• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention discloses a preparation method of lignin-chitosan based fluoride-free high-strength super-hydrophobic paper, and relates to the technical field of papermaking and polymeric functional materials; dissolving alkali lignin in a polar solvent, slowly adding an initiator to an obtained alkali lignin solution, heating to 90-180°C under protection of nitrogen, slowly adding long-chain alkane methoxysilane to react to obtain a modified alkali lignin solution, settling and purifying the modified alkali lignin solution to separate out an alkali lignin modifier, drying for later use, dissolving the alkali lignin modifier in the polar solvent again to obtain an alkali lignin modifier solution, soaking a paper pulp in the solution, stirring and adding chitosan, and performing papermaking to obtain super-hydrophobic paper; the super-hydrophobic paper has strong hydrophobicity, reutilization property and seal-cleaning capacity, is simple in operation, adopts raw materials which are cheap and rich in source, belongs to cyclic comprehensive application of biomass raw materials, and thus has good application prospect and economical benefit in the fields of waterproof protection of transport package, fresh food cold storage and high-end products.
    公开号:NL2025890A
    申请号:NL2025890
    申请日:2020-06-23
    公开日:2021-01-26
    发明作者:Wang Shoujuan；Sun Haodong；Kong Fangong
    申请人:Univ Qilu Technology；
    IPC主号:
    专利说明:

    Preparation method of lighin-chitosan based fluoride-free high-strength super-hydrophobic paper
    TECHNICAL FIELD The present invention discloses a preparation method of lignin-chitosan based fluoride-free high-strength super-hydrophobic paper, and relates to the technical field of papermaking and polymeric functional materials.
    BACKGROUD Lignin is wide in resource in the nature, is an essential component in plant raw materials, ranking only second to cellulose, and is one of the richest natural high polymers of the nature. Lignin combines cellulose with hemicellulose by a chemical or physical method, to increase the physical strength of wood, so that wood can completely grow in a natural environment without corrosion. In pulping and papermaking processes, lignin is removed by a digesting process, and cellulose is remained to be used for producing paper. The removed lignin mainly exists in a black liquor, while lignin adopted in the present invention is separated from alkaline papermaking black liquor, and thus belongs to economic cyclic utilization of plant raw materials.
    Chitosan is also known as deacetylated chitin, is the only amino polysaccharide found in large quantities in nature, with chemical name of polyglucosamine (1-4)-2-amino-B-D-glucose, is a six-membered ring high- molecular compound, contains three active groups including primary and secondary hydroxyl groups and amino, and can form hydrogen bond connection with cellulose.
    The present invention provides a preparation method of lignin-chitosan based fluoride-free high-strength super-hydrophobic paper, which processes fiber by utilizing modified lignin and chitosan to form high-strength super-hydrophobic paper, a contact angle of the super-hydrophobic paper is greater than 150°, a sliding angle is smaller than 10°, due to superstrong hydrophobic and oleophilic properties, the super-hydrophobic paper can be used for transport package, especially package and transport of fresh food and chilled food, and compared with a polymerization isolation coating and a wax coating on a paper surface in waterproof property, the super-hydrophobic paper obtained in the present invention is more economical, simple in operation, adopts raw materials which are cheap and rich in source, is fluoride-free and good in safety, belongs to cyclic comprehensive application of biomass raw materials, and thus has good application prospect and economical benefit.
    SUMMARY Directed to problems of the prior art, the present invention provides a preparation method of lignin-chitosan based fluoride-free high-strength super- hydrophobic paper, which modifies soaked fiber pulp by utilizing modified lignin and chitosan in a mechanical solvent, to obtain super-hydrophobic lignin-chitosan high- strength fiber paper.
    A specific scheme provided by the present invention is: a preparation method of lignin-chitosan based fluoride-free high-strength super-hydrophobic paper, comprising: dissolving alkali lignin in a polar solvent, slowly adding an initiator to an obtained alkali lignin solution, heating to 90- 180°C under protection of nitrogen, slowly adding long-chain alkane methoxysilane to react to obtain a modified alkali lignin solution, settling and purifying the modified alkali lignin solution to separate out an alkali lignin modifier, and drying for later use, and dissolving the alkali lignin modifier in the polar solvent again to obtain an alkali lignin modifier solution, soaking a paper pulp in the solution, stirring and adding chitosan, and performing papermaking to obtain super-hydrophobic paper.
