CN112980167A - Degradable agricultural mulching film and preparation method thereof - Google Patents
Degradable agricultural mulching film and preparation method thereof Download PDFInfo
- Publication number
- CN112980167A CN112980167A CN202110219604.5A CN202110219604A CN112980167A CN 112980167 A CN112980167 A CN 112980167A CN 202110219604 A CN202110219604 A CN 202110219604A CN 112980167 A CN112980167 A CN 112980167A
- Authority
- CN
- China
- Prior art keywords
- borate
- mulching film
- temperature
- powder
- film
- Prior art date
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 47
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 36
- 239000004626 polylactic acid Substances 0.000 claims abstract description 36
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 7
- 239000005060 rubber Substances 0.000 claims abstract description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052796 boron Inorganic materials 0.000 claims abstract description 6
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 6
- 239000000945 filler Substances 0.000 claims abstract description 6
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 5
- 239000000314 lubricant Substances 0.000 claims abstract description 5
- 239000004014 plasticizer Substances 0.000 claims abstract description 5
- 239000002250 absorbent Substances 0.000 claims abstract description 3
- 230000002745 absorbent Effects 0.000 claims abstract description 3
- 230000003449 preventive effect Effects 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 47
- 238000000071 blow moulding Methods 0.000 claims description 33
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 241000196324 Embryophyta Species 0.000 claims description 16
- 229910021538 borax Inorganic materials 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 14
- 238000007664 blowing Methods 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 10
- 238000010096 film blowing Methods 0.000 claims description 10
- 238000005469 granulation Methods 0.000 claims description 10
- 230000003179 granulation Effects 0.000 claims description 10
- 238000004804 winding Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 239000004328 sodium tetraborate Substances 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 229920002472 Starch Polymers 0.000 claims description 8
- 239000008107 starch Substances 0.000 claims description 7
- 235000019698 starch Nutrition 0.000 claims description 7
- CHHHXKFHOYLYRE-UHFFFAOYSA-M 2,4-Hexadienoic acid, potassium salt (1:1), (2E,4E)- Chemical compound [K+].CC=CC=CC([O-])=O CHHHXKFHOYLYRE-UHFFFAOYSA-M 0.000 claims description 6
- 229920002907 Guar gum Polymers 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 239000000665 guar gum Substances 0.000 claims description 6
- 235000010417 guar gum Nutrition 0.000 claims description 6
- 229960002154 guar gum Drugs 0.000 claims description 6
- 235000010241 potassium sorbate Nutrition 0.000 claims description 6
- 239000004302 potassium sorbate Substances 0.000 claims description 6
- 229940069338 potassium sorbate Drugs 0.000 claims description 6
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 6
- 229920001285 xanthan gum Polymers 0.000 claims description 6
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 5
- 235000003261 Artemisia vulgaris Nutrition 0.000 claims description 4
- 240000006891 Artemisia vulgaris Species 0.000 claims description 4
- 241001474374 Blennius Species 0.000 claims description 4
- 244000056139 Brassica cretica Species 0.000 claims description 4
- 235000003351 Brassica cretica Nutrition 0.000 claims description 4
- 235000003343 Brassica rupestris Nutrition 0.000 claims description 4
- QFOHBWFCKVYLES-UHFFFAOYSA-N Butylparaben Chemical compound CCCCOC(=O)C1=CC=C(O)C=C1 QFOHBWFCKVYLES-UHFFFAOYSA-N 0.000 claims description 4
- 244000275012 Sesbania cannabina Species 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- AUTNMGCKBXKHNV-UHFFFAOYSA-P diazanium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [NH4+].[NH4+].O1B([O-])OB2OB([O-])OB1O2 AUTNMGCKBXKHNV-UHFFFAOYSA-P 0.000 claims description 4
- 235000010228 ethyl p-hydroxybenzoate Nutrition 0.000 claims description 4
- 239000004403 ethyl p-hydroxybenzoate Substances 0.000 claims description 4
- NUVBSKCKDOMJSU-UHFFFAOYSA-N ethylparaben Chemical compound CCOC(=O)C1=CC=C(O)C=C1 NUVBSKCKDOMJSU-UHFFFAOYSA-N 0.000 claims description 4
- 235000010460 mustard Nutrition 0.000 claims description 4
- QELSKZZBTMNZEB-UHFFFAOYSA-N propylparaben Chemical compound CCCOC(=O)C1=CC=C(O)C=C1 QELSKZZBTMNZEB-UHFFFAOYSA-N 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 3
- 229940043351 ethyl-p-hydroxybenzoate Drugs 0.000 claims description 3
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 claims description 3
- 235000010232 propyl p-hydroxybenzoate Nutrition 0.000 claims description 3
- 239000004405 propyl p-hydroxybenzoate Substances 0.000 claims description 3
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 claims description 3
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 claims description 3
- 239000000230 xanthan gum Substances 0.000 claims description 3
- 235000010493 xanthan gum Nutrition 0.000 claims description 3
- 229940082509 xanthan gum Drugs 0.000 claims description 3
- HJVAFZMYQQSPHF-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;boric acid Chemical compound OB(O)O.OCCN(CCO)CCO HJVAFZMYQQSPHF-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- BCZXFFBUYPCTSJ-UHFFFAOYSA-L Calcium propionate Chemical compound [Ca+2].CCC([O-])=O.CCC([O-])=O BCZXFFBUYPCTSJ-UHFFFAOYSA-L 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004287 Dehydroacetic acid Substances 0.000 claims description 2
- 241000522215 Dipteryx odorata Species 0.000 claims description 2
- 235000019738 Limestone Nutrition 0.000 claims description 2
- 240000006240 Linum usitatissimum Species 0.000 claims description 2
- 235000004431 Linum usitatissimum Nutrition 0.000 claims description 2
- 229920000161 Locust bean gum Polymers 0.000 claims description 2
- OTRAYOBSWCVTIN-UHFFFAOYSA-N OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N Chemical compound OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N OTRAYOBSWCVTIN-UHFFFAOYSA-N 0.000 claims description 2
- ANYOWCGQTZYSBH-UHFFFAOYSA-N OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N Chemical compound OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N ANYOWCGQTZYSBH-UHFFFAOYSA-N 0.000 claims description 2
- DOVLHZIEMGDZIW-UHFFFAOYSA-N [Cu+3].[O-]B([O-])[O-] Chemical compound [Cu+3].[O-]B([O-])[O-] DOVLHZIEMGDZIW-UHFFFAOYSA-N 0.000 claims description 2
- XLLZUKPXODPNPP-UHFFFAOYSA-N [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] XLLZUKPXODPNPP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 claims description 2
- QBLDFAIABQKINO-UHFFFAOYSA-N barium borate Chemical compound [Ba+2].[O-]B=O.[O-]B=O QBLDFAIABQKINO-UHFFFAOYSA-N 0.000 claims description 2
- MGFANRQPPVHYBW-UHFFFAOYSA-N barium(2+);boric acid;hydrogen borate Chemical compound [Ba+2].OB(O)O.OB(O)O.OB([O-])[O-] MGFANRQPPVHYBW-UHFFFAOYSA-N 0.000 claims description 2
- XBJJRSFLZVLCSE-UHFFFAOYSA-N barium(2+);diborate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]B([O-])[O-].[O-]B([O-])[O-] XBJJRSFLZVLCSE-UHFFFAOYSA-N 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 229960004365 benzoic acid Drugs 0.000 claims description 2
- 235000010331 calcium propionate Nutrition 0.000 claims description 2
- 239000004330 calcium propionate Substances 0.000 claims description 2
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 claims description 2
- 235000011132 calcium sulphate Nutrition 0.000 claims description 2
- 235000010261 calcium sulphite Nutrition 0.000 claims description 2
