CN113527778B - Preparation method and application of nano lignin latex - Google Patents
Preparation method and application of nano lignin latex Download PDFInfo
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- CN113527778B CN113527778B CN202110907183.5A CN202110907183A CN113527778B CN 113527778 B CN113527778 B CN 113527778B CN 202110907183 A CN202110907183 A CN 202110907183A CN 113527778 B CN113527778 B CN 113527778B
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- 229920005610 lignin Polymers 0.000 title claims abstract description 187
- 229920000126 latex Polymers 0.000 title claims abstract description 124
- 239000004816 latex Substances 0.000 title claims abstract description 119
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 61
- 239000004094 surface-active agent Substances 0.000 claims abstract description 25
- 239000008394 flocculating agent Substances 0.000 claims description 46
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 17
- 239000011593 sulfur Substances 0.000 claims description 17
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- 238000004073 vulcanization Methods 0.000 claims description 16
- 239000003599 detergent Substances 0.000 claims description 13
- PNGBYKXZVCIZRN-UHFFFAOYSA-M sodium;hexadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCS([O-])(=O)=O PNGBYKXZVCIZRN-UHFFFAOYSA-M 0.000 claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 230000020477 pH reduction Effects 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 150000003841 chloride salts Chemical class 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 32
- 229920001971 elastomer Polymers 0.000 abstract description 24
- 239000005060 rubber Substances 0.000 abstract description 24
- 230000008569 process Effects 0.000 abstract description 20
- 239000002245 particle Substances 0.000 abstract description 14
- 238000005054 agglomeration Methods 0.000 abstract description 8
- 230000002776 aggregation Effects 0.000 abstract description 8
- 230000009471 action Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 3
- 238000005096 rolling process Methods 0.000 description 42
- 239000011259 mixed solution Substances 0.000 description 39
- 238000003756 stirring Methods 0.000 description 38
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 30
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 30
- 238000001035 drying Methods 0.000 description 28
- 238000010079 rubber tapping Methods 0.000 description 28
- 229920003048 styrene butadiene rubber Polymers 0.000 description 28
- 238000004080 punching Methods 0.000 description 22
- 238000010907 mechanical stirring Methods 0.000 description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- 235000021355 Stearic acid Nutrition 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 15
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 15
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 15
- 239000008117 stearic acid Substances 0.000 description 15
- 239000011787 zinc oxide Substances 0.000 description 15
- 229920000298 Cellophane Polymers 0.000 description 14
- 238000003723 Smelting Methods 0.000 description 14
- 230000032683 aging Effects 0.000 description 14
- 238000005520 cutting process Methods 0.000 description 14
- 239000003292 glue Substances 0.000 description 14
- 238000007731 hot pressing Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 238000001914 filtration Methods 0.000 description 13
- 238000005189 flocculation Methods 0.000 description 13
- 230000016615 flocculation Effects 0.000 description 13
- 238000004806 packaging method and process Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000002174 Styrene-butadiene Substances 0.000 description 10
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 10
- 239000011115 styrene butadiene Substances 0.000 description 10
- 238000010002 mechanical finishing Methods 0.000 description 9
- 230000003712 anti-aging effect Effects 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241000282326 Felis catus Species 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 244000131522 Citrus pyriformis Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 244000269722 Thea sinensis Species 0.000 description 2
- 235000006468 Thea sinensis Nutrition 0.000 description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 2
- -1 alkyl glycoside Chemical class 0.000 description 2
- 235000020279 black tea Nutrition 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 235000013348 organic food Nutrition 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229940113115 polyethylene glycol 200 Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Paper (AREA)
Abstract
The invention discloses a preparation method and application of nano lignin latex, wherein the preparation method of the nano lignin latex comprises the following steps: (1) Mixing the acid-out lignin with a surfactant to obtain nano lignin; (2) And mixing the nano lignin and the rubber latex to obtain the nano lignin latex. According to the invention, the surfactant is added into the acid-out lignin, so that the long-term particle size stability of the acid-out lignin is maintained, the nano lignin is prepared, and then the nano lignin is filled into the rubber, so that the mechanical property of the rubber can be effectively improved. The invention directly utilizes the wet mixing method to mix rubber, the hydrogen bond action exists between the lignin precipitated in the black liquor and water molecules, and the surfactant can reduce the agglomeration of the lignin in the mixing process, thereby achieving good dispersion effect. The method has the advantages of simple equipment, short process flow, convenient operation and optimistic industrial production prospect.
Description
Technical Field
The invention belongs to the technical field of nano material application, and particularly relates to a preparation method and application of nano lignin latex.
Background
The lignin is the first aromatic high polymer existing in nature, has a three-dimensional network structure, is good in thermal stability, corrosion resistance and mechanical property, is rich in source, low in price, renewable and degradable. The paper-making waste water accounts for 30% of national industrial waste water, and the lignin in waste liquid discharged by producing 1 ton of paper is close to 0.5 ton. Therefore, it has been well recognized in various societies to separate and recover lignin from environmental protection or from the viewpoint of resource utilization. The method for extracting lignin by an acidification method is still a commonly adopted method at present, but the lignin extracted by the acidification method is easy to agglomerate, and the agglomeration of the lignin is aggravated along with the increase of acidification time, so that how to prepare the nano lignin with uniform particle size and high stability in black liquor has important significance.
With the rapid development of nanotechnology, nanomaterials are widely used in chemical industry, ecological agriculture, organic food processing industry, medical industry and other fields. The research of lignin for rubber reinforcement starts in 1929, and in order to realize large-scale application of lignin in rubber materials, the problems that the lignin is not good enough in dispersibility in a rubber phase, poor in compatibility with a rubber matrix and the like are urgently needed to be solved. Therefore, the invention provides a preparation method of nano lignin latex and application thereof in rubber, so as to effectively solve the problems.
Disclosure of Invention
The invention aims to: the invention aims to solve the technical problem of the prior art and provides a preparation method of nano lignin latex.
The invention also aims to solve the technical problem of providing the application of the nano lignin latex in rubber fillers.
In order to solve the first technical problem, the invention discloses a preparation method of nano lignin latex, which comprises the following steps:
(1) Mixing the acid-out lignin with a surfactant to obtain nano lignin;
(2) And mixing the nano lignin and the rubber latex to obtain the nano lignin latex.
