CN104277391A - Degradable solid mulching film by virtue of blending modification of humic acid (HA)/polyvinyl alcohol (PVA) - Google Patents
Degradable solid mulching film by virtue of blending modification of humic acid (HA)/polyvinyl alcohol (PVA) Download PDFInfo
- Publication number
- CN104277391A CN104277391A CN201410485532.9A CN201410485532A CN104277391A CN 104277391 A CN104277391 A CN 104277391A CN 201410485532 A CN201410485532 A CN 201410485532A CN 104277391 A CN104277391 A CN 104277391A
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- polyvinyl alcohol
- humic acids
- pva
- solid
- mulch film
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- Granted
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- 239000004021 humic acid Substances 0.000 title claims abstract description 55
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 48
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 48
- 238000002156 mixing Methods 0.000 title claims abstract description 33
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 title abstract description 10
- 230000004048 modification Effects 0.000 title abstract 3
- 238000012986 modification Methods 0.000 title abstract 3
- 239000007787 solid Substances 0.000 title abstract 3
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000007822 coupling agent Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000314 lubricant Substances 0.000 claims abstract description 7
- 238000003490 calendering Methods 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 6
- 230000008961 swelling Effects 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract 7
- 239000002362 mulch Substances 0.000 claims description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 239000004902 Softening Agent Substances 0.000 claims description 10
- 239000008188 pellet Substances 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- -1 N, N '-methylene Chemical group 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 5
- 239000008116 calcium stearate Substances 0.000 claims description 5
- 235000013539 calcium stearate Nutrition 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- 229910021538 borax Inorganic materials 0.000 claims description 3
- 239000004328 sodium tetraborate Substances 0.000 claims description 3
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 3
- 229960001124 trientine Drugs 0.000 claims description 3
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 239000004014 plasticizer Substances 0.000 abstract 3
- 239000007788 liquid Substances 0.000 abstract 2
- 238000000071 blow moulding Methods 0.000 abstract 1
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 2
- 238000012271 agricultural production Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 125000004151 quinonyl group Chemical group 0.000 description 2
- GPLIMIJPIZGPIF-UHFFFAOYSA-N 2-hydroxy-1,4-benzoquinone Chemical compound OC1=CC(=O)C=CC1=O GPLIMIJPIZGPIF-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000012675 alcoholic extract Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a preparation method and an application of a degradable solid mulching film by virtue of blending modification of humic acid (HA)/polyvinyl alcohol (PVA). The preparation method comprises the following steps: stirring PVA and water at the mass ratio of 1: (1-3) at room temperature, swelling, raising the temperature to 80-100 DEG C, adding a plasticizer, raising the temperature to 150-180 DEG C and reacting for 0.5-1 hour to obtain pre-plasticized PVA sol; weighting humic acid powder according to the mass ratio of PVA to HA being 1: (0.8-1.5), mixing HA, the plasticizer and a coupling agent according to the mass ratio of HA to plasticizer to coupling agent being 1: (0.1-0.3): (0.01-0.04) and heating 0.5-1 hour to obtain a molten thick liquid, adding the molten thick liquid in the pre-plasticized PVA sol, adding a crosslinking agent and a lubricant, mixing at 180-200 DEG C, granulating and carrying out blow molding or calendaring to obtain the degradable solid mulching film by virtue of blending modification of HA/PVA. The mulching film has the advantages of good mechanical properties and degradability and low cost and is suitable for widespread popularization and application.
Description
Technical field
The present invention relates to a kind of humic acids/solid-state mulch film of polyvinyl alcohol blending modified degradable, belong to agricultural production application field.
Background technology
For realizing the object of agricultural production and income, utilizing plastic film to carry out culture underglass technology and being adopted by vast farmers.But common agricultural plastic ground membrane is polyethylene or polyvinyl chloride macromolecular compound mainly; this material has excellent physicals; but be difficult to degraded under field conditions (factors); use rear very difficult recycling; " white pollution " problem remained is difficult to solve, and safety and the Sustainable development of agriculture production in serious threat, reduce farmland mulch and remain; protect the fields ecotope, and the most feasible method eliminating plastic film " white pollution " is exploitation and uses degradable mulch.
