
It is a kind of), alkylbenzene ketone (one of α, α-diethoxy acetophenone, alpha-hydroxyalkyl benzophenone and α-amine alkyl phenones) and hexichol
One of ketone class (one of benzophenone and 2,4 dihydroxyl benzophenone).
The thermal initiator is organic peroxide (benzoyl peroxide, methyl ethyl ketone peroxide, inorganic peroxide such as mistake
One of ammonium sulfate, potassium peroxydisulfate and sodium peroxydisulfate), one in azo-initiator (azodiisobutyronitrile) and ammonium ceric nitrate
Kind.
The crosslinking agent is N,N methylene bis acrylamide.
Embodiment 1
Pretreated offal 0.18g is weighed, is placed in the beaker of 50mL, the acrylic acid and acrylic acid that degree of neutralization is 80%
Sodium neutralizer, crosslinking agent N, N- methylene-bisacrylamide, photoinitiator benzoin dimethylether, thermal initiator ammonium sulfate, according to
Mass ratio is uniformly mixed for 30:100:0.06:1.0:0.25, is ultrasonically treated 1min, mixed liquor is placed under the ultraviolet lamp of 250W
3min is irradiated, ultraviolet lamp is 20cm at a distance from mixed liquor, then takes out composite hydrogel, is placed in ethyl alcohol and impregnates, overnight
(12h) removes unreacted monomer and reacts incomplete oligomer, obtain pure composite hydrogel, do for 60 DEG C in baking oven
It is dry to constant weight, obtain dry composite hydrogel TS-PAA-1.
Embodiment 2
Pretreated offal 0.24g is weighed, is placed in the beaker of 50mL, the acrylic acid and acrylic acid that degree of neutralization is 85%
Sodium neutralizer, crosslinking agent N, N- methylene-bisacrylamide, photoinitiator benzoin dimethylether, thermal initiator ammonium persulfate, are pressed
It is uniformly mixed according to mass ratio for 40:100:0.08:0.8:0.20, is ultrasonically treated 1min, mixed liquor is placed in the ultraviolet lamp of 250W
Lower irradiation 4min, ultraviolet lamp are 25cm at a distance from mixed liquor, then take out composite hydrogel, are placed in ethyl alcohol and impregnate, overnight
(15h) removes unreacted monomer and reacts incomplete oligomer, obtain pure composite hydrogel, do for 70 DEG C in baking oven
It is dry to constant weight, obtain dry composite hydrogel TS-PAA-2.
Embodiment 3
Weigh pretreated offal 0.24g, be placed in the beaker of 100mL, degree of neutralization be 75% acrylic acid neutralizer,
Crosslinking agent N, N- methylene-bisacrylamide, photoinitiator benzoin dimethylether are 40:100:0.05:0.85 according to mass ratio
It is uniformly mixed, is ultrasonically treated 1min, mixed liquor is placed under the ultraviolet lamp of 250W and irradiates 4min, ultraviolet lamp is at a distance from mixed liquor
For 25cm, composite hydrogel is then taken out, is placed in ethyl alcohol and impregnates, overnight (for 24 hours), unreacted monomer is removed and reacts endless
Full oligomer obtains pure composite hydrogel, and 80 DEG C of dryings obtain dry composite hydrogel TS-PAA-3 to constant weight in baking oven.
Embodiment 4
Pretreated offal 0.18g is weighed, is placed in the beaker of 50mL, the acrylic acid and acrylic acid that degree of neutralization is 80%
Sodium neutralizer, crosslinking agent N, N- methylene-bisacrylamide, photoinitiator benzoin dimethylether, thermal initiator ammonium sulfate, according to
Mass ratio is uniformly mixed for 30:100:0.06:1.0:0.25, is ultrasonically treated 1min, mixed liquor is placed under the ultraviolet lamp of 50W and is shone
25min is penetrated, ultraviolet lamp is 15cm at a distance from mixed liquor, then takes out composite hydrogel, is placed in ethyl alcohol and impregnates, overnight
(12h) removes unreacted monomer and reacts incomplete oligomer, obtain pure composite hydrogel, do for 60 DEG C in baking oven
It is dry to constant weight, obtain dry composite hydrogel TS-PAA-4.