- ILOKQJWLMPPMQU-UHFFFAOYSA-N calcium;oxido(oxo)borane Chemical compound [Ca+2].[O-]B=O.[O-]B=O ILOKQJWLMPPMQU-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 235000019258 dehydroacetic acid Nutrition 0.000 claims description 2
- 229940061632 dehydroacetic acid Drugs 0.000 claims description 2
- JEQRBTDTEKWZBW-UHFFFAOYSA-N dehydroacetic acid Chemical compound CC(=O)C1=C(O)OC(C)=CC1=O JEQRBTDTEKWZBW-UHFFFAOYSA-N 0.000 claims description 2
- PGRHXDWITVMQBC-UHFFFAOYSA-N dehydroacetic acid Natural products CC(=O)C1C(=O)OC(C)=CC1=O PGRHXDWITVMQBC-UHFFFAOYSA-N 0.000 claims description 2
- HQYGGVLSRVLMEE-UHFFFAOYSA-N dimagnesium dioxidoboranyloxy(dioxido)borane Chemical compound [Mg+2].[Mg+2].[O-]B([O-])OB([O-])[O-] HQYGGVLSRVLMEE-UHFFFAOYSA-N 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- OPGYRRGJRBEUFK-UHFFFAOYSA-L disodium;diacetate Chemical compound [Na+].[Na+].CC([O-])=O.CC([O-])=O OPGYRRGJRBEUFK-UHFFFAOYSA-L 0.000 claims description 2
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000451 gelidium spp. gum Substances 0.000 claims description 2
- 239000010440 gypsum Substances 0.000 claims description 2
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- 239000003112 inhibitor Substances 0.000 claims description 2
- ZPPSOOVFTBGHBI-UHFFFAOYSA-N lead(2+);oxido(oxo)borane Chemical compound [Pb+2].[O-]B=O.[O-]B=O ZPPSOOVFTBGHBI-UHFFFAOYSA-N 0.000 claims description 2
- 239000006028 limestone Substances 0.000 claims description 2
- 239000000711 locust bean gum Substances 0.000 claims description 2
- 235000010420 locust bean gum Nutrition 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- YZUWTDQUEUJLAR-UHFFFAOYSA-N magnesium;boron;oxygen(2-) Chemical compound [B].[O-2].[Mg+2] YZUWTDQUEUJLAR-UHFFFAOYSA-N 0.000 claims description 2
- LOCZQLKNTOXJDV-UHFFFAOYSA-N magnesium;oxido(oxo)borane Chemical compound [Mg+2].[O-]B=O.[O-]B=O LOCZQLKNTOXJDV-UHFFFAOYSA-N 0.000 claims description 2
- AAWVBZMCMMRKSG-UHFFFAOYSA-N manganese(2+);tetraborate Chemical compound [Mn+2].[Mn+2].[Mn+2].[Mn+2].[Mn+2].[Mn+2].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] AAWVBZMCMMRKSG-UHFFFAOYSA-N 0.000 claims description 2
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- 239000004292 methyl p-hydroxybenzoate Substances 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- PYUBPZNJWXUSID-UHFFFAOYSA-N pentadecapotassium;pentaborate Chemical compound [K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] PYUBPZNJWXUSID-UHFFFAOYSA-N 0.000 claims description 2
- VPOLVWCUBVJURT-UHFFFAOYSA-N pentadecasodium;pentaborate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] VPOLVWCUBVJURT-UHFFFAOYSA-N 0.000 claims description 2
- JVUYWILPYBCNNG-UHFFFAOYSA-N potassium;oxido(oxo)borane Chemical compound [K+].[O-]B=O JVUYWILPYBCNNG-UHFFFAOYSA-N 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 2
- 235000010234 sodium benzoate Nutrition 0.000 claims description 2
- 239000004299 sodium benzoate Substances 0.000 claims description 2
- 229960003885 sodium benzoate Drugs 0.000 claims description 2
- 235000017454 sodium diacetate Nutrition 0.000 claims description 2
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
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- IJJNTMLAAKKCML-UHFFFAOYSA-N tribenzyl borate Chemical compound C=1C=CC=CC=1COB(OCC=1C=CC=CC=1)OCC1=CC=CC=C1 IJJNTMLAAKKCML-UHFFFAOYSA-N 0.000 claims description 2
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 claims description 2
- BOOITXALNJLNMB-UHFFFAOYSA-N tricyclohexyl borate Chemical compound C1CCCCC1OB(OC1CCCCC1)OC1CCCCC1 BOOITXALNJLNMB-UHFFFAOYSA-N 0.000 claims description 2
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 claims description 2
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- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 claims description 2
- RTMBXAOPKJNOGZ-UHFFFAOYSA-N tris(2-methylphenyl) borate Chemical compound CC1=CC=CC=C1OB(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C RTMBXAOPKJNOGZ-UHFFFAOYSA-N 0.000 claims description 2
- YZYKZHPNRDIPFA-UHFFFAOYSA-N tris(trimethylsilyl) borate Chemical compound C[Si](C)(C)OB(O[Si](C)(C)C)O[Si](C)(C)C YZYKZHPNRDIPFA-UHFFFAOYSA-N 0.000 claims description 2
- ZMCWFMOZBTXGKI-UHFFFAOYSA-N tritert-butyl borate Chemical compound CC(C)(C)OB(OC(C)(C)C)OC(C)(C)C ZMCWFMOZBTXGKI-UHFFFAOYSA-N 0.000 claims description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 2
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- ZYGAMJLTPLERBC-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid propan-2-ol Chemical compound B(O)(O)OC(C)(C)C(C)(C)O.C(C)(C)O ZYGAMJLTPLERBC-UHFFFAOYSA-N 0.000 claims 1
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- CNVULGHYDPMIHD-UHFFFAOYSA-L bis[(2-hydroxybenzoyl)oxy]lead Chemical compound [Pb+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O CNVULGHYDPMIHD-UHFFFAOYSA-L 0.000 description 1
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- HEYYNPBHZQPMJJ-UHFFFAOYSA-L dibenzoyloxylead Chemical compound C=1C=CC=CC=1C(=O)O[Pb]OC(=O)C1=CC=CC=C1 HEYYNPBHZQPMJJ-UHFFFAOYSA-L 0.000 description 1
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- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
- PHNWGDTYCJFUGZ-UHFFFAOYSA-L hexyl phosphate Chemical compound CCCCCCOP([O-])([O-])=O PHNWGDTYCJFUGZ-UHFFFAOYSA-L 0.000 description 1
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- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 1
- YJOMWQQKPKLUBO-UHFFFAOYSA-L lead(2+);phthalate Chemical compound [Pb+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O YJOMWQQKPKLUBO-UHFFFAOYSA-L 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G13/00—Protecting plants
- A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
- A01G13/0256—Ground coverings
- A01G13/0268—Mats or sheets, e.g. nets or fabrics
- A01G13/0275—Films
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- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- 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
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
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- 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
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
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- 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
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/04—Alginic acid; Derivatives thereof
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- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- 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
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- Polymers & Plastics (AREA)
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- General Health & Medical Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
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- Biological Depolymerization Polymers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a degradable agricultural mulching film and a preparation method thereof. The agricultural mulching film consists of film-grade polylactic acid, plant rubber powder, a boron crosslinking agent, an antibacterial mildew preventive, a plasticizer, a lubricant, a heat stabilizer, an antioxidant, an ultraviolet absorbent and a filler, has good biodegradability, can reach 80 percent of degradation rate in soil in 90 days, can be completely degraded in 120 days, does not pollute the environment, is safe and environment-friendly, avoids white pollution, and meets the requirements of social sustainable development; in addition, the mulching film has the advantages of high strength, good toughness and good ultraviolet resistance, can show extensibility and high ductility, fully meets the agricultural production requirements, and has a very good popularization and application prospect.
