CN104693710A - Biodegradable stone paper and preparation method thereof - Google Patents
Biodegradable stone paper and preparation method thereof Download PDFInfo
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- CN104693710A CN104693710A CN201510128311.0A CN201510128311A CN104693710A CN 104693710 A CN104693710 A CN 104693710A CN 201510128311 A CN201510128311 A CN 201510128311A CN 104693710 A CN104693710 A CN 104693710A
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- 239000004575 stone Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 38
- -1 polyethylene Polymers 0.000 claims abstract description 35
- 229920006167 biodegradable resin Polymers 0.000 claims abstract description 21
- 239000007822 coupling agent Substances 0.000 claims abstract description 20
- 229920000229 biodegradable polyester Polymers 0.000 claims abstract description 16
- 239000004622 biodegradable polyester Substances 0.000 claims abstract description 16
- 229920006238 degradable plastic Polymers 0.000 claims abstract description 12
- 239000012764 mineral filler Substances 0.000 claims description 24
- 239000006185 dispersion Substances 0.000 claims description 19
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 17
- 230000002087 whitening effect Effects 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 12
- 229920002961 polybutylene succinate Polymers 0.000 claims description 10
- 239000004631 polybutylene succinate Substances 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 9
- 239000004327 boric acid Substances 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- 238000003490 calendering Methods 0.000 claims description 7
- 238000005266 casting Methods 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000005453 pelletization Methods 0.000 claims description 7
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 7
- 235000019359 magnesium stearate Nutrition 0.000 claims description 6
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 150000001893 coumarin derivatives Chemical class 0.000 claims description 5
- XFYGZLLKHFLLPA-UHFFFAOYSA-N N1=CC=CC2=CC=CC=C12.C1(=CC=CC=C1)C1=NNC=C1 Chemical compound N1=CC=CC2=CC=CC=C12.C1(=CC=CC=C1)C1=NNC=C1 XFYGZLLKHFLLPA-UHFFFAOYSA-N 0.000 claims description 4
- 241001597008 Nomeidae Species 0.000 claims description 4
- XLTRGZZLGXNXGD-UHFFFAOYSA-N benzene;1h-pyrazole Chemical class C=1C=NNC=1.C1=CC=CC=C1 XLTRGZZLGXNXGD-UHFFFAOYSA-N 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 2
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 12
- 239000011347 resin Substances 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004698 Polyethylene Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 229920000573 polyethylene Polymers 0.000 abstract description 3
- 239000002075 main ingredient Substances 0.000 abstract description 2
- 238000005282 brightening Methods 0.000 abstract 1
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 1
- 239000001569 carbon dioxide Substances 0.000 abstract 1
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 239000011256 inorganic filler Substances 0.000 abstract 1
- 229910003475 inorganic filler Inorganic materials 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 11
- 229920003023 plastic Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 229920000379 polypropylene carbonate Polymers 0.000 description 6
- 235000011089 carbon dioxide Nutrition 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000003413 degradative effect Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229920000954 Polyglycolide Polymers 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229920000704 biodegradable plastic Polymers 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
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- 238000007639 printing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
- 229940006015 4-hydroxybutyric acid Drugs 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 229920010741 Ultra High Molecular Weight Polyethylene (UHMWPE) Polymers 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
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- 239000003963 antioxidant agent Substances 0.000 description 1
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- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- UVCJGUGAGLDPAA-UHFFFAOYSA-N ensulizole Chemical compound N1C2=CC(S(=O)(=O)O)=CC=C2N=C1C1=CC=CC=C1 UVCJGUGAGLDPAA-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical class CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
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- 231100000869 headache Toxicity 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 239000013535 sea water Substances 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses biodegradable stone paper and a preparation method thereof, and belongs to the technical field of light industrial papermaking. Main ingredients of the stone paper comprise, 50-75 parts of inorganic filler, 20-45 parts of full biodegradable resin, 1-5 parts of coupling agent, 1-5 parts of dispersing agent and 0.5-1.5 parts of brightening agent, wherein the full biodegradable resin is a mixture of carbon-dioxide-based full-degradable plastic and biodegradable polyester. The stone paper prepared by the preparation method is a full-degradable material, and the problem that existing stone paper regards polyethylene as a base body, and resin is not degradable is solved. The stone paper has a series of advantages that the strength is higher, the folding endurance is high, and the whiteness is high.
