CN105801994A - Preparation method for grape preservative film master batches containing rare earth complex - Google Patents
Preparation method for grape preservative film master batches containing rare earth complex Download PDFInfo
- Publication number
- CN105801994A CN105801994A CN201610176113.6A CN201610176113A CN105801994A CN 105801994 A CN105801994 A CN 105801994A CN 201610176113 A CN201610176113 A CN 201610176113A CN 105801994 A CN105801994 A CN 105801994A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- preparation
- master batch
- compound
- earth compounding
- 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
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 79
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 235000009754 Vitis X bourquina Nutrition 0.000 title claims abstract description 28
- 235000012333 Vitis X labruscana Nutrition 0.000 title claims abstract description 28
- 235000014787 Vitis vinifera Nutrition 0.000 title claims abstract description 28
- 239000003755 preservative agent Substances 0.000 title abstract description 15
- 230000002335 preservative effect Effects 0.000 title abstract description 15
- 240000006365 Vitis vinifera Species 0.000 title 1
- 241000219095 Vitis Species 0.000 claims abstract description 55
- 239000000843 powder Substances 0.000 claims abstract description 40
- -1 lanthanum ions Chemical class 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 27
- 229910052613 tourmaline Inorganic materials 0.000 claims abstract description 25
- 229940070527 tourmaline Drugs 0.000 claims abstract description 25
- 239000011032 tourmaline Substances 0.000 claims abstract description 25
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims abstract description 16
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 14
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 13
- 238000005253 cladding Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 12
- 238000012986 modification Methods 0.000 claims abstract description 12
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 6
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 54
- 238000013329 compounding Methods 0.000 claims description 51
- 239000000243 solution Substances 0.000 claims description 48
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 42
- 239000002994 raw material Substances 0.000 claims description 32
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 24
- 229920002101 Chitin Polymers 0.000 claims description 20
- 239000002244 precipitate Substances 0.000 claims description 18
- 230000021736 acetylation Effects 0.000 claims description 16
- 238000006640 acetylation reaction Methods 0.000 claims description 16
- 239000012153 distilled water Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000004898 kneading Methods 0.000 claims description 14
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 13
- 150000004676 glycans Chemical class 0.000 claims description 12
- 229920001282 polysaccharide Polymers 0.000 claims description 12
- 239000005017 polysaccharide Substances 0.000 claims description 12
- 235000013311 vegetables Nutrition 0.000 claims description 12
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 12
- 238000005453 pelletization Methods 0.000 claims description 11
- 229910052779 Neodymium Inorganic materials 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 9
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 8
- 230000008030 elimination Effects 0.000 claims description 8
- 238000003379 elimination reaction Methods 0.000 claims description 8
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical compound [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 claims description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- DGVVPRHPLWDELQ-UHFFFAOYSA-N acetic acid;samarium Chemical compound [Sm].CC(O)=O.CC(O)=O.CC(O)=O DGVVPRHPLWDELQ-UHFFFAOYSA-N 0.000 claims description 2
- DUSUCKWNBGMKRV-UHFFFAOYSA-N acetic acid;yttrium Chemical compound [Y].CC(O)=O DUSUCKWNBGMKRV-UHFFFAOYSA-N 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 claims description 2
- 229910000245 dravite Inorganic materials 0.000 claims description 2
- 229910000244 elbaite Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- IDIJOAIHTRIPRC-UHFFFAOYSA-J hexaaluminum;sodium;2,2,4,4,6,6,8,8,10,10,12,12-dodecaoxido-1,3,5,7,9,11-hexaoxa-2,4,6,8,10,12-hexasilacyclododecane;iron(2+);triborate;tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Fe+2].[Fe+2].[Fe+2].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-][Si]1([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O1 IDIJOAIHTRIPRC-UHFFFAOYSA-J 0.000 claims description 2
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 2
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 claims description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- BCYBEIXXOVNETJ-UHFFFAOYSA-K samarium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Sm+3] BCYBEIXXOVNETJ-UHFFFAOYSA-K 0.000 claims description 2
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 claims description 2
- 229910000246 schorl Inorganic materials 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- DEXZEPDUSNRVTN-UHFFFAOYSA-K yttrium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Y+3] DEXZEPDUSNRVTN-UHFFFAOYSA-K 0.000 claims description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 abstract description 14
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 abstract description 14
- 239000011347 resin Substances 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 4
- 238000000071 blow moulding Methods 0.000 abstract description 2
- 244000005700 microbiome Species 0.000 abstract description 2
- 230000029058 respiratory gaseous exchange Effects 0.000 abstract description 2
- 241000219094 Vitaceae Species 0.000 abstract 2
- 235000021021 grapes Nutrition 0.000 abstract 2
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 235000009392 Vitis Nutrition 0.000 description 27
- 239000010408 film Substances 0.000 description 23