Description
Technical Field
The invention belongs to the technical field of agricultural films, and particularly relates to a degradable agricultural mulching film and a preparation method thereof.
Background
An agricultural film is a film used for surface covering in agricultural production. The organic fertilizer can not only improve the soil temperature and maintain the soil fertility and water and soil, but also has the functions of controlling weeds, preventing and treating plant diseases and insect pests, controlling drought and waterlogging, inhibiting salt, improving near-surface photo-thermal conditions, maintaining the sanitation and cleanness of agricultural products and the like. It can effectively promote the growth and development of crops, increase yield and raise agricultural benefits. The use of the mulching film technology helps agricultural yield and production efficiency to double, enables productivity to realize leap, and simultaneously changes an agricultural production mode to be used as a 'white revolution' of agriculture. Since the introduction of plastic film covering technology into China in the 20 th century and the 80 th era, plastic films such as PVC, PE and the like are widely applied in China agriculture, the use of the plastic films is rapidly increased, and the plastic films help agricultural production to achieve the effects of saving water, increasing the yield and increasing the agricultural income. With the development of economy and the adjustment of rural industrial structure, the market demand of the rural industry in China on plastic films is continuously rising. In the development of agriculture, plastic film covering technology has important significance in stabilizing high agricultural yield. Meanwhile, in order to meet the requirements of various aspects of agricultural production, the agricultural plastic film has various varieties and specifications, is widely applied to the field of plastic greenhouses in the rural planting industry, utilizes the plastic greenhouses to carry out facility cultivation of vegetables, flowers and the like, plays a special important role in relieving the supply-demand contradiction of vegetables in off season, and has remarkable social benefit and practical huge economic benefit.
However, although the mulching film technology can well play roles in heat preservation, moisture preservation, yield increase, income increase and the like, agricultural mulching films in China mainly take petroleum-based high-molecular polymers as main components, and the main components are polypropylene, polyvinyl chloride and the like. These materials are not easily degraded and are very stable. They are difficult to degrade by light and heat under natural conditions, and microorganisms are also difficult to degrade, with complete degradation taking 200 to 400 years. After the plastic film is used for a period of time, the plastic film can scatter in the field, so that not only is the visual pollution caused, but also the accumulation of residual plastic film in soil cultivation is more serious, so that the soil is compacted, the permeability is poor, the water flow and root system development of crops are hindered, and finally the yield of the crops is reduced. Domestic and foreign researches show that the plastic agricultural film is not permeable and is easy to generate high temperature, which causes burning, heatstroke, mould propagation, pest damage and the like of crop seedlings, the thickness of the agricultural film is generally less than 0.02 mm, and the recycling is difficult to implement. The plastic agricultural film contains heavy metals such as lead and cadmium, and can affect human health through a food chain after long-term accumulation. The livestock die from poisoning by eating residual membranes by mistake; incorrect treatment methods, such as incineration and release of toxic gases, have a great impact on agricultural production and the ecological environment. By developing the film material which can be directly degraded on site, the pollution caused by the non-degradable plastic film can be overcome, and the cost of the time, the labor force and the like for recovering the mulching film is saved.
The degradable plastic film on the market at present belongs to an additive type degradable plastic film, for example, components (starch, calcium carbonate and the like) which can trigger plastics to degrade are added into a plastic matrix. However, the degradable plastic film has poor processing performance, the physical property and the appearance of the manufactured plastic film product are poor, certain fixed conditions are required for degradation, the degradability is poor, and after the plastic film is discarded, the plastic film is either placed in a closed garbage disposal system or exposed in a natural environment with unfixed conditions, and the fixed conditions required for degradation of the plastic film are difficult to achieve, so that the plastic film cannot be well degraded in the garbage disposal system or the natural environment due to condition limitation.
Polylactic acid (PLA) polylactic acid, also known as polylactide, is a polyester polymer obtained by polymerizing lactic acid as a main raw material, is a novel biodegradable material, and is made from a starch raw material provided by a renewable plant resource (such as corn). The starch raw material is saccharified to obtain glucose, the glucose and a certain strain are fermented to prepare high-purity lactic acid, and polylactic acid with a certain molecular weight is synthesized by a chemical synthesis method, so that the polylactic acid has good biodegradability, a film product prepared from the polylactic acid has stable performance at normal temperature, can be automatically decomposed at the ambient temperature of more than 55 ℃ or under the action of oxygen enrichment and microorganisms, and the waste polylactic acid film can be completely degraded by microorganisms in the nature to finally generate carbon dioxide and water without polluting the environment, so that the polylactic acid film is very favorable for protecting the environment and is a well-known environment-friendly material. The polylactic acid plastic is buried in soil for degradation, generated carbon dioxide directly enters soil organic matters or is absorbed by plants, and is not discharged into the air, so that the greenhouse effect is not caused, but the fracture elongation, the tear strength and the fracture strength of the polylactic acid plastic are lower, so that the polylactic acid plastic has the defects of poor toughness, high brittleness, easy bending deformation, poor impact resistance, poor flexibility and poor elasticity in the use process of being used as an agricultural mulching film, and the application of the polylactic acid plastic in the fields with higher requirements on the flexibility of films, sheets and the like is influenced. In the actual use process, the agricultural mulching film in the prior art is usually very thin, the ductility is relatively weak, people can pull the film in the process of installing and using the plastic film in the greenhouse, or when the wind power level is high, the plastic film is not resistant to pulling and is easy to break, the whole film is further broken under the action of tension, and the actual physical property requirements of the final product cannot be met by using the polylactic acid film which is not modified as the agricultural mulching film.
