CN104059320B - Novel biodegradable synthetic paper - Google Patents
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Abstract
The invention provides novel biodegradable synthetic paper which is characterized in that raw materials comprise degradable chitosan hydrochloride-acrylamide-allylamine hydrochloride macromolecular resin, inorganic fillers, a folding modifier, an antistatic agent, a mixed accelerant and a lubricant. The novel biodegradable synthetic paper provided by the invention can be biodegraded to avoid environmental pollution. Meanwhile, the synthetic paper is not easy to embrittle and crack, good in ductility and toughness and folding and tear-resistant.
Description
Technical field
The present invention relates to technical field of polymer materials, particularly relate to a kind of biodegradable synthetic paper.
Background technology
Paper-making industry is the important industry of the relation national economic development, and the purposes of paper relates to the every aspect of society and people's life.Along with socioeconomic high speed development, demand and the consumption of global paper product constantly increase.
Traditional paper-making industry is putative to the damage and pollution of environment always, and is the industry that timber and energy consumption are large.The straw pulp, wood pulp, bamboo pulp, flaxen fiber etc. of what the raw material of plain paper used at present is all vegetable fibre.By inference, common wood pulp paper, often producing 1 ton of paper approximately needs 4 tons of timber, is equivalent to the large tree of felling 23 strain.The world today, particularly China, because the forest reserves are gradually few, paper raw material demand becomes a new difficult problem, paper industry is loss green resource greatly, destroy the physical environment that people depend on for existence, the operation such as boiling, bleaching, washing on the other hand in paper industry pulp production can discharge a large amount of waste gas and waste water, can severe contamination and deterioration ecotope.
Along with the enhancing of global environmental consciousness, a large amount of pollution problem pay attention to day by days that the general fibre paper that people produce traditional paper-making industry produces in preparation process.For solving this quagmire for a long time, the synthetic paper being called as " environment protecting paper " is researched and developed widely by people, so-called synthetic paper is exactly with macromolecular materials such as synthetic resins for main raw material, the matrix material jointly formed with certain organic or inorganic particle components.The matrix material of now widely used synthetic paper is all polymer plastic, especially polyolefin resin, as polyvinyl chloride, polypropylene, it comes from petroleum base, source is non-renewable, and, because these body materials belong to the material of non-biodegradable, often use in use procedure and once namely abandon, cannot recycle, still certain pollution can be caused to environment, therefore, need the synthetic paper providing environment more friendly, in addition, the easy embrittlement of material of traditional polyolefins is broken, ductility and toughness poor, this kind of synthetic paper is when bending, easily rupture in bending place, have a strong impact on its application.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of novel biodegradable synthetic paper, and it can biological degradation, and avoid environmental pollution, meanwhile, not easily embrittlement is broken, and ductility and good toughness, folding is tear-resistant.
For solving the problems of the technologies described above, the invention provides a kind of novel biodegradable synthetic paper, its raw material comprises degradable macromolecule resin, mineral filler, folding properties-correcting agent, static inhibitor, mixed accelerators and lubricant.
Wherein, the weight part of described each raw material is respectively degradable macromolecule resin 100 weight part, mineral filler 50 ~ 150 weight part, folding properties-correcting agent 30 ~ 50 weight part, static inhibitor 10 ~ 30 weight part, mixed accelerators 20 ~ 40 weight part, lubricant 10 ~ 30 weight part.
Wherein, described mineral filler can select one or more mixing in calcium carbonate, silicon-dioxide, montmorillonite, titanium dioxide or talcum powder.
Wherein, described static inhibitor adopts one or more mixing in polyvinyl chloride, polypropylene, polyethylene terephthalate, ethoxylated alkyl acid amide etc., for preventing the course of processing or product generation electrostatic.
Wherein, described lubricant is preferably one or more mixing in polyethylene wax, stearic acid.
Wherein, described degradable macromolecule resin is yam starch-chitosan hydrochloride-acrylamide-allylamine hydrochloride resin.
