CN115340724A - Starch-based antibacterial material and preparation method thereof - Google Patents
Starch-based antibacterial material and preparation method thereof Download PDFInfo
- Publication number
- CN115340724A CN115340724A CN202210814038.7A CN202210814038A CN115340724A CN 115340724 A CN115340724 A CN 115340724A CN 202210814038 A CN202210814038 A CN 202210814038A CN 115340724 A CN115340724 A CN 115340724A
- Authority
- CN
- China
- Prior art keywords
- starch
- antibacterial
- parts
- based antibacterial
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002472 Starch Polymers 0.000 title claims abstract description 178
- 239000008107 starch Substances 0.000 title claims abstract description 176
- 235000019698 starch Nutrition 0.000 title claims abstract description 176
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 128
- 239000000463 material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 50
- 239000003153 chemical reaction reagent Substances 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000008187 granular material Substances 0.000 claims description 23
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 239000012752 auxiliary agent Substances 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 15
- 239000004743 Polypropylene Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 229920001155 polypropylene Polymers 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- -1 polybutylene terephthalate-adipate Polymers 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 12
- 229920001971 elastomer Polymers 0.000 claims description 12
- 239000005060 rubber Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 229920003023 plastic Polymers 0.000 claims description 11
- 239000004033 plastic Substances 0.000 claims description 11
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229920002261 Corn starch Polymers 0.000 claims description 7
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 7
- 229940106681 chloroacetic acid Drugs 0.000 claims description 7
- 239000008120 corn starch Substances 0.000 claims description 7
- 229920001610 polycaprolactone Polymers 0.000 claims description 7
- 239000004632 polycaprolactone Substances 0.000 claims description 7
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 7
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 6
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 6
- 239000004626 polylactic acid Substances 0.000 claims description 6
- 229920000098 polyolefin Polymers 0.000 claims description 6
- 229920002379 silicone rubber Polymers 0.000 claims description 6
- 239000004945 silicone rubber Substances 0.000 claims description 6
- PNVPNXKRAUBJGW-UHFFFAOYSA-N (2-chloroacetyl) 2-chloroacetate Chemical compound ClCC(=O)OC(=O)CCl PNVPNXKRAUBJGW-UHFFFAOYSA-N 0.000 claims description 5
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 5
- 239000004713 Cyclic olefin copolymer Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 4
- 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 4
- 229930195725 Mannitol Natural products 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229920006237 degradable polymer Polymers 0.000 claims description 4
- 238000001746 injection moulding Methods 0.000 claims description 4
- 239000000594 mannitol Substances 0.000 claims description 4
- 235000010355 mannitol Nutrition 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229920001592 potato starch Polymers 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229920002545 silicone oil Polymers 0.000 claims description 4
- 239000000600 sorbitol Substances 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- QEYMMOKECZBKAC-UHFFFAOYSA-N 3-chloropropanoic acid Chemical compound OC(=O)CCCl QEYMMOKECZBKAC-UHFFFAOYSA-N 0.000 claims description 3
- UQNMBHOXSQYAAC-UHFFFAOYSA-N 3-chloropropanoyl 3-chloropropanoate Chemical compound ClCCC(=O)OC(=O)CCCl UQNMBHOXSQYAAC-UHFFFAOYSA-N 0.000 claims description 3
- IPLKGJHGWCVSOG-UHFFFAOYSA-N 4-chlorobutanoic acid Chemical compound OC(=O)CCCCl IPLKGJHGWCVSOG-UHFFFAOYSA-N 0.000 claims description 3
- VAXCCWFPTAPDMK-UHFFFAOYSA-N 4-chlorobutanoyl 4-chlorobutanoate Chemical compound ClCCCC(=O)OC(=O)CCCCl VAXCCWFPTAPDMK-UHFFFAOYSA-N 0.000 claims description 3
- YSXDKDWNIPOSMF-UHFFFAOYSA-N 5-chloropentanoic acid Chemical compound OC(=O)CCCCCl YSXDKDWNIPOSMF-UHFFFAOYSA-N 0.000 claims description 3
- PQPUKJABODCPQZ-UHFFFAOYSA-N 5-chloropentanoyl 5-chloropentanoate Chemical compound ClCCCCC(=O)OC(=O)CCCCCl PQPUKJABODCPQZ-UHFFFAOYSA-N 0.000 claims description 3
- QTFPWACIYKUKEW-UHFFFAOYSA-N 6-nitro-1,2-benzothiazol-3-one Chemical compound [O-][N+](=O)C1=CC=C2C(O)=NSC2=C1 QTFPWACIYKUKEW-UHFFFAOYSA-N 0.000 claims description 3
- 244000043261 Hevea brasiliensis Species 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- BFWMWWXRWVJXSE-UHFFFAOYSA-M fentin hydroxide Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(O)C1=CC=CC=C1 BFWMWWXRWVJXSE-UHFFFAOYSA-M 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229920003052 natural elastomer Polymers 0.000 claims description 3
- 229920001194 natural rubber Polymers 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 3
- POPOYOKQQAEISW-UHFFFAOYSA-N ticlatone Chemical compound ClC1=CC=C2C(=O)NSC2=C1 POPOYOKQQAEISW-UHFFFAOYSA-N 0.000 claims description 3
- 240000003183 Manihot esculenta Species 0.000 claims description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 229940100445 wheat starch Drugs 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical compound O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000013067 intermediate product Substances 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 28
- 235000011187 glycerol Nutrition 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 239000002131 composite material Substances 0.000 description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 229910021485 fumed silica Inorganic materials 0.000 description 6
- 238000005469 granulation Methods 0.000 description 6
- 230000003179 granulation Effects 0.000 description 6
- 229920001684 low density polyethylene Polymers 0.000 description 6
- 239000004702 low-density polyethylene Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000003385 bacteriostatic effect Effects 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 244000017020 Ipomoea batatas Species 0.000 description 3
- 235000002678 Ipomoea batatas Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 125000004103 aminoalkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000004181 carboxyalkyl group Chemical group 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000004990 dihydroxyalkyl group Chemical group 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 238000011081 inoculation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- LVDKZNITIUWNER-UHFFFAOYSA-N Bronopol Chemical compound OCC(Br)(CO)[N+]([O-])=O LVDKZNITIUWNER-UHFFFAOYSA-N 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 240000002657 Thymus vulgaris Species 0.000 description 1
- 235000007303 Thymus vulgaris Nutrition 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003000 extruded plastic Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- MMHWNKSVQDCUDE-UHFFFAOYSA-N hexanedioic acid;terephthalic acid Chemical compound OC(=O)CCCCC(O)=O.OC(=O)C1=CC=C(C(O)=O)C=C1 MMHWNKSVQDCUDE-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000001585 thymus vulgaris Substances 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a starch-based antibacterial material and a preparation method thereof. According to the invention, the isothiazolinone antibacterial agent is connected to the starch molecule in a chemical bond combination mode, so that the problem of insufficient compatibility between the starch-based material and the antibacterial agent is effectively solved, and the obtained novel starch-based material has excellent antibacterial performance and good comprehensive mechanical performance; in addition, the method has less synthesis steps, avoids the purification step of intermediate products, reduces the workload and improves the efficiency.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a starch-based antibacterial material and a preparation method thereof.