In the prior art, in order to ensure the film performance, a polylactic acid film and polyethylene are directly blended and blown to form a degradable plastic film, but the degradability of the film is reduced due to the fact that the polyethylene is mixed in raw materials, the full degradation cannot be achieved, and the film and the polyethylene have poor toughness due to the compatibility problem.
The vegetable gum is a kind of natural vegetable gum newly developed in China, is prepared from the prolific vegetable beans, and mainly comprises galactomannan, protein, cellulose, moisture, a small amount of inorganic elements such as calcium, magnesium and the like. The vegetable gum has good water solubility and crosslinking property and high viscosity, and can be widely applied to industries such as petroleum, paper making, food, textile, building and the like. The vegetable gum is not dissolved in any organic solvent such as ethanol, glycerol, formamide and the like, and water is the only solvent of the vegetable gum. The plant glue powder can swell and hydrate to form high-viscosity sol liquid when meeting water, the viscosity of the sol liquid is obviously increased along with the increase of the concentration of the powder, the plant glue liquid belongs to non-Newtonian fluid, and the viscosity of the sol liquid is reduced along with the increase of the shearing speed. The hydrated vegetable gum can generate a crosslinking effect with a plurality of chemical reagents such as borax, dichromate and the like to form non-Newtonian water-based gel with certain viscoelasticity, thereby endowing the base material with good ductility. Besides viscosity, the vegetable gum has strong salt resistance, is not influenced by cations and anions, is non-ionic and does not produce salting-out phenomenon. Meanwhile, the natural property of the vegetable gum reaches 80%, and the vegetable gum is non-toxic and pollution-free, and researches show that the vegetable gum can stop pollution indexes from reaching about 60% in civil use, is a pure natural, green and harmless novel environment-friendly product, and can prevent harmful substances from being generated in the film decomposition process. The plant gum is widely applied to paper making, building, decoration, petrochemical industry and textile industry due to the high molecular characteristics of the plant gum, but the application of the plant gum in the agricultural mulching film industry is rarely reported.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a degradable agricultural mulching film and a preparation method thereof, and solves the problems in the background technology.
One of the technical schemes adopted by the invention for solving the technical problems is as follows: the degradable agricultural mulching film is provided and comprises the following components in parts by weight:
in the invention, the polylactic acid comprises one or more of polymers of lactic acid and copolymers containing lactic acid, and the density is 1.2-1.4g/cm3The tensile strength is 40-60MPa, the elongation at break is 4-10%, the weight average molecular weight is 15-20 ten thousand, the melt index is 5-15, the melting point is 155-185 ℃, and the processing temperature is 170-230 ℃. The chemical structural formula of the polylactic acid is shown as follows:
in a preferred embodiment of the invention, the composition comprises the following components in parts by weight:
in a preferred embodiment of the invention, the plant rubber powder is at least one of xanthan gum powder, sesbania gum powder, guar gum powder, flax gum powder, tonka bean gum powder, agar gum powder, locust bean gum powder and seaweed gum powder.
The boron crosslinking agent is selected from ammonium borate, sodium borate, magnesium borate, aluminum borate, potassium borate, calcium borate, copper borate, zinc borate, lead borate, barium borate, ammonium metaborate, sodium metaborate, magnesium metaborate, aluminum metaborate, potassium metaborate, calcium metaborate, copper metaborate, zinc metaborate, barium metaborate, magnesium diborate, barium triborate, borax, manganese tetraborate, sodium pentaborate, ammonium pentaborate, potassium pentaborate, magnesium hexaborate, sodium octaborate, diammonium tetraborate, diammonium octaborate, borax, trimethyl borate, triethyl borate, triisopropyl borate, tri-tert-butyl borate, triphenyl borate, tricresyl borate, tribenzyl borate, tricyclohexyl borate, tris (trimethylsilyl) borate, isoproxolanol borate, triethanolamine borate, and the like. Wherein, the boron crosslinking agent is preferably sodium borate, borax, trimethyl borate, triethyl borate or triisopropyl borate.
The antibacterial and antifungal agent can inhibit the activity of microorganisms and provide antibacterial and antifungal effects, and is selected from benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, calcium propionate, dehydroacetic acid and its sodium salt, methyl paraben, ethyl paraben, propyl paraben, butyl paraben, sodium diacetate, mustard extract, mugwort, etc. The antibacterial and antifungal agent is preferably potassium sorbate, ethyl p-hydroxybenzoate, propyl p-hydroxybenzoate, butyl p-hydroxybenzoate, semen Brassicae Junceae extract, and folium Artemisiae Argyi.
The plasticizer is capable of increasing the plasticity of the polymer film, so that the elongation, flexibility and flexibility of the polymer film are improved, and is selected from dibutyl phthalate, dioctyl phthalate, diisooctyl phthalate, diheptyl phthalate, diisodecyl phthalate, diisononyl phthalate, butylbenzyl phthalate, butyl glycolate phthalate, dicyclohexyl phthalate, bis (tridecyl) phthalate, bis (2-ethyl) hexyl terephthalate, tricresyl phosphate, diphenyl-2-ethyl) hexyl phosphate, bis (2-ethyl) hexyl adipate, bis (2-ethyl) hexyl sebacate, glycerol, ethylene glycol, polyethylene glycol, epoxy glyceride, epoxy fatty acid monoester, epoxy tetrahydrophthalate, epoxy soybean oil, Epoxy linseed oil, 2-ethylhexyl epoxy stearate, 2-ethylhexyl epoxy soybean oleate, di (2-ethyl) hexyl 4, 5-epoxy tetrahydrophthalate, methyl epoxy acetylricinoleate, ethylene glycol C5-9 acid ester, triethylene glycol C5-9 acid ester, greening paraffin, chlorinated fatty acid ester, 1, 2-propylene glycol diacid polyester, 1, 2-propylene glycol sebacate polyester, phenyl petroleum sulfonate, trimellitate, citrate, pentaerythritol, dipentaerythritol, and the like. Among them, the plasticizer is preferably dioctyl phthalate (DOP), dibutyl phthalate (DBP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), tricresyl phosphate (TCP), epoxidized soybean oil, epoxidized linseed oil, glycerin, ethylene glycol, polyethylene glycol.
The lubricant is selected from the group consisting of paraffin wax, microcrystalline wax, liquid paraffin, low molecular weight polyethylene, oxidized polyethylene wax, stearic acid, fatty acid lower alcohol esters, fatty acid polyol esters, natural waxes, ester waxes and saponified waxes, stearamide or stearamide, oleamide or oleamide, erucamide, N' -ethylene bis stearamide, stearyl alcohol, cetyl alcohol, pentaerythritol, lead stearate, calcium stearate, barium stearate, magnesium stearate, zinc stearate, and the like. Among them, the lubricant is preferably paraffin wax, liquid paraffin wax, stearic acid, fatty acid polyol ester, stearamide or stearamide.