In the step (1), the acid-out lignin is prepared from black liquor by acid-out; preferably, the acid-out lignin is obtained by adding 98% concentrated sulfuric acid to adjust the pH value in the stirring process from the papermaking black liquor in a heating state; preferably, the heating temperature is 50-80 ℃; preferably, the pH is adjusted to a pH of 1.5 to 4.
In the step (1), the surfactant is any one or a combination of more of sodium hexadecylsulfonate, alkyl glycoside (APG), alpha-olefin sulfonate (AOS), fatty Alcohol Sulfate (FAS), fatty Alcohol Ether Sulfate (AES) and fatty acid Methyl Ester Sulfonate (MES); preferably, the surfactant contains sodium hexadecyl sulfonate; further preferably, the mass content of the sodium hexadecyl sulfonate in the surfactant is more than 20%; more preferably, the mass content of the sodium hexadecyl sulfonate in the surfactant is 25-35%; still more preferably, the mass content of the sodium hexadecyl sulfonate in the surfactant is 30%; still further preferably, the surfactant is a detergent; most preferably, the surfactant is white cat lemon black tea detergent.
In the step (1), the surfactant is 1-5wt% of the acidification lignin.
In the step (2), the mass ratio of the nano lignin to the rubber latex is (0.05-0.2): 1.
in the step (2), the mixing treatment is stirring.
Wherein the stirring speed is more than 200 rpm; preferably, the stirring speed is 400-900rpm;
wherein the mixing treatment time is more than 2 min; preferably, the stirring time is 10-30min.
The nano lignin latex obtained by the method is also within the protection scope of the invention.
In order to solve the second technical problem, the invention discloses the application of the nano lignin in rubber.
The application comprises the steps of adding a flocculating agent into lignin latex, mixing and vulcanizing after the lignin latex is flocculated, and carrying out hot press molding to obtain the lignin latex.
Preferably, the application is that a flocculating agent is added into the lignin latex, and after the lignin latex is flocculated, the lignin latex is sheared, cleaned, dried, mixed, vulcanized and hot-pressed to form the lignin latex.
Wherein the flocculating agent is any one or combination of more of an acid compound, a dinitrile diamine formaldehyde condensate and a chloride salt; preferably, the acid compound is any one or combination of hydrochloric acid, sulfuric acid, formic acid and acetic acid; preferably, the chloride salt is magnesium chloride and/or calcium chloride.
Wherein the weight ratio of the lignin latex to the flocculant is (1-10): 1.
preferably, an auxiliary agent is added in the mixing vulcanization.
Wherein, the auxiliary agent is any one or a combination of several of an age resister, a vulcanizing agent, a sulfur accelerator and a lubricant.
The anti-aging agent comprises but is not limited to anti-aging agent 4020NA, anti-aging agent D, anti-aging agent RD, anti-aging agent 124, anti-aging agent MB, anti-aging agent DNP, anti-aging agent NBC, BLE, RD, AW and UOP788.
Wherein the sulfur accelerator includes, but is not limited to, zinc oxide.
Wherein the lubricant includes, but is not limited to, stearic acid.
Wherein the mixing is carried out at 10-35 ℃ for 5-15min
Wherein the drying temperature is 60-70 ℃.
Wherein the hot press forming is hot press forming by a flat vulcanizing machine.
Wherein the hot-press molding is carried out at 130-180 ℃ for 10-40min
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) The method effectively keeps the long-term stability of the lignin nano-particle size by adding the surfactant into the acid-out lignin, effectively avoids the agglomeration of the lignin, keeps the nano-lignin uniform in appearance, uniform and fine in particle size, high in dispersity, uniform in mixing with the matrix and good in compatibility.
(2) The invention directly utilizes a wet mixing method to mix the rubber, the lignin precipitated in the black liquor keeps a certain proportion of water, the hydrogen bond action of the lignin particles is weakened by utilizing the hydrogen bond action generated between the lignin particles and water molecules, and the agglomeration of the lignin in the mixing process is reduced, thereby achieving good dispersion effect.
(3) The method for preparing the nano lignin rubber by using the in-situ one-step method has the advantages of simple equipment, short process flow, convenient operation and optimistic industrial production prospect.
(4) The lignin utilized by the invention is a renewable biomass material, so the method is green and environment-friendly, has low cost and convenient use, and the utilized surfactant is convenient and easy to obtain, low in cost and convenient to use.
(5) The nano lignin prepared by the method can keep uniform and stable particle size and regular appearance for a long time, and forms a covalent crosslinking network with rubber macromolecules when rubber is added, so that the crosslinking degree of the material is improved, the reinforcing effect is realized, and the performance of the rubber is effectively improved.
(6) According to the invention, after lignin is extracted from the black liquor by an acid precipitation method, the surfactant is added into the black liquor, so that the long-term particle size stability of the black liquor is maintained, the nano lignin is prepared, and then the nano lignin is filled into rubber, so that the mechanical property of the rubber can be effectively improved. The invention directly utilizes the wet mixing method to mix rubber, the hydrogen bond action exists between the lignin precipitated in the black liquor and water molecules, and the detergent used as a surfactant can reduce the agglomeration of the lignin in the mixing process, thereby achieving good dispersion effect. The method has the advantages of simple equipment, short process flow, convenient operation and optimistic industrial production prospect.
Drawings
The foregoing and/or other advantages of the invention will become further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
FIG. 1 is scanning electron micrographs of acid out lignin (blank) and different nano-lignin at different times.
FIG. 2 is a SEM image of a cross section of rubber.
Fig. 3 is a particle size distribution diagram of the nano lignin after being left for 15 days, 60 days and 90 days, which are 15 days, 60 days and 90 days from left to right.
Detailed Description
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Product name of the detergent described in the following examples: the white cat lemon black tea detergent with the specification of 2kg is produced by Shanghai and yellow white cat Limited and contains 30wt% of sodium hexadecylsulfonate.
Example 1
(1) Heating the papermaking black liquor to 60 ℃, adding 98% concentrated sulfuric acid to adjust the pH value to 1.5 in the stirring process of 450r/min, filtering and drying to obtain the acid-out lignin.