Wherein, the preparation method of described degradable macromolecule resin comprises,
The first step, weigh 3kg chitosan, add the hydrochloric acid that 5L concentration is 0.3mol/L, be stirred to and dissolve completely, add 500g dicyan diamino, under the condition of 100 DEG C, stir 3h to complete reaction, carry out decompress filter after cooling, filtrate uses dehydrated alcohol Precipitation, suction filtration, filter cake uses absolute ethanol washing again, carries out vacuum-drying subsequently, obtains chitosan hydrochloride;
Second step, 500g yam starch and distilled water are mixed, room temperature is cooled to carry out gelatinization 1h under the condition of 80 DEG C after, add chitosan hydrochloride, 500g allylamine hydrochloride and acrylamide solution prepared by the 2kg the first step subsequently to mix, the usage quantity of acrylamide is 4kg, add initiator ammonium persulfate 60g, glycerol 25g, stir the baking oven interior reaction 3h being placed on 65 DEG C, be down to room temperature, reactant poured in acetone, Precipitation, decompress filter final vacuum is dry, obtains product.
Wherein, described mixed accelerators is vinylformic acid-oligochitosan.
Wherein, described folding properties-correcting agent is sulfhydryl-lignin.
Present invention also offers the degradation method of above-mentioned synthetic paper, be specially each raw material to add in proportion in high-speed mixer (or duct type kneader) and fully mix, the material mixed is sent in Banbury mixer and goes preplasticizing, then forcing machine (or plastics processing mill) is transported to through plasticizing of repeatedly plasticating, the material plastified is through metal detector, calendering formation in rolling press can be sent into, material base in calendering formation, plasticated further after continuous calendering and be rolled into certain thickness film, then draw through doff roll, again through cotton ginning, cooling, thickness measuring, batch and obtain goods.
Beneficial effect of the present invention:
Novel biodegradable synthetic paper provided by the invention can biological degradation, and avoid environmental pollution, meanwhile, not easily embrittlement is broken, and ductility and good toughness, folding is tear-resistant.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of yam starch-chitosan hydrochloride-acrylamide-allylamine hydrochloride resin;
Fig. 2 is the infrared spectrum of vinylformic acid-oligochitosan resin;
Fig. 3 is the infrared spectrum of sulfhydryl-lignin.
Embodiment
The invention provides a kind of novel biodegradable synthetic paper, its raw material comprises degradable macromolecule resin, mineral filler, folding properties-correcting agent, static inhibitor, mixed accelerators and lubricant.
Further, described synthetic paper is only prepared from by above-mentioned raw materials.
The weight part of described each raw material is respectively degradable macromolecule resin 100 weight part, mineral filler 50 ~ 150 weight part, folding properties-correcting agent 30 ~ 50 weight part, static inhibitor 10 ~ 30 weight part, mixed accelerators 20 ~ 40 weight part, lubricant 10 ~ 30 weight part.
Further preferably, the weight part of described each raw material is respectively degradable macromolecule resin 100 weight part, mineral filler 100 weight part, folding properties-correcting agent 40 weight part, static inhibitor 20 weight part, mixed accelerators 30 weight part, lubricant 20 weight part.
Described mineral filler can select one or more mixing in calcium carbonate, silicon-dioxide, montmorillonite, titanium dioxide or talcum powder.
Described static inhibitor adopts one or more mixing in polyvinyl chloride, polypropylene, polyethylene terephthalate, ethoxylated alkyl acid amide etc., for preventing the course of processing or product generation electrostatic.
Described lubricant is preferably one or more mixing in polyethylene wax, stearic acid.