The heat stabilizer is selected from triphenyl phosphite, tribasic lead sulfate, dibasic lead phosphite, dibasic lead stearate, dibasic lead benzoate, tribasic lead maleate, lead stearate, lead salicylate, dibasic lead phthalate, basic lead carbonate, cadmium stearate, barium stearate, calcium stearate, lead stearate, zinc stearate, di-n-butyltin dilaurate, di-n-octyltin dilaurate, di (n) -butyltin maleate, mono-octyl di-n-octyltin dimaleate, di-n-octyltin dimaptoacetate, Jingtin C-102, isooctyl dimcthanolate, dimethyltin dithiolate and compound thereof, pentaerythritol, xylitol, mannitol, sorbitol, trimethylolpropane and the like. Among them, triphenyl phosphite, barium stearate, calcium stearate, di-n-butyltin dilaurate, and di (n) -butyltin maleate are preferable as the heat stabilizer.
The antioxidant is selected from 2, 6-di-tert-butyl-4-methylphenol, 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2 ' -methylenebis (4-methyl-6-tert-butylphenol), 4 ' -thiobis- [ 3-methyl-6-tert-butylphenol ], 2 ' -thiobis- [ 4-methyl-6-tert-butylphenol ], 1,3, 5-bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] -hexahydro-s-triazine, tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -triisocyanate, N ' -di (. beta. -naphthyl) p-phenylenediamine, N ' -diphenyl-p-phenylenediamine, N-phenyl-N ' -cyclohexyl-p-phenylenediamine, dilauryl thiodipropionate, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, triphenyl phosphite, trisnonylphenyl phosphite, tris [ 2.4-di-tert-butylphenyl ] phosphite, diethyleneglycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], and the like. Among them, the antioxidant is preferably dibutylhydroxytoluene (BHT), tert-butylhydroquinone (TBHQ), tris [2, 4-di-tert-butylphenyl ] phosphite (antioxidant 168), tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester (antioxidant 1010), diethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ] (antioxidant 245), and antioxidant Chinox 20N.
The ultraviolet light absorber is selected from 2, 4-dihydroxy benzophenone, 2-hydroxy-4-methoxy benzophenone, 2-hydroxy-4-n-octyloxy benzophenone, phenyl o-hydroxybenzoate, resorcinol monobenzoate, o-nitroaniline, p-cresol, 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2,4, 6-tris (2-hydroxy-4-n-butoxyphenyl) -1,3, 5-s-triazine, 2-cyano-3, 3-diphenylacrylic acid 2-ethylhexyl ester, salicylic acid p-tert-butyl phenyl ester, bisphenol A disalicylate, and mixtures thereof, Bis (3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester), 2' -thiobis (4-tert-octylphenoloxy) nickel and the like. Among them, the ultraviolet absorber is preferably p-tert-butyl benzoate salicylate, bisphenol A disalicylate, 2, 4-dihydroxybenzophenone, and 2-hydroxy-4-methoxybenzophenone (ultraviolet absorber UV-531).
The filler is selected from starch, wood powder and shell powder, calcium carbonate, barium sulfate, calcium sulfate and calcium sulfite, talcum powder, white carbon black, quartz, mica powder, clay, limestone, barite powder, gypsum, diatomite, red mud, wollastonite, aluminum hydroxide, magnesium hydroxide and the like; the starch comprises one or more of corn starch, cassava starch, potato starch, sorghum starch, wheat starch, sweet potato starch and modified starch. The filler can reduce the manufacturing cost of the agricultural mulching film.
In a preferred embodiment of the present invention, the thickness of the mulching film is 20-280 μm.
The second technical scheme adopted by the invention for solving the technical problems is as follows: the preparation method of the degradable agricultural mulching film comprises the following steps:
(1) and (3) drying: drying the polylactic acid raw material and the plant rubber powder. Wherein the drying temperature of the polylactic acid raw material is 50-85 ℃, and the drying time is 20-60 min.
(2) Mixing materials: fully mixing and uniformly stirring polylactic acid and plant rubber powder by using mixing equipment to prepare a primary mixture; and adding the boron crosslinking agent, the antibacterial mildew inhibitor, the plasticizer, the lubricant, the heat stabilizer, the antioxidant, the ultraviolet absorbent and the filler into the primary mixture, and stirring again to obtain a secondary mixture. Wherein the mixing temperature of the primary mixture is room temperature, the stirring speed is 300-3000r/min, and the mixing time is 5-20 min; the mixing temperature of the secondary mixture is 150-.
(3) And (3) extruding and granulating: and adding the secondary mixture into a double-screw extruder for blending, extruding and granulating to obtain master batch particles. Wherein, the extrusion granulation process conditions are as follows: the screw rotation speed is 300r/min, the temperature of the first zone is 80-120 ℃, the temperature of the second zone is 150-.
(4) Blow molding: and drying and dewatering the master batch particles, adding the master batch particles into a storage bin of a film blowing machine, and carrying out blow molding, traction and winding to form a film. Wherein, the blow molding process conditions are as follows: the temperature of the blow molding machine is 160-190 ℃, the distance of the tuyere ring mold is 50-60mm, the blowing angle of cold air from the air ring is 40-55 degrees, the air quantity is 8-12m3/min, and the air pressure is 0.3-0.5 Mpa; the thickness of the film is controlled between 20 and 280 mu m when the film is drawn and wound to form the film.
Compared with the background technology, the technical scheme has the following advantages:
1. the polylactic acid raw material used in the film has good biodegradability, can be completely degraded by microorganisms in nature to finally generate carbon dioxide and water, does not pollute the environment, is safe and environment-friendly, and avoids white pollution; the vegetable gum is selected as the toughening modifier, so that the film forming performance of the plastic is ensured, the film can be fully degraded under natural conditions, the degradation conditions are simple, and the degradation degree is high; the agricultural mulching film is green and environment-friendly, can achieve 80% of degradation rate in soil in 90 days, can be completely degraded in 120 days, cannot cause plastic pollution, and meets the requirements of social sustainable development;
2. the film disclosed by the invention is easy to degrade, and has the advantages of high strength and good toughness, the vegetable gum in the film has good compatibility with polylactic acid, the toughness of the polylactic acid film is increased, and the extensibility and high ductility of the film can be realized under certain conditions, so that the prepared agricultural mulching film has both strength and toughness:
the product has good tensile strength and certain toughness under the condition of drying at room temperature, and can show high ductility and excellent tensile toughness after being soaked in hot water at 50-100 ℃ for 10-60min, or placed in a steam environment at 50-100 ℃ or being showered by the hot water at 50-100 ℃, and can be reshaped after being subjected to extension, stretching and covering;
3. the film also has ultraviolet resistance, can fully meet the agricultural production requirements by considering various performances, is beneficial to the growth and development of crops such as vegetables and fruits, improves the crop yield, is suitable for the protection and cultivation of vegetable greenhouses, and has very good popularization and application prospects;
4. the invention has the advantages of easily obtained raw materials, low hot melting temperature of main raw materials, great reduction of the hot melting temperature of common plastics, realization of application values of energy saving, power saving and consumption reduction, simple preparation process, high production efficiency and easy industrial implementation, avoids great reformation of a factory to a production line by adopting a preparation mode of a blow molding machine, has good economic benefit, can be popularized and applied in a large range, and has important significance for preparing environment-friendly plastics.