Background
Antibacterial agents are usually added to starch-based plastic products to enhance antibacterial property, but the starch-based plastic products have insufficient compatibility with most antibacterial agents, and the added antibacterial agents are easy to separate out, so that the antibacterial property, safety, durability and comprehensive mechanical property of the products are affected.
In patent CN112679895A, a plasticizer, a mold release agent and a bactericide are sequentially added into a polyvinyl alcohol aqueous solution at 40 ℃, stirring is continued for 1h to obtain a uniform solution, the membrane solution is kept stand, vacuumized to remove bubbles, a glass plate is scraped with a membrane, and the membrane is uncovered after drying to obtain an antibacterial membrane which can be used for food packaging, freshness protection bags, medicine packaging and the like. Wherein the antibacterial agent comprises isothiazole, 2-bromo-2-nitro-1, 3-propanediol, phenoxyethanol, etc.
Alotaibi (Development of a sweet potato starch-based coating and its effect on quality attributes of dried sweet potato reconstituted stored [ J ]) A thyme essential oil/Tween 80 stabilizing system and a sweet potato starch/glycerin aqueous solution were mixed together, dispersed in a homogenizer to form an emulsion, and then applied to the surface of fresh shrimp to form a film.
In both of the above two processes, the antibacterial agent is added to the product by blending, and there are the following problems: 1. the antibacterial agent is easy to separate out in the using process, so that the antibacterial property of the product is influenced; 2. the compatibility of the antibacterial agent and the base material is poor, the antibacterial agent is difficult to be uniformly mixed, and the comprehensive mechanical property of the product is influenced.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the technical defects of the background technology and provide a starch-based antibacterial material and a preparation method thereof. According to the invention, the isothiazolinone antibacterial agent is connected to the starch molecule in a chemical bond combination mode, so that the problem of insufficient compatibility between the starch-based material and the antibacterial agent is effectively solved, and the obtained novel starch-based material has excellent antibacterial performance and good comprehensive mechanical performance; in addition, the method has less synthesis steps, avoids the purification step of intermediate products, reduces the workload and improves the efficiency.
The technical scheme adopted by the invention for solving the technical problems is as follows:
in a first aspect, the present invention provides an antibacterial starch comprising a starch having a repeating unit represented by formula I:
in the formula I, at least one group in R1, R2 and R3 is a group structure shown in a formula II; the group structures which are not shown in formula II in R1, R2 and R3 respectively and independently represent any one of carboxyl, ester group, alkyl, hydroxyalkyl, dihydroxyalkyl, carboxyalkyl, aryl, cycloalkyl, aminoalkyl, alkylamine alkyl and hydrogen atom; in the formula I, n is an integer of 200-6000;
in the formula II, R4, R5, R6 and R7 independently represent any one of alkyl, nitro, halogen and hydrogen atoms, R8 represents a benzene ring, and m is a positive integer between 1 and 5.
Preferably, the group structures of R1, R2 and R3 which are not shown in formula II each independently represent any one of a hydrogen atom, an ester group and an alkyl group.
Preferably, R4, R5, R6, and R7 each independently represent any one of a methyl group, an ethyl group, and a hydrogen atom.
More preferably, R4, R5, R6, R7 are hydrogen atoms.
In a second aspect, the present invention provides a method for preparing the antibacterial starch, comprising the following steps:
(1) Soaking and activating 100 parts of starch in 150-300 parts of distilled water for 10-30 hours, washing with a first reagent after suction filtration, adding the activated starch and 200-400 parts of the first reagent into a reaction vessel, uniformly mixing, dropwise adding 200-400 parts of a second reagent and 0.5-3.5 parts of a catalyst, controlling the reaction temperature to be 50-80 ℃ and the reaction time to be 1-4 hours; filtering at room temperature, washing with distilled water, drying, pulverizing, and sieving to obtain esterified starch;
the first reagent comprises one or more of chloroacetic acid, 3-chloropropionic acid, 4-chlorobutyric acid and 5-chlorovaleric acid; the second reagent comprises any one or more of chloroacetic anhydride, 3-chloropropionic anhydride, 4-chlorobutyric anhydride and 5-chlorovaleric anhydride, and the second reagent is the anhydride corresponding to the first reagent; the catalyst is any one or more of concentrated sulfuric acid, p-toluenesulfonic acid and tetrabutylammonium iodide;
(2) Mixing 70-150 parts of antibacterial agent and 160-220 parts of third reagent, adding 55-130 parts of acid-binding agent at room temperature, adding 100 parts of esterified starch prepared in the step (1), heating to 30-80 ℃, reacting for 3-7 hours, cooling to room temperature after the reaction is finished, performing rotary evaporation, washing with water, and performing vacuum drying to obtain antibacterial starch;
the antibacterial agent is any one of 1, 2-benzisothiazolin-3-one, 6-chloro-1, 2-benzisothiazolin-3-one and 6-nitro-1, 2-benzisothiazolin-3-one; the third reagent is any one or more of chloroform, ethyl acetate, acetone, dichloromethane, dimethyl sulfoxide and methanol; the acid-binding agent is any one or more of triethylamine, 4-dimethylamino pyridine and triphenyl tin hydroxide.