(2) And (2) adding 1wt% of detergent into the acid-out lignin obtained in the step (1) to obtain the nano lignin.
(3) Adding 100g of 20% styrene-butadiene rubber latex into a three-necked flask, adding 5g of the nano lignin obtained in the step (2), performing mixing treatment for 10min at about 700r/min by using mechanical stirring, and finishing mixing of the lignin and the styrene-butadiene latex to obtain a lignin latex mixed solution.
(4) And (4) preparing about 600mL of 1% hydrochloric acid as a flocculating agent, stirring the flocculating agent by using mechanical stirring at about 200-300 r/min, slowly pouring the lignin latex mixed solution obtained in the step (3) into the flocculating agent, and placing the mixed lignin latex mixed solution into a bag for later use after flocculation.
(5) Cutting or slicing flocculated floc with scissors, repeatedly washing with clear water for 5-10min, folding cellophane into flat box shape after the floc has no acid liquor smell, placing the minced or sliced floc into a 60 deg.C oven, pouring water every half hour, adding 0.8g of aging agent 4020NA after 2 hours, making into sheet, and continuously drying until the weight of latex is constant.
(6) And (3) continuously thinly passing the product obtained in the step (5) until the roll spacing is minimum, adjusting the roll spacing to be 1mm, adding 2g of ZnO and 1.2g of stearic acid, adjusting the roll spacing to be minimum after mixing, performing rubber tapping for 3 times respectively on the left side and the right side, then punching a triangular bag for 3 times, rolling a coil for 3 times, adjusting the roll spacing to be 1mm, adding 1g of sulfur and 0.24g of vulcanization accelerator CZ, continuously adjusting the roll spacing to be minimum, performing rubber tapping for 3 times respectively on the left side and the right side, then punching the triangular bag for 3 times, and rolling the coil for 3 times.
(7) And (4) reverse-smelting the product obtained in the step (6), adjusting the double rollers to be minimum, thinly passing the product for 1 time, packaging the product in triangular bags for 1-2 times, and finally rolling the product with the thickness of 2mm to obtain the glue. And hot pressing the mixture for 20 minutes by a flat vulcanizing machine at 160 ℃ for curing and forming.
Example 2
(1) Heating the papermaking black liquor to 60 ℃, adding 98% concentrated sulfuric acid to adjust the pH value to 1.5 in the stirring process of 450r/min, filtering and drying to obtain the acid-out lignin.
(2) And (2) adding 1wt% of detergent into the acid-out lignin obtained in the step (1) to obtain the nano lignin.
(3) And (3) adding 100g of 20% styrene-butadiene rubber latex into a three-necked flask, adding 10g of the nano lignin obtained in the step (2), mechanically stirring at about 700r/min for 10min for mixing, and mixing the lignin and the styrene-butadiene rubber latex to obtain a lignin latex mixed solution.
(4) And (4) preparing about 600mL of 1% hydrochloric acid as a flocculating agent, stirring the flocculating agent by using mechanical stirring at about 200-300 r/min, slowly pouring the lignin latex mixed solution obtained in the step (3) into the flocculating agent, and placing the mixed lignin latex mixed solution into a bag for later use after flocculation.
(5) Cutting or slicing flocculated floc with scissors, repeatedly washing with clear water for 5-10min, folding cellophane into flat box shape after floc has no acid liquor taste, placing the minced or sliced floc into a 60 deg.C oven, pouring water every half hour, adding 0.8g aging agent 4020NA after 2 hr, making into sheet, continuously drying, and taking out latex when latex weight is constant.
(6) And (3) continuously thinning and passing the product obtained in the step (5) until the roll distance is minimum, adjusting the roll distance to be 1mm, adding 2g of ZnO and 1.2g of stearic acid, after mixing, adjusting the roll distance to be minimum, performing rubber tapping for 3 times respectively on the left side and the right side, then forming a triangular bag for 3 times, rolling for 3 times, adjusting the roll distance to be 1mm, adding 1g of sulfur and 0.24g of vulcanization accelerator CZ, continuously adjusting the roll distance to be minimum, performing rubber tapping for 3 times respectively on the left side and the right side, forming a triangular bag for 3 times, and rolling for 3 times.
(7) And (4) reverse-smelting the product obtained in the step (6), adjusting the double rollers to be minimum, thinly passing the product for 1 time, packaging the product in triangular bags for 1-2 times, and finally rolling the product with the thickness of 2mm to obtain the glue. And hot pressing the mixture for 20 minutes by a flat vulcanizing machine at 160 ℃ for curing and forming.
Example 3
(1) Heating the papermaking black liquor to 60 ℃, adding 98% concentrated sulfuric acid to adjust the pH value to 1.5 in the stirring process of 450r/min, filtering and drying to obtain the acid-out lignin.
(2) And (2) adding 1wt% of detergent into the acid-out lignin obtained in the step (1) to obtain the nano lignin.
(3) And (3) adding 100g of 20% styrene-butadiene rubber latex into a three-necked flask, adding 15g of the nano lignin obtained in the step (2), mechanically stirring at about 700r/min for 10min for mixing, and mixing the lignin and the styrene-butadiene rubber latex to obtain a lignin latex mixed solution.
(4) And (4) preparing about 600mL of 1% hydrochloric acid as a flocculating agent, stirring the flocculating agent by using mechanical stirring at about 200-300 r/min, slowly pouring the lignin latex mixed solution obtained in the step (3) into the flocculating agent, and placing the mixed lignin latex mixed solution into a bag for later use after flocculation.
(5) Cutting or slicing flocculated floc with scissors, repeatedly washing with clear water for 5-10min, folding cellophane into flat box shape after floc has no acid liquor taste, placing the minced or sliced floc into a 60 deg.C oven, pouring water every half hour, adding 0.8g aging agent 4020NA after 2 hr, making into sheet, continuously drying, and taking out latex when latex weight is constant.