- 238000003860 storage Methods 0.000 description 18
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 12
- 239000007787 solid Substances 0.000 description 10
- 230000000844 anti-bacterial effect Effects 0.000 description 8
- 235000013399 edible fruits Nutrition 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 6
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 102000004190 Enzymes Human genes 0.000 description 5
- 108090000790 Enzymes Proteins 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 240000000560 Citrus x paradisi Species 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000000241 respiratory effect Effects 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 235000021028 berry Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 230000004345 fruit ripening Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229920001184 polypeptide Polymers 0.000 description 2
- 102000004196 processed proteins & peptides Human genes 0.000 description 2
- 108090000765 processed proteins & peptides Proteins 0.000 description 2
- LXNHXLLTXMVWPM-UHFFFAOYSA-N pyridoxine Chemical compound CC1=NC=C(CO)C(CO)=C1O LXNHXLLTXMVWPM-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 102100034279 Calcium-binding mitochondrial carrier protein Aralar2 Human genes 0.000 description 1
- AUNGANRZJHBGPY-UHFFFAOYSA-N D-Lyxoflavin Natural products OCC(O)C(O)C(O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-UHFFFAOYSA-N 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 208000007443 Neurasthenia Diseases 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 description 1
- 229930003471 Vitamin B2 Natural products 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000008485 antagonism Effects 0.000 description 1
- 206010003549 asthenia Diseases 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 108010084210 citrin Proteins 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- RADKZDMFGJYCBB-UHFFFAOYSA-N pyridoxal hydrochloride Natural products CC1=NC=C(CO)C(C=O)=C1O RADKZDMFGJYCBB-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229960002477 riboflavin Drugs 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 235000019164 vitamin B2 Nutrition 0.000 description 1
- 239000011716 vitamin B2 Substances 0.000 description 1
- 235000019158 vitamin B6 Nutrition 0.000 description 1
- 239000011726 vitamin B6 Substances 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 229940011671 vitamin b6 Drugs 0.000 description 1
Classifications
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Preparation And Processing Of Foods (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention relates to a preparation method for grape preservative film master batches containing rare earth complex.The grape preservative film master batches are formed by using LLDPE as carrier resin and adding tourmaline powder, the rare earth complex, kieselguhr, oleamide and sodium stearate through cladding dispersing, interface modification, material mixing, extruding and grain cutting.The molar ratio of lanthanum ions, yttrium ions, samarium ions and cerium ions in the rare earth complex is (2.90-3.00): (0.45-0.50): (0.95-1.05): (1.15-1.25).The master batches prepared through the method are added into LLDPE resin according to the proportion of 4-8%, the mixture is subjected to blow molding to form a film, and the film is used for retaining freshness of grapes and packaging the grapes and can restrain the respiration intensity and growth of microorganisms on the surface in the storing process, slow down the softening process and prolong the refreshing time by 7-10 days under the normal temperature condition.
Description
Technical field
The preparation method that the present invention relates to functional plastic film master batch, the preparation method being specifically related to a kind of grape fresh-keeping film master batch containing rare earth compounding.
Background technology
Fructus Vitis viniferae (VitisviniferaL.) Vitaceae Vitis bejuco, Fructus Vitis viniferae is one of big fruit of China four, and Fructus Vitis viniferae is not only delicious good to eat, and nutritive value is significantly high.In ripe berry, Fructus Vitis viniferae sugar content is up to 10%～30%, based on glucose.Multiple fruit acid in Fructus Vitis viniferae contributes to digestion, suitably eats a little Fructus Vitis viniferae more, can invigorating the spleen and regulating the stomach.Containing mineral calcium, potassium, phosphorus, ferrum and multivitamin B1, vitamin B2, vitamin B6, vitamin C and Citrin etc. in Fructus Vitis viniferae, possibly together with the aminoacid of multiple needed by human body, often food Fructus Vitis viniferae is of great advantage to neurasthenia, overfatigue.Fructus Vitis viniferae is one of least long keeping fruit in berries, Fructus Vitis viniferae gather easily dehydration, threshing under rearmounted room temperature, rot.The Repiration of Fructus Vitis viniferae consumes nutrition, causes fruit-vegetable quality decline, failure, weight saving, dehydration and aging.The breathing of grape fruit belongs to non-transition type, and Grape stems is the most active part of physiological activity in fruit ear, does not only belong to type of respiratory climacteric, and respiratory intensity is fruit 8～14 times.This is the main physiological that Fructus Vitis viniferae carpopodium in storage is apt to deteriorate.Fructus Vitis viniferae moisture loss during preserving is mainly evaporation, namely dehydration 3%～6% can obviously reduce fruit-vegetable quality, make that its surface shrinkage, gloss are disappeared, cell spaces increases, organize and become spongy, normal Repiration is made to be affected, promote the activity of enzyme, accelerate tissue aging and largely reducing the intrinsic storability of fruit and vegerable and premunition.In addition fungus is easily caused Fructus Vitis viniferae and rots.Therefore grape fresh-keeping storage is particularly significant.