Embodiment 5
Pretreated offal 0.18g is weighed, is placed in the beaker of 50mL, the acrylic acid and acrylic acid that degree of neutralization is 80%
Sodium neutralizer, crosslinking agent N, N- methylene-bisacrylamide, photoinitiator benzoin dimethylether, thermal initiator ammonium sulfate, according to
Mass ratio is uniformly mixed for 30:100:0.06:1.0:0.25, is ultrasonically treated 1min, mixed liquor is placed under the ultraviolet lamp of 500W
3min is irradiated, ultraviolet lamp is 50cm at a distance from mixed liquor, then takes out composite hydrogel, is placed in ethyl alcohol and impregnates, overnight
(12h) removes unreacted monomer and reacts incomplete oligomer, obtain pure composite hydrogel, do for 60 DEG C in baking oven
It is dry to constant weight, obtain dry composite hydrogel TS-PAA-5.
Embodiment 6
Pretreated offal 0.18g is weighed, is placed in the beaker of 50mL, the acrylic acid and acrylic acid that degree of neutralization is 80%
Sodium neutralizer, crosslinking agent N, N- methylene-bisacrylamide, photoinitiator benzoin dimethylether, thermal initiator ammonium sulfate, according to
Mass ratio is uniformly mixed for 30:100:0.06:1.0:0.25, is ultrasonically treated 1min, mixed liquor is placed under the ultraviolet lamp of 500W
3min is irradiated, ultraviolet lamp is 25cm at a distance from mixed liquor, then takes out composite hydrogel, is placed in ethyl alcohol and impregnates, overnight
(12h) removes unreacted monomer and reacts incomplete oligomer, obtain pure composite hydrogel, do for 60 DEG C in baking oven
It is dry to constant weight, obtain dry composite hydrogel TS-PAA-6.
Comparative example 1
Pretreated offal 0.00g (i.e. no offal) is weighed, is placed in the beaker of 50mL, degree of neutralization is the third of 80%
Olefin(e) acid and sodium acrylate neutralizer, crosslinking agent N,N methylene bis acrylamide, photoinitiator benzoin dimethylether, thermal initiator
Ammonium sulfate is uniformly mixed for 30:100:0.06:1.0:0.25 according to mass ratio, is ultrasonically treated 1min, mixed liquor is placed in 250W
Ultraviolet lamp under irradiate 3min, ultraviolet lamp is 20cm at a distance from mixed liquor, then takes out composite hydrogel, is placed in ethyl alcohol and soaks
Bubble removes unreacted monomer and reacts incomplete oligomer overnight (12h), obtains pure composite hydrogel, in baking oven
60 DEG C of dryings obtain dry composite hydrogel TS-PAA-7 to constant weight.
Water imbibition test:
The compound water congealing rubber pulverizing that the obtained offal base composite hydrogel of above-described embodiment 1-6 and comparative example 1 are obtained,
40-80 mesh is crossed, 0.05g composite hydrogel powder is taken, is placed in 250mL conical flask, enough distilled water or 0.9wt% is added
NaCl solution, sealing, conical flask is placed in isothermal vibration water-bath, at room temperature, t min is shaken, with 300 mesh Nylon Bag mistakes
Filter, stands 30min, weighing, and water suction front and back hydrogel quality is denoted as M respectively0And Mt, calculating absorbent time according to formula (1) is t
When water absorbent rate Qt(g/g)。
The maximum adsorption for the composite hydrogel that the obtained offal base composite hydrogel of embodiment 1-6 and comparative example 1 obtain
Multiplying power is as shown in table 1.
The maximum of the composite hydrogel that the obtained offal base composite hydrogel of 1 embodiment 1-6 of table and comparative example 1 obtain is inhaled
Attached multiplying power
As shown in Table 1, the multiplying power that resulting composite hydrogel adsorbs distilled water under the conditions of embodiment 1-6 is greater than pair
The multiplying power of the absorption multiplying power of the NaCl solution of 0.9wt%, adsorptive distillation water is greater than 4000g/g, adsorbs the NaCl solution of 0.9wt%
Multiplying power show better water absorbing properties in 1751-2082g/g, the resulting composite hydrogel TS-PAA-2 of embodiment 2, it is maximum
It inhales distilled water multiplying power and reaches 4257g/g, the NaCl solution multiplying power for inhaling 0.9wt% reaches 2082g/g.Compound water congealing without adding offal
The water imbibition of glue is lower, and the multiplying power of adsorptive distillation water is 1372g/g, and the multiplying power for adsorbing the NaCl solution of 0.9wt% is only 453g/
g.Therefore, resulting composite hydrogel water absorbing properties with higher under the conditions of embodiment 1-6.
By taking hydrogel TS-PAA-1 resulting under the conditions of embodiment 1 as an example, detailed analysis is carried out to experimental result.