Description
Technical field
The present invention relates to a kind of biodegradable stone paper and preparation method thereof, belong to light industry pulp technology for making paper.
Background technology
Current paper on the market is mainly divided into two kinds, a kind of is traditional enamelled paper, one is synthetic paper or is called stone paper, wherein the main raw material of enamelled paper is wood pulp, annual global paper produces, consumption has reached 3.2 hundred million tons, if the trees need cutting down 4 average 20 years age of trees with paper per ton make raw material, so within 1 year, just has nearly 1,300,000,000 such large trees to disappear from the earth, the water pollutions simultaneously produced because of papermaking, the problem of the world community headache especially such as atmospheric pollution.Thus current each state research synthetic paper of all trying to be the first also is called stone paper, is mainly mixed by the paper rolled or the technique such as blown film is made by plastics such as a large amount of mineral fillers and organism PE, PP.
Chinese patent CN103788461A obtains modified filler after putting forward that modification is carried out in mineral filler, then mixes in advance with ultrahigh molecular weight polyethylene(UHMWPE) UHMWPE, compatilizer, antioxidant, auxiliary agent, melt extrude, granulation, obtains master batch, then master batch hot pressing film forming is obtained stone paper.But this with PE, PP stone paper that is matrix resin because resin is not degraded, be difficult to again reclaim, abandon and can white pollution be caused.
Chinese patent CN102690078A proposes a kind of formula of stone paper of degrading.Its component is as follows: superfine CaCO-3 55 ~ 70 parts, biodegradation agent 20 ~ 10 parts, polypropylene 10 ~ 25 parts, maleic anhydride grafted polyethylene material 5 ~ 7 parts.Biological degradation agent prescription, is made up of following weight part: low molecular weight hydrocarbons 10 parts, thermooxidizing promotor 9 parts, epoxy soybean oil 2 parts, catalyzer 0.1 part.Its feature be used by catalyzer, under the condition of light and heat, make organism change into the less segment of molecular weight, play degradation effect.But this mode by adding catalyzer, not only may also exist secondary pollution, and its degradation property has complicacy and high cost, it is made to be difficult to be promoted.
Chinese patent CN103131145B discloses a kind of complete biodegradable rich mineral paper material and preparation method thereof, its matrix resin is that aliphatics or semi-aromatic polyester are as PLA, PBS, PBAT etc., these are all can biodegradable plastics, solve environmental issue, too crisp (as PLA) that but these resins have, some degradation speeds are too fast, and the cost in storage process there being degradation (as PBS) is high (as PBAT), limits it and applies.
The degradable stone paper of this patent research, employing be the PPC of fully biodegradable be resin main ingredient.PPC is formed by carbonic acid gas and propylene oxide copolymer, realizes industrialization at home, and cost lower than other biological degradative plastics, and has good mechanical property and processing characteristics.Mutually can be learnt from other's strong points to offset one's weaknesses by PPC and other plastic blends of degrading, regulate the mechanical property of degradable intermingling material, thermal characteristics and degradation property further.Therefore take to be that the degradable resin of main composition is prepared stone paper for matrix and not only can be obtained and have high folding endurance with PPC, high strength, whiteness, waterproof, the paper material of a series of excellent properties such as stable, and can solve at present on the market in stone paper organism cannot reclaim and produce the problem polluted, expanded again the Application Areas of various degradable material above simultaneously.
Summary of the invention
The object of the invention is to solve problems of the prior art, a kind of biodegradable stone paper and preparation method thereof is provided, this stone paper can natural degradation, low price, stable performance, convenient and practical, solve on the market in stone paper organism cannot reclaim and produce the problem polluted.
For achieving the above object, the technical solution used in the present invention is:
A kind of biodegradable stone paper, is characterized in that, be made up of the component of following weight part:
Described complete biodegradable resin is carbon dioxide-base complete degradable plastic, and its structural formula is as follows:
In structural formula: m=500 ~ 2000.