(6) And (3) continuously thinly passing the product obtained in the step (5) until the roll spacing is minimum, adjusting the roll spacing to be 1mm, adding 2g of ZnO and 1.2g of stearic acid, adjusting the roll spacing to be minimum after mixing, performing rubber tapping for 3 times respectively on the left side and the right side, then punching a triangular bag for 3 times, rolling a coil for 3 times, adjusting the roll spacing to be 1mm, adding 1g of sulfur and 0.24g of vulcanization accelerator CZ, continuously adjusting the roll spacing to be minimum, performing rubber tapping for 3 times respectively on the left side and the right side, then punching the triangular bag for 3 times, and rolling the coil for 3 times.
(7) And (4) reverse-smelting the product obtained in the step (6), adjusting the double rollers to be minimum, thinly passing the product for 1 time, packaging the product in triangular bags for 1-2 times, and finally rolling the product with the thickness of 2mm to obtain the glue. And hot pressing the mixture for 20 minutes by a flat vulcanizing machine at 160 ℃ for curing and forming.
Example 4
(1) Heating the papermaking black liquor to 60 ℃, adding 98% concentrated sulfuric acid to adjust the pH value to 1.5 in the stirring process of 450r/min, filtering and drying to obtain the acid-out lignin.
(2) And (2) adding 1wt% of detergent into the acid-out lignin obtained in the step (1) to obtain the nano lignin.
(3) Firstly, adding 100g of 20% styrene-butadiene rubber latex into a three-necked flask, adding 20g of the nano lignin obtained in the step (2), carrying out mixing treatment for 10min at about 700r/min by using mechanical stirring, and finishing mixing of the lignin and the styrene-butadiene latex to obtain a lignin latex mixed solution.
(4) And (4) preparing about 600mL of 1% hydrochloric acid as a flocculating agent, stirring the flocculating agent by using mechanical stirring at about 200-300 r/min, slowly pouring the lignin latex mixed solution obtained in the step (3) into the flocculating agent, and placing the mixed lignin latex mixed solution into a bag for later use after flocculation.
(5) Cutting or slicing flocculated floc with scissors, repeatedly washing with clear water for 5-10min, folding cellophane into flat box shape after floc has no acid liquor taste, placing the minced or sliced floc into a 60 deg.C oven, pouring water every half hour, adding 0.8g aging agent 4020NA after 2 hr, making into sheet, continuously drying, and taking out latex when latex weight is constant.
(6) And (3) continuously thinly passing the product obtained in the step (5) until the roll spacing is minimum, adjusting the roll spacing to be 1mm, adding 2g of ZnO and 1.2g of stearic acid, adjusting the roll spacing to be minimum after mixing, performing rubber tapping for 3 times respectively on the left side and the right side, then punching a triangular bag for 3 times, rolling a coil for 3 times, adjusting the roll spacing to be 1mm, adding 1g of sulfur and 0.24g of vulcanization accelerator CZ, continuously adjusting the roll spacing to be minimum, performing rubber tapping for 3 times respectively on the left side and the right side, then punching the triangular bag for 3 times, and rolling the coil for 3 times.
(7) And (4) reverse-smelting the product obtained in the step (6), adjusting the double rollers to be minimum, thinly passing the product for 1 time, packaging the product in triangular bags for 1-2 times, and finally rolling the product with the thickness of 2mm to obtain the glue. And hot pressing the mixture for 20 minutes by a flat vulcanizing machine at 160 ℃ for curing and forming.
Comparative example 1:
(1) 100g of 20% styrene-butadiene rubber latex is added into a three-necked flask, and the mixture is mechanically stirred at about 700r/min for 10 min.
(2) Preparing about 600mL of 1% hydrochloric acid as a flocculating agent, stirring the flocculating agent by using a machine for stirring at about 200-300 r/min, slowly pouring the styrene-butadiene rubber latex in the step (1) into the flocculating agent, and putting the mixed latex into a bag for later use after the mixed latex is flocculated.
(3) Cutting or slicing flocculated floc with scissors, repeatedly washing with clear water for 5-10min, folding cellophane into flat box shape after floc has no acid liquor taste, placing the minced or sliced floc into a 60 deg.C oven, pouring water every half hour, adding 0.8g aging agent 4020NA after 2 hr, making into sheet, continuously drying, and taking out latex when latex weight is constant.
(4) And (3) continuously thinly passing the product obtained in the step (3), slowly thinly passing the product until the roller distance is minimum, adjusting the roller distance to be 1mm, adding 2g of ZnO and 1.2g of stearic acid, adjusting the roller distance to be minimum after mixing, performing rubber tapping for 3 times respectively on the left side and the right side, then punching triangular bags for 3 times, rolling the rolls for 3 times, adjusting the roller distance to be 1mm, adding 1g of sulfur and 0.24g of vulcanization accelerator CZ, continuously adjusting the roller distance to be minimum, performing rubber tapping for 3 times respectively on the left side and the right side, then punching triangular bags for 3 times, and rolling the rolls for 3 times.
(5) And (4) back-smelting the product obtained in the step (4), adjusting the double rollers to the minimum, passing through the thin film for 1 time, beating the thin film for 1-2 times, and finally rolling the thin film to obtain the glue with the thickness of 2 mm. And hot pressing the mixture for 20 minutes by a flat vulcanizing machine at 160 ℃ for curing and forming.
Comparative example 2
(1) Heating the papermaking black liquor to 60 ℃, adding 98% concentrated sulfuric acid to adjust the pH value to 1.5 in the stirring process of 450r/min, filtering and drying to obtain the acid-out lignin.
(2) Firstly, adding 100g of 20% styrene-butadiene rubber latex into a three-necked flask, adding 5g of acidification lignin obtained in the step (1), carrying out mixing treatment for 10min at about 700r/min by using mechanical stirring, and finishing mixing of the lignin and the styrene-butadiene latex to obtain a lignin latex mixed solution.
(3) Preparing about 600mL of 1-2% hydrochloric acid as a flocculating agent, stirring the flocculating agent by using a machine for stirring at about 200-300 r/min, slowly pouring the lignin latex mixed solution obtained in the step (3) into the flocculating agent, and placing the mixed lignin latex mixed solution into a bag for later use after flocculation.
(4) Cutting or slicing flocculated floc with scissors, repeatedly washing with clear water for 5-10min, folding cellophane into flat box shape after the floc has no acid liquor smell, placing the minced or sliced floc into a 60 deg.C oven, pouring water every half hour, adding 0.8g of aging agent 4020NA after 2 hours, making into sheet, and continuously drying until the weight of latex is constant.