As shown in Figure 1, under the conditions of embodiment 1, maximum of the composite hydrogel to the NaCl solution of distilled water and 0.9wt%
Adsorbing multiplying power is respectively 4019g/g and 2034g/g.The imbibition process of the composite hydrogel is first quick and back slow, right at imbibition 1 minute
The absorption multiplying power of the NaCl solution of distilled water and 0.9wt% is respectively 3379 and 1321g/g, when the imbibition time is 5 minutes, to steaming
The absorption multiplying power of distilled water and the NaCl solution of 0.9wt% is respectively 3840 and 1920g/g.After 10 minutes, absorption multiplying power tends to
Gently.Composite hydrogel water absorbing properties with higher.
Water-retaining property test:
The obtained offal base composite hydrogel of a certain amount of above-described embodiment 1-6 is placed in enough distilled water, is absorbed water molten
It is swollen up to balance after, take out swelling equilibrium after hydrogel, weigh hydrogel after about 80g swelling equilibrium, quality is denoted as m0, it is placed in 40
In DEG C -60 DEG C of drying box, dry certain time, weighing record hydrogel quality, when drying time is t min, water-setting colloid
Amount is denoted as mt, the water retention property W of composite hydrogel is calculated according to formula (2)R。
By taking hydrogel TS-PAA-1 resulting under the conditions of embodiment 1 as an example, detailed analysis is carried out to experimental result.
As shown in Figure 2,3, for TS-PAA-1 (resulting hydrogel under the conditions of embodiment 1), (figure under the conditions of 60 DEG C
Shown in 2), first three hour, water-retaining property decline is most fast, and 3-17.5 hours, water-retaining property continued to decline, and after being greater than 17.5 hours, protects
Aqueous decline slows down, and after 24 hours, water-retaining property is about 0.02%.Under normal temperature condition (shown in Fig. 3), water-retaining property at first 4 days,
Decline most fast, after 4 days, water-retaining property continues to decline, and decrease speed is slowed by, and at 15 days, the water-retaining property of hydrogel is 37.9%,
TS-PAA-2, TS-PAA-3, TS-PAA-4, TS-PAA-5 and TS-PAA-6 show similar property, and water-retaining property difference is not
Greatly, it can be seen that, such hydrogel has good water retention property.
Influence to specific retesion of soil:
Soil after taking 100g dry, sieving, soil particle is about 3mm, be separately added into mass fraction be 0.0%, 0.5%,
1.0%, 1.5% and 2.0% xerogel is uniformly mixed, and is added in the glass tube that is sealed with non-woven fabrics of bottom that (diameter is
4cm), the glass tube equipped with composite soil is fixed on vertically on iron stand, from dropwise addition distilled water suitable for reading, until first drips from bottom
When exudation, stops plus water is weighed to no longer seep water, the gross mass of water front and back glass tube earth pillar is added to be denoted as W respectively0And W1, according to
Formula (3) calculates specific retesion of soil WH。
By taking hydrogel TS-PAA-1 resulting under the conditions of embodiment 1 as an example, detailed analysis is carried out to experimental result.
As shown in Figure 4, the specific retention of soil, and the increase of specific retesion of soil can be improved in the addition of TS-PAA-1 hydrogel
Increase with the increase of hydrogel additional amount, the additional amount of composite hydrogel is 0.0%, 0.5%, 1.0%, 1.5%, 2.0%
When, specific retesion of soil is increased separately from 38.49% to 42.69,51.13,73.36 and 81.85%.It can be seen that such water-setting
Glue being capable of larger raising specific retesion of soil.
Influence to soil ph:
The preparation of the soil liquid: the tap water of the quality such as addition into 2000g dry soil impregnates 12h, intermediate not timing
Stirring stands, filters to obtain soil aqueous solution stoste, take a certain amount of soil aqueous solution stoste respectively, with the HCl of 0.1mol/L and
0.1mol/L NaOH adjusts pH value, obtains the soil aqueous solution that pH value is 5-9.
Taking 100mL pH value is the soil aqueous solution of 5-9, is separately added into 0.1g xerogel, and 2h is placed in sealing, and filtering takes
Layer clear liquid, surveys pH value.
By taking hydrogel TS-PAA-1 resulting under the conditions of embodiment 1 as an example, detailed analysis is carried out to experimental result.
As shown in figure 5, the addition of composite hydrogel makes the pH value of the soil liquid when the pH value of native soil solution is acid
Increase, when the pH value of native soil solution is 5.00 and 6.00, after hydrogel is added, pH value increases to 5.49 and 6.31；Work as original
When the pH value of the soil liquid is alkalinity, the addition of composite hydrogel reduces the pH value of the soil liquid, the pH value of native soil solution
When being 8.00 and 9.00, after hydrogel is added, pH value is reduced to 7.46 and 7.82 respectively.It can be seen that TS-PAA-1 Compound Water
The addition of gel can improve the soda acid performance of soil.