Detailed Description
In the following examples, the polylactic acid starting material can be obtained by purchasing commercially available products such as NatureWorks 4060D, 4043D, 2002D, and zhejiang sea revede 190. The remaining components are commercially available unless otherwise noted.
In the following examples, the degradation experiments of the films were carried out as follows: collecting surface soil of farmland, sieving with 32 mesh sieve to remove obvious plant and stone. Adjusting the water content of the soil to 40% -60%, adjusting the pH value of the soil to 6.0-8.0, and placing the soil in a container. Cutting the test film into 50mmx50mm landfill samples, filling a layer of nylon window screen on each of the upper and lower sides, burying the samples in soil with the burying depth of 8-10cm, observing the samples under the open air natural condition, taking out the samples and weighing the samples every 15 days, and observing the weight loss rates of different burying times to obtain degradation rate data.
Example 1
100 parts of polylactic acid raw material (American NatureWorks 4060D) and 5 parts of xanthan powder are weighed and dried. Mixing and stirring the dried polylactic acid and xanthan powder for 10min at the speed of 500r/min by using a high-speed mixer to prepare a primary mixture; adding 0.05 part of borax, 0.2 part of potassium sorbate, 2.5 parts of glycerol, 0.8 part of stearic acid, 1 part of triphenyl phosphite, 0.6 part of antioxidant 1010, 0.05 part of 2-hydroxy-4-methoxybenzophenone and 2 parts of corn starch into the primary mixture, and stirring for 5min at the temperature of 160-sand-doped 200 ℃ and the rotating speed of 3000r/min to obtain a secondary mixture. Adding the secondary mixture into a double-screw extruder for blending, extruding and granulating to obtain master batch particles; wherein, the extrusion granulation process conditions are as follows: the spiral rotating speed is 300r/min, the temperature of the first zone is 80-120 ℃, the temperature of the second zone is 150-. Drying and dewatering the master batch particles, adding the master batch particles into a stock bin of a film blowing machine, and carrying out blow molding, traction and winding to form a film; wherein, the blow molding process conditions are as follows: the temperature of the blow molding machine is 160-190 ℃, the distance of the tuyere ring mold is 50-60mm, the blowing angle of cold air from the tuyere ring is 40-55 degrees, and the air quantity is 8-12m3Min, and wind pressure of 0.3-0.5 MPa.
Through tests, the thickness of the degradable agricultural mulching film is 250-280 mu m, the tensile strength is 58MPa, the elongation at break is 39%, the elongation at break reaches 124% after the degradable agricultural mulching film is immersed in hot water at the temperature of 80 ℃ for 30min, the degradation rate of the degradable agricultural mulching film reaches 82% after the degradable agricultural mulching film is buried in soil for 90 days, and the degradable agricultural mulching film can be completely degraded after the degradable agricultural mulching film is buried for 120 days.
Example 2
100 parts of polylactic acid raw material (American NatureWorks 4060D) and 10 parts of guar gum powder are weighed and dried. Mixing and stirring the dried polylactic acid and guar gum powder for 10min at the speed of 500r/min by using a high-speed mixer to prepare a primary mixture; and adding 0.1 part of sodium borate, 0.5 part of mustard extract, 4 parts of glycerol, 1 part of stearic acid, 1 part of triphenyl phosphite, 0.8 part of antioxidant 168, 0.08 part of 2, 4-dihydroxy benzophenone and 5 parts of calcium carbonate into the primary mixture, and stirring for 5min at the temperature of 160-200 ℃ and the rotating speed of 3000r/min to obtain a secondary mixture. Adding the secondary mixture into a double-screw extruder for blending, extruding and granulating to obtain master batch particles; wherein, the extrusion granulation process conditions are as follows: the spiral rotating speed is 300r/min, the temperature of the first zone is 80-120 ℃, the temperature of the second zone is 150-. Drying and dewatering the master batch particles, adding the master batch particles into a stock bin of a film blowing machine, and carrying out blow molding, traction and winding to form a film; wherein, the blow molding process conditions are as follows: the temperature of the blow molding machine is 160-190 ℃, the distance of the tuyere ring mold is 50-60mm, the blowing angle of cold air from the tuyere ring is 40-55 degrees, and the air quantity is 8-12m3Min, and wind pressure of 0.3-0.5 MPa.
Tests prove that the degradable agricultural mulching film has the thickness of 140-160 mu m, the tensile strength of 46MPa and the elongation at break of 48 percent, the elongation at break of 178 percent after being soaked in hot water at the temperature of 80 ℃ for 30min, the degradation rate of 86 percent after being buried in soil for 90 days, and the mulching film can be completely degraded after being buried for 120 days.
Example 3
100 parts of polylactic acid raw material (Zhejiang sea REVODE190) and 10 parts of agar powder are weighed and dried. Mixing and stirring the dried polylactic acid and the dried agar powder for 5min at the speed of 800r/min by using a high-speed mixer to prepare a primary mixture; adding 0.05 part of trimethyl borate into the primary mixtureEster, 0.5 part of mustard extract, 2 parts of ethylene glycol, 1 part of paraffin, 2 parts of di-n-butyltin dilaurate, 1 part of antioxidant 245 and 0.08 part of 2, 4-dihydroxy benzophenone are stirred for 5min at the temperature of 160-plus 200 ℃ and the rotating speed of 3000r/min to obtain a secondary mixture. Adding the secondary mixture into a double-screw extruder for blending, extruding and granulating to obtain master batch particles; wherein, the extrusion granulation process conditions are as follows: the spiral rotating speed is 300r/min, the temperature of the first zone is 80-120 ℃, the temperature of the second zone is 150-. Drying and dewatering the master batch particles, adding the master batch particles into a stock bin of a film blowing machine, and carrying out blow molding, traction and winding to form a film; wherein, the blow molding process conditions are as follows: the temperature of the blow molding machine is 160-190 ℃, the distance of the tuyere ring mold is 50-60mm, the blowing angle of cold air from the tuyere ring is 40-55 degrees, and the air quantity is 8-12m3Min, and wind pressure of 0.3-0.5 MPa.
Tests prove that the degradable agricultural mulching film has the thickness of 120-130 mu m, the tensile strength of 52MPa and the elongation at break of 22 percent, the elongation at break of 115 percent after being soaked in hot water at the temperature of 80 ℃ for 30min, the degradation rate of the mulching film reaches 80 percent after being buried in soil for 90 days, and the mulching film can be completely degraded after being buried for 120 days.