Described complete biodegradable resin is the mixture of carbon dioxide-base complete degradable plastic and biodegradable polyester.
Described biodegradable polyester is one or more the mixture in poly(lactic acid) (PLA), poly butylene succinate (PBS), poly-hexane diacid-terephthalic acid-butylene terephthalate (PBAT).
Described mineral filler is polynite, SiO
2, one or more mixture in calcium carbonate.
Described coupling agent is one or both the mixture in boric acid ester, silicone coupling agents.
Described dispersion agent is one or more the mixture in sodium stearate, calcium stearate, Magnesium Stearate.
Described whitening agent is one or more the mixture in diphenyl ethylene derivatives, phenylpyrazole quinoline derivant, benzimidizole derivatives, benzene pyrazole derivatives, coumarin derivatives and Naphthalamide derivatives and titanium dioxide.
Prepare a method for above-mentioned biodegradable stone paper, comprise the steps:
1) complete biodegradable resin and mineral filler are put into baking oven, dry at 20-80 DEG C then mixed stir after add coupling agent, dispersion agent and whitening agent and stir 30-240s;
2) component after above-mentioned mixing is joined further plasticizing extruding pelletization in the equidirectional parallel double-screw extruder of length-to-diameter ratio >=40 and obtain stone paper masterbatch, extrusion temperature is 150-190 DEG C;
3) by the technological forming that stone paper masterbatch combines through calendering technology and casting technique, stone paper is obtained.
In order to ensure rich mineral paper material complete biodegradable, free from environmental pollution, we have selected complete biodegradable resin is carrier, abandon original not biodegradable conventional plastic-polyethylene, after Biodegradable resin is resolved into carbonic acid gas and water completely by microorganism, ore powder is back to nature also, thus reaches the object of real environmental protection.
Biodegradable material refers under physical environment and/or specific environment (soil, compost or seawater etc.), can be decomposed into the organic material such as carbonic acid gas and water completely by microorganism.At present, biological degradation examination criteria general is in the world ASTMD6400, EN13432 and AS4736, poly butylene succinate (PBS) is mainly contained by the resin of biological degradation standard detection, poly-succinic-hexanodioic acid-butanediol ester (PBSA), poly(lactic acid) (PLA), poly-hexane diacid-terephthalic acid-butylene terephthalate (PBAT), polycaprolactone (PCL), polyglycolic acid (PGA), poly-succinic-terephthalic acid-butanediol ester (PBST), polypropylene carbonate (PPC), poly-ethylene carbonate (PBC) and PHA series (such as poly butyric ester (PHB), polyhydroxybutyrate-valerate (PHBV), polyhydroxybutyrate-capronate (PHBHX), poly-3, 4 hydroxybutyric acid ester (P3, 4-HB) etc.
For complete biodegradable polymkeric substance and the poor problem of ore powder consistency, we take special to brighten, the technique means such as coupling and dispersion, make a high proportion of mineral filler obtain well dispersion in the carrier compatible with interface.
Mineral filler microcosmic is generally irregular or spherical fine particle, specific surface area is large, and oil absorbency is high, easy reunion, is difficult to disperse in resin, therefore, in ore powder, introduce such as citric acid ester type whitening agent, can greatly reduce its specific surface area, improve its dispersiveness; Dispersed in order to improve it further, such as erucicamide class dispersion agent can also be added; By adding the compound of hydroxyl or carboxyl, forming hydrogen bond action between carbonyl and mineral filler respectively and on resin, playing compatibilization; By introducing Borate Ester as Coupling, improving the interface interaction between resin and filler further, improving consistency between the two.
Hinge structure of the present invention has the following advantages:
The invention solves existing stone paper with conventional plastic polyethylene for the non-biodegradable problem of carrier, this material can complete biodegradable; The mixture that carbon dioxide-base complete degradable plastic or carbon dioxide-base complete degradable plastic and biodegradable polyester are the mixture of properties-correcting agent is added in stone paper, ensure that the complete biodegradable of stone paper, really reach the object of environmental protection, combine with the preparation method of stone paper, simple, be easy to realize.