(5) And (5) continuously thinning and passing the product obtained in the step (4) until the roll distance is minimum, adjusting the roll distance to be 1mm, adding 2g of ZnO and 1.2g of stearic acid, after mixing, adjusting the roll distance to be minimum, performing rubber tapping for 3 times respectively on the left side and the right side, then forming a triangular bag for 3 times, rolling for 3 times, adjusting the roll distance to be 1mm, adding 1g of sulfur and 0.24g of vulcanization accelerator CZ, continuously adjusting the roll distance to be minimum, performing rubber tapping for 3 times respectively on the left side and the right side, forming a triangular bag for 3 times, and rolling for 3 times.
(6) And (4) reverse-smelting the product obtained in the step (5), adjusting the double rollers to be minimum, thinly passing the product for 1 time, packaging the product in triangular bags for 1-2 times, and finally rolling the product with the thickness of 2mm to obtain the glue. And hot pressing the mixture for 20 minutes by a flat vulcanizing machine at 160 ℃ for curing and forming.
Comparative example 3
(1) Heating the papermaking black liquor to 60 ℃, adding 98% concentrated sulfuric acid to adjust the pH value to 1.5 in the stirring process of 450r/min, filtering and drying to obtain the acid-out lignin.
(2) And (2) adding 100g of 20% styrene-butadiene rubber latex into a three-necked flask, adding 10g of acid-separated lignin obtained in the step (1), mechanically stirring at about 700r/min for 10min for mixing, and mixing the lignin and the styrene-butadiene latex to obtain a lignin latex mixed solution.
(3) And (4) preparing about 600mL of 1-2% hydrochloric acid as a flocculating agent, stirring the flocculating agent by using mechanical stirring at about 200-300 r/min, slowly pouring the lignin latex mixed solution obtained in the step (3) into the flocculating agent, and placing the mixed lignin latex mixed solution into a bag for later use after flocculation.
(4) Cutting or slicing flocculated floc with scissors, repeatedly washing with clear water for 5-10min, folding cellophane into flat box shape after floc has no acid liquor taste, placing the minced or sliced floc into a 60 deg.C oven, pouring water every half hour, adding 0.8g aging agent 4020NA after 2 hr, making into sheet, continuously drying, and taking out latex when latex weight is constant.
(5) And (3) continuously thinly passing the product obtained in the step (4), slowly thinly passing the product until the roller distance is minimum, adjusting the roller distance to be 1mm, adding 2g of ZnO and 1.2g of stearic acid, adjusting the roller distance to be minimum after mixing, performing rubber tapping for 3 times respectively on the left side and the right side, then punching triangular bags for 3 times, rolling the rolls, adjusting the roller distance to be 1mm, adding 1g of sulfur and 0.24g of vulcanization accelerator CZ, continuously adjusting the roller distance to be minimum, performing rubber tapping for 3 times respectively on the left side and the right side, then punching triangular bags for 3 times, and rolling the rolls for 3 times.
(6) And (4) reverse-smelting the product obtained in the step (5), adjusting the double rollers to be minimum, thinly passing the product for 1 time, packaging the product in triangular bags for 1-2 times, and finally rolling the product with the thickness of 2mm to obtain the glue. And hot pressing the mixture for 20 minutes by a flat vulcanizing machine at 160 ℃ for curing and forming.
Comparative example 4
(1) Heating the papermaking black liquor to 60 ℃, adding 98% concentrated sulfuric acid to adjust the pH value to 1.5 in the stirring process of 450r/min, filtering and drying to obtain the acid-out lignin.
(2) Firstly, adding 100g of 20% styrene-butadiene rubber latex into a three-necked flask, adding 15g of acidified lignin obtained in the step (1), carrying out mixing treatment for 10min at about 700r/min by using mechanical stirring, and finishing mixing of the lignin and the styrene-butadiene latex to obtain a lignin latex mixed solution.
(3) And (4) preparing about 600mL of 1-2% hydrochloric acid as a flocculating agent, stirring the flocculating agent by using mechanical stirring at about 200-300 r/min, slowly pouring the lignin latex mixed solution obtained in the step (3) into the flocculating agent, and placing the mixed lignin latex mixed solution into a bag for later use after flocculation.
(4) Cutting or slicing flocculated floc with scissors, repeatedly washing with clear water for 5-10min, folding cellophane into flat box shape after floc has no acid liquor taste, placing the minced or sliced floc into a 60 deg.C oven, pouring water every half hour, adding 0.8g aging agent 4020NA after 2 hr, making into sheet, continuously drying, and taking out latex when latex weight is constant.
(5) And (5) continuously thinning and passing the product obtained in the step (4) until the roll distance is minimum, adjusting the roll distance to be 1mm, adding 2g of ZnO and 1.2g of stearic acid, after mixing, adjusting the roll distance to be minimum, performing rubber tapping for 3 times respectively on the left side and the right side, then forming a triangular bag for 3 times, rolling for 3 times, adjusting the roll distance to be 1mm, adding 1g of sulfur and 0.24g of vulcanization accelerator CZ, continuously adjusting the roll distance to be minimum, performing rubber tapping for 3 times respectively on the left side and the right side, forming a triangular bag for 3 times, and rolling for 3 times.
(6) And (4) reverse-smelting the product obtained in the step (5), adjusting the double rollers to be minimum, thinly passing the product for 1 time, packaging the product in triangular bags for 1-2 times, and finally rolling the product with the thickness of 2mm to obtain the glue. And hot pressing the mixture for 20 minutes by a flat vulcanizing machine at 160 ℃ for curing and forming.
Comparative example 5
(1) Heating the papermaking black liquor to 60 ℃, adding 98% concentrated sulfuric acid to adjust the pH value to 1.5 in the stirring process of 450r/min, filtering and drying to obtain the acid-out lignin.
(2) Firstly, adding 100g of 20% styrene-butadiene rubber latex into a three-necked flask, adding 20g of acidified lignin obtained in the step (1), carrying out mixing treatment for 10min at about 700r/min by using mechanical stirring, and finishing mixing of the lignin and the styrene-butadiene latex to obtain a lignin latex mixed solution.