China's rare earth resources enriches, and rare earth develops exists great potential.Rare earth and derivant thereof can as antimicrobial antistaling agents, Ca2+It is the ion maintaining antibacterial normal activity, and lanthanum ion has antagonism Ca2+Effect, so antibacterial normal activities can be interfered by lanthanum ion, cause bacterial death, in Rare Earth Lanthanum coordination antibacterial, part enhances anti-microbial property simultaneously.Cerium ion has hydrolysis, it is possible to fracture polypeptide chain, and enzyme is protein, so cerium ion makes the polypeptide chain in enzyme rupture；In addition cerium ion is to the displacement of metal ion and competition in enzyme thus have impact on the physiological function of enzyme, therefore can suppress Repiration, delaying senility by affecting enzymatic activity.Rare earth has the stronger ability removing hydroxyl radical free radical, reduces free radical and occurs, and weakens active oxygen injury, delayed fruit ripening and senescence, extends Fructus Vitis viniferae shelf life.Tourmaline Ye Shi China is rich in mineral resources, and tourmaline powder anion releasing can effective killing pathogenic bacteria.Its mechanism essentially consists in after anion is combined with antibacterial, makes antibacterial produce the change of structure or the transfer of energy, causes bacterial death.Vegetable polysaccharides is abundant Renewable resource, itself has certain antibacterial effect, and acetylizad vegetable polysaccharides has the stronger ability removing hydroxyl radical free radical.
At present, the main controlled atmosphere storage of Grape Fresh Keeping Technology, pressure regulation be fresh-keeping, electronic fresh-keeping technology, biological way of keeping fresh, cold storing and fresh-keeping, fresh chemically etc..Though physical method is nontoxic and compares effectively, but relatively costly, needs specific appointed condition, be not suitable for commonly used；And adopt chemical drugs to make antistaling agent, the problem such as residual hazard further relating to some medicine.
Summary of the invention
For the deficiency that existing grape fresh-keeping is packed.The preparation method that the invention provides the good lower-cost master batch of a kind of anti-bacterial refreshing, it is characterized in that: with LLDPE for vector resin, interpolation tourmaline powder, rare earth compounding, kieselguhr, oleamide, sodium stearate are processed by cladding dispersion, interface modification, mixing of materials, extrusion pelletizing.Master batch prepared by this method, adds in LLDPE resin with the ratio of 4～8%, after thin film is made in blowing, packs for grape fresh-keeping, can suppress respiratory intensity and surface microorganism growth in storage, and normal temperature condition prolongs storage period 7～10 days.
The technical scheme is that for realizing the purpose of the present invention
1, the preparation of rare earth compounding
(1) vegetable polysaccharides of 2 weight portions is dissolved in the acetic acid solution of 60 weight portions; after stirring, adding the methanol of 80 weight portions, solution is no longer sticky; add the acetic anhydride of 1 weight portion; after reacting 1h at temperature 30 DEG C, the thick liquid of reaction gained is joined in the ethanol of 150 weight portions, filtering precipitate after precipitation generation; with absolute ethanol washing 3 times; after dissolving with acetic acid solution again, elimination insoluble matter, obtain acetylation vegetable polysaccharides solution.
(2) according to lanthanum, yttrium, neodymium, cerium ion the ratio that mol ratio is 2.90～3.00:0.45～0.50:0.95～1.05:1.15～1.25, weigh the compound of lanthanum, the compound of yttrium, the compound of neodymium and the compound of cerium respectively and be mixed into rare earth compound, and join in distilled water with the weight part ratio of 15, obtain rare earth compound mixed aqueous solution after being entirely capable of dissolving；According to weight ratios such as vegetable polysaccharides and rare earth compounds; rare earth compound mixed aqueous solution is slowly added dropwise to acetylation vegetable polysaccharides solution; regulating reaction system pH to 7.0, react 6～7 hours under rotating speed 1000r/min, 25～30 DEG C of conditions of temperature, product precipitates out with precipitation form；Filter after precipitate, remove unreacted rare earth ion with distilled water wash, dry in vacuum drying oven, grind into powder, obtain rare earth compounding.
2, the preparation of master batch
(1) by the rare earth compounding of 21～25 weight portions, the kieselguhr of 2～3 weight portions, composite it is placed in blender, adds 1.1～1.3 weight portion oleamides, after cladding dispersion 15min, obtain raw material I；
(2) 12～14 parts by weight of tourmaline powder are placed in high-speed kneading machine and mediate after 10min, add 1.1～1.3 weight portion sodium stearates, after carrying out interface modification 20min, become raw material II；
(3) raw material II and raw material I being placed in mixer and be mixed into compound, the LLDPE mixing 10min adding 55.7～63.1 weight portions obtains mixed material；
(4) mixed material is placed in double screw extruder extrude pelletizing be master batch.Utilize blow molding machine to adopt common process condition, prepare a kind of grape fresh-keeping film containing rare earth compounding further.