Carbon dioxide-base degradative plastics belongs to complete biodegradable plastics class, can be degradable in physical environment, there is the advantages such as good gas barrier property, the transparency and complete biodegradable, the product of biodegradable polyester has: poly butyric ester and multipolymer thereof, the aliphatic polyesters such as poly(lactic acid), butanediol ester multipolymer, pla-pcl.The mixture that the blended resin being properties-correcting agent by carbon dioxide-base degradative plastics and biodegradable polyester is combined, makes it greatly be strengthened by the effect that microorganism is decomposed into the organic material such as carbonic acid gas and water completely.
Biodegradable stone paper provided by the invention is for biological degradation function agent with carbon dioxide-base degradative plastics, when biodegradable stone paper contacts after appropriate time with moisture content, make the carbon dioxide-base activation be evenly distributed in stone paper, and biological decomposition occurs, thus realize natural degradation.The present invention comprises calcium carbonate, SiO
2, polynite mineral filler and allocate other auxiliary materials such as dispersion agent, coupling agent, whitening agent into, the effect accelerating disintegration is played in mineral filler, when biodegradable stone paper contacts after appropriate time with moisture content, after making to be evenly distributed in the carbon dioxide-base activation in stone paper, mineral filler is disintegration thereupon, and there is biolytic phenomenon, form a large amount of hole, and then reach the object of fast decoupled.In addition, as calcium carbonate, SiO
2, polynite the use of mineral filler greatly can reduce the cost of stone paper, without the need to cutting down timber, make it more be conducive to the popularization of efforts at environmental protection.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but the present invention is not limited only to these examples, and under the prerequisite for departing from present inventive concept, any improvement of doing all drops within protection scope of the present invention.
Embodiment 1:
A kind of biodegradable stone paper, is made up of the component of following weight part:
Described complete biodegradable resin is carbon dioxide-base complete degradable plastic.
Described mineral filler is polynite, SiO
2with the mixture of calcium carbonate, its ratio of quality and the number of copies is 2:1:1.
Described coupling agent is boric acid ester.
Described dispersion agent is sodium stearate and Magnesium Stearate, and its ratio of quality and the number of copies is 1:1.
Described whitening agent is the mixture of diphenyl ethylene derivatives, phenylpyrazole quinoline derivant, benzimidizole derivatives and Naphthalamide derivatives, and its ratio of quality and the number of copies is 1:2:1:3.
Prepare a method for above-mentioned biodegradable stone paper, comprise the steps:
1) complete biodegradable resin and mineral filler are put into baking oven, dry at 20 DEG C then mixed stir after add coupling agent, dispersion agent and whitening agent and stir 30s;
2) component after above-mentioned mixing is joined further plasticizing extruding pelletization in the equidirectional parallel double-screw extruder of length-to-diameter ratio >=40 and obtain stone paper masterbatch, extrusion temperature is 150 DEG C;
3) by the technological forming that stone paper masterbatch combines through calendering technology and casting technique, stone paper is obtained.
Embodiment 2:
A kind of biodegradable stone paper, is made up of the component of following weight part:
Described complete biodegradable resin is the mixture of carbon dioxide-base complete degradable plastic and biodegradable polyester, and its ratio of quality and the number of copies is 2:1.
Described biodegradable polyester is the mixture of poly(lactic acid) (PLA), poly butylene succinate (PBS), poly-hexane diacid-terephthalic acid-butylene terephthalate (PBAT), and its ratio of quality and the number of copies is 2:2:1.
Described mineral filler is polynite and SiO
2mixture, its ratio of quality and the number of copies is 2:1.
Described coupling agent is the mixture of boric acid ester and silicone coupling agents, and its ratio of quality and the number of copies is 1:1.
Described dispersion agent is the mixture of sodium stearate, calcium stearate and Magnesium Stearate, and its ratio of quality and the number of copies is 3:2:1.
Described whitening agent is the mixture of diphenyl ethylene derivatives, phenylpyrazole quinoline derivant, benzimidizole derivatives, benzene pyrazole derivatives, coumarin derivatives and Naphthalamide derivatives and titanium dioxide, and its ratio of quality and the number of copies is 1:1:2:1:3:1:1.