Described degradable macromolecule resin is yam starch-chitosan hydrochloride-acrylamide-allylamine hydrochloride resin, and further, its preparation method is specially,
The first step, weigh 3kg chitosan, add the hydrochloric acid that 5L concentration is 0.3mol/L, be stirred to and dissolve completely, add 500g dicyan diamino, under the condition of 100 DEG C, stir 3h to complete reaction, carry out decompress filter after cooling, filtrate uses dehydrated alcohol Precipitation, suction filtration, filter cake uses absolute ethanol washing again, carries out vacuum-drying subsequently, obtains chitosan hydrochloride;
Second step, 500g yam starch and distilled water are mixed, room temperature is cooled to carry out gelatinization 1h under the condition of 80 DEG C after, add chitosan hydrochloride, 500g allylamine hydrochloride and acrylamide solution prepared by the 2kg the first step subsequently to mix, the usage quantity of acrylamide is 4kg, add initiator ammonium persulfate 60g, glycerol 25g, stir the baking oven interior reaction 3h being placed on 65 DEG C, be down to room temperature, reactant poured in acetone, Precipitation, decompress filter final vacuum is dry, obtains product.
Chitosan derives from chitin, and be present in the housing of crustaceans, joint branch class animal, have good film-forming type, biocompatibility and biodegradability, its degraded product can improve micro-ecological environment in soil, can not cause environmental pollution.
Yam starch is a kind of straight chain and attachment natural high moleculer eompound by the polycondensation of A-glucose, and containing a large amount of hydrophilic hydroxyl in its molecule, starch source is extensive, cheap, biodegradable.
The present invention by chitosan hydrochloride, acrylamide, allylamine hydrochloride being condensed together, and adds potato starch graft further, forms one both biodegradable, meanwhile, can be good at the polymer resin ensureing to form synthetic paper effect.
Described mixed accelerators is vinylformic acid-oligochitosan, and its preparation method is specially:
It is in the dilute hydrochloric acid of 4.7 that 1kg oligochitosan, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride 600g, N-hydroxy-succinamide 300g are dissolved in 3LpH value, be stirred to after dissolving completely and add 500g vinylformic acid, room temperature lower magnetic force stirring reaction 72 h.After having reacted, reaction product is slowly poured into 150 mL dehydrated alcohols, stir and make the abundant Precipitation of chitosan derivatives, vacuum filtration, get filter cake seasoning and obtain product.
Described folding properties-correcting agent is sulfhydryl-lignin, its preparation method is specially, and adds 1kg Thiovanic acid, 0.35kg diacetyl oxide, the acetic acid of 1L36% and the 300g vitriol oil successively, fully stir in reaction vessel, add 2kg xylogen dry sample again, stir, mix, be put in subsequently in 40 DEG C of baking ovens and take out after constant temperature 2d, suction filtration, after distilled water fully washs, drying under reduced pressure under normal temperature, obtains sulfhydryl-lignin.
Present invention also offers the degradation method of above-mentioned synthetic paper, be specially each raw material to add in proportion in high-speed mixer (or duct type kneader) and fully mix, the material mixed is sent in Banbury mixer and goes preplasticizing, then forcing machine (or plastics processing mill) is transported to through plasticizing of repeatedly plasticating, the material plastified is through metal detector, calendering formation in rolling press can be sent into, material base in calendering formation, plasticated further after continuous calendering and be rolled into the film of 30 ~ 200 μm, then draw through doff roll, again through cotton ginning, cooling, thickness measuring, batch and obtain goods.
Below adopt embodiment to describe embodiments of the present invention in detail, to the present invention, how utilisation technology means solve technical problem whereby, and the implementation procedure reaching technique effect can fully understand and implement according to this.
The preparation of embodiment 1 yam starch-chitosan hydrochloride-acrylamide-allylamine hydrochloride resin
Weigh 3kg chitosan, add the hydrochloric acid that 5L concentration is 0.3mol/L, be stirred to and dissolve completely, add 500g dicyan diamino, 3h is stirred to complete reaction under the condition of 100 DEG C, decompress filter is carried out after cooling, filtrate uses dehydrated alcohol Precipitation, suction filtration, filter cake uses absolute ethanol washing again, carry out vacuum-drying subsequently, obtain chitosan hydrochloride, 500g yam starch and distilled water are mixed, room temperature is cooled to carry out gelatinization 1h under the condition of 80 DEG C after, add chitosan hydrochloride prepared by the 2kg the first step subsequently, 500g allylamine hydrochloride and acrylamide solution mix, the usage quantity of acrylamide is 4kg, add initiator ammonium persulfate 60g, glycerol 25g, stir the baking oven interior reaction 3h being placed on 65 DEG C, be down to room temperature, reactant is poured in acetone, Precipitation, decompress filter final vacuum is dry, obtain product, the infrared spectrum of prepared product as shown in Figure 1.