Humic acids (HA) is a kind of organic macromolecule compound that occurring in nature extensively exists, and is the main component of soil ulmin in rich soil, exists in a large number in coal, marsh, pond, irrigation canals and ditches mud.Containing multiple functional groups such as alcoholic extract hydroxyl group, phenolic hydroxyl group, hydroxyquinone, enol base, quinonyl, half quinonyl, methoxyl group, amido, carboxyls in humic acids molecular structure, humic acids derives from animals and plants remains, existing carbohydrate and protein-based structural unit, also have a large amount of photoactivatable groups, having can be degradable and can be converted into the characteristic of fertilizer after degraded.Because humic acids has good chemistry and biological activity, the investigation and application of humic acids mulch film also result in the very big concern of people.But because humic acids itself does not have thermoplasticity, also without definite melting point, thus the current research about humic acids mulch film and report are only limitted to humic acids liquid-state mulch film, and due to technology and operation use on problem do not obtain large scale application always.
Summary of the invention
For the present Research of humic acids mulch film, the present invention proposes one utilizes polyvinyl alcohol (PVA) and humic acids (HA) to carry out blending and modifying, thus the new solution of obtained humic acids/solid-state mulch film of polyvinyl alcohol degradable, make product more can realistic application needs.
The object of the present invention is to provide a kind of method preparing humic acids/solid-state mulch film of polyvinyl alcohol blending modified degradable.
object of the present invention is achieved through the following technical solutions:
(1) by polyvinyl alcohol with water by polyvinyl alcohol: the mass ratio of water=1:1 ~ 3 mixes, then after at room temperature stirring swelling 1 ~ 2 h, be warming up to 80 ~ 100 DEG C, add the softening agent of 0.1 ~ 0.3 times of polyvinyl alcohol weight, continue to be warming up to 150 ~ 180 DEG C of stirring reaction 0.5 ~ 1 h, the polyvinyl alcohol colloidal sol obtaining pre-plasticising is for subsequent use.
(2) by polyvinyl alcohol: the mass ratio of humic acids=1:0.8 ~ 1.5 takes 200 ~ 400 object humic acids powder, again by humic acids: softening agent: the mass ratio of coupling agent=1:0.1 ~ 0.3:0.01 ~ 0.04 takes softening agent and coupling agent, by load weighted humic acids, softening agent and coupling agent mix, stir, then heat 0.5 ~ 1 h and obtain melting magma, melting magma is joined in the obtained pre-Plasticised Polyvinyl alcosol of step (1), and humic acids in mass ratio: linking agent: the ratio of lubricant=100:0.3 ~ 0.5:0.1 ~ 0.4 adds linking agent and lubricant, granulation after 180 ~ 200 DEG C of mixing 15 ~ 60 min, obtain the pellet of blending and modifying.
(3) pellet step (2) obtained, in 180 ~ 200 DEG C of extrusion-blown modlings or calendering, obtains humic acids/solid-state mulch film of polyvinyl alcohol blending modified degradable.
The softening agent used is ethylene glycol, one or more in glycerol, tributyl citrate, tributyl acetylcitrate, dioctyl phthalate (DOP);
The coupling agent used is silane coupling agent;
The linking agent used is borax, N, N '-methylene radical acrylamide, one or more in triethylene tetramine;
The lubricant used is one or more in calcium stearate or Magnesium Stearate.
the present invention has the following advantages:
(1) pass through after polyvinyl alcohol and the pre-plasticising of humic acids difference, the Particular craft technology of blending and modifying has prepared the solid-state mulch film product of degradable humic acids again, compared with original humic acids liquid-state mulch film, more meet traditional plastic mulching cultivation technology needs, more easily for wide farmers accepts.