Prepare a method for above-mentioned biodegradable stone paper, comprise the steps:
1) complete biodegradable resin and mineral filler are put into baking oven, dry at 80 DEG C then mixed stir after add coupling agent, dispersion agent and whitening agent and stir 240s;
2) component after above-mentioned mixing is joined further plasticizing extruding pelletization in the equidirectional parallel double-screw extruder of length-to-diameter ratio >=40 and obtain stone paper masterbatch, extrusion temperature is 190 DEG C;
3) by the technological forming that stone paper masterbatch combines through calendering technology and casting technique, stone paper is obtained.
Embodiment 3:
A kind of biodegradable stone paper, is made up of the component of following weight part:
Described complete biodegradable resin is the mixture of carbon dioxide-base complete degradable plastic and biodegradable polyester, and its ratio of quality and the number of copies is 2:1.
Described biodegradable polyester is the mixture of poly(lactic acid) (PLA) and poly-hexane diacid-terephthalic acid-butylene terephthalate (PBAT), and its ratio of quality and the number of copies is 1:2.
Described mineral filler is SiO
2with the mixture of calcium carbonate, its ratio of quality and the number of copies is 3:1.
Described coupling agent is boric acid ester.
Described dispersion agent is the mixture of sodium stearate and Magnesium Stearate, and its ratio of quality and the number of copies is 2:1.
Described whitening agent is the mixture of diphenyl ethylene derivatives and titanium dioxide, and its ratio of quality and the number of copies is 3:1.
Prepare a method for above-mentioned biodegradable stone paper, comprise the steps:
1) complete biodegradable resin and mineral filler are put into baking oven, dry at 60 DEG C then mixed stir after add coupling agent, dispersion agent and whitening agent and stir 200s;
2) component after above-mentioned mixing is joined further plasticizing extruding pelletization in the equidirectional parallel double-screw extruder of length-to-diameter ratio >=40 and obtain stone paper masterbatch, extrusion temperature is 180 DEG C;
3) by the technological forming that stone paper masterbatch combines through calendering technology and casting technique, stone paper is obtained.
Embodiment 4:
A kind of biodegradable stone paper, is made up of the component of following weight part:
Described complete biodegradable resin is the mixture of carbon dioxide-base complete degradable plastic and biodegradable polyester, and its ratio of quality and the number of copies is 2:1.
Described biodegradable polyester is the mixture of poly(lactic acid) (PLA) and poly-hexane diacid-terephthalic acid-butylene terephthalate (PBAT), and its ratio of quality and the number of copies is 1:2.
Described mineral filler is the mixture of polynite and calcium carbonate, and its ratio of quality and the number of copies is 5:1.
Described coupling agent is boric acid ester.
Described dispersion agent is the mixture of sodium stearate and Magnesium Stearate, and its ratio of quality and the number of copies is 2:1.
Described whitening agent is the mixture of diphenyl ethylene derivatives, coumarin derivatives and Naphthalamide derivatives and titanium dioxide, and its ratio of quality and the number of copies is 2:1:2:3.
Prepare a method for above-mentioned biodegradable stone paper, comprise the steps:
1) complete biodegradable resin and mineral filler are put into baking oven, dry at 55 DEG C then mixed stir after add coupling agent, dispersion agent and whitening agent and stir 120s;
2) component after above-mentioned mixing is joined further plasticizing extruding pelletization in the equidirectional parallel double-screw extruder of length-to-diameter ratio >=40 and obtain stone paper masterbatch, extrusion temperature is 155 DEG C;
3) by the technological forming that stone paper masterbatch combines through calendering technology and casting technique, stone paper is obtained.
Embodiment 5:
A kind of biodegradable stone paper, is made up of the component of following weight part:
Described complete biodegradable resin is the mixture of carbon dioxide-base complete degradable plastic and biodegradable polyester, and its ratio of quality and the number of copies is 3:1.
Described biodegradable polyester is the mixture of poly(lactic acid) (PLA) and poly-hexane diacid-terephthalic acid-butylene terephthalate (PBAT), and its ratio of quality and the number of copies is 2:1.
Described mineral filler is polynite.
Described coupling agent is boric acid ester.
Described dispersion agent is sodium stearate.