    According to the preparation method, dissolving alkali lignin in any polar solvent out of acetone, dioxane, N,N-dimethylformamide and DMSO.
    According to the preparation method, slowly adding a triethylamine or sodium alkoxide initiator with mass concentration of 1%-10% to an obtained alkali lignin solution.
    According to the preparation method, slowly adding an initiator to an obtained alkali lignin solution, heating to 90-180°C under the protection of nitrogen, and slowly adding long-chain alkane methoxysilane with mass concentration of 1%- 20% to react to obtain a modified alkali lignin solution.
    According to the preparation method, reacting for 2-10h to obtain a modified alkali lignin solution. According to the preparation method, the long-chain alkane methoxysilane refers to that from dodecyl! trimethylsilane to octadecy! trimethylsilane.
    According to the preparation method, dissolving alkali lignin in a polar solvent, to obtain an alkali lignin solution with mass concentration of 5%-15%.
    According to the preparation method, the mass fraction of a modified alkali lignin solution obtained after reacting is 5%-15%.
    According to the preparation method, the mass percent of chitosan is
    0.01%-0.2%.
    According to the preparation method, the paper pulp is one or mixed pulp of several out of needlebush pulp, hardwood pulp, old newpaper or straw pulp, bamboo pulp and sugarcane pulp.
    According to the preparation method, the mass percent of paper pulp in papermaking is 10%-40%.
    According to the preparation method, the beating degree of the paper pulp is 30°SR-50°SR.
    A lignin-chitosan based fluoride-free high-strength super-hydrophobic paper, prepared according to the foregoing preparation method.
    An application implemented by utilizing the lignin-chitosan based fluoride- free high-strength super-hydrophobic paper.
    The present invention has the following benefits: the present invention provides a preparation method of lignin-chitosan based fluoride-iree high-strength super-hydrophobic paper, in which, alkali lignin is dissolved in a polar solvent to obtain a lignin solution, an initiator is added to the lignin solution, and pretreatment is performed on lignin in the solution by utilizing strong basicity of the initiator to increase the quantity of phenolic hydroxyl groups, heating is performed under the protection of nitrogen to generate hydrolysis reaction with long-chain alkane methoxysilane, so as to realize silylation of lignin and obtain super-hydrophobic modified lignin of a net stereostructure of a long- chain alkane methoxysilane framework, meanwhile, lignin contains a large quantity of hydroxide radicals and has certain rigidity, which lays good foundation for grafting reagents with low surface energy and constructing rough surfaces, so that fiber soaked in an alkali lignin modifier solution can adsorb modified lignin to have a super-hydrophobic property, meanwhile, chitosan is added to the system, hydroxyl groups and amino groups of chitosan from hydrogen bonds with fiber, so as to greatly promote the strength properties of fiber, and compared with existing paper, the super-hydrophobic paper has remarkable mechanical strength, and meanwhile, contact angles of super-hydrophobic lignin paper all reach above 150°, and the super-hydrophobic property of paper is remarkable, thereby being suitable for application with special requirements such as water resistance and moisture resistance.
    BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow diagram of a method of the present invention; FIG. 2 is a schematic infrared spectrum contrast diagram of alkali lignin before and after modification, infrared absorption peaks at 1064cm! and 7200m! respectively representing the stretching vibration of an O-Si-O bond and an Si-C bond, indicating that a graft has already exist on lignin.
    FIG. 3 is an SEM diagram of original paper, paper fibre being smooth and clear and distinct.
    FIG. 4 is an SEM diagram of modified paper, particles attaching to the surface of paper fiber, to form a rough surface.
    FIG. 5 is a picture of a paper contact angle, a contact angle being 155°.
    DESCRIPTION OF THE EMBODIMENTS The present invention provides a preparation method of lignin-chitosan based fluoride-free high-strength super-hydrophobic paper, comprising: dissolving alkali lignin in a polar solvent, slowly adding an initiator to an obtained alkali lignin solution, heating to 90- 180°C under protection of nitrogen, slowly adding long-chain alkane methoxysilane to react to obtain a modified alkali lignin solution, settling and purifying the modified alkali lignin solution to separate out an alkali lignin modifier, and drying for later use, and dissolving the alkali lignin modifier in the polar solvent again to obtain an atkali lignin modifier solution, soaking a paper pulp in the solution, stirring and adding chitosan, and performing papermaking to obtain super-hydrophobic paper.