(2) humic acid material wide material sources are the animal and plant resources rotted, and compared with starch based degradable mulch, price is more cheap, there is not the problem of striving grain with people.
(3) do not introduce environmentally harmful pharmaceutical chemicals, can environmental-protection fully-degradable be realized, generally can realize degradable after 3-5 month in use.
Embodiment
embodiment 1:
1) get PVA 20 kg, add 30 kg water, after at room temperature stirring swelling 1 h, be warming up to 80 ~ 100 DEG C, add mixture 3 kg that volume ratio is 1:1 ethylene glycol and glycerol, be warming up to 160 DEG C of stirring reaction 0.5 h, the PVA colloidal sol obtaining pre-plasticising is for subsequent use.
2) get and be crushed to 300 object HA powder 20 kg, add ethylene glycol and glycerol mixture 3 kg that volume ratio is 1:1, silane coupling agent 0.3 kg, after being uniformly mixed heating 0.5 h, join in the obtained pre-plasticising PVA colloidal sol of step (1), and adding borax 0.08 kg and calcium stearate 0.04 kg, granulation after 180 DEG C of mixing 30 min, obtains the pellet of blending and modifying.
3) by above-mentioned pellet in 180 ~ 200 DEG C of extrusion-blown modlings or calendering, obtain humic acids/solid-state mulch film of polyvinyl alcohol blending modified degradable.
After tested, the obtained solid-state mulching film stretching intensity of humic acids/polyvinyl alcohol blending modified degradable is 4.28 MPa, and elongation at break is 267.6%, and soil buries method degraded 50% and needs about 70 days.
embodiment 2:
1) get PVA 20 kg, add 40 kg water, after at room temperature stirring swelling 1 h, be warming up to 80 ~ 100 DEG C, add 3 kg tributyl citrates, be warming up to 160 DEG C of stirring reaction 0.5 h, the PVA colloidal sol obtaining pre-plasticising is for subsequent use.
2) get and be crushed to 400 object HA powder 30 kg, add tributyl citrate 3 kg, silane coupling agent 0.4 kg, after being uniformly mixed heating 0.5 h, join in the obtained pre-plasticising PVA colloidal sol of step (1), and add N, N '-methylene radical acrylamide 0.09kg and calcium stearate 0.04 kg, granulation after 180 DEG C of mixing 30 min, obtains the pellet of blending and modifying.
3) by above-mentioned pellet in 180 ~ 200 DEG C of extrusion-blown modlings or calendering, obtain humic acids/solid-state mulch film of polyvinyl alcohol blending modified degradable.
After tested, the obtained solid-state mulching film stretching intensity of humic acids/polyvinyl alcohol blending modified degradable is 3.52 MPa, and elongation at break is 156.8%, and soil buries method degraded 50% and needs about 60 days.
embodiment 3:
1) get PVA 20 kg, add 30 kg water, after at room temperature stirring swelling 1 h, be warming up to 80 ~ 100 DEG C, add mixture 3 kg that volume ratio is 1:1 ethylene glycol and glycerol, be warming up to 170 DEG C of stirring reaction 0.5 h, the PVA colloidal sol obtaining pre-plasticising is for subsequent use.
2) get and be crushed to 300 object HA powder 16 kg, add mixture 3 kg that volume ratio is 1:1 ethylene glycol and glycerol, silane coupling agent 0.3 kg, after being uniformly mixed heating 0.5 h, join in the obtained pre-plasticising PVA colloidal sol of step (1), and adding triethylene tetramine 0.06 kg and calcium stearate 0.04 kg, granulation after 190 DEG C of mixing 30 min, obtains the pellet of blending and modifying.
3) by above-mentioned pellet in 180 ~ 200 DEG C of extrusion-blown modlings or calendering, obtain humic acids/solid-state mulch film of polyvinyl alcohol blending modified degradable.