Example 4
100 parts of polylactic acid raw material (Zhejiang sea REVODE190) and 30 parts of xanthan gum powder are weighed and dried. Mixing and stirring the dried polylactic acid and xanthan powder for 5min at the speed of 800r/min by using a high-speed mixer to prepare a primary mixture; adding 0.3 part of trimethyl borate, 1.5 parts of mugwort, 0.5 part of ethylene glycol, 1 part of paraffin, 2 parts of di-n-butyltin dilaurate, 1 part of antioxidant 245 and 0.08 part of p-tert-butyl phenyl salicylate into the primary mixture, and stirring for 5min at the temperature of 160-200 ℃ and the rotating speed of 3000r/min to obtain a secondary mixture. Adding the secondary mixture into a double-screw extruder for blending, extruding and granulating to obtain master batch particles; wherein, the extrusion granulation process conditions are as follows: the spiral rotation speed is 300r/min, the temperature of the first zone is 80-120 ℃, the temperature of the second zone is 150-The temperature of the five zones is 180-200 ℃, the retention time of the materials in the screw is 3-5min, and the pressure is 10-15 Mpa. Drying and dewatering the master batch particles, adding the master batch particles into a stock bin of a film blowing machine, and carrying out blow molding, traction and winding to form a film; wherein, the blow molding process conditions are as follows: the temperature of the blow molding machine is 160-190 ℃, the distance of the tuyere ring mold is 50-60mm, the blowing angle of cold air from the tuyere ring is 40-55 degrees, and the air quantity is 8-12m3Min, and wind pressure of 0.3-0.5 MPa.
Tests prove that the degradable agricultural mulching film has the thickness of 20-30 microns, the tensile strength of 32MPa and the elongation at break of 86%, the elongation at break reaches 247% after being soaked in hot water at 80 ℃ for 30min, the degradation rate of the mulching film reaches 90% after being buried in soil for 90 days, and the mulching film can be completely degraded after being buried for 120 days.
Example 5
100 parts of polylactic acid raw material (Zhejiang sea REVODE190) and 25 parts of guar gum powder are weighed and dried. Mixing and stirring the dried polylactic acid and guar gum powder for 5min at the speed of 800r/min by using a high-speed mixer to prepare a primary mixture; and adding 0.25 part of sodium borate, 2 parts of potassium sorbate, 2 parts of epoxidized soybean oil, 1 part of paraffin, 2 parts of triphenyl phosphite, 0.5 part of antioxidant Chinox 20N and 0.05 part of 2, 4-dihydroxy benzophenone into the primary mixture, and stirring for 5min at the temperature of 160-200 ℃ and the rotating speed of 3000r/min to obtain a secondary mixture. Adding the secondary mixture into a double-screw extruder for blending, extruding and granulating to obtain master batch particles; wherein, the extrusion granulation process conditions are as follows: the spiral rotating speed is 300r/min, the temperature of the first zone is 80-120 ℃, the temperature of the second zone is 150-. Drying and dewatering the master batch particles, adding the master batch particles into a stock bin of a film blowing machine, and carrying out blow molding, traction and winding to form a film; wherein, the blow molding process conditions are as follows: the temperature of the blow molding machine is 160-190 ℃, the distance of the tuyere ring mold is 50-60mm, the blowing angle of cold air from the tuyere ring is 40-55 degrees, and the air quantity is 8-12m3Min, and wind pressure of 0.3-0.5 MPa.
Tests prove that the degradable agricultural mulching film has the thickness of 40-50 mu m, the tensile strength of 36MPa and the elongation at break of 64%, the elongation at break of 192% after being soaked in hot water at the temperature of 80 ℃ for 30min, the degradation rate of 91% after being buried in soil for 90 days, and the mulching film can be completely degraded after being buried for 120 days.
Example 6
100 parts of polylactic acid raw material (American NatureWorks 4043D) and 10 parts of sesbania gum powder are weighed and dried. Mixing and stirring the dried polylactic acid and sesbania gum powder for 5min at the speed of 800r/min by using a high-speed mixer to prepare a primary mixture; adding 0.1 part of borax, 1 part of ethyl p-hydroxybenzoate, 2 parts of epoxidized soybean oil, 2 parts of stearamide, 2 parts of triphenyl phosphite, 0.5 part of antioxidant 168, 0.5 part of antioxidant 1010, 0.05 part of 2, 4-dihydroxy benzophenone and 20 parts of corn starch into the primary mixture, and stirring for 5min at the temperature of 160-200 ℃ and the rotating speed of 3000r/min to obtain a secondary mixture. Adding the secondary mixture into a double-screw extruder for blending, extruding and granulating to obtain master batch particles; wherein, the extrusion granulation process conditions are as follows: the spiral rotating speed is 300r/min, the temperature of the first zone is 80-120 ℃, the temperature of the second zone is 150-. Drying and dewatering the master batch particles, adding the master batch particles into a stock bin of a film blowing machine, and carrying out blow molding, traction and winding to form a film; wherein, the blow molding process conditions are as follows: the temperature of the blow molding machine is 160-190 ℃, the distance of the tuyere ring mold is 50-60mm, the blowing angle of cold air from the tuyere ring is 40-55 degrees, and the air quantity is 8-12m3Min, and wind pressure of 0.3-0.5 MPa.
Through tests, the thickness of the degradable agricultural mulching film is 150-160 mu m, the tensile strength is 44MPa, the elongation at break is 57%, the elongation at break reaches 144% after the degradable agricultural mulching film is immersed in hot water at the temperature of 80 ℃ for 30min, the degradation rate of the mulching film reaches 86% after the degradable agricultural mulching film is buried in soil for 90 days, and the mulching film can be completely degraded after the degradable agricultural mulching film is buried for 120 days.
Example 7
100 parts of polylactic acid raw material (American NatureWorks 2002D) and 15 parts of seaweed gel powder are weighed and dried. The dried polylactic acid and the seaweed glue powder are mixed in a high-speed mixerMixing and stirring for 5min under the condition of 800r/min to prepare a primary mixture; adding 0.15 part of borax, 0.5 part of mugwort, 1 part of glycerol, 2 parts of stearamide, 2 parts of triphenyl phosphite, 0.8 part of antioxidant 1010, 0.05 part of 2, 4-dihydroxy benzophenone and 0.5 part of clay into the primary mixture, and stirring for 5min at the temperature of 160-sand-doped 200 ℃ and the rotating speed of 3000r/min to obtain a secondary mixture. Adding the secondary mixture into a double-screw extruder for blending, extruding and granulating to obtain master batch particles; wherein, the extrusion granulation process conditions are as follows: the spiral rotating speed is 300r/min, the temperature of the first zone is 80-120 ℃, the temperature of the second zone is 150-. Drying and dewatering the master batch particles, adding the master batch particles into a stock bin of a film blowing machine, and carrying out blow molding, traction and winding to form a film; wherein, the blow molding process conditions are as follows: the temperature of the blow molding machine is 160-190 ℃, the distance of the tuyere ring mold is 50-60mm, the blowing angle of cold air from the tuyere ring is 40-55 degrees, and the air quantity is 8-12m3Min, and wind pressure of 0.3-0.5 MPa.
Through tests, the thickness of the degradable agricultural mulching film is 100-105 microns, the tensile strength is 40MPa, the elongation at break is 42%, the elongation at break reaches 136% after the degradable agricultural mulching film is immersed in hot water at the temperature of 80 ℃ for 30min, the degradation rate of the mulching film reaches 78% after the degradable agricultural mulching film is buried in soil for 90 days, and the mulching film can be completely degraded after the degradable agricultural mulching film is buried for 120 days.
Example 8
100 parts of polylactic acid raw material (American NatureWorks 2002D) and 15 parts of agar powder are weighed and dried. Mixing and stirring the dried polylactic acid and the dried agar powder for 5min at the speed of 800r/min by using a high-speed mixer to prepare a primary mixture; adding 0.15 part of trimethyl borate, 1 part of potassium sorbate, 1 part of glycerol, 1.5 parts of stearic acid, 2 parts of triphenyl phosphite, 1 part of antioxidant Chinox 20N and 0.05 part of 2-hydroxy-4-methoxybenzophenone into the primary mixture, and stirring for 5min at the temperature of 160-200 ℃ and the rotating speed of 3000r/min to obtain a secondary mixture. Adding the secondary mixture into a double-screw extruder for blending, extruding and granulating to obtain master batch particles; wherein, the extrusion granulation process conditions are as follows: the spiral rotating speed is 300r/min, the temperature of the first zone is 80-120 ℃, the temperature of the second zone is 150-. Drying and dewatering the master batch particles, adding the master batch particles into a stock bin of a film blowing machine, and carrying out blow molding, traction and winding to form a film; wherein, the blow molding process conditions are as follows: the temperature of the blow molding machine is 160-190 ℃, the distance of the tuyere ring mold is 50-60mm, the blowing angle of cold air from the tuyere ring is 40-55 degrees, and the air quantity is 8-12m3Min, and wind pressure of 0.3-0.5 MPa.
Tests prove that the degradable agricultural mulching film has the thickness of 130-140 mu m, the tensile strength of 48MPa and the elongation at break of 46 percent, the elongation at break of 152 percent after being soaked in hot water at the temperature of 80 ℃ for 30min, the degradation rate of the mulching film reaches 80 percent after being buried in soil for 90 days, and the mulching film can be completely degraded after being buried for 120 days.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A degradable agricultural mulching film is characterized in that: the composition comprises the following components in parts by weight:
2. the degradable agricultural mulching film according to claim 1, wherein: the composition comprises the following components in parts by weight:
3. the degradable agricultural mulching film according to claim 1, wherein: the plant rubber powder is at least one of xanthan gum powder, sesbania gum powder, guar gum powder, flax gum powder, tonka bean gum powder, agar gum powder, locust bean gum powder and seaweed gum powder.
4. The degradable agricultural mulching film according to claim 1, wherein: the boron crosslinking agent is at least one of ammonium borate, sodium borate, magnesium borate, aluminum borate, potassium borate, calcium borate, copper borate, zinc borate, lead borate, barium borate, ammonium metaborate, sodium metaborate, magnesium metaborate, aluminum metaborate, potassium metaborate, calcium metaborate, copper metaborate, zinc metaborate, barium metaborate, magnesium diborate, barium triborate, borax, manganese tetraborate, sodium pentaborate, ammonium pentaborate, potassium pentaborate, magnesium hexaborate, sodium octaborate, diammonium tetraborate, diammonium octaborate, borax, trimethyl borate, triethyl borate, triisopropyl borate, tri-tert-butyl borate, triphenyl borate, tricresyl borate, tribenzyl borate, tricyclohexyl borate, tris (trimethylsilyl) borate, isopropanol pinacol borate and triethanolamine borate.
5. The degradable agricultural mulching film according to claim 1, wherein: the antibacterial mildew preventive is at least one of benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, calcium propionate, dehydroacetic acid and sodium salt thereof, methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, propyl p-hydroxybenzoate, butyl p-hydroxybenzoate, sodium diacetate, mustard extract and mugwort.
6. The degradable agricultural mulching film according to claim 1, wherein: the filler is at least one of starch, wood powder and shell powder, calcium carbonate, barium sulfate, calcium sulfate and calcium sulfite, talcum powder, white carbon black, quartz, mica powder, clay, limestone, barite powder, gypsum, diatomite, red mud, wollastonite, aluminum hydroxide and magnesium hydroxide.
7. The degradable agricultural mulching film according to claim 1, wherein: the thickness of the mulching film is 20-280 μm.
8. The preparation method of the degradable agricultural mulching film according to any one of claims 1 to 7, wherein the method comprises the following steps: the method comprises the following steps:
(1) and (3) drying: drying the polylactic acid raw material and the plant rubber powder;
(2) mixing materials: fully mixing and uniformly stirring polylactic acid and plant rubber powder by using mixing equipment to prepare a primary mixture; adding a boron crosslinking agent, an antibacterial mildew inhibitor, a plasticizer, a lubricant, a heat stabilizer, an antioxidant, an ultraviolet absorbent and a filler into the primary mixture, and stirring again to obtain a secondary mixture;
(3) and (3) extruding and granulating: adding the secondary mixture into a double-screw extruder for blending, extruding and granulating to obtain master batch particles; wherein, the extrusion granulation process conditions are as follows: a homodromous double-rotation screw extruder is used, the screw rotation speed is 100-120 ℃ C., the temperature of the first zone is 80-120 ℃, the temperature of the second zone is 150-180 ℃, the temperature of the third zone is 190-210 ℃, the temperature of the fourth zone is 190-210 ℃, the temperature of the fifth zone is 180-200 ℃, the residence time of the materials in the screw is 3-5min, and the pressure is 10-15 MPa;
(4) blow molding: and drying and dewatering the master batch particles, adding the master batch particles into a storage bin of a film blowing machine, and carrying out blow molding, traction and winding to form a film.
9. The preparation method of the degradable agricultural mulching film according to claim 8, wherein the preparation method comprises the following steps: in the step (1), the mixing temperature of the primary mixture is room temperature, the stirring speed is 300-3000r/min, and the mixing time is 5-20 min; the mixing temperature of the secondary mixture is 150-.
10. The method of claim 8The preparation method of the degradable agricultural mulching film is characterized by comprising the following steps: in the step (4), the blow molding process conditions are as follows: the temperature of the blow molding machine is 160-190 ℃, the distance of the tuyere ring mold is 50-60mm, the blowing angle of cold air from the tuyere ring is 40-55 degrees, and the air quantity is 8-12m3Min, and wind pressure of 0.3-0.5 MPa.
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