CN104059320A - 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, relate in particular to a kind of biodegradable synthetic paper.
background technology
Paper-making industry is the important industry that is related to the 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 of what the raw material of plain paper used at present is all vegetable fibre, wood pulp, bamboo pulp, flaxen fiber etc.By inference, common wood pulp paper, 1 ton of paper of every production approximately needs 4 tons of timber, is equivalent to cut down the large tree of 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 greatly loss green resource, destroyed the physical environment that people depend on for existence, a large amount of waste gas and waste water are discharged in the operation meeting such as the boiling in paper industry pulp production, bleaching, washing on the other hand, can severe contamination and worsen 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 that is called as " environment protecting paper " is researched and developed widely by people, so-called synthetic paper is exactly taking macromolecular materials such as synthetic resins as main raw material, with certain common matrix material forming of organic or inorganic particulate composition.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 abiotic degradability, in use procedure, often use and once abandon, cannot recycle, still can cause certain pollution to environment, therefore, need to provide environment more friendly synthetic paper, in addition, the easy embrittlement of material of traditional polyolefins is broken, ductility and toughness are poor, this class synthetic paper is in the time of 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, avoids environmental pollution, and meanwhile, be difficult for embrittlement and break, 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 parts, mineral filler 50 ~ 150 weight parts, folding properties-correcting agent 30 ~ 50 weight parts, static inhibitor 10 ~ 30 weight parts, mixed accelerators 20 ~ 40 weight parts, lubricant 10 ~ 30 weight parts.
Wherein, described mineral filler can be selected 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 static.
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, adding 5L concentration is the hydrochloric acid of 0.3mol/L, is stirred to completely and dissolves, add 500g dicyan diamino, under the condition of 100 DEG C, stir 3h to complete reaction, carry out decompress filter after cooling, filtrate is used dehydrated alcohol Precipitation, suction filtration, filter cake is used absolute ethanol washing again, carries out subsequently vacuum-drying, obtains chitosan hydrochloride;
Second step, 500g yam starch and distilled water are mixed, under the condition of 80 DEG C, carry out being cooled to room temperature after gelatinization 1h, add subsequently chitosan hydrochloride, 500g allylamine hydrochloride and acrylamide solution prepared by the 2kg the first step to mix, the usage quantity of acrylamide is 4kg, add initiator ammonium persulfate 60g, glycerol 25g, stir and be placed on the interior reaction of the baking oven 3h of 65 DEG C, be down to room temperature, reactant poured in acetone into 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.
The present invention also provides the degradation method of above-mentioned synthetic paper, be specially each raw material is added in proportion in high-speed mixer (or duct type kneader) and fully mixed, the material mixing is sent to and in Banbury mixer, goes preplasticizing, then be transported to forcing machine (or plastics processing mill) through the plasticizing of repeatedly plasticating, the material having plastified is through metal detector, can send into calendering formation in rolling press, material base in calendering formation, after continuous calendering, further plasticated 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, avoids environmental pollution, and meanwhile, be difficult for embrittlement and break, ductility and good toughness, folding is tear-resistant.
brief description of the drawings
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 parts, mineral filler 50 ~ 150 weight parts, folding properties-correcting agent 30 ~ 50 weight parts, static inhibitor 10 ~ 30 weight parts, mixed accelerators 20 ~ 40 weight parts, lubricant 10 ~ 30 weight parts.
Further preferably, the weight part of described each raw material is respectively degradable macromolecule resin 100 weight parts, mineral filler 100 weight parts, folding properties-correcting agent 40 weight parts, static inhibitor 20 weight parts, mixed accelerators 30 weight parts, lubricant 20 weight parts.
Described mineral filler can be selected 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 static.
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, adding 5L concentration is the hydrochloric acid of 0.3mol/L, is stirred to completely and dissolves, add 500g dicyan diamino, under the condition of 100 DEG C, stir 3h to complete reaction, carry out decompress filter after cooling, filtrate is used dehydrated alcohol Precipitation, suction filtration, filter cake is used absolute ethanol washing again, carries out subsequently vacuum-drying, obtains chitosan hydrochloride;
Second step, 500g yam starch and distilled water are mixed, under the condition of 80 DEG C, carry out being cooled to room temperature after gelatinization 1h, add subsequently chitosan hydrochloride, 500g allylamine hydrochloride and acrylamide solution prepared by the 2kg the first step to mix, the usage quantity of acrylamide is 4kg, add initiator ammonium persulfate 60g, glycerol 25g, stir and be placed on the interior reaction of the baking oven 3h of 65 DEG C, be down to room temperature, reactant poured in acetone into Precipitation, decompress filter final vacuum is dry, obtains product.
Chitosan derives from chitin, is present in the housing of crustaceans, joint branch class animal, has good film-forming type, biocompatibility and biodegradability, and 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 being formed by the polycondensation of A-glucose, contains a large amount of hydrophilic hydroxyls in its molecule, and starch source is extensive, cheap, biodegradable.