Described whitening agent is the mixture of coumarin derivatives and titanium dioxide, and its ratio of quality and the number of copies is 2:1.
Prepare a method for above-mentioned biodegradable stone paper, comprise the steps:
1) complete biodegradable resin and mineral filler are put into baking oven, dry at 70 DEG C then mixed stir after add coupling agent, dispersion agent and whitening agent and stir 160s;
2) component after above-mentioned mixing is joined further plasticizing extruding pelletization in the equidirectional parallel double-screw extruder of length-to-diameter ratio >=40 and obtain stone paper masterbatch, extrusion temperature is 165 DEG C;
3) by the technological forming that stone paper masterbatch combines through calendering technology and casting technique, stone paper is obtained.
Comparative sample is Chinese patent CN102690078A stone paper sample.
Following table is the performance perameter of embodiments of the invention and comparative example:
Can judge from detection, the stone paper that the present invention obtains reaches quality standards completely in performance, compared with comparative sample, the multinomial performance of paper is better than comparative sample, especially embodiment 5 more occupies obvious advantage in printing, the tensile index of paper, folding endurance, whiteness and smoothness are obviously better than other embodiments and contrast sample, and printing acid-fast alkali-proof obviously takes advantage.
The foregoing is only better embodiment of the present invention; protection scope of the present invention is not limited with above-mentioned embodiment; in every case those of ordinary skill in the art modify or change according to the equivalence that disclosed content is done, and all should include in the protection domain recorded in claims.
Claims (9)
1. a biodegradable stone paper, is characterized in that, is made up of the component of following weight part:
Complete biodegradable resin 20-45 part
Mineral filler 50-75 part
Coupling agent 1-5 part
Dispersion agent 1-5 part
Whitening agent 0.5-1.5 part.
2. according to the biodegradable stone paper described in claim 1, it is characterized in that, described complete biodegradable resin is carbon dioxide-base complete degradable plastic, and its structural formula is as follows:
In structural formula: m=500 ~ 2000.
3. according to claim 1 or 2, moor biodegradable stone paper, it is characterized in that, described complete biodegradable resin is the mixture of carbon dioxide-base complete degradable plastic and biodegradable polyester.
4. biodegradable stone paper according to claim 3, it is characterized in that, described biodegradable polyester is one or more the mixture in poly(lactic acid) (PLA), poly butylene succinate (PBS), poly-hexane diacid-terephthalic acid-butylene terephthalate (PBAT).
5. biodegradable stone paper according to claim 1, is characterized in that, described mineral filler is one or more the mixture in polynite, SiO2, calcium carbonate.
6. biodegradable stone paper according to claim 1, is characterized in that, described coupling agent is one or both in boric acid ester, silicone coupling agents.
7. biodegradable stone paper according to claim 1, is characterized in that, described dispersion agent is one or more the mixture in sodium stearate, calcium stearate, Magnesium Stearate.
8. according to the biodegradable stone paper described in claim 1, it is characterized in that, described whitening agent is one or more the mixture in diphenyl ethylene derivatives, phenylpyrazole quinoline derivant, benzimidizole derivatives, benzene pyrazole derivatives, coumarin derivatives and Naphthalamide derivatives and titanium dioxide.
9. a preparation method for biodegradable stone paper, comprises the steps:
1) complete biodegradable resin and mineral filler are put into baking oven, dry at 20-80 DEG C then mixed stir after add coupling agent, dispersion agent and whitening agent and stir 30-240s;
2) component after above-mentioned mixing is joined further plasticizing extruding pelletization in the equidirectional parallel double-screw extruder of length-to-diameter ratio >=40 and obtain stone paper masterbatch, extrusion temperature is 150-190 DEG C;
3) by the technological forming that stone paper masterbatch combines through calendering technology and casting technique, stone paper is obtained.