Preferably, in the step (1), the starch is any one or more of corn starch, tapioca starch, potato starch, wheat starch and pea starch.
Preferably, in the step (1), the catalyst is p-toluenesulfonic acid.
Preferably, in the step (1), the reaction temperature is 65-75 ℃, and the reaction time is 2-3 h.
Preferably, in the step (2), the antibacterial agent is 1, 2-benzisothiazolin-3-one.
Preferably, in the step (2), the third reagent is any one or two of acetone and ethyl acetate.
Preferably, in the step (2), the acid scavenger is triethylamine.
Preferably, in the step (2), the antibacterial agent is 100 to 130 parts, the third reagent is 190 to 210 parts, and the acid-binding agent is 80 to 100 parts.
Preferably, in the step (2), the temperature is raised to 50-60 ℃ and the reaction is carried out for 4-6 h.
In a third aspect, the present invention provides a method for preparing a starch-based antibacterial material, comprising the steps of:
the starch-based antibacterial material comprises a fully degradable starch-based antibacterial material, partially degradable starch-based antibacterial plastic and partially degradable starch-based antibacterial rubber;
the preparation method of the starch-based antibacterial material comprises the following steps:
(1) Soaking 100 parts of starch in 150-300 parts of distilled water for activation for 10-30 h, washing with a first reagent after suction filtration, adding the activated starch and 200-400 parts of the first reagent into a reaction vessel, uniformly mixing, dropwise adding 200-400 parts of a second reagent and 0.5-3.5 parts of a catalyst, controlling the reaction temperature at 50-80 ℃ and the reaction time at 1-4 h; filtering at room temperature, washing with distilled water, drying, pulverizing, and sieving to obtain esterified starch;
the first reagent comprises one or more of chloroacetic acid, 3-chloropropionic acid, 4-chlorobutyric acid and 5-chlorovaleric acid; the second reagent comprises any one or more of chloroacetic anhydride, 3-chloropropionic anhydride, 4-chlorobutyric anhydride and 5-chlorovaleric anhydride, and the second reagent is the anhydride corresponding to the first reagent; the catalyst is any one or more of concentrated sulfuric acid, p-toluenesulfonic acid and tetrabutylammonium iodide;
(2) Mixing 70-150 parts of antibacterial agent and 160-220 parts of third reagent, adding 55-130 parts of acid-binding agent at room temperature, adding 100 parts of esterified starch prepared in the step (1), heating to 30-80 ℃, reacting for 3-7 hours, cooling to room temperature after the reaction is finished, performing rotary evaporation, washing with water, and performing vacuum drying to obtain antibacterial starch;
the antibacterial agent is any one of 1, 2-benzisothiazolin-3-one, 6-chloro-1, 2-benzisothiazolin-3-one and 6-nitro-1, 2-benzisothiazolin-3-one; the third reagent is any one or more of chloroform, ethyl acetate, acetone, dichloromethane, dimethyl sulfoxide and methanol; the acid-binding agent is any one or more of triethylamine, 4-dimethylamino pyridine and triphenyl tin hydroxide;
(3a) When the antibacterial starch prepared in the step (2) is used for preparing the fully degradable starch-based antibacterial material, the preparation method comprises the following steps:
vacuum drying the antibacterial starch prepared in the step (2) at 30-60 ℃ for 2-5 h, blending 30-100 parts of the antibacterial starch, 0-70 parts of degradable polymer and 9-35 parts of auxiliary agent in an extruder, extruding and granulating, and molding the obtained granules by an injection molding machine or a film making machine to obtain the fully degradable starch-based antibacterial material;
(3b) When the antibacterial starch prepared in the step (2) is used for preparing the partially degradable starch-based antibacterial plastic, the preparation method comprises the following steps:
vacuum drying the antibacterial starch prepared in the step (2) at 30-60 ℃ for 2-5 h, blending 10-50 parts of the antibacterial starch, 50-90 parts of polyolefin material and 5-30 parts of auxiliary agent in an extruder, extruding and granulating, and molding the obtained granules by an injection molding machine or a film making machine to obtain the partially degradable starch-based antibacterial plastic;
(3c) When the antibacterial starch prepared in the step (2) is used for preparing the partially degradable starch-based antibacterial rubber, the preparation method comprises the following steps:
and (3) drying the antibacterial starch prepared in the step (2) at 30-60 ℃ for 2-5 h in vacuum, and putting 5-30 parts of the antibacterial starch, 70-95 parts of rubber material and 20-60 parts of auxiliary agent into a vacuum kneader or internal mixer to obtain the partially degradable starch-based antibacterial rubber.
Preferably, in the step (3 a), the degradable polymer is any one or more of polylactic acid (PLA), polybutylene terephthalate-adipate (PBAT), polycaprolactone (PCL) and polyvinyl alcohol (PVA).
Preferably, in the step (3 a), the auxiliary is a plasticizing auxiliary; the plasticizing auxiliary agent is any one or more of glycerol, sucrose, mannitol, sorbitol and propylene glycol.
Preferably, in the step (3 a), the temperature of the extruder barrel is 120-180 ℃, and the rotation speed of the screw is 50-500 rpm.
Preferably, in the step (3 b), the formula of the partially degradable starch-based antibacterial plastic is as follows: 10-30 parts of antibacterial starch, 70-90 parts of polyolefin material and 5-15 parts of auxiliary agent.
Preferably, in the step (3 b), the polyolefin material is any one or more of Linear Low Density Polyethylene (LLDPE), low Density Polyethylene (LDPE), polypropylene (PP), polyolefin elastomer (POE), and Cyclic Olefin Copolymer (COC).
Preferably, in the step (3 b), the auxiliary is a plasticizing auxiliary; the plasticizing auxiliary agent is any one or more of glycerol, sucrose, mannitol, sorbitol and propylene glycol.
Preferably, in the step (3 b), the temperature of the extruder barrel is 120-220 ℃, more preferably 120-190 ℃ and the screw rotation speed is 50-500 rpm.
Preferably, in the step (3 c), the rubber is any one or more of Natural Rubber (NR), silicone rubber and Styrene Butadiene Rubber (SBR).