Under the grape fresh-keeping film containing rare earth compounding that the present invention is prepared and widely used 20 DEG C of conditions of common preservative film on market, the Fructus Vitis viniferae rotting rate of storage, soluble solid and Fructus Vitis viniferae hardness are compared, result shows, the grape fresh-keeping film of rare earth compounding prepared by the employing present invention is in storage, the rotting rate of Fructus Vitis viniferae has difference in first 8 days but is not clearly, when the 10th day, adopting common preservative film rotting rate is 91.2%, and adopting the grape fresh-keeping film containing rare earth compounding of the present invention, the rotting rate of Fructus Vitis viniferae is only 28.7%；Soluble solid and Fructus Vitis viniferae hardness, be significantly higher than common preservative film.
Tourmaline powder of the present invention is the mixture of one or more arbitrary proportions in dravite powder, schorl powder, elbaite powder, tsilaisite powder；Described tourmaline powder particle diameter is 1.3～6.5 μm.
Acetic acid solution mass percent concentration of the present invention is 2%.
Vegetable polysaccharides of the present invention is the mixture of one or more arbitrary proportions in starch, fructose, cellulose, chitin.
The compound of lanthanum of the present invention is the one in lanthanum hydroxide, lanthanum acetate, Lanthanum (III) nitrate, lanthanum chloride.
The compound of yttrium of the present invention is the one in Yttrium trihydroxide, acetic acid yttrium, Yttrium trinitrate, Yttrium chloride(Y2Cl6).
The compound of samarium of the present invention is the one in Samarium trihydroxide., acetic acid samarium, samaric nitrate, samarium trichloride.
The compound of cerium of the present invention is the one in cerium hydroxide, cerous acetate, cerous nitrate, cerium chloride.
In cladding dispersive process of the present invention, the rotating speed of blender is 250r/min, and temperature is 102 ± 1 DEG C.
The rotating speed of interfacial modification process high speed kneader of the present invention is 500r/min, and temperature is 105 ± 1 DEG C.
In mixing of materials process of the present invention, the rotating speed of mixer is 120r/min, and temperature is 108 ± 1 DEG C.
In extrusion pelletizing process of the present invention twin-screw extruder barrel temperature control in 130～140 DEG C of I district, 145～150 DEG C of II district, 150～155 DEG C of III district, 160～165 DEG C of IV district, 155～160 DEG C of V district, die head 155～160 DEG C.
The invention has the beneficial effects as follows: the tourmaline powder that 1. adopts, rare earth, natural plant polyose aboundresources, can effectively reduce cost；2. the tourmaline powder that adopts, rare earth, natural plant polyose are harmless, the material safety prepared, and can relieved pack for fresh food；3. the tourmaline powder that adopts, rare earth, natural plant polyose itself have sterilizing fresh-keeping function, can effectively strengthen anti-bacterial refreshing effect by the mode such as modified, composite.
Accompanying drawing explanation
The sample that Fig. 1 is prepared by the embodiment of the present invention 1 packs 20 DEG C of impacts on the Fructus Vitis viniferae rotting rate of storage with common preservative film.
The sample that Fig. 2 is prepared by the embodiment of the present invention 1 packs 20 DEG C of impacts on the Fructus Vitis viniferae soluble solid of storage with common preservative film.
Fig. 3 is the impact of the Fructus Vitis viniferae hardness at the sample prepared by the embodiment of the present invention 1 packs 20 DEG C with common preservative film on storage.
Detailed description of the invention
In order to the present invention is better understood from, it is described further in conjunction with accompanying drawing.
In Fig. 1, two curves represent the rotting rate of common preservative film and the 10 days processes of storage of the grape fresh-keeping film containing rare earth compounding of the present invention respectively.As can be seen from the figure, when adopting the grape fresh-keeping film containing rare earth compounding of the present invention storage to the 3rd day, Fructus Vitis viniferae rotting rate is only 3.25%, storage was by the 10th day, rotting rate is also only 28.7, and when adopting the storage of common preservative film to the 3rd day, Fructus Vitis viniferae rotting rate is 5.25%, storage was by the 10th day, and rotting rate is up to 89.7.As shown in Figure 1.
In Fig. 2, two curves represent common preservative film and the soluble solid content of grape fruit in the 10 days processes of storage of the grape fresh-keeping film containing rare earth compounding of the present invention respectively.It can be seen that along with the prolongation of storage time, the grape fruit adopting the grape fresh-keeping film fruit grain hardness containing rare earth compounding of the present invention to pack compared to common preservative film, remain in that higher content.As shown in Figure 2.
In Fig. 3, two curves represent common preservative film and the 25 days process Fructus Vitis viniferae hardness of storage of the grape fresh-keeping film containing rare earth compounding of the present invention respectively.Although it can be seen that prolongation over time, the hardness of Fructus Vitis viniferae also gradually reduces, but the speed reduced is lower than common preservative film.As shown in Figure 3.
Embodiment 1
The component of master batch is made up of linear low density polyethylene (LLDPE) 5.94kg, tourmaline powder 1.4kg, rare earth compounding 2.2kg, kieselguhr 0.25kg, oleamide 0.11kg, sodium stearate 0.10kg.