The present invention is by chitosan hydrochloride, acrylamide, allylamine hydrochloride are condensed together, and further adds potato starch graft, forms one both biodegradable, meanwhile, can be good at ensureing to form the polymer resin of synthetic paper effect.
Described mixed accelerators is vinylformic acid-oligochitosan, and its preparation method is specially:
It is in 4.7 dilute hydrochloric acid that 1kg oligochitosan, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride 600g, N-hydroxy-succinamide 300g are dissolved in to 3LpH value, be stirred to completely and add 500g vinylformic acid, room temperature lower magnetic force stirring reaction 72 h after dissolving.After having reacted, slowly pour reaction product into 150 mL dehydrated alcohols, stir and make the abundant Precipitation of chitosan derivatives, vacuum filtration, gets filter cake seasoning and obtains product.
Described folding properties-correcting agent is sulfhydryl-lignin, its preparation method is specially, and adds successively acetic acid and the 300g vitriol oil of 1kg Thiovanic acid, 0.35kg diacetyl oxide, 1L36% in reaction vessel, fully stirs, add again 2kg xylogen to be dried sample, 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.
The present invention also provides the degradation method of above-mentioned synthetic paper, be specially each raw material is added in proportion in high-speed mixer (or duct type kneader) and fully mixed, the material mixing is sent to and in Banbury mixer, goes preplasticizing, then be transported to forcing machine (or plastics processing mill) through the plasticizing of repeatedly plasticating, the material having plastified is through metal detector, can send into calendering formation in rolling press, material base in calendering formation, after continuous calendering, further plasticated and be rolled into the film of 30～200 μ m, 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 of 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, adding 5L concentration is the hydrochloric acid of 0.3mol/L, be stirred to completely and dissolve, add 500g dicyan diamino, under the condition of 100 DEG C, stir 3h to complete reaction, after cooling, carry out decompress filter, filtrate is used dehydrated alcohol Precipitation, suction filtration, filter cake is used absolute ethanol washing again, carry out subsequently vacuum-drying, obtain chitosan hydrochloride, 500g yam starch and distilled water are mixed, under the condition of 80 DEG C, carry out being cooled to room temperature after gelatinization 1h, the chitosan hydrochloride that adds subsequently the 2kg the first step to prepare, 500g allylamine hydrochloride and acrylamide solution mix, the usage quantity of acrylamide is 4kg, add initiator ammonium persulfate 60g, glycerol 25g, stir and be placed on the interior reaction of the baking oven 3h of 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 4.7 dilute hydrochloric acid that 1kg oligochitosan, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride 600g, N-hydroxy-succinamide 300g are dissolved in to 3LpH value, be stirred to completely and add 500g vinylformic acid, room temperature lower magnetic force stirring reaction 72 h after dissolving.After having reacted, slowly pour reaction product into 150 mL dehydrated alcohols, stir and make the abundant Precipitation of chitosan derivatives, vacuum filtration, gets filter cake seasoning and obtains product, and the infrared spectrum of product as shown in Figure 2.
The preparation of embodiment 3 sulfhydryl-lignins
In reaction vessel, add successively acetic acid and the 300g vitriol oil of 1kg Thiovanic acid, 0.35kg diacetyl oxide, 1L36%, fully stir, add again 2kg xylogen to be dried sample, 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 papers 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 mixing is sent to and in Banbury mixer, goes preplasticizing, then be transported to forcing machine (or plastics processing mill) through the plasticizing of repeatedly plasticating, the material having plastified is through metal detector, can send into calendering formation in rolling press, material base in calendering formation, after continuous calendering, further plasticated and be rolled into the film of 150 μ m, 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 mixing is sent to and in Banbury mixer, goes preplasticizing, then be transported to forcing machine (or plastics processing mill) through the plasticizing of repeatedly plasticating, the material having plastified is through metal detector, can send into calendering formation in rolling press, material base in calendering formation, after continuous calendering, further plasticated and be rolled into the film of 150 μ m, then draw through doff roll, again through cotton ginning, cooling, thickness measuring, batch and obtain goods.
The preparation of comparative example 2 synthetic papers 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 mixing is sent to and in Banbury mixer, goes preplasticizing, then be transported to forcing machine (or plastics processing mill) through the plasticizing of repeatedly plasticating, the material having plastified is through metal detector, can send into calendering formation in rolling press, material base in calendering formation, after continuous calendering, further plasticated and be rolled into the film of 150 μ m, then draw through doff roll, again through cotton ginning, cooling, thickness measuring, batch and obtain goods.
Biological degradability is evaluated
Synthetic paper 1 prepared by embodiment 4, synthetic paper 2 prepared by comparative example 1, synthetic paper 3 and traditional PP synthetic paper prepared by comparative example 2 are embedded in the soil in field, the degraded areas of in the past postevaluation (5cm × 5cm) at three months, 1-is at all without any degraded; 2-degraded areas exceedes 0% and is still less than 30%; 3-degraded areas exceedes 30% and is still less than 70%; 4-degraded areas is more than 70%.