Preferably, in the step (3 c), the auxiliary agent is any one or more of hydroxy silicone oil, 2-mercaptobenzothiazole, 2' -dithiodibenzothiazole, zinc oxide, white carbon black and ethyl orthosilicate.
Preferably, in the step (3 c), when the antibacterial starch prepared in the step (2) is used for preparing the partially degradable starch-based antibacterial rubber, the preparation method comprises the following steps:
vacuum drying the antibacterial starch prepared in the step (2) at 30-60 ℃ for 2-5 h, putting 70 parts of raw methyl vinyl silicone rubber and 0.8 part of hydroxyl silicone oil into a vacuum kneading machine, and kneading for 10 minutes at 70 ℃; adding 30 parts of fumed silica subjected to surface treatment in 5 batches, adding the next batch of fumed silica subjected to surface treatment after kneading into a mass, adding all the fumed silica subjected to surface treatment, kneading into a mass, introducing steam, raising the temperature in the kneader to 150 ℃, simultaneously vacuumizing to-0.05 MPa, keeping the temperature and pressure for 2 hours to prepare a silica gel mass, naturally cooling to 80 ℃ at room temperature, adding 30 parts of the antibacterial starch and 0.5 part of tetraethoxysilane with the silicon dioxide content of 40% in 5 batches, and adding the antibacterial starch and the tetraethoxysilane of the next batch after mixing into a mass each time; after the mixture is mixed and agglomerated, the temperature is raised to 100 ℃, and the vacuum pumping is carried out for 1 hour, thus obtaining the partially degradable starch-based antibacterial rubber.
In a fourth aspect, the invention provides a starch-based antibacterial material, which is prepared by the preparation method of the starch-based antibacterial material.
The basic principle of the invention is as follows:
the synthetic route of the antibacterial starch is as follows:
in the formula III, R1 and R2 independently represent any one of carboxyl, ester group, alkyl, hydroxyalkyl, dihydroxyalkyl, carboxyalkyl, aryl, cycloalkyl, aminoalkyl, alkylamine alkyl and hydrogen atom, and m is a positive integer between 1 and 5; in the above reaction, when R1 and R2 are hydrogen atoms, the above reaction may occur.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, the acid-binding agent is added, so that the reaction balance between the isothiazolinone antibacterial agent and the esterified starch is moved to the direction of the product, and the conversion rate of the reaction is improved; compared with the prior art, the method has the advantages that the synthesis steps are reduced, the purification step of intermediate products is avoided, the workload is reduced, and the efficiency is improved;
(2) The isothiazolinone antibacterial agent is connected to the starch molecule through a chemical bond by using the chloroanhydride, so that the problem of poor compatibility of the antibacterial agent and the starch is solved;
(3) The invention can exert respective advantages through the chemical combination of the isothiazolinone antibacterial agent and the starch: the isothiazolinone antibacterial agent has broad spectrum, high efficiency and environmental friendliness; the starch can be completely degraded and has wide sources; the prepared antibacterial starch and the compound thereof have excellent antibacterial performance and good comprehensive mechanical performance.
Drawings
FIG. 1 is a schematic representation of the dimensions of a specimen in the tensile strength test of the present invention.
Detailed Description
For a better understanding of the present invention, reference is made to the following examples. It should be understood that these examples are for further illustration of the invention and are not intended to limit the scope of the invention. In addition, it should be understood that the invention is not limited to the above-described embodiments, but is capable of various modifications and changes within the scope of the invention.
Example 1
(1) Soaking 30g of corn starch in 60mL of distilled water for 24h, carrying out suction filtration, washing with chloroacetic acid, then adding activated starch and 98g of chloroacetic acid into a reaction vessel, dropwise adding 98g of chloroacetic anhydride and 0.6g of p-toluenesulfonic acid, controlling the temperature of an oil bath at 70 ℃, and reacting for 2.5h; filtering at room temperature, washing with distilled water, drying, pulverizing, and sieving to obtain esterified starch;
(2) Mixing 19g of 1, 2-benzisothiazolin-3-one and 30mL of acetone, adding 13mL of triethylamine at room temperature, heating to 50 ℃, slowly adding 15g of the obtained esterified starch while stirring, reacting for 6 hours, after the reaction is finished, carrying out rotary evaporation at 50 ℃, washing with water, and drying to obtain antibacterial starch;
(3) And (3) drying the prepared antibacterial starch for 2 hours in vacuum at 50 ℃, mixing the antibacterial starch with glycerol according to the weight ratio of 100:35, then feeding the mixed materials into a double screw to extrude and granulate, controlling the temperature of a machine barrel to be 135 ℃, the temperature of a machine head to be 130 ℃, and the rotating speed of the screw to be 200rpm, and granulating to obtain particles with uniform size and uniform texture, namely the antibacterial starch particles.
The structure of the obtained antibacterial starch is shown as follows:
example 2
(1) Soaking 30g of corn starch in 60mL of distilled water for 24h, carrying out suction filtration, washing with chloroacetic acid, then adding activated starch and 98g of chloroacetic acid into a reaction vessel, dropwise adding 98g of chloroacetic anhydride and 0.6g of p-toluenesulfonic acid, controlling the temperature of an oil bath at 70 ℃, and reacting for 2.5h; filtering at room temperature, washing with distilled water, drying, pulverizing, and sieving to obtain esterified starch;
(2) Mixing 19g1, 2-benzisothiazolin-3-one with 30mL of acetone, adding 13mL of triethylamine at room temperature, heating to 50 ℃, slowly adding 15g of the obtained esterified starch while stirring, reacting for 6 hours, after the reaction is finished, carrying out rotary evaporation at 50 ℃, washing with water, and drying to obtain antibacterial starch;
(3) The prepared antibacterial starch is dried for 2 hours in vacuum at 50 ℃, the antibacterial starch, polypropylene (Yanshan petrochemical F1608) and glycerol are uniformly mixed according to the ratio of 30: 70: 9, then the mixed materials are fed into a double screw to be extruded and granulated, the temperature of a double screw cylinder is 175 ℃, the head temperature is 170 ℃, the rotating speed of the screw is 260rpm, and granules with uniform size and uniform texture, namely the antibacterial starch/polypropylene composite product granules, are obtained through granulation.