(3) And (4) preparing about 600mL of 1-2% hydrochloric acid as a flocculating agent, stirring the flocculating agent by using mechanical stirring at about 200-300 r/min, slowly pouring the lignin latex mixed solution obtained in the step (3) into the flocculating agent, and placing the mixed lignin latex mixed solution into a bag for later use after flocculation.
(4) Cutting or slicing flocculated floc with scissors, repeatedly washing with clear water for 5-10min, folding cellophane into flat box shape after floc has no acid liquor taste, placing the minced or sliced floc into a 60 deg.C oven, pouring water every half hour, adding 0.8g aging agent 4020NA after 2 hr, making into sheet, continuously drying, and taking out latex when latex weight is constant.
(5) And (3) continuously thinly passing the product obtained in the step (4), slowly thinly passing the product until the roller distance is minimum, adjusting the roller distance to be 1mm, adding 2g of ZnO and 1.2g of stearic acid, adjusting the roller distance to be minimum after mixing, performing rubber tapping for 3 times respectively on the left side and the right side, then punching triangular bags for 3 times, rolling the rolls, adjusting the roller distance to be 1mm, adding 1g of sulfur and 0.24g of vulcanization accelerator CZ, continuously adjusting the roller distance to be minimum, performing rubber tapping for 3 times respectively on the left side and the right side, then punching triangular bags for 3 times, and rolling the rolls for 3 times.
(6) And (4) reverse-smelting the product obtained in the step (5), adjusting the double rollers to be minimum, thinly passing the product for 1 time, packaging the product in triangular bags for 1-2 times, and finally rolling the product with the thickness of 2mm to obtain the glue. Hot pressing for 20 minutes by a flat vulcanizing machine at 160 ℃ and curing and molding.
Comparative example 6
(1) Heating the papermaking black liquor to 60 ℃, adding 98% concentrated sulfuric acid to adjust the pH value to 1.5 in the stirring process of 450r/min, filtering and drying to obtain the acid-out lignin.
(2) And (2) adding 1wt% of diethylene glycol into the acid-out lignin obtained in the step (1) to obtain the nano lignin.
(3) Firstly, adding 100g of 20% styrene-butadiene rubber latex into a three-necked flask, adding 20g of the nano lignin obtained in the step (2), carrying out mixing treatment for 10min at about 700r/min by using mechanical stirring, and finishing mixing of the lignin and the styrene-butadiene latex to obtain a lignin latex mixed solution.
(4) And (4) preparing about 600mL of 1% hydrochloric acid as a flocculating agent, stirring the flocculating agent by using mechanical stirring at about 200-300 r/min, slowly pouring the lignin latex mixed solution obtained in the step (3) into the flocculating agent, and placing the mixed lignin latex mixed solution into a bag for later use after flocculation.
(5) Cutting or slicing flocculated floc with scissors, repeatedly washing with clear water for 5-10min, folding cellophane into flat box shape after the floc has no acid liquor smell, placing the minced or sliced floc into a 60 deg.C oven, pouring water every half hour, adding 0.8g of aging agent 4020NA after 2 hours, making into sheet, and continuously drying until the weight of latex is constant.
(6) And (3) continuously thinning and passing the product obtained in the step (5) until the roll distance is minimum, adjusting the roll distance to be 1mm, adding 2g of ZnO and 1.2g of stearic acid, after mixing, adjusting the roll distance to be minimum, performing rubber tapping for 3 times respectively on the left side and the right side, then punching triangular bags for 3 times, rolling for 3 times, adjusting the roll distance to be 1mm, adding 1g of sulfur and 0.24g of vulcanization accelerator CZ, continuously adjusting the roll distance to be minimum, performing rubber tapping for 3 times respectively on the left side and the right side, punching triangular bags for 3 times, and rolling for 3 times.
(7) And (4) reverse-smelting the product obtained in the step (6), adjusting the double rollers to be minimum, thinly passing the product for 1 time, packaging the product in triangular bags for 1-2 times, and finally rolling the product with the thickness of 2mm to obtain the glue. And hot pressing the mixture for 20 minutes by a flat vulcanizing machine at 160 ℃ for curing and forming.
Comparative example 7
(1) Heating the papermaking black liquor to 60 ℃, adding 98% concentrated sulfuric acid to adjust the pH value to 1.5 in the stirring process of 450r/min, filtering and drying to obtain the acid-out lignin.
(2) And (2) adding 1wt% of triisopropanolamine into the acid-out lignin obtained in the step (1) to obtain the nano lignin.
(3) And (3) adding 100g of 20% styrene-butadiene rubber latex into a three-necked flask, adding 20g of the nano lignin obtained in the step (2), mechanically stirring at about 700r/min for 10min for mixing, and mixing the lignin and the styrene-butadiene rubber latex to obtain a lignin latex mixed solution.
(4) Preparing about 600mL of 1% hydrochloric acid as a flocculating agent, stirring the flocculating agent under mechanical stirring of about 200-300 r/min, slowly pouring the lignin latex mixed solution obtained in the step (3) into the flocculating agent, and placing the mixed lignin latex mixed solution into a bag for later use after flocculation.
(5) Cutting or slicing flocculated floc with scissors, repeatedly washing with clear water for 5-10min, folding cellophane into flat box shape after floc has no acid liquor taste, placing the minced or sliced floc into a 60 deg.C oven, pouring water every half hour, adding 0.8g aging agent 4020NA after 2 hr, making into sheet, continuously drying, and taking out latex when latex weight is constant.
(6) And (3) continuously thinning and passing the product obtained in the step (5) until the roll distance is minimum, adjusting the roll distance to be 1mm, adding 2g of ZnO and 1.2g of stearic acid, after mixing, adjusting the roll distance to be minimum, performing rubber tapping for 3 times respectively on the left side and the right side, then punching triangular bags for 3 times, rolling for 3 times, adjusting the roll distance to be 1mm, adding 1g of sulfur and 0.24g of vulcanization accelerator CZ, continuously adjusting the roll distance to be minimum, performing rubber tapping for 3 times respectively on the left side and the right side, punching triangular bags for 3 times, and rolling for 3 times.
(7) And (4) reverse-smelting the product obtained in the step (6), adjusting the double rollers to be minimum, thinly passing the product for 1 time, packaging the product in triangular bags for 1-2 times, and finally rolling the product with the thickness of 2mm to obtain the glue. And hot pressing the mixture for 20 minutes by a flat vulcanizing machine at 160 ℃ for curing and forming.
Comparative example 8:
(1) Heating the papermaking black liquor to 60 ℃, adding 98% concentrated sulfuric acid to adjust the pH value to 1.5 in the stirring process of 450r/min, filtering and drying to obtain the acid-out lignin.
(2) And (2) adding 1wt% of polyethylene glycol 200 into the acid-out lignin obtained in the step (1) to obtain the nano lignin.
(3) Firstly, adding 100g of 20% styrene-butadiene rubber latex into a three-necked flask, adding 20g of the nano lignin obtained in the step (2), carrying out mixing treatment for 10min at about 700r/min by using mechanical stirring, and finishing mixing of the lignin and the styrene-butadiene latex to obtain a lignin latex mixed solution.
(4) And (4) preparing about 600mL of 1% hydrochloric acid as a flocculating agent, stirring the flocculating agent by using mechanical stirring at about 200-300 r/min, slowly pouring the lignin latex mixed solution obtained in the step (3) into the flocculating agent, and placing the mixed lignin latex mixed solution into a bag for later use after flocculation.
(5) Cutting or slicing flocculated floc with scissors, repeatedly washing with clear water for 5-10min, folding cellophane into flat box shape after floc has no acid liquor taste, placing the minced or sliced floc into a 60 deg.C oven, pouring water every half hour, adding 0.8g aging agent 4020NA after 2 hr, making into sheet, continuously drying, and taking out latex when latex weight is constant.
(6) And (3) continuously thinning and passing the product obtained in the step (5) until the roll distance is minimum, adjusting the roll distance to be 1mm, adding 2g of ZnO and 1.2g of stearic acid, after mixing, adjusting the roll distance to be minimum, performing rubber tapping for 3 times respectively on the left side and the right side, then punching triangular bags for 3 times, rolling for 3 times, adjusting the roll distance to be 1mm, adding 1g of sulfur and 0.24g of vulcanization accelerator CZ, continuously adjusting the roll distance to be minimum, performing rubber tapping for 3 times respectively on the left side and the right side, punching triangular bags for 3 times, and rolling for 3 times.
(7) And (4) reverse-smelting the product obtained in the step (6), adjusting the double rollers to be minimum, thinly passing the product for 1 time, packaging the product in triangular bags for 1-2 times, and finally rolling the product with the thickness of 2mm to obtain the glue. And hot pressing the mixture for 20 minutes by a flat vulcanizing machine at 160 ℃ for curing and forming.
Comparative example 9:
(1) Heating the papermaking black liquor to 60 ℃, adding 98% concentrated sulfuric acid to adjust the pH value to 1.5 in the stirring process of 450r/min, filtering and drying to obtain the acid-out lignin.
(2) And (2) adding 1wt% of glycol into the acid-out lignin obtained in the step (1) to obtain the nano lignin.
(3) Firstly, adding 100g of 20% styrene-butadiene rubber latex into a three-necked flask, adding 20g of the nano lignin obtained in the step (2), carrying out mixing treatment for 10min at about 700r/min by using mechanical stirring, and finishing mixing of the lignin and the styrene-butadiene latex to obtain a lignin latex mixed solution.
(4) Preparing about 600mL of 1% hydrochloric acid as a flocculating agent, stirring the flocculating agent under mechanical stirring of about 200-300 r/min, slowly pouring the lignin latex mixed solution obtained in the step (3) into the flocculating agent, and placing the mixed lignin latex mixed solution into a bag for later use after flocculation.
(5) Cutting or slicing flocculated floc with scissors, repeatedly washing with clear water for 5-10min, folding cellophane into flat box shape after the floc has no acid liquor smell, placing the minced or sliced floc into a 60 deg.C oven, pouring water every half hour, adding 0.8g of aging agent 4020NA after 2 hours, making into sheet, and continuously drying until the weight of latex is constant.
(6) And (3) continuously thinly passing the product obtained in the step (5) until the roll spacing is minimum, adjusting the roll spacing to be 1mm, adding 2g of ZnO and 1.2g of stearic acid, adjusting the roll spacing to be minimum after mixing, performing rubber tapping for 3 times respectively on the left side and the right side, then punching a triangular bag for 3 times, rolling a coil for 3 times, adjusting the roll spacing to be 1mm, adding 1g of sulfur and 0.24g of vulcanization accelerator CZ, continuously adjusting the roll spacing to be minimum, performing rubber tapping for 3 times respectively on the left side and the right side, then punching the triangular bag for 3 times, and rolling the coil for 3 times.
(7) And (4) reverse-smelting the product obtained in the step (6), adjusting the double rollers to be minimum, thinly passing the product for 1 time, packaging the product in triangular bags for 1-2 times, and finally rolling the product with the thickness of 2mm to obtain the glue. And hot pressing the mixture for 20 minutes by a flat vulcanizing machine at 160 ℃ for curing and forming.
Comparative example 10:
(1) Heating the papermaking black liquor to 60 ℃, adding 98% concentrated sulfuric acid to adjust the pH value to 1.5 in the stirring process of 450r/min, filtering and drying to obtain the acid-out lignin.
(2) And (2) adding 1wt% of propylene glycol into the acid-out lignin obtained in the step (1) to obtain the nano lignin.
(3) Firstly, adding 100g of 20% styrene-butadiene rubber latex into a three-necked flask, adding 20g of the nano lignin obtained in the step (2), carrying out mixing treatment for 10min at about 700r/min by using mechanical stirring, and finishing mixing of the lignin and the styrene-butadiene latex to obtain a lignin latex mixed solution.
(4) Preparing about 600mL of 1% hydrochloric acid as a flocculating agent, stirring the flocculating agent under mechanical stirring of about 200-300 r/min, slowly pouring the lignin latex mixed solution obtained in the step (3) into the flocculating agent, and placing the mixed lignin latex mixed solution into a bag for later use after flocculation.