The preparation method of offal base composite hydrogel provided by the invention causes method using ultraviolet radioactive, with waste tobacco stem
For raw material, acrylic acid and sodium acrylate are monomer, and offal base composite hydrogel is synthesized in the presence of photoinitiator and crosslinking agent, with
The method of conventional synthesis composite hydrogel such as solution polymerization process, suspension emulsion polymerization, which is compared, has the reaction time short, less energy consumption,
It is without secondary pollution without adding other reaction dissolvents, handle the advantages that easy.The present invention provides a kind of new for the recycling of offal
Approach can make the offal of lower utility value be converted into the composite hydrogel of high added value.And the composite hydrogel has
Higher water suction and water retention property can be used as water-retaining agent and be applied to agricultural, the fields such as industry.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details and legend shown and described herein.
Claims (9)
1. a kind of preparation method of offal base composite hydrogel, which comprises the steps of:
Step 1: pretreated offal, acrylic acid and sodium acrylate neutralizer, initiator and crosslinking agent being mixed, by mixed liquor
Ultraviolet light irradiation 3-25min is carried out at room temperature, obtains composite hydrogel；
Wherein, the power of the ultraviolet lamp is 50~500W, and the ultraviolet lamp is 15~50cm, institute at a distance from the mixed liquor
Stating right in acrylic acid and sodium acrylate neutralizer is 75%~85%, and the quality of the initiator is the acrylic acid and third
The 0.85%~1.25% of the quality of olefin(e) acid sodium neutralizer, the quality of the crosslinking agent are that the acrylic acid and sodium acrylate neutralize
The 0.05~0.08% of the quality of liquid；
Step 2: the composite hydrogel is placed in methanol or ethyl alcohol and is impregnated, stand 12~for 24 hours, remove unreacted monomer and
Incomplete oligomer is reacted, and dry；
Wherein, drying temperature is 50~100 DEG C, 4~12h of drying time.
2. the preparation method of offal base composite hydrogel as described in claim 1, which is characterized in that the pretreatment of the offal
Include:
The offal is crushed, 40 meshes is crossed, is placed in 10%NaOH solution, 2h is stirred at 95 DEG C, supernatant liquor is abandoned, to residue
NaClO and H is added in mixed liquor2O2Mixed liquor stirs 2h in ice-water bath, filters and washs to neutrality, dry to constant weight, crushes
120 meshes are crossed afterwards.
3. the preparation method of offal base composite hydrogel as claimed in claim 2, which is characterized in that the acrylic acid and propylene
The preparation of sour sodium neutralizer includes:
Acrylic monomers is added dropwise in 20%NaOH solution, it is stirring while adding, obtain acrylic acid and sodium acrylate neutralizer；
Wherein, the acrylic monomers and the ratio of NaOH are controlled, so that the neutralization of the acrylic acid and sodium acrylate neutralizer
Degree is 75%~85%.
4. the preparation method of offal base composite hydrogel as claimed in claim 1,2 or 3, which is characterized in that the initiator
For single photoinitiator or the mixed initiator of photoinitiator and thermal initiator composition.
5. the preparation method of offal base composite hydrogel as claimed in claim 4, which is characterized in that the photoinitiator is benzene
One of acyloin and derivative, benzil class, alkylbenzene ketone and benzophenone.
6. the preparation method of offal base composite hydrogel as claimed in claim 5, which is characterized in that the thermal initiator is to have
One of machine peroxide, azo-initiator and ammonium ceric nitrate.
7. the preparation method of offal base composite hydrogel as claimed in claim 6, which is characterized in that the benzoin and derivative
Object is one of styrax, benzoin dimethylether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether；The benzene is even
Acyl class is diphenylethan and α, one of alpha, alpha-dimethyl oxygroup-α-phenyl acetophenone；The alkylbenzene ketone is α, α-diethyl
One of oxygroup acetophenone, alpha-hydroxyalkyl benzophenone and α-amine alkyl phenones；The benzophenone is benzophenone and 2,4-
One of dihydroxy benaophenonel.
8. the preparation method of offal base composite hydrogel as claimed in claim 6, which is characterized in that the organic peroxide
For benzoyl peroxide, methyl ethyl ketone peroxide, in inorganic peroxide such as ammonium persulfate, potassium peroxydisulfate and sodium peroxydisulfate one
Kind；The azo-initiator is azodiisobutyronitrile.
9. the preparation method of offal base composite hydrogel as claimed in claim 1,2 or 3, which is characterized in that the crosslinking agent
For N,N methylene bis acrylamide.
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