Example 3
The rest conditions are the same as the example 2, except that in the step c, the antibacterial starch, the linear low density polyethylene (LLDPE 620) and the glycerol are uniformly mixed according to the ratio of 30: 70: 9, then the mixed materials are fed into a double screw to be extruded and granulated, the temperature of a double screw cylinder is 190 ℃, the temperature of a machine head is 180 ℃, the rotating speed of the screw is 200rpm, and granules with uniform size and uniform texture, namely the antibacterial starch/linear low density polyethylene composite product granules, are obtained through granulation.
Example 4
The rest conditions are the same as the example 2, except that in the step c, the antibacterial starch, low density polyethylene (TAISOX 6520G) and glycerol are uniformly mixed according to the ratio of 30: 70: 9, then the mixed materials are fed into a double screw to be extruded and granulated, the temperature of a double screw cylinder is 190 ℃, the temperature of a machine head is 180 ℃, the rotating speed of the screw is 200rpm, and granules with uniform size and uniform texture, namely the antibacterial starch/low density polyethylene composite product granules, are obtained through granulation.
Example 5
The other conditions were the same as in example 2, except that in step c the antibacterial starch was mixed with the polyolefin elastomer (Vistamaxx) TM 6202 Mixing glycerol and the raw materials uniformly according to the ratio of 30: 70: 9, feeding the mixed materials into a double screw to extrude and granulate, wherein the temperature of a double screw machine barrel is 190 ℃, the temperature of a machine head is 180 ℃, the rotating speed of the screw is 220rpm, and granulating to obtain particles with uniform size and uniform texture, namely the particles of the antibacterial starch/polyolefin elastomer composite product.
Example 6
The rest conditions are the same as the example 2, except that in the step c, the antibacterial starch, the cycloolefin copolymer (TOPAS 8007) and the glycerol are uniformly mixed according to the ratio of 30: 70: 9, then the mixed materials are fed into a double screw to be extruded and granulated, the temperature of a double screw cylinder is 190 ℃, the temperature of a machine head is 180 ℃, the rotating speed of the screw is 240rpm, and granules with uniform size and uniform texture, namely the antibacterial starch/cycloolefin copolymer composite product granules, are obtained through granulation.
Example 7
The other conditions were the same as in example 2 except that in step c, the antibacterial starch was mixed with polylactic acid (A)
V554X 51) and glycerol are uniformly mixed according to the ratio of 30: 70: 9, then the mixed materials are fed into a double screw to be extruded and granulated, the temperature of a cylinder of the double screw is 175 ℃, the temperature of a machine head is 170 ℃, the rotating speed of the screw is 200rpm, and granules with uniform size and uniform texture, namely the antibacterial starch/polylactic acid composite product granules, are obtained through granulation.
Example 8
The rest conditions are the same as the example 2, except that in the step c, the antibacterial starch, the polybutylene terephthalate-adipate (ECO-A05) and the glycerol are uniformly mixed according to the ratio of 30: 70: 9, then the mixed materials are fed into a double screw to be extruded and granulated, the temperature of a double screw cylinder is 180 ℃, the temperature of a machine head is 175 ℃, the rotating speed of the screw is 220rpm, and granules with uniform size and uniform texture, namely the antibacterial starch/polybutylene terephthalate-adipate composite product granules, are obtained through granulation.
Example 9
The same conditions as in example 2 are followed, except that in step c the antibacterial starch is combined with polycaprolactone (Andur 6APLM @)
442 Uniformly mixing glycerol and the raw materials according to the ratio of 30: 70: 9, feeding the mixed materials into a double-screw extruder to extrude and granulate, wherein the temperature of the double-screw extruder barrel is 135 ℃, the temperature of a machine head is 130 ℃, and the rotating speed of the screw is 220rpm, and granulating to obtain particles with uniform size and uniform texture, namely the particles of the antibacterial starch/polycaprolactone composite product.
Example 10
The same procedure as in example 2 except that in step c, 70g of raw methyl vinyl silicone rubber (constant 110-1S) and 0.8g of silicone oil were charged into a vacuum kneader and kneaded at 70 ℃ for 10 minutes; adding 30g of surface-treated fumed silica into 5 batches of the mixture, adding the next batch of surface-treated fumed silica into the mixture after kneading the mixture into a mass, introducing steam into the kneader after all the surface-treated fumed silica is added and kneaded into the mass to raise the temperature in the kneader to 150 ℃, vacuumizing the kneader to-0.05 MPa, preserving heat and maintaining pressure for 2 hours to prepare silica gel masses, naturally cooling the silica gel masses to 80 ℃ at room temperature, adding 30g of antibacterial starch and 0.5g of ethyl orthosilicate with the silicon dioxide content of 40% into the 5 batches of the mixture, and adding the next batch of antibacterial starch and the ethyl orthosilicate into the mixture after each time of mixing the mixture into the mass; after mixing and agglomerating, heating to 100 ℃, and vacuumizing for 1 hour to obtain the antibacterial starch/silicone rubber composite product.
Comparative example 1
Vacuum drying corn starch at 50 deg.C for 2 hr, mixing starch and glycerol at a ratio of 100:35, feeding the mixed material into twin-screw extruder, granulating, and granulating at barrel temperature of 135 deg.C, head temperature of 130 deg.C, screw rotation speed of 200rpm to obtain uniform granules, i.e. starch product granules.
Comparative example 2
Vacuum drying corn starch at 50 ℃ for 2h, uniformly mixing the starch, 1, 2-benzisothiazolin-3-one and glycerol according to the ratio of 100: 3: 35, feeding the mixed material into a double screw extruder, extruding and granulating, controlling the temperature of a machine barrel at 135 ℃, the temperature of a machine head at 130 ℃, the rotating speed of the screw at 200rpm, and granulating to obtain uniform particles, namely the starch/antibacterial agent composite product particles.
Comparative example 3
The rest of the conditions were the same as in example 2, except that no acid-binding agent was added in step b.
Comparative example 4
Vacuum drying corn starch at 50 deg.C for 2h, mixing starch, glycerol, 1, 2-benzisothiazolin-3-one and polypropylene (Yanshan petrochemical F1608) at 30: 9: 3: 70, feeding the mixed material into twin screw extruder, granulating, controlling barrel temperature at 175 deg.C, head temperature at 170 deg.C, screw rotation speed at 260rpm, and granulating to obtain uniform granules, i.e. starch/polypropylene/antibacterial agent composite product granules.