The preparation of embodiment 2 vinylformic acid-oligochitosan
It is in the dilute hydrochloric acid of 4.7 that 1kg oligochitosan, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride 600g, N-hydroxy-succinamide 300g are dissolved in 3LpH value, be stirred to after dissolving completely and add 500g vinylformic acid, room temperature lower magnetic force stirring reaction 72 h.After having reacted, reaction product is slowly poured into 150 mL dehydrated alcohols, stir and make the abundant Precipitation of chitosan derivatives, vacuum filtration, get filter cake seasoning and obtain product, the infrared spectrum of product as shown in Figure 2.
The preparation of embodiment 3 sulfhydryl-lignin
1kg Thiovanic acid, 0.35kg diacetyl oxide, the acetic acid of 1L36% and the 300g vitriol oil is added successively in reaction vessel, abundant stirring, add 2kg xylogen dry sample again, stir, mix, be put in subsequently in 40 DEG C of baking ovens and take out after constant temperature 2d, suction filtration, after distilled water fully washs, drying under reduced pressure under normal temperature, obtain product, the infrared spectrum of product as shown in Figure 3.
The preparation of embodiment 4 synthetic paper 1
Macromolecule resin 10kg prepared by embodiment 1, mineral filler titanium dioxide 10kg, folding properties-correcting agent 4kg prepared by embodiment 3, static inhibitor polypropylene 2kg, mixed accelerators 3kg prepared by embodiment 2, lubricant polyethylene wax 2kg adds in high-speed mixer and fully mixes, the material mixed is sent in Banbury mixer and goes preplasticizing, then forcing machine (or plastics processing mill) is transported to through plasticizing of repeatedly plasticating, the material plastified is through metal detector, calendering formation in rolling press can be sent into, material base in calendering formation, plasticated further after continuous calendering and be rolled into the film of 150 μm, then draw through doff roll, again through cotton ginning, cooling, thickness measuring, batch and obtain goods.
The preparation of comparative example 1 synthetic paper 2
Macromolecule resin 10kg prepared by embodiment 1, mineral filler titanium dioxide 10kg, static inhibitor polypropylene 2kg, mixed accelerators 3kg prepared by embodiment 2, lubricant polyethylene wax 2kg adds in high-speed mixer and fully mixes, the material mixed is sent in Banbury mixer and goes preplasticizing, then forcing machine (or plastics processing mill) is transported to through plasticizing of repeatedly plasticating, the material plastified is through metal detector, calendering formation in rolling press can be sent into, material base in calendering formation, plasticated further after continuous calendering and be rolled into the film of 150 μm, then draw through doff roll, again through cotton ginning, cooling, thickness measuring, batch and obtain goods.
The preparation of comparative example 2 synthetic paper 3
Macromolecule resin 10kg prepared by embodiment 1, mineral filler titanium dioxide 10kg, folding properties-correcting agent 4kg prepared by embodiment 3, static inhibitor polypropylene 2kg, lubricant polyethylene wax 2kg adds in high-speed mixer and fully mixes, the material mixed is sent in Banbury mixer and goes preplasticizing, then forcing machine (or plastics processing mill) is transported to through plasticizing of repeatedly plasticating, the material plastified is through metal detector, calendering formation in rolling press can be sent into, material base in calendering formation, plasticated further after continuous calendering and be rolled into the film of 150 μm, then draw through doff roll, again through cotton ginning, cooling, thickness measuring, batch and obtain goods.