    Meanwhile, the present invention provides a lignin-chitosan based fluoride- free high-strength super-hydrophobic paper prepared by utilizing the foregoing preparation method.
    Alkali lignin processed with long-chain alkane methoxysilane to obtain modified alkali lignin, and a chemical equation is as follows:
    ~~ J = Ho on he 0) oF Ng | © de © an GP ein ee A cx,
    Ï The following further describes the present invention in combination with drawings and specific embodiments, so that technicians of the field may better understand and implement the present invention, however, the embodiments 5 should not be deemed as limitation to the present invention. Embodiment 1 a. taking 5g of needlebush pulp (absolutely dry), defibering for 3min, filtering to remove moisture to be processed; b. dissolving alkali lignin in DMF to prepare an alkali lignin solution with mass fraction of 10%, dissolving sodium methoxide in ethanol to prepare a sodium methoxide solution with mass fraction of 2%, slowly mixing the alkali lignin solution with the sodium methoxide solution, heating to 90°C under the protection of nitrogen, then slowly adding tetradecyl trimethoxy silane with mass fraction of
    3.5%, reacting and stirring for 5h to form a steady modified alkali lignin solution; settling and separating out modified alkali lignin with ethanol to obtain an alkali lignin modifier which is then dried for later use; and c. dissolving the alkali lignin modifier in DMF to prepare an alkali lignin modifier solution with mass fraction of 5%, soaking the needlebush fiber after being processed in a in the alkali lignin modifier solution, stirring for 2h at room temperature and then adding 0.01% chitosan to continue to stir for 1.5h, papermaking beating degree being 30°SR and mass percent of paper pulp being 10%, and drying to obtain a micro-nano modified and alkali lignin modified paper, the surface contact angle of which reaching 152°, which reaches a super- hydrophobicity level.
    Embodiment 2 a. taking 5g of hardwood pulp (absolutely dry), defibering for 4min, filtering to remove moisture to be processed; b. dissolving alkali lignin in DMF to prepare an alkali lignin solution with mass fraction of 10%, dissolving sodium methoxide in ethanol to prepare a sodium methoxide solution with mass fraction of 1%, slowly mixing the alkali lignin solution with the sodium methoxide solution, heating to 110°C under the protection of nitrogen, then slowly adding dodecyl trimethoxy silane with mass fraction of 1%, reacting and stirring for 4h to form a steady modified alkali lignin solution; settling and separating out modified alkali lignin with ethanol to obtain an alkali lignin modifier which is then dried for later use; and c. dissolving the alkali lignin modifier in DMF to prepare an alkali lignin modifier solution with mass fraction of 10%, soaking the hardwood fiber after being processed in a in the alkali lignin modifier solution, stirring for 3h at room temperature and then adding 0.08% chitosan to continue to stir for 1h, papermaking beating degree being 35°SR and mass percent of paper pulp being 20%, and drying to obtain a micro-nano modified and alkali lignin modified paper, the surface contact angle of which reaching 154°, which reaches a super- hydrophobicity level.
    Embodiment 3 a. taking bg of straw pulp (absolutely dry), defibering for 6min, filtering to remove moisture to be processed; b. dissolving alkali lignin in DMF to prepare an alkali lignin solution with mass fraction of 11%, dissolving sodium methoxide in ethanol to prepare a sodium methoxide solution with mass fraction of 3%, slowly mixing the alkali lignin solution with the sodium methoxide solution, heating to 125°C under the protection of nitrogen, then slowly adding cetyl! trimethoxy silane with mass fraction of 7%, reacting and stirring for 6h to form a steady modified alkali lignin solution; settling and separating out modified alkali lignin with ethanol to obtain an alkali lignin modifier which is then dried for later use; and c. dissolving the alkali lignin modifier in DMF to prepare an alkali lignin modifier solution with mass fraction of 11%, soaking the straw fiber after being processed in a in the alkali lignin modifier solution, stirring for 5h at room temperature and then adding 0.06% chitosan to continue to stir for 1h,
    papermaking beating degree being 40°SR and mass percent of paper pulp being 25%, and drying to obtain a micro-nano modified and alkali lignin modified paper, the surface contact angle of which reaching 150°, which reaches a super- hydrophobicity level.