Effects of the embodiment
1. Test of bacteriostatic Property
The bacteriostatic performance test is carried out according to GB/T31402-2015. The resulting product pellets were pressed into 40mm by 1mm pieces using a press vulcanizer. Sucking 0.4mL of different inoculation solutions into a disposable culture dish, covering the prepared plate on the inoculation solution, slightly pressing a film downwards to enable the bacteria solution to diffuse around, ensuring that the bacteria solution does not overflow from the edge of the film, covering a culture dish cover, placing the culture dish cover in an incubator with the temperature of 35 +/-1 ℃ and the relative humidity of not less than 90 percent for culturing for 24 hours, and carrying out colony recovery counting.
The results of the bacteriostatic performance test of the starch-based antibacterial materials prepared in examples 1 to 10 and comparative examples 1 to 4 of the present invention are shown in table 1.
TABLE 1 results of the bacteriostatic properties of the starch-based antibacterial materials prepared in examples 1 to 10 of the present invention and comparative examples 1 to 4
As can be seen from Table 1:
(1) The comparison between the example 1 and the comparative example 1 shows that the antibacterial starch obtained by grafting the antibacterial agent on the starch has good antibacterial effect;
(2) Compared with the comparative example 2, the antibacterial starch has better antibacterial performance, and the antibacterial agent is poor in dispersion and antibacterial effect due to poor compatibility of the raw starch and the antibacterial agent;
(3) Compared with the comparative example 3, in the example 2, after the acid-binding agent is added in the reaction process, the bacteriostatic effect of the obtained product particles is higher than that of the product particles without the acid-binding agent, because hydrogen halide is generated in the reaction process, and the hydrogen halide generated in the reaction can be effectively removed by adding the acid-binding agent, so that the conversion rate of the reaction is improved;
(4) Compared with the comparative example 4, the product particles prepared by blending the raw starch, the antibacterial agent and the polypropylene have poorer antibacterial effect, which shows that the compatibility of the raw starch, the antibacterial agent and the polypropylene blending system is poor, and the antibacterial effect of the final product is influenced;
(5) Examples 2 to 10 showed good inhibitory effects on escherichia coli and staphylococcus aureus, which indicates that the antibacterial starch obtained by grafting the antibacterial agent with starch has good compatibility with PP, LLDPE, LDPE, POE, COC, PLA, PBAT, PCL, and methyl vinyl silicone rubber.
2. Tensile Strength test
Tensile Strength test part 2 of the determination of tensile Properties of plastics according to GB/T1040.2-2006: test conditions of molded and extruded plastics test conditions of "type 5A" test conditions the test was carried out and the samples were injection molded with the dimensions shown in FIG. 1, the total length being 75mm and the thickness being 2mm.
And (3) performing a tensile test on an electronic universal testing machine, wherein the tensile speed is 50mm/min, the environmental temperature is 23 ℃, the relative humidity is 50 +/-5%, and the test result is the average value of the test data of 5 sample bars.
The results of mechanical property tests of the starch-based antibacterial materials prepared in examples 1 to 9 of the present invention and comparative examples 1 to 4 are shown in table 2.
TABLE 2 mechanical Property test results of starch-based antibacterial materials prepared in examples 1 to 9 of the present invention and comparative examples 1 to 4
The mechanical property test results of the starch-based antibacterial material prepared in example 10 of the present invention are shown in table 3.
TABLE 3 mechanical Property test results of the starch-based antibacterial material obtained in example 10 of the present invention
| Performance test items | Performance test method | Performance test data |
| Hardness of | ASTM D-2240 | 59A |
| Tensile strength | ASTM D-412 | 7.3MPa |
| Elongation at break | ASTM D-412 | 362％ |
| Tear strength | ASTM D-624 | 2.1×10 4 N/m |
| Degree of plasticity | ASTM D-926 | 251 |
As can be seen from table 2:
(1) Compared with the comparative example 1, the antibacterial starch obtained by grafting the antibacterial agent on the starch is obviously improved in tensile strength and elongation at break, so that the comprehensive mechanical property of the starch can be improved after the starch is grafted with the antibacterial agent;
(2) Compared with the blend of the original starch and the antibacterial agent, the antibacterial starch obtained by grafting the antibacterial agent on the original starch has obviously improved tensile strength and elongation at break compared with the blend of the original starch and the antibacterial agent, which shows that the problem of insufficient compatibility between the starch and the antibacterial agent is effectively solved by connecting the antibacterial agent on starch molecules, and the comprehensive mechanical property of the product is improved;
(3) Compared with the blend of the original starch and the polypropylene, the antibacterial starch grafted with the antibacterial agent and the polypropylene are blended to obtain a product with improved tensile strength and elongation at break compared with the blend of the original starch and the polypropylene, because the blend system of the original starch, the antibacterial agent and the polypropylene has poor compatibility and the antibacterial agent has poor dispersion effect, so that the mechanical property of the product is influenced;
(4) Compared with the embodiment 1, the comprehensive mechanical properties of the product particles prepared in the embodiments 2 to 9 are remarkably improved, which shows that the antibacterial starch obtained by grafting the antibacterial agent with the starch has good blending performance with PP, LLDPE, LDPE, POE, COC, PLA, PBAT and PCL, and the product obtained after blending has good comprehensive mechanical properties.
The above description is not intended to limit the invention, nor is the invention limited to the examples set forth above. Those skilled in the art should also realize that changes, modifications, additions and substitutions can be made without departing from the true spirit and scope of the invention.