(5) Cutting or slicing flocculated floc with scissors, repeatedly washing with clear water for 5-10min, folding cellophane into flat box shape after the floc has no acid liquor smell, placing the minced or sliced floc into a 60 deg.C oven, pouring water every half hour, adding 0.8g of aging agent 4020NA after 2 hours, making into sheet, and continuously drying until the weight of latex is constant.
(6) And (3) continuously thinly passing the product obtained in the step (5) until the roll spacing is minimum, adjusting the roll spacing to be 1mm, adding 2g of ZnO and 1.2g of stearic acid, adjusting the roll spacing to be minimum after mixing, performing rubber tapping for 3 times respectively on the left side and the right side, then punching a triangular bag for 3 times, rolling a coil for 3 times, adjusting the roll spacing to be 1mm, adding 1g of sulfur and 0.24g of vulcanization accelerator CZ, continuously adjusting the roll spacing to be minimum, performing rubber tapping for 3 times respectively on the left side and the right side, then punching the triangular bag for 3 times, and rolling the coil for 3 times.
(7) And (4) reverse-smelting the product obtained in the step (6), adjusting the double rollers to be minimum, thinly passing the product for 1 time, packaging the product in triangular bags for 1-2 times, and finally rolling the product with the thickness of 2mm to obtain the glue. And hot pressing the mixture for 20 minutes by a flat vulcanizing machine at 160 ℃ for curing and forming.
(1) The particle size distribution of lignin in table 1 shows that, with the increase of time, the nano lignin (acid-out lignin + detergent, example 4) has uniform particle size, non-uniform agglomeration, strong stability and regular morphology, and the change of particle size with time after adding several other surfactants is not much different from that of a blank sample without adding surfactants, so that the nano lignin has no effect on reducing the agglomeration phenomenon of lignin.
TABLE 1 particle size data for different times of acidified lignin under various surfactants
| Surface active agent | 2 days | 7 days | 15 days | 30 |
60 days | 90 days |
| / | 123.9nm | 222.6nm | 450nm | 1.4μm | 3μm | 10μm |
| Liquid detergent | 98.92nm | 98.92nm | 98.92nm | 123.9nm | 123.9nm | 212.7nm |
| Diethylene glycol | 120nm | 250nm | 400nm | 1.6μm | 3.2μm | 12μm |
| Triisopropanolamine | 125nm | 235nm | 450nm | 1.4μm | 4μm | 11μm |
| Polyethylene glycol | 120nm | 200nm | 460nm | 1.7μm | 4.5μm | 10μm |
| Ethylene glycol | 130nm | 220nm | 440nm | 1.5μm | 3.2μm | 12μm |
| Propylene glycol | 120nm | 240nm | 480nm | 1.8μm | 4.2μm | 11μm |
(2) According to the SEM image (figure 1) and the particle size image 3 of the nano lignin, the nano lignin prepared by adding the detergent as the surfactant is uniform in appearance, good in dispersity and not prone to agglomeration along with the increase of time.
(3) Through SEM (figure 2) of the cross section of the rubber of example 4, the nano lignin is uniformly dispersed in the matrix, the section is flat, the compatibility of the particles and the matrix becomes good, and the result is consistent with the result of mechanical properties.
(4) Through the mechanical properties of the examples 1 to 4 and the comparative examples 1 to 5, it can be found that the mechanical properties of the rubber added with the nano lignin filler are improved, and the mechanical properties such as tensile strength, stress at definite elongation and the like are further improved along with the increase of the filler amount, which indicates that the nano lignin and the rubber molecular chain form a cross-linked network, the compatibility of the lignin and the rubber matrix is improved, and the reinforcing effect is better, while the comparative examples 6 to 10 show that the nano lignin added with other surfactants does not have the reinforcing effect.
TABLE 2 tensile Property data for the rubbers of the examples
The present invention provides a method for preparing nano lignin latex and a thought and a method for using the same, and a method and a way for implementing the technical scheme are many, and the above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, a plurality of modifications and embellishments can be made without departing from the principle of the present invention, and these modifications and embellishments should also be regarded as the protection scope of the present invention. All the components not specified in this embodiment can be implemented by the prior art.
Claims (4)
1. The preparation method of the nano lignin latex is characterized by comprising the following steps:
(1) Mixing the acid-out lignin with a surfactant to obtain nano lignin;
(2) Mixing the nano lignin and rubber latex to obtain nano lignin latex;
(3) Adding a flocculating agent into the lignin latex, mixing and vulcanizing after the lignin latex is flocculated, and carrying out hot press molding to obtain the lignin latex;
in the step (1), the surfactant is a liquid detergent containing 30wt% of sodium hexadecylsulfonate; the surfactant is 1-5wt% of the acidification lignin;
in the step (2), the mass ratio of the nano lignin to the rubber latex is (0.05-0.2): 1;
in the step (3), the weight ratio of the lignin latex to the flocculant is (1-10): 1.
2. the production method according to claim 1, wherein in the step (2), the mixing treatment is performed at a rotation speed of 200rpm or more for 2min or more.
3. The preparation method according to claim 1, wherein the flocculant is any one or a combination of an acid compound, a dinitrile diamine formaldehyde condensate and a chloride salt.
4. The preparation method according to claim 1, characterized in that an auxiliary agent is added in the mixing vulcanization; wherein, the auxiliary agent is any one or a combination of several of an age resister, a vulcanizing agent, a sulfur accelerator and a lubricant.
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| NL73361C (en) * | 1945-07-07 | |||
| GB709991A (en) * | 1951-03-01 | 1954-06-02 | Dunlop Rubber Co | Improvements in compounding rubber |
| US2844548A (en) * | 1954-07-28 | 1958-07-22 | Us Rubber Co | Method for the incorporation of lignin into synthetic rubber |
| US3984362A (en) * | 1972-04-19 | 1976-10-05 | Canadian Patents And Development Limited | Reinforcing polymers with laundered amorphous lignin |
| WO1999042526A1 (en) * | 1998-02-23 | 1999-08-26 | Polyphalt Inc. | Lignin based colloidal compositions |
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2021
- 2021-08-09 CN CN202110907183.5A patent/CN113527778B/en active Active
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