    Embodiment 4 a. taking bg of straw pulp and waste paper pulp (absolutely dry), defibering for 5min, filtering to remove moisture to be processed; b. dissolving alkali lignin in DMF to prepare an alkali lignin solution with mass fraction of 12%, dissolving sodium methoxide in ethanol to prepare a sodium methoxide solution with mass fraction of 5%, slowly mixing the alkali lignin solution with the sodium methoxide solution, heating to 130°C under the protection of nitrogen, then slowly adding cetyl! trimethoxy silane with mass fraction of 12%, reacting and stirring for 8h to form a steady modified alkali lignin solution; settling and separating out modified alkali lignin with ethanol to obtain an alkali lignin modifier which is then dried for later use; and c. dissolving the alkali lignin modifier in DMF to prepare an alkali lignin modifier solution with mass fraction of 13%, soaking the pulp fiber after being processed in a in the alkali lignin modifier solution, stirring for 8h at room temperature and then adding 0.15% chitosan to continue to stir for 1h, papermaking beating degree being 40°SR and mass percent of paper pulp being 35%, and drying to obtain a micro-nano modified and alkali lignin modified paper, the surface contact angle of which reaching 153°, which reaches a super- hydrophobicity level.
    Embodiment 5 a. taking 5g of bamboo pulp (absolutely dry), defibering for 8min, filtering to remove moisture to be processed; b. dissolving alkali lignin in DMF to prepare an alkali lignin solution with mass fraction of 15%, dissolving sodium methoxide in ethanol to prepare a sodium methoxide solution with mass fraction of 6%, slowly mixing the alkali lignin solution with the sodium methoxide solution, heating to 150°C under the protection of nitrogen, then slowly adding cetyl trimethoxy silane with mass fraction of 16%, reacting and stirring for 2h to form a steady modified alkali lignin solution; settling and separating out modified alkali lignin with ethanol to obtain an alkali lignin modifier which is then dried for later use; and c. dissolving the alkali lignin modifier in DMF to prepare an alkali lignin modifier solution with mass fraction of 15%, soaking the bamboo pulp fiber after being processed in a in the alkali lignin modifier solution, stirring for 5h at room temperature and then adding 0.05% chitosan, papermaking beating degree being 45°SR and mass percent of paper pulp being 35%, and drying to obtain a micro- nano modified and alkali lignin modified paper, the surface contact angle of which reaching 151°, which reaches a super-hydrophobicity level.
    Embodiment 6 a. taking 5g of sugarcane pulp {absolutely dry), defibering for 5min, filtering to remove moisture to be processed; b. dissolving alkali lignin in DMF to prepare an alkali lignin solution with mass fraction of 5%, dissolving sodium methoxide in ethanol to prepare a sodium methoxide solution with mass fraction of 4%, slowly mixing the alkali lignin solution with the sodium methoxide solution, heating to 180°C under the protection of nitrogen, then slowly adding octadecyl trimethoxy silane with mass fraction of 20%, reacting and stirring for 10h to form a steady modified alkali lignin solution; settling and separating out modified alkali lignin with ethanol to obtain an alkali lignin modifier which is then dried for later use; and c. dissolving the alkali lignin modifier in DMF to prepare an alkali lignin modifier solution with mass fraction of 12%, soaking the sugarcane pulp fiber after being processed in a in the alkali lignin modifier solution, stirring for 4h at room temperature and then adding 0.2% chitosan, papermaking beating degree being 50°SR and mass percent of paper pulp being 40%, and drying to obtain a micro- nano modified and alkali lignin modified paper, the surface contact angle of which reaching 155°, which reaches a super-hydrophobicity level. Detection experiment is performed on the mechanical properties of paper, table 1 is a physical and mechanical property table of super-hydrophobic paper.
    Table 1 Samples Compressive Burst index Tearing Folding strength (KN/M2) | (kPa m /g) strength number Embodiment | 12.6 8.137 18.981 3189 OO hl Embodiment | 11.6 7.891 16.678 2915 Oe Embodiment | 10.89 7.589 15.889 2600 em Oe Pe Embodiment | 11.78 8.087 17.785 2998 Oe Embodiment | 11.07 7.995 17.077 2890 Sne i Embodiment | 10.98 7.789 16.876 2789 ee It is known from table 1 that the physical-mechanical properties of paper are greatly improved after chitosan is added.
    In embodiment 1, mechanical properties of raw paper are compared with those of super-hydrophobic paper.