After tested, the obtained solid-state mulching film stretching intensity of humic acids/polyvinyl alcohol blending modified degradable is 5.66 MPa, and elongation at break is 324.8%, and soil buries method degraded 50% and needs about 80 days.
Claims (5)
1. a preparation method for humic acids/solid-state mulch film of polyvinyl alcohol blending modified degradable, is characterized in that: comprise the steps:
(1) by polyvinyl alcohol with water by polyvinyl alcohol: the mass ratio of water=1:1 ~ 3 mixes, then after at room temperature stirring swelling 1 ~ 2 h, be warming up to 80 ~ 100 DEG C, add the softening agent of 0.1 ~ 0.3 times of polyvinyl alcohol weight, continue to be warming up to 150 ~ 180 DEG C of stirring reaction 0.5 ~ 1 h, the polyvinyl alcohol colloidal sol obtaining pre-plasticising is for subsequent use;
(2) by polyvinyl alcohol: the mass ratio of humic acids=1:0.8 ~ 1.5 takes 200 ~ 400 object humic acids powder, again by humic acids: softening agent: the mass ratio of coupling agent=1:0.1 ~ 0.3:0.01 ~ 0.04 takes softening agent and coupling agent, by load weighted humic acids, softening agent and coupling agent mix, stir, then heat 0.5 ~ 1 h and obtain melting magma, melting magma is joined in the obtained pre-Plasticised Polyvinyl alcosol of step (1), and humic acids in mass ratio: linking agent: the ratio of lubricant=100:0.3 ~ 0.5:0.1 ~ 0.4 adds linking agent and lubricant, granulation after 180 ~ 200 DEG C of mixing 15 ~ 60 min, obtain the pellet of blending and modifying,
(3) pellet step (2) obtained, in 180 ~ 200 DEG C of extrusion-blown modlings or calendering, obtains humic acids/solid-state mulch film of polyvinyl alcohol blending modified degradable.
2. the preparation method of a kind of humic acids as claimed in claim 1/solid-state mulch film of polyvinyl alcohol blending modified degradable, is characterized in that: the softening agent of use is ethylene glycol, one or more in glycerol, tributyl citrate, tributyl acetylcitrate, dioctyl phthalate (DOP).
3. the preparation method of a kind of humic acids as claimed in claim 1/solid-state mulch film of polyvinyl alcohol blending modified degradable, is characterized in that: the coupling agent of use is silane coupling agent.
4. the preparation method of a kind of humic acids as claimed in claim 1/solid-state mulch film of polyvinyl alcohol blending modified degradable, is characterized in that: the linking agent of use is borax, N, N '-methylene radical acrylamide, one or more in triethylene tetramine.
5. the preparation method of a kind of humic acids as claimed in claim 1/solid-state mulch film of polyvinyl alcohol blending modified degradable, is characterized in that: the lubricant of use is one or more in calcium stearate or Magnesium Stearate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410485532.9A CN104277391B (en) | 2014-09-22 | 2014-09-22 | A kind of humic acids/polyvinyl alcohol blending modified degradable solid-state mulch film |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410485532.9A CN104277391B (en) | 2014-09-22 | 2014-09-22 | A kind of humic acids/polyvinyl alcohol blending modified degradable solid-state mulch film |
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| Publication Number | Publication Date |
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| CN104277391A true CN104277391A (en) | 2015-01-14 |
| CN104277391B CN104277391B (en) | 2016-08-17 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104672700A (en) * | 2015-02-04 | 2015-06-03 | 苏州康华净化系统工程有限公司 | Polyvinyl chloride material and preparation method thereof |
| CN107141674A (en) * | 2017-05-24 | 2017-09-08 | 浙江理工大学 | A kind of polyvinyl alcohol and phosphate compound blend film and preparation method thereof |
| CN110294909A (en) * | 2019-06-20 | 2019-10-01 | 江苏省农业科学院 | A kind of method that biomass by hydrolyzation residue prepares water-resistant type biological plastics |
| CN110615958A (en) * | 2019-08-16 | 2019-12-27 | 山东森工新材料科技有限公司 | Humic acid composite gel material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101481508A (en) * | 2008-01-11 | 2009-07-15 | 山东科技大学 | Humic acid multifunctional degradable black mulch film |
| CN101589681A (en) * | 2009-07-10 | 2009-12-02 | 李保华 | Completely degraded plastic film and production method thereof |
| CN103373879A (en) * | 2013-07-10 | 2013-10-30 | 湖南中烟工业有限责任公司 | Degradable solid mulching film special for tobacco and preparation method of degradable solid mulching film |
| CN104017316A (en) * | 2014-05-30 | 2014-09-03 | 新疆大学 | Composite material containing polyvinyl alcohol and soapstone modified with quaternary ammonium salt of fulvic acid, and preparation method, products and applications of the composite material |
-
2014
- 2014-09-22 CN CN201410485532.9A patent/CN104277391B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481508A (en) * | 2008-01-11 | 2009-07-15 | 山东科技大学 | Humic acid multifunctional degradable black mulch film |
| CN101589681A (en) * | 2009-07-10 | 2009-12-02 | 李保华 | Completely degraded plastic film and production method thereof |
| CN103373879A (en) * | 2013-07-10 | 2013-10-30 | 湖南中烟工业有限责任公司 | Degradable solid mulching film special for tobacco and preparation method of degradable solid mulching film |
| CN104017316A (en) * | 2014-05-30 | 2014-09-03 | 新疆大学 | Composite material containing polyvinyl alcohol and soapstone modified with quaternary ammonium salt of fulvic acid, and preparation method, products and applications of the composite material |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104672700A (en) * | 2015-02-04 | 2015-06-03 | 苏州康华净化系统工程有限公司 | Polyvinyl chloride material and preparation method thereof |
| CN107141674A (en) * | 2017-05-24 | 2017-09-08 | 浙江理工大学 | A kind of polyvinyl alcohol and phosphate compound blend film and preparation method thereof |
| CN110294909A (en) * | 2019-06-20 | 2019-10-01 | 江苏省农业科学院 | A kind of method that biomass by hydrolyzation residue prepares water-resistant type biological plastics |
| CN110294909B (en) * | 2019-06-20 | 2022-03-22 | 江苏省农业科学院 | Method for preparing water-resistant bioplastic from biomass hydrolysis residues |
| CN110615958A (en) * | 2019-08-16 | 2019-12-27 | 山东森工新材料科技有限公司 | Humic acid composite gel material and preparation method thereof |
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| CN104277391B (en) | 2016-08-17 |
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Effective date of registration: 20150916 Address after: The North Industrial Park of Ji'an city of Jiangxi province Xingan County 331300 Applicant after: JIANGXI SHUANGJIA TECHNOLOGY DEVELOPMENT CO., LTD. Address before: 343009 Ji'an City, Jiangxi province Qingyuan District School Road No. 28 Applicant before: Jinggangshan University |
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Address after: The North Industrial Park of Ji'an city of Jiangxi province Xingan County 331300 Patentee after: Jiangxi Shuangjia Technology Co.,Ltd. Address before: The North Industrial Park of Ji'an city of Jiangxi province Xingan County 331300 Patentee before: JIANGXI SHUANGJIA TECHNOLOGY DEVELOPMENT Co.,Ltd. |
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Denomination of invention: A degradable solid mulching film modified by humic acid / polyvinyl alcohol blend Effective date of registration: 20201218 Granted publication date: 20160817 Pledgee: Jiangxi Xingan Rural Commercial Bank Co.,Ltd. Pledgor: Jiangxi Shuangjia Technology Co.,Ltd. Registration number: Y2020980009525 |
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