Master batch is prepared according to the following steps:
1, the preparation of rare earth compounding
(1) 2kg chitin is dissolved in 60L acetic acid solution, after stirring, adds 80L methanol; solution is no longer sticky; add acetic anhydride 1L, after reacting 1h at temperature 30 DEG C, the thick liquid of reaction gained is joined in 150 ethanol; precipitation is had to generate; leach solid, with absolute ethanol washing 3 times, then after dissolving with acetic acid solution; elimination insoluble matter, obtains acetylation chitin solution.
(2) according to lanthanum, yttrium, neodymium, the mol ratio of cerium ion is the 2.95:0.50:0.95:1.10 Lanthanum (III) nitrate weighing total amount 2kg respectively, Yttrium trinitrate, neodymium nitrate, cerous nitrate, it is dissolved in 10L distilled water, rare earth nitrate aqueous solution is slowly added dropwise to acetylation chitin solution, control rotating speed 1000r/min, temperature 25 DEG C, react 6 hours, pH value of solution is regulated to 7.0, product precipitates out with flocculent deposit form, filter after precipitate, unreacted metal ion is removed with distilled water wash, vacuum drying oven dries, grind, obtain buff powder, it is rare earth compounding.
2, the preparation of master batch
(1) by 2.2kg rare earth compounding, 0.25kg kieselguhr, composite being placed in blender, add 0.14kg oleamide, at rotating speed 250r/min, temperature is become raw material I after carrying out cladding dispersion 15min under 102 ± 1 DEG C of conditions；
(2) being placed in high-speed kneading machine by 1.4kg tourmaline powder, be 500r/min at rotating speed, temperature is mediate after 10min under 105 ± 1 DEG C of conditions, after being placed in high-speed kneading machine to mediate 10min, adds 0.10kg sodium stearate, becomes raw material II after interface modification 20min；
(3) raw material II and raw material I are placed in mixer and are mixed into compound, add 5.94kg linear low density polyethylene (LLDPE) mixing 10min and obtain mixed material；
(4) mixed material is placed in double screw extruder, mixed material is placed in double screw extruder, controlling extruder barrel temperature: 132 DEG C of I district, 150 DEG C of II district, 155 DEG C of III district, 161 DEG C of IV district, 158 DEG C of V district, die head 160 DEG C, extrusion pelletizing is master batch.
Embodiment 2
The component of master batch is made up of linear low density polyethylene (LLDPE) 5.69kg, tourmaline powder 1.3kg, rare earth compounding 2.5kg, kieselguhr 0.30kg, oleamide 0.12kg, sodium stearate 0.09kg.
Master batch is prepared according to the following steps:
1, the preparation of rare earth compounding
(1) 2kg chitin is dissolved in 60L acetic acid solution, after stirring, adds 80L methanol; solution is no longer sticky; add acetic anhydride 1L, after reacting 1h at temperature 30 DEG C, the thick liquid of reaction gained is joined in 150 ethanol; precipitation is had to generate; leach solid, with absolute ethanol washing 3 times, then after dissolving with acetic acid solution; elimination insoluble matter, obtains acetylation chitin solution.
(2) according to lanthanum, yttrium, neodymium, the mol ratio of cerium ion is the 2.95:0.50:0.95:1.10 Lanthanum (III) nitrate weighing total amount 2kg respectively, Yttrium trinitrate, neodymium nitrate, cerous nitrate, it is dissolved in 10L distilled water, rare earth nitrate aqueous solution is slowly added dropwise to acetylation chitin solution, control rotating speed 1000r/min, temperature 25 DEG C, react 6 hours, pH value of solution is regulated to 7.0, product precipitates out with flocculent deposit form, filter after precipitate, unreacted metal ion is removed with distilled water wash, vacuum drying oven dries, grind, obtain buff powder, it is rare earth compounding.
2, the preparation of master batch
(1) by 2.5kg rare earth compounding, 0.30kg kieselguhr, composite being placed in blender, add 0.12kg oleamide, at rotating speed 250r/min, temperature is become raw material I after carrying out cladding dispersion 15min under 102 ± 1 DEG C of conditions；
(2) being placed in high-speed kneading machine by 1.3kg tourmaline powder, be 500r/min at rotating speed, temperature is mediate after 10min under 105 ± 1 DEG C of conditions, after being placed in high-speed kneading machine to mediate 10min, adds 0.09kg sodium stearate, becomes raw material II after interface modification 20min；
(3) raw material II and raw material I are placed in mixer and are mixed into compound, add 5.69kg linear low density polyethylene (LLDPE) mixing 10min and obtain mixed material；
(4) mixed material is placed in double screw extruder, mixed material is placed in double screw extruder, controlling extruder barrel temperature: 135 DEG C of I district, 150 DEG C of II district, 155 DEG C of III district, 160 DEG C of IV district, 155 DEG C of V district, die head 155 DEG C, extrusion pelletizing is master batch.
Embodiment 3
The component of master batch is made up of linear low density polyethylene (LLDPE) 5.89kg, tourmaline powder 1.2kg, rare earth compounding 2.4kg, kieselguhr 0.30kg, oleamide 0.11kg, sodium stearate 0.10kg.