    Table 2 is comparison of mechanical properties of raw paper of neediebush pulp and super-hydrophobic paper of embodiment 1. Table 2 Compressive strength Samples Compressive Burst index Tearing Folding strength (KN/M2) | (kPa-m /g) strength number Super- 12.6 8.137 18.981 3189 hydrophobic paper It is known from table 2 that the physical-mechanical properties of paper are greatly promoted by modification, thereby providing more powerful durability in the problem of transportation in the future.
    Table 3 is comparison of mechanical properties of raw paper of hardwood pulp and super-hydrophobic paper of embodiment 2.
    Table 3 Samples Compressive Burst index Tearing Folding strength (KN/M2) | (kPa m 3/g) strength number (mN-m2/g) Super- 11.6 7.891 16.678 2915 hydrophobic paper Table 4 is comparison of mechanical properties of raw paper of straw pulp and super-hydrophobic paper of embodiment 3. Table 4 Samples Compressive Burst index Tearing Folding strength (KN/M2) | (kPa-m /g) strength number (mN:m /9) Super- 10.89 7.589 15.889 2600 hydrophobic oe Table 5 is comparison of mechanical properties of raw paper of straw pulp and waste paper pulp and super-hydrophobic paper of embodiment 4. Table 5 Samples Compressive Burst index Tearing Folding strength (KN/M2) | {(kPa:m2 /g) strength number en ag, Super- 11.78 8.087 17.785 2998 hydrophobic = Ge Table 6 is comparison of mechanical properties of raw paper of bamboo pulp and super-hydrophobic paper of embodiment 5. Table6 Samples Compressive Burst index Tearing Folding strength (KN/M 2) | (kPa-m /g) strength number |
    Super- 11.07 7.995 17.077 2890 hydrophobic paper Table 7 is comparison of mechanical properties of raw paper of straw pulp and waste paper pulp and super-hydrophobic paper of embodiment 6. Table 7 Samples Compressive Burst index Tearing Folding strength (KN/M 2) | (kPa -m /g) strength number (mN-m /q) Super- 10.98 7.789 16.876 2789 hydrophobic paper Application of a polar solvent and an initiator of alkali lignin are flexibly combined according to actual conditions on the premise of not departing from the technical scheme of the present invention, the surface contact angle of obtained paper reaches 150° and above, and the obtained paper belongs to super- hydrophobic paper, with compressive strength all reaching more than 10KN/M 2, burst index all reaching more than 7kPa'm /g, tearing strength all reaching more than 15mN-m /g, and folding numbers all exceeding 2500. Other reagents used in the present invention are all reagents that may be purchased or prepared in the prior art, and are not further described herein.
    The foregoing embodiments are merely preferred embodiments for sufficiently describing the present invention, and the protection scope of the present invention is not limited herein.
    Equivalent substitution or transformation made by technicians of the technical field on the basis of the present invention all fall within the protection scope of the present invention.
    The protection scope of the present invention should be subject to the claims.
    权利要求:
    Claims (10)
    [1]
    A method of manufacturing a fluoride-free and lignin-chitosan-based superhydrophobic paper which is of high strength, comprising: dissolving an alkaline lignin in a polar solvent, slowly adding an initiator to a resulting solution of alkaline lignin, heating to 90-180 ° C under a nitrogen protection, adding a methoxysilane long chain alkane slowly to react and obtain a modified alkaline lignin solution, stabilizing and purifying the modified alkaline lignin solution so as to separating an alkaline lignin modifier, and drying it for later use, and redissolving the alkaline lignin modifier in the polar solvent to obtain an alkaline lignin modifier solution, soaking paper pulp in the solution, stirring and adding chitosan, and to perform a papermaking process to obtain a superhydrophobic paper.
    [2]
    A manufacturing method according to claim 1, comprising dissolving alkaline lignin in a polar solvent such as acetone, dioxane, N, N-dimethylformamide and DMSO.
    [3]
    A manufacturing method according to claim 1 or 2, comprising slowly adding a triethylamine or sodium alkoxide initiator in a mass concentration of 1% -10% with respect to a obtained alkaline lignin solution.
    [4]
    A manufacturing method according to claim 3, comprising slowly adding an initiator to a obtained alkaline lignin solution, heating to 90-180 ° C under a protection of nitrogen, slowly adding a methoxysilane long chain alkane in a mass concentration of 1% -20% to react and obtain a modified solution of alkaline lignin.
    [5]
    A manufacturing process according to claim 4, wherein the methoxysilane long chain alkane has the meaning of a dodecyltrimethylisilane to an octadecylirimethylisilane.
    [6]
    A manufacturing method according to claim 4 or 5, wherein the mass percentage of chitosan is 0.01% - 0.2%.
    [7]
    A manufacturing method according to claim 1 or 6, wherein the paper pulp is a pulp of conifer pulp, hardwood pulp, old newspaper or straw pulp paper, bamboo pulp and sugar cane pulp, or a pulp mixture of various combinations thereof.
    [8]
    Manufacturing method according to claim 7, wherein the grinding degree of the paper pulp is 30 ° SR-50 ° SR.
    [9]
    A fluoride-free and lignin-chitosan based superhydrophobic paper which is of high strength and which is made by a method of manufacture according to any one of claims 1-8.
    [10]
    The use carried out using the fluoride-free and lignin-chitosan based high strength superhydrophobic paper of claim 9.
    类似技术:
    公开号 | 公开日 | 专利标题
    Andrade et al.2014|Dissolving pulp production from sugar cane bagasse
    FI126649B|2017-03-31|New process for the preparation of microcellulose
    WO2016175593A1|2016-11-03|Method for preparing pulp by using red algae, and method for preparing paper by using same
    CN107746584B|2020-05-19|Preparation method of waterproof cellophane
    Latip et al.2019|Structural and morphological studies on alkaline pre-treatment of oil palm empty fruit bunch | fiber for composite production
    AU2020101037A4|2020-07-23|Preparation method of lignin-chitosan based fluoride-free high-strength super-hydrophobic paper
    Kumneadklang et al.2019|Characterization of cellulose fiber isolated from oil palm frond biomass
    Rehman et al.2018|Ecofriendly isolation of cellulose from eucalyptus lenceolata: A novel approach
    Megashah et al.2018|Characteristics of cellulose from oil palm mesocarp fibres extracted by multi-step pretreatment methods
    CN107881842B|2020-03-27|Method for preparing high-strength corrugated base paper by using straws and waste paper pulp
    AU2020101036A4|2020-07-23|Preparation method of super-hydrophobic lignin sponge with oil-water separation function
    CN103510418A|2014-01-15|New process for black liquor free chemical preparation of pulp
    CN107915783A|2018-04-17|A kind of method that carboxymethyl cellulose is prepared using waste paper as raw material
    CN110272682B|2021-03-30|Preparation method of lignin/resin super-hydrophobic insulating corrosion-resistant coating
    Zhang et al.2019|Preparation of carboxymethyl cellulose from tea stalk and its use as a paper-strengthening agent
    CN106480772A|2017-03-08|Dissolving pulp
    CN107075799B|2019-10-08|The preparation method of cellulose
    Zahari et al.2018|Enhanced performance of cellulose from palm oil empty fruit bunch | Via acetylation and silylation
    Ek et al.2014|WOBAMA: Wood based materials and fuels
    Östberg et al.2013|Some aspects on the activation of dissolving pulps and the influence on the reactivity in a following viscose stage
    RU2333304C1|2008-09-10|Glue for cellulose materials processing
    Ting2019|Comparative properties analysis between microcrystalline cellulose and cellulose nanocrystals extracted from rice straw
    Surip et al.2012|Nanofibers from oil palm trunk |: preparation & chemical analysis
    Zhai et al.2016|NaOH-thiourea aqueous solution treatment of cellulose fiber and its effects on bulk and softness
    CN109972403A|2019-07-05|A kind of processing and treating method of plant fiber
    同族专利:
    公开号 | 公开日
    CN110241648A|2019-09-17|
    AU2020101037A4|2020-07-23|
    CN110241648B|2021-11-02|
    ZA202002969B|2021-06-30|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CN105061787B|2015-07-29|2016-08-17|封开县嘉诚纸业有限公司|A kind of crosslinking alkali lignin and preparation method and application|
    CN107503228B|2017-07-25|2019-07-16|昆明理工大学|A kind of preparation method of the high-intensitive ultra-hydrophobic paper based on LBL self-assembly and thermal induction processing|
    CN109518539A|2018-11-08|2019-03-26|上海纳旭实业有限公司|Preparation method of modified lignin resin and paper fiber composite material and products thereof and application|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    CN201910547030.7A|CN110241648B|2019-06-24|2019-06-24|Preparation method of lignin-chitosan-based fluorine-free high-strength super-hydrophobic paper|
    [返回顶部]