In the present invention, the tensile index of paper, tear index, folding endurance are respectively according to national standard paper and the quantitative measurement (GB/T 451.2-2002) of cardboard, the mensuration constant speed stretching 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, adopt the folding resistance of the synthetic paper that raw material provided by the invention is prepared into higher than the performance of traditional PP synthetic paper, biodegradability is strong, is a kind of good environmental protection synthetic paper.
All above-mentioned these intellecture properties of primary enforcement, do not set 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 amendment, 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, be only preferred embodiment of the present invention, is not the restriction of the present invention being made to other form, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations.But every technical solution of the present invention content that do not depart from, any simple modification, equivalent variations and the remodeling above embodiment done according to technical spirit of the present invention, still belong to the protection domain of technical solution of the present invention.
Claims (9)
1. a novel biodegradable synthetic paper, is characterized in that: raw material comprises degradable yam starch-chitosan hydrochloride-acrylamide-allylamine hydrochloride resin macromolecule resin, mineral filler, folding properties-correcting agent, static inhibitor, mixed accelerators and lubricant.
2. synthetic paper as claimed in claim 1, is characterized in that: the weight part of described each raw material is respectively degradable macromolecule resin 100 weight parts, mineral filler 50 ~ 150 weight parts, folding properties-correcting agent 30 ~ 50 weight parts, static inhibitor 10 ~ 30 weight parts, mixed accelerators 20 ~ 40 weight parts, lubricant 10 ~ 30 weight parts.
3. synthetic paper as claimed in claim 1 or 2, is characterized in that: described mineral filler can be selected one or more mixing in calcium carbonate, silicon-dioxide, montmorillonite, titanium dioxide or talcum powder.
4. the synthetic paper as described in claims 1 to 3, 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 static.
5. the synthetic paper as described in claim 1 to 4, is characterized in that: described lubricant is preferably one or more mixing in polyethylene wax, stearic acid.
6. the synthetic paper as described in claim 1 to 5, is characterized in that: the preparation method of described degradable macromolecule resin comprises,
The first step, weigh 3kg chitosan, adding 5L concentration is the hydrochloric acid of 0.3mol/L, is stirred to completely and dissolves, add 500g dicyan diamino, under the condition of 100 DEG C, stir 3h to complete reaction, carry out decompress filter after cooling, filtrate is used dehydrated alcohol Precipitation, suction filtration, filter cake is used absolute ethanol washing again, carries out subsequently vacuum-drying, obtains chitosan hydrochloride;
Second step, 500g yam starch and distilled water are mixed, under the condition of 80 DEG C, carry out being cooled to room temperature after gelatinization 1h, add subsequently chitosan hydrochloride, 500g allylamine hydrochloride and acrylamide solution prepared by the 2kg the first step to mix, the usage quantity of acrylamide is 4kg, add initiator ammonium persulfate 60g, glycerol 25g, stir and be placed on the interior reaction of the baking oven 3h of 65 DEG C, be down to room temperature, reactant poured in acetone into Precipitation, decompress filter final vacuum is dry, obtains product.
7. the synthetic paper as described in claim 1 to 6, is characterized in that: described mixed accelerators is vinylformic acid-oligochitosan.
8. the synthetic paper as described in claim 1 to 7, is characterized in that: described folding properties-correcting agent is sulfhydryl-lignin.
9. the degradation method of synthetic paper described in claim 1 to 8, it is characterized in that: each raw material is added in proportion in high-speed mixer (or duct type kneader) and fully mixed, the material mixing is sent to and in Banbury mixer, goes preplasticizing, then be transported to forcing machine (or plastics processing mill) through the plasticizing of repeatedly plasticating, the material having plastified is through metal detector, can send into calendering formation in rolling press, material base in calendering formation, after continuous calendering, further plasticated 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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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN105219004A (en) * | 2015-11-05 | 2016-01-06 | 蒋金香 | A kind of degradable plant fibre paper and preparation method thereof |
| CN107603070A (en) * | 2017-10-16 | 2018-01-19 | 河北凯成包装股份有限公司 | The processing technology of Polymer Synthesizing 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 |
| CN116289301A (en) * | 2023-03-22 | 2023-06-23 | 冠宏化工（扬州）有限公司 | Modified filler for papermaking and preparation method thereof |
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| CN1202166C (en) * | 2001-04-23 | 2005-05-18 | 齐齐哈尔齐塑塑料制品有限公司 | Process for preparing synthetic polyolefin paper |
| CN101195674B (en) * | 2006-12-06 | 2011-06-08 | 新疆大学 | Method for producing starch based amphiprotic absorbent resin with semi-interpenetrating network configuration |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN105219004A (en) * | 2015-11-05 | 2016-01-06 | 蒋金香 | A kind of degradable plant fibre paper and preparation method thereof |
| CN107603070A (en) * | 2017-10-16 | 2018-01-19 | 河北凯成包装股份有限公司 | The processing technology of Polymer Synthesizing 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 |
| CN116289301A (en) * | 2023-03-22 | 2023-06-23 | 冠宏化工（扬州）有限公司 | Modified filler for papermaking 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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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 |
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