Master batch is prepared according to the following steps:
1, the preparation of rare earth compounding
(1) 2kg chitin is dissolved in 60L acetic acid solution, after stirring, adds 80L methanol; solution is no longer sticky; add acetic anhydride 1L, after reacting 1h at temperature 30 DEG C, the thick liquid of reaction gained is joined in 150 ethanol; precipitation is had to generate; leach solid, with absolute ethanol washing 3 times, then after dissolving with acetic acid solution; elimination insoluble matter, obtains acetylation chitin solution.
(2) according to lanthanum, yttrium, neodymium, the mol ratio of cerium ion is the 2.95:0.50:0.95:1.10 Lanthanum (III) nitrate weighing total amount 2kg respectively, Yttrium trinitrate, neodymium nitrate, cerous nitrate, it is dissolved in 10L distilled water, rare earth nitrate aqueous solution is slowly added dropwise to acetylation chitin solution, control rotating speed 1000r/min, temperature 25 DEG C, react 6 hours, pH value of solution is regulated to 7.0, product precipitates out with flocculent deposit form, filter after precipitate, unreacted metal ion is removed with distilled water wash, vacuum drying oven dries, grind, obtain buff powder, it is rare earth compounding.
2, the preparation of master batch
(1) by 2.4kg rare earth compounding, 0.30kg kieselguhr, composite being placed in blender, add 0.14kg oleamide, at rotating speed 250r/min, temperature is become raw material I after carrying out cladding dispersion 15min under 102 ± 1 DEG C of conditions；
(2) being placed in high-speed kneading machine by 1.2kg tourmaline powder, be 500r/min at rotating speed, temperature is mediate after 10min under 105 ± 1 DEG C of conditions, after being placed in high-speed kneading machine to mediate 10min, adds 0.10kg sodium stearate, becomes raw material II after interface modification 20min；
(3) raw material II and raw material I are placed in mixer and are mixed into compound, add 5.89kg linear low density polyethylene (LLDPE) mixing 10min and obtain mixed material；
(4) mixed material is placed in double screw extruder, mixed material is placed in double screw extruder, controlling extruder barrel temperature: 130 DEG C of I district, 145 DEG C of II district, 155 DEG C of III district, 160 DEG C of IV district, 160 DEG C of V district, die head 155 DEG C, extrusion pelletizing is master batch.
Embodiment 4
The component of master batch is made up of linear low density polyethylene (LLDPE) 5.94kg, tourmaline powder 1.4kg, rare earth compounding 2.2kg, kieselguhr 0.25kg, oleamide 0.11kg, sodium stearate 0.10kg.
Master batch is prepared according to the following steps:
1, the preparation of rare earth compounding
(1) 2kg chitin is dissolved in 60L acetic acid solution, after stirring, adds 80L methanol; solution is no longer sticky; add acetic anhydride 1L, after reacting 1h at temperature 30 DEG C, the thick liquid of reaction gained is joined in 150 ethanol; precipitation is had to generate; leach solid, with absolute ethanol washing 3 times, then after dissolving with acetic acid solution; elimination insoluble matter, obtains acetylation chitin solution.
(2) according to lanthanum, yttrium, neodymium, the mol ratio of cerium ion is the 3.00:0.45:1.00:1.25 Lanthanum (III) nitrate weighing total amount 2kg respectively, Yttrium trinitrate, neodymium nitrate, cerous nitrate, it is dissolved in 10L distilled water, rare earth nitrate aqueous solution is slowly added dropwise to acetylation chitin solution, control rotating speed 1000r/min, temperature 25 DEG C, react 6 hours, pH value of solution is regulated to 7.0, product precipitates out with flocculent deposit form, filter after precipitate, unreacted metal ion is removed with distilled water wash, vacuum drying oven dries, grind, obtain buff powder, it is rare earth compounding.
2, the preparation of master batch
(1) by 2.2kg rare earth compounding, 0.25kg kieselguhr, composite being placed in blender, add 0.14kg oleamide, at rotating speed 250r/min, temperature is become raw material I after carrying out cladding dispersion 15min under 102 ± 1 DEG C of conditions；
(2) being placed in high-speed kneading machine by 1.4kg tourmaline powder, be 500r/min at rotating speed, temperature is mediate after 10min under 105 ± 1 DEG C of conditions, after being placed in high-speed kneading machine to mediate 10min, adds 0.10kg sodium stearate, becomes raw material II after interface modification 20min；
(3) raw material II and raw material I are placed in mixer and are mixed into compound, add 5.94kg linear low density polyethylene (LLDPE) mixing 10min and obtain mixed material；
(4) mixed material is placed in double screw extruder, mixed material is placed in double screw extruder, controlling extruder barrel temperature: 132 DEG C of I district, 150 DEG C of II district, 155 DEG C of III district, 161 DEG C of IV district, 158 DEG C of V district, die head 160 DEG C, extrusion pelletizing is master batch.
Embodiment 5
The component of master batch is made up of linear low density polyethylene (LLDPE) 5.69kg, tourmaline powder 1.3kg, rare earth compounding 2.5kg, kieselguhr 0.30kg, oleamide 0.12kg, sodium stearate 0.09kg.
Master batch is prepared according to the following steps:
1, the preparation of rare earth compounding
(1) 2kg chitin is dissolved in 60L acetic acid solution, after stirring, adds 80L methanol; solution is no longer sticky; add acetic anhydride 1L, after reacting 1h at temperature 30 DEG C, the thick liquid of reaction gained is joined in 150 ethanol; precipitation is had to generate; leach solid, with absolute ethanol washing 3 times, then after dissolving with acetic acid solution; elimination insoluble matter, obtains acetylation chitin solution.
(2) according to lanthanum, yttrium, neodymium, the mol ratio of cerium ion is the 3.00:0.45:1.00:1.25 Lanthanum (III) nitrate weighing total amount 2kg respectively, Yttrium trinitrate, neodymium nitrate, cerous nitrate, it is dissolved in 10L distilled water, rare earth nitrate aqueous solution is slowly added dropwise to acetylation chitin solution, control rotating speed 1000r/min, temperature 25 DEG C, react 6 hours, pH value of solution is regulated to 7.0, product precipitates out with flocculent deposit form, filter after precipitate, unreacted metal ion is removed with distilled water wash, vacuum drying oven dries, grind, obtain buff powder, it is rare earth compounding.
2, the preparation of master batch
(1) by 2.5kg rare earth compounding, 0.30kg kieselguhr, composite being placed in blender, add 0.12kg oleamide, at rotating speed 250r/min, temperature is become raw material I after carrying out cladding dispersion 15min under 102 ± 1 DEG C of conditions；
(2) being placed in high-speed kneading machine by 1.3kg tourmaline powder, be 500r/min at rotating speed, temperature is mediate after 10min under 105 ± 1 DEG C of conditions, after being placed in high-speed kneading machine to mediate 10min, adds 0.09kg sodium stearate, becomes raw material II after interface modification 20min；
(3) raw material II and raw material I are placed in mixer and are mixed into compound, add 5.69kg linear low density polyethylene (LLDPE) mixing 10min and obtain mixed material；
(4) mixed material is placed in double screw extruder, mixed material is placed in double screw extruder, controlling extruder barrel temperature: 135 DEG C of I district, 150 DEG C of II district, 155 DEG C of III district, 160 DEG C of IV district, 155 DEG C of V district, die head 155 DEG C, extrusion pelletizing is master batch.
Embodiment 6
The component of master batch is made up of linear low density polyethylene (LLDPE) 5.89kg, tourmaline powder 1.2kg, rare earth compounding 2.4kg, kieselguhr 0.30kg, oleamide 0.11kg, sodium stearate 0.10kg.
Master batch is prepared according to the following steps:
1, the preparation of rare earth compounding
(1) 2kg chitin is dissolved in 60L acetic acid solution, after stirring, adds 80L methanol; solution is no longer sticky; add acetic anhydride 1L, after reacting 1h at temperature 30 DEG C, the thick liquid of reaction gained is joined in 150 ethanol; precipitation is had to generate; leach solid, with absolute ethanol washing 3 times, then after dissolving with acetic acid solution; elimination insoluble matter, obtains acetylation chitin solution.
(2) according to lanthanum, yttrium, neodymium, the mol ratio of cerium ion is the 3.00:0.45:1.00:1.25 Lanthanum (III) nitrate weighing total amount 2kg respectively, Yttrium trinitrate, neodymium nitrate, cerous nitrate, it is dissolved in 10L distilled water, rare earth nitrate aqueous solution is slowly added dropwise to acetylation chitin solution, control rotating speed 1000r/min, temperature 25 DEG C, react 6 hours, pH value of solution is regulated to 7.0, product precipitates out with flocculent deposit form, filter after precipitate, unreacted metal ion is removed with distilled water wash, vacuum drying oven dries, grind, obtain buff powder, it is rare earth compounding.
2, the preparation of master batch
(1) by 2.4kg rare earth compounding, 0.30kg kieselguhr, composite being placed in blender, add 0.14kg oleamide, at rotating speed 250r/min, temperature is become raw material I after carrying out cladding dispersion 15min under 102 ± 1 DEG C of conditions；
(2) being placed in high-speed kneading machine by 1.2kg tourmaline powder, be 500r/min at rotating speed, temperature is mediate after 10min under 105 ± 1 DEG C of conditions, after being placed in high-speed kneading machine to mediate 10min, adds 0.10kg sodium stearate, becomes raw material II after interface modification 20min；
(3) raw material II and raw material I are placed in mixer and are mixed into compound, add 5.89kg linear low density polyethylene (LLDPE) mixing 10min and obtain mixed material；
(4) mixed material is placed in double screw extruder, mixed material is placed in double screw extruder, controlling extruder barrel temperature: 130 DEG C of I district, 145 DEG C of II district, 155 DEG C of III district, 160 DEG C of IV district, 160 DEG C of V district, die head 155 DEG C, extrusion pelletizing is master batch.
Claims (9)
1. a preparation method for the grape fresh-keeping film master batch containing rare earth compounding, is characterized in that:
The preparation of rare earth compounding:
(1) vegetable polysaccharides of 2 weight portions is dissolved in the acetic acid solution of 60 weight portions; after stirring, adding the methanol of 80 weight portions, solution is no longer sticky; add the acetic anhydride of 1 weight portion; after reacting 1h at temperature 30 DEG C, the thick liquid of reaction gained is joined in the ethanol of 150 weight portions, filtering precipitate after precipitation generation; with absolute ethanol washing 3 times; after dissolving with acetic acid solution again, elimination insoluble matter, obtain acetylation vegetable polysaccharides solution；
(2) according to lanthanum, yttrium, neodymium, cerium ion the ratio that mol ratio is 2.90～3.00:0.45～0.50:0.95～1.05:1.15～1.25, weigh the compound of lanthanum, the compound of yttrium, the compound of neodymium and the compound of cerium respectively and be mixed into rare earth compound, and join in distilled water with the weight part ratio of 15, obtain rare earth compound mixed aqueous solution after being entirely capable of dissolving；According to weight ratios such as vegetable polysaccharides and rare earth compounds; rare earth compound mixed aqueous solution is slowly added dropwise to acetylation vegetable polysaccharides solution; regulating reaction system pH to 7.0, react 6～7 hours under rotating speed 1000r/min, 25～30 DEG C of conditions of temperature, product precipitates out with precipitation form；Filter after precipitate, remove unreacted rare earth ion with distilled water wash, dry in vacuum drying oven, grind into powder, obtain rare earth compounding；
The preparation of master batch:
(1) by the rare earth compounding of 21～25 weight portions, the kieselguhr of 2～3 weight portions, composite it is placed in blender, adds 1.1～1.3 weight portion oleamides, after cladding dispersion 15min, obtain raw material I；
(2) 12～14 parts by weight of tourmaline powder are placed in high-speed kneading machine and mediate after 10min, add 1.1～1.3 weight portion sodium stearates, after carrying out interface modification 20min, become raw material II；
(3) raw material II and raw material I being placed in mixer and be mixed into compound, the LLDPE mixing 10min adding 55.7～63.1 weight portions obtains mixed material；
(4) mixed material is placed in double screw extruder extrude pelletizing be master batch.
2. the preparation method of a kind of grape fresh-keeping film master batch containing rare earth compounding according to claim 1, is characterized in that the mixture that described tourmaline powder is one or more arbitrary proportions in dravite powder, schorl powder, elbaite powder, tsilaisite powder；Described tourmaline powder particle diameter is 1.3～6.5 μm.
3. the preparation method of a kind of grape fresh-keeping film master batch containing rare earth compounding according to claim 1, is characterized in that described acetic acid solution mass percent concentration is 2%.
4. the preparation method of a kind of grape fresh-keeping film master batch containing rare earth compounding according to claim 1, is characterized in that the mixture that described vegetable polysaccharides is one or more arbitrary proportions in starch, fructose, cellulose, chitin.
5. the preparation method of a kind of grape fresh-keeping film master batch containing rare earth compounding according to claim 1, is characterized in that the compound of described lanthanum is the one in lanthanum hydroxide, lanthanum acetate, Lanthanum (III) nitrate, lanthanum chloride；The compound of described yttrium is the one in Yttrium trihydroxide, acetic acid yttrium, Yttrium trinitrate, Yttrium chloride(Y2Cl6)；The compound of samarium of the present invention is the one in Samarium trihydroxide., acetic acid samarium, samaric nitrate, samarium trichloride；The compound of cerium of the present invention is the one in cerium hydroxide, cerous acetate, cerous nitrate, cerium chloride.
6. the preparation method of a kind of grape fresh-keeping film master batch containing rare earth compounding according to claim 1, is characterized in that in described cladding dispersive process, the rotating speed of blender is 250r/min, and temperature is 102 ± 1 DEG C.
7. the preparation method of a kind of grape fresh-keeping film master batch containing rare earth compounding according to claim 1, is characterized in that the rotating speed of described interfacial modification process high speed kneader is 500r/min, and temperature is 105 ± 1 DEG C.
8. the preparation method of a kind of grape fresh-keeping film master batch containing rare earth compounding according to claim 1, is characterized in that in described mixing of materials process, the rotating speed of mixer is 120r/min, and temperature is 108 ± 1 DEG C.
9. the preparation method of a kind of grape fresh-keeping film master batch containing rare earth compounding according to claim 1, it is characterized in that in described extrusion pelletizing process, twin-screw extruder barrel temperature controls in 130～140 DEG C of I district, 145～150 DEG C of II district, 150～155 DEG C of III district, 160～165 DEG C of IV district, 155～160 DEG C of V district, die head 155～160 DEG C.
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