Biological degradability is evaluated
Synthetic paper 2 prepared by the synthetic paper 1 embodiment 4 prepared, comparative example 1, synthetic paper 3 prepared by comparative example 2 and traditional PP synthetic paper are embedded in the soil in field, the degraded areas of the in the past postevaluation (5cm × 5cm) at three months, 1-is at all without any degraded; 2-degraded areas is still less than 30% more than 0%; 3-degraded areas is still less than 70% more than 30%; 4-degraded areas is more than 70%.
In the present invention, the tensile index of paper, tear index, folding endurance are respectively according to the measurement (GB/T 451.2-2002) that national standard paper and paperboard is quantitative, the mensuration constant rate of extension method (100mm/min) (GB/T 22898-2008) of paper tensile strength, the mensuration (GB/T 455-2002) of the tearability of paper, mensuration (GB/T 457-2008) method of folding endurance is tested.
Table 1 between each paper performance test.
Table 1
As can be seen from Table 1, the folding resistance of the synthetic paper adopting raw material provided by the invention to be prepared into is higher than the performance of traditional PP synthetic paper, and biodegradability is strong, is a kind of good environmental protection synthetic paper.
All above-mentioned this intellecture properties of primary enforcement, not setting restriction this product innovation of other forms of enforcement and/or novel method.Those skilled in the art will utilize this important information, and foregoing is revised, to realize similar implementation status.But all modifications or transformation belong to the right of reservation based on product innovation of the present invention.
The above is only preferred embodiment of the present invention, and be not restriction the present invention being made to other form, any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the Equivalent embodiments of equivalent variations.But everyly do not depart from technical solution of the present invention content, any simple modification, equivalent variations and the remodeling done above embodiment according to technical spirit of the present invention, still belong to the protection domain of technical solution of the present invention.
Claims (5)
1. a novel biodegradable synthetic paper, is characterized in that raw material comprises:
Degradable yam starch-chitosan hydrochloride-acrylamide-allylamine hydrochloride resin macromolecule resin 100 weight part
Mineral filler 50 ~ 150 weight part
Folding properties-correcting agent 30 ~ 50 weight part
Static inhibitor 10 ~ 30 weight part
Mixed accelerators 20 ~ 40 weight part
Lubricant 10 ~ 30 weight part
The preparation method of described degradable yam starch-chitosan hydrochloride-acrylamide-allylamine hydrochloride resin macromolecule resin is specially:
The first step, weigh 3kg chitosan, add the hydrochloric acid that 5L concentration is 0.3mol/L, be stirred to and dissolve completely, add 500g dicyan diamino, under the condition of 100 DEG C, stir 3h to complete reaction, carry out decompress filter after cooling, filtrate uses dehydrated alcohol Precipitation, suction filtration, filter cake uses absolute ethanol washing again, carries out vacuum-drying subsequently, obtains chitosan hydrochloride;
Second step, 500g yam starch and distilled water are mixed, room temperature is cooled to carry out gelatinization 1h under the condition of 80 DEG C after, add chitosan hydrochloride, 500g allylamine hydrochloride and acrylamide solution prepared by the 2kg the first step subsequently to mix, the usage quantity of acrylamide is 4kg, add initiator ammonium persulfate 60g, glycerol 25g, stir the baking oven interior reaction 3h being placed on 65 DEG C, be down to room temperature, reactant poured in acetone, Precipitation, decompress filter final vacuum is dry, obtains product;
Described mixed accelerators is vinylformic acid-oligochitosan, and its preparation method is specially:
It is in the dilute hydrochloric acid of 4.7 that 1kg oligochitosan, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride 600g, N-N-Hydroxysuccinimide 300g are dissolved in 3LpH value, be stirred to after dissolving completely and add 500g vinylformic acid, room temperature lower magnetic force stirring reaction 72 h.After having reacted, reaction product is slowly poured into 150 mL dehydrated alcohols, stir and make the abundant Precipitation of chitosan derivatives, vacuum filtration, get filter cake seasoning and obtain product;
Described folding properties-correcting agent is sulfhydryl-lignin, and its preparation method is specially:
1kg Thiovanic acid, 0.35kg diacetyl oxide, the acetic acid of 1L36% and the 300g vitriol oil is added successively in reaction vessel, abundant stirring, add 2kg xylogen dry sample again, stir, mix, be put in subsequently in 40 DEG C of baking ovens and take out after constant temperature 2d, suction filtration, after distilled water fully washs, drying under reduced pressure under normal temperature, obtains sulfhydryl-lignin.
2. biodegradable synthetic paper novel as claimed in claim 1, is characterized in that: described mineral filler can select one or more mixing in calcium carbonate, silicon-dioxide, montmorillonite, titanium dioxide or talcum powder.
3. biodegradable synthetic paper novel as claimed in claim 1 or 2, it is characterized in that: described static inhibitor adopts one or more mixing in polyvinyl chloride, polypropylene, polyethylene terephthalate, ethoxylated alkyl acid amide etc., for preventing the course of processing or product generation electrostatic.
4. the novel biodegradable synthetic paper as described in claim 1-3 any one, is characterized in that: described lubricant is preferably one or more mixing in polyethylene wax, stearic acid.
5. the degradation method of biodegradable synthetic paper novel described in claim 1, it is characterized in that: each raw material is added in proportion in high-speed mixer or duct type kneader and fully mix, the material mixed is sent in Banbury mixer and goes preplasticizing, then forcing machine or plastics processing mill is transported to through plasticizing of repeatedly plasticating, the material plastified is through metal detector, calendering formation in rolling press can be sent into, material base in calendering formation, plasticated further after continuous calendering and be rolled into certain thickness film, then draw through doff roll, again through cotton ginning, cooling, thickness measuring, batch and obtain goods.
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| CN105198284A (en) * | 2015-08-18 | 2015-12-30 | 浙江华川实业集团有限公司 | Environmentally-friendly paper and preparing method thereof |
| CN105219004B (en) * | 2015-11-05 | 2017-12-29 | 广州景盛纸制品有限公司 | A kind of degradable plant fibre paper and preparation method thereof |
| CN107603070B (en) * | 2017-10-16 | 2022-04-19 | 河北凯成包装股份有限公司 | Processing technology of high-molecular synthetic paper |
| CN108129786A (en) * | 2017-12-20 | 2018-06-08 | 宁波爱克创威新材料科技有限公司 | A kind of super-hydrophobic tear-resistant plant fiber paper and preparation method thereof |
| CN112080960A (en) * | 2020-09-30 | 2020-12-15 | 王雪峰 | Special fire-resistant, mildew-proof and moisture-proof agent for plant fiber products and preparation method thereof |
| CN116289301B (en) * | 2023-03-22 | 2023-10-10 | 冠宏化工（扬州）有限公司 | Modified filler for papermaking and preparation method thereof |
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| CN1381521A (en) * | 2001-04-23 | 2002-11-27 | 黑龙江齐塑塑料制品有限责任公司 | Process for preparing synthetic polyolefin paper |
| CN101195674A (en) * | 2006-12-06 | 2008-06-11 | 新疆大学 | Method for producing starch based amphiprotic absorbent resin with semi-interpenetrating network configuration |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1381521A (en) * | 2001-04-23 | 2002-11-27 | 黑龙江齐塑塑料制品有限责任公司 | Process for preparing synthetic polyolefin paper |
| CN101195674A (en) * | 2006-12-06 | 2008-06-11 | 新疆大学 | Method for producing starch based amphiprotic absorbent resin with semi-interpenetrating network configuration |
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Inventor after: Yang Junhui Inventor after: Ye Donglin Inventor after: Li Yong Inventor after: Chen Jiazhang Inventor before: Bai Chunsheng |
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Effective date of registration: 20180104 Address after: 343100 Shenzhen Avenue, Jinggangshan economic and Technological Development Zone, Ji'an, Jiangxi Province, No. 286 Patentee after: Jiangxi crown new material Polytron Technologies Inc Address before: 235000 Anhui city of Huaibei province Longhu project area after a road east to the north of Zhang Xu Patentee before: The Huaibei rich safe heavy industry company limited |