Claims (10)
1. The preparation method of the starch-based antibacterial material is characterized by comprising the following steps:
the starch-based antibacterial material comprises a fully degradable starch-based antibacterial material, partially degradable starch-based antibacterial plastic and partially degradable starch-based antibacterial rubber;
the preparation method of the starch-based antibacterial material comprises the following steps:
(1) Soaking 100 parts of starch in 150-300 parts of distilled water for activation for 10-30 h, washing with a first reagent after suction filtration, adding the activated starch and 200-400 parts of the first reagent into a reaction vessel, uniformly mixing, dropwise adding 200-400 parts of a second reagent and 0.5-3.5 parts of a catalyst, controlling the reaction temperature at 50-80 ℃ and the reaction time at 1-4 h; filtering at room temperature, washing with distilled water, drying, pulverizing, and sieving to obtain esterified starch;
the first reagent comprises one or more of chloroacetic acid, 3-chloropropionic acid, 4-chlorobutyric acid and 5-chlorovaleric acid; the second reagent comprises any one or more of chloroacetic anhydride, 3-chloropropionic anhydride, 4-chlorobutyric anhydride and 5-chlorovaleric anhydride, and the second reagent is the anhydride corresponding to the first reagent; the catalyst is any one or more of concentrated sulfuric acid, p-toluenesulfonic acid and tetrabutylammonium iodide;
(2) Mixing 70-150 parts of antibacterial agent and 160-220 parts of third reagent, adding 55-130 parts of acid-binding agent at room temperature, adding 100 parts of esterified starch prepared in the step (1), heating to 30-80 ℃, reacting for 3-7 hours, cooling to room temperature after the reaction is finished, performing rotary evaporation, washing with water, and performing vacuum drying to obtain antibacterial starch;
the antibacterial agent is any one of 1, 2-benzisothiazolin-3-one, 6-chloro-1, 2-benzisothiazolin-3-one and 6-nitro-1, 2-benzisothiazolin-3-one; the third reagent is any one or more of chloroform, ethyl acetate, acetone, dichloromethane, dimethyl sulfoxide and methanol; the acid-binding agent is any one or more of triethylamine, 4-dimethylaminopyridine and triphenyltin hydroxide;
(3a) When the antibacterial starch prepared in the step (2) is used for preparing the fully degradable starch-based antibacterial material, the preparation method comprises the following steps:
vacuum drying the antibacterial starch prepared in the step (2) at 30-60 ℃ for 2-5 h, blending 30-100 parts of the antibacterial starch, 0-70 parts of degradable polymer and 9-35 parts of auxiliary agent in an extruder, extruding and granulating, and molding the obtained granules by an injection molding machine or a film making machine to obtain the fully degradable starch-based antibacterial material;
(3b) When the antibacterial starch prepared in the step (2) is used for preparing the partially degradable starch-based antibacterial plastic, the preparation method comprises the following steps:
vacuum drying the antibacterial starch prepared in the step (2) at 30-60 ℃ for 2-5 h, blending 10-50 parts of the antibacterial starch, 50-90 parts of polyolefin material and 5-30 parts of auxiliary agent in an extruder, extruding and granulating, and molding the obtained granules by an injection molding machine or a film making machine to obtain the partially degradable starch-based antibacterial plastic;
(3c) When the antibacterial starch prepared in the step (2) is used for preparing the partially degradable starch-based antibacterial rubber, the preparation method comprises the following steps:
and (3) drying the antibacterial starch prepared in the step (2) at 30-60 ℃ for 2-5 h in vacuum, and putting 5-30 parts of the antibacterial starch, 70-95 parts of rubber material and 20-60 parts of auxiliary agent into a vacuum kneader or internal mixer to obtain the partially degradable starch-based antibacterial rubber.
2. The method for preparing a starch-based antibacterial material according to claim 1, wherein in the step (1), the starch is any one or more of corn starch, tapioca starch, potato starch, wheat starch and pea starch.
3. The method for preparing a starch-based antibacterial material according to claim 1, wherein in step (3 a), the degradable polymer is one or more of polylactic acid, polybutylene terephthalate-adipate, polycaprolactone and polyvinyl alcohol.
4. The method for preparing a starch-based antibacterial material according to claim 1, wherein in the step (3 a), the auxiliary agent is a plasticizing auxiliary agent; the plasticizing auxiliary agent is any one or more of glycerol, sucrose, mannitol, sorbitol and propylene glycol.
5. The method for preparing a starch-based antibacterial material according to claim 1, wherein in the step (3 b), the formula of the partially degradable starch-based antibacterial plastic is as follows: 10-30 parts of antibacterial starch, 70-90 parts of polyolefin material and 5-15 parts of auxiliary agent.
6. The method for preparing a starch-based antibacterial material according to claim 1, wherein in the step (3 b), the polyolefin material is any one or more of linear low density polyethylene, polypropylene, polyolefin elastomer, and cyclic olefin copolymer.
7. The method for preparing a starch-based antibacterial material according to claim 1, wherein in the step (3 b), the auxiliary is a plasticizing auxiliary; the plasticizing auxiliary agent is any one or more of glycerol, sucrose, mannitol, sorbitol and propylene glycol.
8. The method for preparing a starch-based antibacterial material according to claim 1, wherein in the step (3 c), the rubber is any one or more of natural rubber, silicone rubber and styrene butadiene rubber.
9. The method for preparing the starch-based antibacterial material according to claim 1, wherein in the step (3 c), the auxiliary agent is any one or more of hydroxy silicone oil, 2-mercaptobenzothiazole, 2' -dithiodibenzothiazole, zinc oxide, white carbon black and ethyl orthosilicate.