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| CN201510128311.0A CN104693710A (en) | 2015-03-23 | 2015-03-23 | Biodegradable stone paper and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105113323A (en) * | 2015-07-31 | 2015-12-02 | 杜德光 | Stone paper and preparation method therefor |
| CN106565941A (en) * | 2015-10-10 | 2017-04-19 | 深圳市联创科技集团有限公司 | Formula of composite nanoparticle modified polybutylene-succinate and preparation method thereof |
| CN107011634A (en) * | 2016-07-26 | 2017-08-04 | 北京工商大学 | Biodegradable transparent polyester film that a kind of inorganic nano-filler is modified and preparation method thereof |
| CN109082082A (en) * | 2018-03-09 | 2018-12-25 | 广州啡形科技有限公司 | A kind of degradable food contact composition and preparation method thereof that coffee grounds polymerize |
| CN109181100A (en) * | 2018-07-24 | 2019-01-11 | 边继庆 | The production method and its application of stone paper masterbatch composition, master batch |
| CN113372594A (en) * | 2021-07-07 | 2021-09-10 | 广州市永鑫华新型材料有限公司 | Degradable plastic mulching film based on PBAT and preparation method thereof |
| CN113429751A (en) * | 2021-06-16 | 2021-09-24 | 山西兰花华明纳米材料股份有限公司 | Biodegradable functional granules and preparation method thereof |
| CN113444350A (en) * | 2021-08-18 | 2021-09-28 | 中国地质大学（北京） | Biodegradable mineral composite paper and preparation method thereof |
| WO2024103558A1 (en) * | 2022-11-17 | 2024-05-23 | 达亚帆布(上海)有限公司 | Advertising and decorative flexible film material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1422898A (en) * | 2002-12-12 | 2003-06-11 | 中山大学 | Degradable polymer/natural mineal filler composite material and preparation method thereof |
| CN103131145A (en) * | 2013-03-25 | 2013-06-05 | 山东汇盈新材料科技有限公司 | Completely biodegradable stone paper material and preparation method thereof |
| WO2014108518A1 (en) * | 2013-01-11 | 2014-07-17 | Norner Ip As | Process |
-
2015
- 2015-03-23 CN CN201510128311.0A patent/CN104693710A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1422898A (en) * | 2002-12-12 | 2003-06-11 | 中山大学 | Degradable polymer/natural mineal filler composite material and preparation method thereof |
| WO2014108518A1 (en) * | 2013-01-11 | 2014-07-17 | Norner Ip As | Process |
| CN103131145A (en) * | 2013-03-25 | 2013-06-05 | 山东汇盈新材料科技有限公司 | Completely biodegradable stone paper material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王献红等: "《二氧化碳的固定和利用》", 30 June 2011, 化学工业出版社 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105113323A (en) * | 2015-07-31 | 2015-12-02 | 杜德光 | Stone paper and preparation method therefor |
| CN106565941A (en) * | 2015-10-10 | 2017-04-19 | 深圳市联创科技集团有限公司 | Formula of composite nanoparticle modified polybutylene-succinate and preparation method thereof |
| CN107011634A (en) * | 2016-07-26 | 2017-08-04 | 北京工商大学 | Biodegradable transparent polyester film that a kind of inorganic nano-filler is modified and preparation method thereof |
| CN109082082A (en) * | 2018-03-09 | 2018-12-25 | 广州啡形科技有限公司 | A kind of degradable food contact composition and preparation method thereof that coffee grounds polymerize |
| CN109181100A (en) * | 2018-07-24 | 2019-01-11 | 边继庆 | The production method and its application of stone paper masterbatch composition, master batch |
| CN113429751A (en) * | 2021-06-16 | 2021-09-24 | 山西兰花华明纳米材料股份有限公司 | Biodegradable functional granules and preparation method thereof |
| CN113372594A (en) * | 2021-07-07 | 2021-09-10 | 广州市永鑫华新型材料有限公司 | Degradable plastic mulching film based on PBAT and preparation method thereof |
| CN113372594B (en) * | 2021-07-07 | 2023-06-13 | 广东永鑫华新型材料有限公司 | PBAT-based degradable plastic mulching film and preparation method thereof |
| CN113444350A (en) * | 2021-08-18 | 2021-09-28 | 中国地质大学（北京） | Biodegradable mineral composite paper and preparation method thereof |
| WO2024103558A1 (en) * | 2022-11-17 | 2024-05-23 | 达亚帆布(上海)有限公司 | Advertising and decorative flexible film material |
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