10. A starch-based antibacterial material, characterized in that it is prepared by the method for preparing a starch-based antibacterial material according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210814038.7A CN115340724B (en) | 2022-07-11 | 2022-07-11 | Starch-based antibacterial material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210814038.7A CN115340724B (en) | 2022-07-11 | 2022-07-11 | Starch-based antibacterial material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115340724A true CN115340724A (en) | 2022-11-15 |
| CN115340724B CN115340724B (en) | 2023-10-24 |
Family
ID=83947655
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210814038.7A Active CN115340724B (en) | 2022-07-11 | 2022-07-11 | Starch-based antibacterial material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115340724B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115141432A (en) * | 2022-07-11 | 2022-10-04 | 浙江科技学院 | Antibacterial starch and preparation method thereof |
| CN116120719A (en) * | 2022-12-16 | 2023-05-16 | 福州大学 | Antibacterial reinforced waterproof degradable high polymer material |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20050020073A (en) * | 2003-08-20 | 2005-03-04 | (주) 티셀 | Antimicrobial deodorant adhesives |
| WO2009095618A2 (en) * | 2008-02-01 | 2009-08-06 | Roquette Freres | Method for preparing thermoplastic compositions based on plasticized starch and resulting compositions |
| CN106084272A (en) * | 2016-06-24 | 2016-11-09 | 安徽德琳环保发展（集团）有限公司 | A kind of antibacterial starch degradable thin film of caprolactone grafting and preparation method thereof |
| WO2017121242A1 (en) * | 2016-01-13 | 2017-07-20 | 广州市海珥玛植物油脂有限公司 | Plasticised biodegradable polyester film and preparation method therefor |
| CN110330773A (en) * | 2019-07-19 | 2019-10-15 | 深圳利琒环保材料有限公司 | A kind of controllable full-biodegradable mulch and preparation method thereof |
| CN110615975A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Antibacterial and mildewproof polylactic acid composition, foaming bead, preparation method of foaming bead and formed body |
| CN111269670A (en) * | 2020-03-30 | 2020-06-12 | 浙江大胜达包装股份有限公司 | Preparation method of modified starch adhesive |
| CN113025016A (en) * | 2021-03-26 | 2021-06-25 | 广州暨明科技有限公司 | Degradable antibacterial material for medical care and health care and preparation method thereof |
| US20220073706A1 (en) * | 2020-12-09 | 2022-03-10 | Jiangnan University | Self-reinforced Starch-based Multifunctional Materials and Processing Method thereof |
-
2022
- 2022-07-11 CN CN202210814038.7A patent/CN115340724B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20050020073A (en) * | 2003-08-20 | 2005-03-04 | (주) 티셀 | Antimicrobial deodorant adhesives |
| WO2009095618A2 (en) * | 2008-02-01 | 2009-08-06 | Roquette Freres | Method for preparing thermoplastic compositions based on plasticized starch and resulting compositions |
| CA2712898A1 (en) * | 2008-02-01 | 2009-08-06 | Roquette Freres | Method for preparing thermoplastic compositions based on plasticized starch and resulting compositions |
| WO2017121242A1 (en) * | 2016-01-13 | 2017-07-20 | 广州市海珥玛植物油脂有限公司 | Plasticised biodegradable polyester film and preparation method therefor |
| CN106084272A (en) * | 2016-06-24 | 2016-11-09 | 安徽德琳环保发展（集团）有限公司 | A kind of antibacterial starch degradable thin film of caprolactone grafting and preparation method thereof |
| CN110615975A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Antibacterial and mildewproof polylactic acid composition, foaming bead, preparation method of foaming bead and formed body |
| CN110330773A (en) * | 2019-07-19 | 2019-10-15 | 深圳利琒环保材料有限公司 | A kind of controllable full-biodegradable mulch and preparation method thereof |
| CN111269670A (en) * | 2020-03-30 | 2020-06-12 | 浙江大胜达包装股份有限公司 | Preparation method of modified starch adhesive |
| US20220073706A1 (en) * | 2020-12-09 | 2022-03-10 | Jiangnan University | Self-reinforced Starch-based Multifunctional Materials and Processing Method thereof |
| CN113025016A (en) * | 2021-03-26 | 2021-06-25 | 广州暨明科技有限公司 | Degradable antibacterial material for medical care and health care and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 陈艺彩;谢小保;施庆珊;欧阳友生;陈仪本;: "异噻唑啉酮衍生物类工业杀菌剂的研究进展", 精细与专用化学品, no. 01, pages 55 - 58 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115141432A (en) * | 2022-07-11 | 2022-10-04 | 浙江科技学院 | Antibacterial starch and preparation method thereof |
| CN116120719A (en) * | 2022-12-16 | 2023-05-16 | 福州大学 | Antibacterial reinforced waterproof degradable high polymer material |
| CN116120719B (en) * | 2022-12-16 | 2024-07-05 | 福州大学 | Antibacterial reinforced waterproof degradable high polymer material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115340724B (en) | 2023-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115340724A (en) | Starch-based antibacterial material and preparation method thereof | |
| KR101834283B1 (en) | Blends of a polylactic acid and a water soluble polymer | |
| TWI668265B (en) | Hydrophobic thermoplastic starch and method for manufacturing the same | |
| CN113354929B (en) | Low-precipitation biodegradable PLA alloy, preparation method thereof and straw material | |
| CN113248798B (en) | starch/cellulose/PBAT composite film and preparation method thereof | |
| CN109988335B (en) | Ferrocenyl Schiff base and preparation method and application thereof | |
| CN101743279A (en) | Carboxy-modified polyvinyl alcohol as co-stabilizer for PVC | |
| CN114889285A (en) | Low-temperature heat-sealing biodegradable composite film and preparation process thereof | |
| CN113736088A (en) | Polysilsesquioxane, PLA alloy and straw material | |
| CN114292350B (en) | Hemicellulose cinnamate, preparation method thereof and application thereof in biodegradable composite material | |
| JP2017516882A (en) | Method for incorporating wet natural fibers and starch into thermoplastics | |
| CN1278268A (en) | The reaction of polyhydroxy polymer or derivatives thereof with lactone | |
| JPH11255801A (en) | Biodegradable graft polymer and preparation thereof | |
| CN112795149A (en) | Biodegradable polyester PBAT composite material and preparation method thereof | |
| CN112662144A (en) | Preparation method of plastic particles beneficial to degradation | |
| CN115141432B (en) | Antibacterial starch and preparation method thereof | |
| CN116355313A (en) | Lignin/polypropylene composite material with high mechanical property and preparation method thereof | |
| CN111286164B (en) | Biodegradable plastic and preparation method thereof | |
| CN113896955A (en) | Starch-based sheet composition and preparation method thereof | |
| CN111944288A (en) | Modified PLA material for biodegradable mulching film and preparation method thereof | |
| JP6274107B2 (en) | Method for producing cellulose derivative and method for producing cellulose resin composition | |
| CN111925592A (en) | Glass fiber-added polypropylene plastic and preparation method thereof | |
| CN110804291A (en) | Biodegradable composite material and preparation method thereof | |
| CN1308384C (en) | Biodegradable resin composition | |
| CN114106358B (en) | Modified bio-based material, composite material, raw materials thereof, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |