CN109536079B - Wet preparation process of bio-based multifunctional constant viscose - Google Patents

Abstract

A wet process for preparing biologic multifunctional viscose is characterized by that the lignin-rubber phase solvent (modified lignin) is mixed with natural rubber by wet mixing to obtain biologic multifunctional viscose. The lignin-rubber phase solvent is a depolarized lignin product obtained by modifying lignin, has stable performance, can be uniformly mixed into natural rubber by adopting a wet blending technology, can realize good combination of the interface between the lignin and the natural rubber, and can realize multifunctionality of the obtained product.

Description

Wet preparation process of bio-based multifunctional constant viscose

Technical Field

The invention relates to the technical field of rubber preparation, in particular to a wet preparation process of a bio-based multifunctional constant adhesive.

Background

Rubber and plastic are important strategic materials indispensable in national economy, and play an irreplaceable important role in daily life and industrial and agricultural production of people, such as transportation industry, wherein rubber is widely used for damping products such as rubber springs on trains, conveyer belts adopted by subways and tires of automobiles and the like. The rubber and plastic products also have wide application in the aspects of information sensing, agriculture, forestry, water conservancy, medical care and military fields.

The rubber and plastic filler (or mixed material) is one of the indispensable most important components in rubber and plastic products, and the consumption of the filler is large, so that the cost of the rubber and plastic can be reduced, the mechanical property of the final product can be effectively enhanced, and other functions of electric conduction, heat conduction, magnetism and the like are endowed to the rubber and plastic products. The rubber reinforcing filler with the largest dosage at present is carbon black, the carbon black has excellent affinity with most rubber matrixes and excellent reinforcing effect on rubber, but the carbon black is derived from petrochemical resources and is a product obtained by incomplete combustion or thermal decomposition of carbon-containing petrochemical resources (such as petroleum, natural gas, coal and the like) under the condition of oxygen deficiency. Obviously, excessive dependence on carbon black is not beneficial to sustainable development, so rubber and plastic fillers which are renewable, environment-friendly, low in density, rich in reserves, low in cost and excellent in reinforcing effect are always the targets of extensive researchers.

The biomass filler (or mixture) applied to polymers such as rubber and plastic mainly comprises cellulose, lignin, chitin and the like (Polymer, 2014,55, 995-. Due to wide application export and market of cellulose, the use cost of chitin is high, while industrial lignin is generally burnt to generate electricity and heat, and market entrances of other applications are smaller and cannot be matched with the yield of lignin. Therefore, how to realize the successful application of the lignin in rubber and plastic products is very important.

Lignin is one of the most important components of plants, and forms the trunk of the plant together with cellulose and hemicellulose, and the lignin can play a role in adhesion and insect prevention. Lignin is also one of the most important renewable aromatic resources, and its basic building blocks in plants are three phenylpropanoid building blocks: p-hydroxyphenyl, guaiacyl and syringyl. These basic units are connected to each other by various types of C-C bonds or C-O bonds to form a three-dimensional type polyphenol macromolecule (Ind. Eng. chem. Res.,2016,55, 8691-8705). The application of the lignin in polymer materials is undoubtedly an important way for utilizing the lignin with high efficiency and high added value, and is expected to form a new material capable of being applied industrially. On the one hand, the problem of resource utilization of industrial lignin can be solved; on the other hand, the serious dependence of the polymer industry on fossil resources is reduced, which has great significance for improving the utilization rate of biomass resources, protecting the natural environment and the sustainable development of the society. Due to reactive functional groups such as carboxyl and hydroxyl groups that can react in lignin molecules, the compatibility and reactivity between lignin and many polymers have been reported in a great deal of research, including lignin/thermoplastic resin composites (e.g., polyolefins, polyvinyl chloride, PLA, PBS, PBAT, etc.), such as: a lignin-epoxy resin composite material with application number CN201110417428.2 and a preparation method thereof, lignin is used as a base material, epoxy resin, a curing agent, a toughening agent and the like are uniformly mixed with the lignin, and the lignin-based composite material is obtained by prepressing, hot-pressing and curing molding; lignin/thermosetting resin composites (mainly including phenolic resins, epoxy resins, and polyurethanes, etc.), such as: the application number is CN201810030050.2, the water-soluble phenolic resin composite material with low formaldehyde content for casting and the preparation method thereof, because a large amount of alkali lignin is used in the resin, the cost can be reduced, the release amount of formaldehyde and phenol in the casting process can be greatly reduced, compared with the similar products, the resin is more environment-friendly and has low toxicity, and the continuous and healthy development of the casting industry is facilitated; and blends with natural rubbers, such as: the preparation method of the lignin calcium carbonate compound modified rubber material with the application number of CN201710873830.9 comprises the following steps: preparing lignin calcium carbonate compound, plasticating natural rubber NR, mixing the materials, preparing a rubber compound sheet, and vulcanizing the rubber compound sheet. The lignin is used as an organic modifier of calcium carbonate, so that the compatibility of the calcium carbonate and a rubber matrix can be improved; and the calcium carbonate can prevent the agglomeration of lignin in the mixing process and promote the dispersion of the lignin in the matrix. In a word, the lignin and the calcium carbonate show a synergistic reinforcing effect when being used as fillers, and the lignin can improve the mechanical property of the calcium carbonate in the composite material and has a modification effect on the calcium carbonate; according to the lignin/carbon black/nitrile rubber composite material with the application number of CN201710957263.5 and the preparation method thereof, a dynamic coordination crosslinking network is constructed between chain segments of nitrile rubber and between phase interfaces of lignin and nitrile rubber under the action of a coordination vulcanizing agent, so that the composite material has excellent comprehensive mechanical property, the problem of poor physical property caused by poor compatibility of lignin and nitrile rubber is solved, the tensile strength can be 15-35 MPa, and the elongation at break is 250-700%; the lignin partially replaces carbon black to reinforce the rubber, has wide sources, is renewable, and saves petrochemical resources.

Compared with common rubber reinforcing agents such as carbon black and white carbon black, the lignin has the advantages that: (1) raw rubber and cost are saved; (2) lignin molecules contain a large amount of phenolic hydroxyl groups, so that the effects of aging resistance and oxidation resistance can be achieved, and the addition amount of rubber antioxidant can be saved; (3) the structural unit of the lignin molecule has similarity with PF resin, and can partially replace the common metal and rubber adhesive (cobalt salt and m-methylene system); (4) the processing performance of the lignin is excellent, rubber operation oil and softener can be reduced, and the phenomenon of powder flying in the processing process is better than that of white carbon black and carbon black; (5) the lignin density is less than that of the white carbon black and the carbon black, and when the lignin is used for tires, the tires can be lightened, and the purpose of saving energy is achieved.

The application of lignin in polymers such as rubber and the like needs to realize good dispersion of lignin, ensure the stability of lignin source and performance, and simultaneously perform depolarization processing on the lignin to enhance the interface combination of the lignin and the polymers such as nonpolar rubber and the like. Researchers believe that the existing lignin modification method can only improve the dispersion degree of lignin in a rubber matrix, but cannot obviously improve the interface combination of the lignin and the nonpolar rubber. How to improve the dispersion degree of lignin in polymer matrixes such as rubber and the like and improve the compatibility of the lignin and the polymer matrixes are the key points for realizing the application of the lignin in the polymers such as rubber and the like.

The processing method for mixing and adding the lignin in the rubber comprises a dry mixing method, a peptization coprecipitation method, a wet mixing method and a dynamic heat treatment process.

Dry blending refers to a process for directly mixing the lignin dry powder with rubber, similar to the processing of carbon black and silica filled reinforced rubber (Bioresources,2014,9(1): 1387-6763; Polymer,2014,55(26): 6754-6763). The dry mixing method has the advantages that: the method is simple and efficient, can directly utilize the existing rubber processing instruments and equipment, and is easy to industrialize; the disadvantages are that: the agglomeration of the lignin directly dry-mixed in the rubber matrix is very serious, so the reinforcing efficiency is low, namely the actual application effect is not good.

The lignin/rubber latex coprecipitation process is to disperse lignin in an aqueous solution in advance, then mix the lignin with rubber latex uniformly, and then prepare rubber/lignin coprecipitation rubber through the working procedures of coprecipitation, washing, drying and the like (Advanced Materials Research,2008,47: 93-96; rubber industry, 2018, 65, 885-889). This excellent dispersion is maintained during co-precipitation and subsequent rubber compounding processes, since lignin and latex are easily mixed homogeneously in solution. The lignin/latex coprecipitation process has the advantages that: the dispersion of lignin in the rubber matrix is better, so the reinforcing efficiency is higher. The disadvantages are that: the coprecipitation method has complex process, time-consuming filtration and drying rate, too low efficiency and difficult industrialization.

Unlike conventional dry mixing, the wet mixing and dynamic heat treatment processes first mix the lignin and rubber which contain a certain amount of water (usually 50% water content). The water can form hydrogen bonds with lignin to reduce the strong hydrogen bonding of lignin, i.e. the aggregation/bonding between lignin particles is weakened by water, so as to improve the lignin dispersing effect. Then, before adding rubber auxiliary agent, dynamic heat treatment is carried out, the rubber material is subjected to heat mixing on a mixing machine with the temperature of above 100 ℃, during which, under the strong shearing of high-temperature mixing, lignin generates certain free radicals, thereby realizing chemical grafting with the rubber and further improving the interface combination and dispersion degree of the lignin, and removing the water in the rubber (Journal of Applied Polymer Science,1978,22: 1885-. The method has the disadvantages of low efficiency, high temperature for removing water, strict temperature control, and reduced crystallization property of natural rubber and comprehensive performance of rubber products.

In summary, the successful application of lignin in polymer products such as rubber still has the following problems: 1) the source difference of the lignin is large, and the performance is unstable; 2) due to the difference in surface properties, lignin does not disperse well and does not perform a good interfacial bond in rubber.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a wet preparation process of a bio-based multifunctional constant viscose glue, which is characterized in that a lignin-rubber phase solvent (modified lignin) is mixed and added into natural rubber by wet blending to produce the bio-based multifunctional constant viscose glue. The lignin-rubber phase solvent is a depolarized lignin product obtained by modifying lignin, has stable performance, can be uniformly mixed into natural rubber by adopting a wet blending technology, can realize good combination of the interface between the lignin and the natural rubber, and can realize multifunctionality of the obtained product.

In order to achieve the purpose, the invention provides the following technical scheme: a wet preparation process of bio-based multifunctional constant viscose glue comprises the following steps:

(1) dissolving the lignin rubber phase solvent in water, and uniformly stirring at normal temperature to form a stable dispersion liquid with the mass concentration of 0.5-5%;

(2) adding 2-50% of lignin-rubber phase solvent aqueous dispersion relative to the mass fraction of the natural rubber into the natural rubber, uniformly mixing, adding an auxiliary agent with the mass fraction being less than 1% of the mass fraction of the natural rubber, mixing and stirring by using a stirrer at normal temperature, and reacting for 30-90 minutes;

(3) and (3) introducing the reacted mixture into a glue airing groove for airing glue: reacting in a glue drying tank at normal temperature for 3-4 days, then wrinkling with a crepe machine, filter pressing, dewatering, removing impurities, cleaning, fully oxidizing in shade, drying in the sun for 1-2 days on day 15.

(4) Granulating, drying, briquetting, forming into glue and packaging.

Preferably, the auxiliary agent in the step 2) is two or more of a coupling agent, a surface modifier, a surfactant and an anti-aging agent.

Preferably, the rotating speed of the stirrer in the step 2) is 50-60rmp, and the mixture is in a liquid state; the rotation speed of the stirrer is more than 1000rmp, and the mixture is solidified into gel.

Preferably, the tread rubber can be produced by adding 2-5% of lignin-rubber phase solvent aqueous dispersion into the natural rubber in the step 2); the anti-slippery low-rolling-resistance rubber can be produced by adding 5-10% of lignin-rubber phase solvent aqueous dispersion into natural rubber; adding 10-15% by mass of lignin-rubber phase solvent aqueous dispersion into natural rubber to produce inner liner rubber; adding 15-20% by mass of lignin-rubber phase solvent aqueous dispersion into natural rubber to produce steel wire rubber; the composite rubber can be produced by adding 20-50% of lignin-rubber phase solvent aqueous dispersion into natural rubber.

Compared with the prior art, the invention has the beneficial effects that:

1. the invention can replace partial natural rubber, reduce the cost and reduce the external dependence of China on the natural rubber;

2. the lignin-rubber phase solvent is used as a dispersant, so that the aggregation effect among the fillers can be effectively reduced, and the interaction between the polymer and the fillers is increased;

3. the invention adopts wet preparation, but does not need precipitation process, can well disperse the lignin rubber phase solvent in the natural rubber and generate good interface combination, thus improving the overall performance of the final rubber finished product, and particularly obviously improving the adhesive force of steel wires to different degrees;

4. the functionality of the rubber finished product can be adjusted by adjusting the mixing amount of the lignin-rubber phase solvent;

5. the invention really realizes the industrial application of lignin in rubber, and the lignin-rubber phase solvent is depolarized modified lignin, has stable quality and can ensure the application stability of the lignin in the mixing of natural rubber.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

A wet preparation process of bio-based multifunctional constant viscose glue comprises the following steps:

(1) dissolving the lignin rubber phase solvent in water, and uniformly stirring at normal temperature to form a stable dispersion liquid with the mass concentration of 0.5-5%;

(2) adding 2-50% of lignin-rubber phase solvent aqueous dispersion relative to the mass fraction of the natural rubber into the natural rubber, uniformly mixing, adding an auxiliary agent with the mass fraction being less than 1% of the mass fraction of the natural rubber, mixing and stirring by using a stirrer at normal temperature, and reacting for 30-90 minutes;

(3) and (3) introducing the reacted mixture into a glue airing groove for airing glue: reacting in a glue drying tank at normal temperature for 3-4 days, then wrinkling with a crepe machine, filter pressing, dewatering, removing impurities, cleaning, fully oxidizing in shade, drying in the sun for 1-2 days on day 15.

(4) Granulating, drying, briquetting, forming into glue and packaging.

Wherein, the auxiliary agent in the step 2) is two or more of a coupling agent, a surface modifier, a surfactant and an anti-aging agent.

Wherein, the rotating speed of the stirrer in the step 2) is 50-60rmp, and the mixture is in a liquid state; the rotation speed of the stirrer is more than 1000rmp, and the mixture is solidified into gel.

Wherein, the tread rubber can be produced by adding 2-5% of lignin rubber phase solvent aqueous dispersion into the natural rubber in the step 2); the anti-slippery low-rolling-resistance rubber can be produced by adding 5-10% of lignin-rubber phase solvent aqueous dispersion into natural rubber; adding 10-15% by mass of lignin-rubber phase solvent aqueous dispersion into natural rubber to produce inner liner rubber; adding 15-20% by mass of lignin-rubber phase solvent aqueous dispersion into natural rubber to produce steel wire rubber; the composite rubber can be produced by adding 20-50% of lignin-rubber phase solvent aqueous dispersion into natural rubber.

Example 1:

a wet process preparation process for producing bio-based tread rubber, comprising the steps of:

(1) dissolving the lignin rubber phase solvent in water, and uniformly stirring at normal temperature to form a stable dispersion liquid with the mass concentration of 3%;

(2) adding lignin rubber phase solvent aqueous dispersion with the mass fraction of 3 percent relative to the natural rubber into the natural rubber, uniformly mixing, adding silane coupling agent with the mass fraction of 0.1 percent relative to the natural rubber and dodecyl dimethyl betaine with the mass fraction of 0.2 percent relative to the natural rubber, mixing and stirring by adopting a stirrer at normal temperature at the rotating speed of 55rmp, and reacting for 35 minutes;

(3) and (3) introducing the reacted mixture into a glue airing groove for airing glue: reacting in a glue drying tank at normal temperature for 3 days, then performing wrinkle processing by a crepe machine, performing filter pressing, dewatering, impurity removal and cleaning, fully oxidizing in a shade place to dry the glue, and drying for 1 day at 15 days;

(4) granulating, drying, briquetting, forming into glue and packaging, wherein the obtained glue forming product is a bio-based tread rubber, and the pair of the quality detection data of the bio-based tread rubber and the quality detection data of the natural rubber is shown in a table I:

table one:

quality parameter	Unit of	Natural rubber NR20	Bio-based tread rubber
				Hardness of	Shore A	69	76
Tensile strength	MPa	26.8	25.1
				Elongation at break	％	553	516
Stress at 100% definite elongation	MPa	3.54	4.69
				Stress at definite elongation of 300%	MPa	14.33	17.34
Tear strength	kN/m	118	104
				Adhesive force	N/25mm	915	1141
Hardness after aging	Shore A	76	83
				Tensile strength after aging	MPa	16.57	16.71
Elongation at break after aging	％	245	221
				100% stress at definite elongation after aging	MPa	5.875	6.77
Tear strength after aging	kN/m	87	96
				Adhesion after aging	N/25mm	936	1295
Mooney viscosity ML (1+4)100 DEG C		32.2	47.5

Note: the aging was carried out at 100 ℃ for 72 hours.

As can be seen from the data in Table I: the hardness, stress at definite elongation and adhesive force of the bio-based tread rubber are obviously improved, and the comprehensive performance is obviously improved.

Example 2:

a wet preparation process for producing bio-based anti-slippery low rolling resistance glue comprises the following steps:

(1) dissolving the lignin rubber phase solvent in water, and uniformly stirring at normal temperature to form a stable dispersion liquid with the mass concentration of 2%;

(2) adding 7% of lignin rubber phase solvent aqueous dispersion relative to the mass fraction of natural rubber into the natural rubber, uniformly mixing, adding 0.3% of silane coupling agent, 0.1% of tetradecyl dimethyl betaine and 0.2% of sodium lignosulfonate relative to the mass fraction of the natural rubber, mixing and stirring by using a stirrer at normal temperature at the rotating speed of 50rmp, and reacting for 55 minutes;

(3) and (3) introducing the reacted mixture into a glue airing groove for airing glue: reacting in a glue drying tank at normal temperature for 4 days, then performing wrinkle processing by a crepe machine, performing filter pressing, dewatering, impurity removal and cleaning, fully oxidizing in a shade place to dry the glue, and drying for 2 days at 15 days;

(4) granulating, drying, briquetting, gelatinizing and packaging, wherein the obtained gelatinizing product is bio-based anti-wet-skid low-rolling-resistance rubber, and the comparison of the obtained gelatinizing product and the quality detection data of the natural rubber is shown in a table II:

table two:

quality parameter	Unit of	Natural rubber NR20	Bio-based anti-slippery low-rolling-resistance glue
				Hardness of	Shore A	69	80
Tensile strength	MPa	26.8	24.9
				Elongation at break	％	553	546
Stress at 100% definite elongation	MPa	3.54	5.69
				Stress at definite elongation of 300%	MPa	14.33	19.85
Tear strength	kN/m	118	113
				Adhesive force	N/25mm	915	1247
Hardness after aging	Shore A	76	98
				Tensile strength after aging	MPa	16.57	17.1
Elongation at break after aging	％	245	241
				100% stress at definite elongation after aging	MPa	5.875	8.17
Tear strength after aging	kN/m	87	112
				Adhesion after aging	N/25mm	936	1390
Mooney viscosity ML (1+4)100 DEG C		32.2	51.4

Note: the aging was carried out at 100 ℃ for 72 hours.

As can be seen from the data in Table II: the hardness, stress at definite elongation and adhesive force of the bio-based anti-slippery low-rolling-resistance adhesive are obviously improved, and the comprehensive performance is obviously improved.

Example 3: (for airtight layer glue)

A wet process for producing bio-based air barrier adhesives, comprising the steps of:

(1) dissolving the lignin rubber phase solvent in water, and uniformly stirring at normal temperature to form a stable dispersion liquid with the mass concentration of 1.5%;

(2) adding 12% of lignin rubber phase solvent aqueous dispersion relative to the mass fraction of natural rubber into the natural rubber, uniformly mixing, adding 0.1% of silane coupling agent, 0.2% of tetradecyl dimethyl betaine and 0.1% of sodium dodecyl benzene sulfonate relative to the mass fraction of the natural rubber, mixing and stirring by adopting a stirrer at normal temperature at the rotating speed of 60rmp, and reacting for 70 minutes;

(3) and (3) introducing the reacted mixture into a glue airing groove for airing glue: reacting in a glue drying tank at normal temperature for 3 days, then performing wrinkle processing by a crepe machine, performing filter pressing, dewatering, impurity removal and cleaning, fully oxidizing in a shade place to dry the glue, and drying for 1 day at 15 days;

(4) granulating, drying, briquetting, gelatinizing and packaging, wherein the obtained gelatinizing product is bio-based inner liner rubber, and the comparison of the obtained gelatinizing product and the quality detection data of the natural rubber is shown in the third table:

table three:

quality parameter	Unit of	Commercial airtight glue QMJ-1	Bio-based inner liner rubber
				Hardness of	Shore A	47	52
Tensile strength	MPa	6.2	5.7
				Elongation at break	％	749	674
Stress at 100% definite elongation	MPa	1.0	1.4
				Stress at definite elongation of 300%	MPa	2.4	2.7
Tear strength	kN/m	29	27
				Adhesive force	N/25mm	915	1292
Permanent deformation	％	34	36
				Hardness after aging	Shore A	50	56
Tensile strength after aging	MPa	6.1	4.9
				Elongation at break after aging	％	678	596
100% stress at definite elongation after aging	MPa	1.3	1.7
				Tear strength after agingDegree of rotation	kN/m	28	28
Adhesion after aging	N/25mm	936	1425
				Permanent deformation after aging	％	27	28
Mooney viscosity ML (1+4)100 DEG C		65	52

Note: the aging was carried out at 100 ℃ for 72 hours.

As can be seen from the data in Table three: the hardness, the stress at definite elongation, the adhesive force and the permanent deformation of the bio-based air-tight layer adhesive are obviously improved, and the comprehensive performance is obviously improved.

Example 4:

a wet preparation process for producing bio-based steel sericin, comprising the following steps:

(1) dissolving the lignin rubber phase solvent in water, and uniformly stirring at normal temperature to form a stable dispersion liquid with the mass concentration of 2.5%;

(2) adding the lignin rubber phase solvent aqueous dispersion with the mass percent of 18 percent relative to the natural rubber into the natural rubber, uniformly mixing, adding 0.2 percent of silane coupling agent, 0.3 percent of tetradecyl dimethyl betaine and 0.15 percent of sodium dodecyl benzene sulfonate relative to the mass percent of the natural rubber, mixing and stirring by a stirrer at normal temperature at the rotating speed of 1100rmp, and reacting for 80 minutes;

(3) and (3) introducing the reacted mixture into a glue airing groove for airing glue: reacting in a glue drying tank at normal temperature for 3 days, then performing wrinkle processing by a crepe machine, performing filter pressing, dewatering, impurity removal and cleaning, fully oxidizing in a shade place to dry the glue, and drying for 2 days at 15 days;

(4) granulating, drying, briquetting, gelatinizing and packaging, wherein the obtained gelatinizing product is bio-based steel wire glue, and the pair of the obtained gelatinizing product and the quality detection data of the natural rubber is shown in the following table four:

table four:

quality parameter	Unit of	Natural rubber NR20	Bio-based steel silk glue
				Hardness of	Shore A	69	87
Tensile strength	MPa	26.8	26.1
				Elongation at break	％	553	557
Stress at 100% definite elongation	MPa	3.54	5.91
				Stress at definite elongation of 300%	MPa	14.33	23.2
Tear strength	kN/m	118	110
				Adhesive force	N/25mm	915	1312
Hardness after aging	Shore A	76	119
				Tensile strength after aging	MPa	16.57	18.3
Elongation at break after aging	％	245	255
				100% stress at definite elongation after aging	MPa	5.875	10.21
Tear strength after aging	kN/m	87	121
				Adhesion after aging	N/25mm	936	1625
Mooney viscosity ML (1+4)100 DEG C		32.2	57.4

Note: the aging was carried out at 100 ℃ for 72 hours.

As can be seen from the data in table four: the hardness, the stress at definite elongation and the adhesive force of the bio-based steel wire glue are obviously improved, and the comprehensive performance is obviously improved.

Example 5:

a wet preparation process for producing bio-based composite adhesive comprises the following steps:

(1) dissolving the lignin rubber phase solvent in water, and uniformly stirring at normal temperature to form a stable dispersion liquid with the mass concentration of 5.5%;

(2) adding 25% of lignin rubber phase solvent aqueous dispersion relative to the mass fraction of natural rubber into the natural rubber, uniformly mixing, adding 0.3% of silane coupling agent, 0.1% of dodecyl dihydroxy ethyl betaine and 0.5% of sodium dodecyl benzene sulfonate relative to the mass fraction of the natural rubber, mixing and stirring by adopting a stirrer at normal temperature at the rotating speed of 1300rmp, and reacting for 70 minutes;

(3) and (3) introducing the reacted mixture into a glue airing groove for airing glue: reacting in a glue drying tank at normal temperature for 3 days, then performing wrinkle processing by a crepe machine, performing filter pressing, dewatering, impurity removal and cleaning, fully oxidizing in a shade place to dry the glue, and drying for 1 day at 15 days;

(4) granulating, drying, briquetting, gelatinizing and packaging, wherein the obtained gelatinizing product is bio-based composite rubber, and the mass detection data of the bio-based composite rubber and natural rubber are shown in the table five:

table five:

quality parameter	Unit of	Natural rubber NR20	Bio-based composite adhesive
				Hardness of	Shore A	69	75
Tensile strength	MPa	26.8	25.3
				Elongation at break	％	553	537
Stress at 100% definite elongation	MPa	3.54	6.91
				Stress at definite elongation of 300%	MPa	14.33	25.3
Tear strength	kN/m	118	114
				Adhesive force	N/25mm	915	1287
Hardness after aging	Shore A	76	99
				Tensile strength after aging	MPa	16.57	19.3
Elongation at break after aging	％	245	263
				100% stress at definite elongation after aging	MPa	5.875	11.4
Tear strength after aging	kN/m	87	113
				Adhesion after aging	N/25mm	936	1496
Mooney viscosity ML (1+4)100 DEG C		32.2	46.9

Note: the aging was carried out at 100 ℃ for 72 hours.

As can be seen from the data in Table five: the hardness, the stress at definite elongation and the adhesive force of the bio-based composite adhesive are obviously improved, and the comprehensive performance is obviously improved.

Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (7)

1. A wet preparation process of a bio-based multifunctional constant viscose glue is characterized by comprising the following steps: the method comprises the following steps:

(1) dissolving the lignin rubber phase solvent in water, and uniformly stirring at normal temperature to form a stable dispersion liquid with the mass concentration of 0.5-5%;

(2) adding 2-50% of lignin-rubber phase solvent aqueous dispersion relative to the mass fraction of the natural rubber into the natural rubber, uniformly mixing, adding an auxiliary agent with the mass fraction being less than 1% of the mass fraction of the natural rubber, mixing and stirring by using a stirrer at normal temperature, and reacting for 30-90 minutes;

(3) and (3) introducing the reacted mixture into a glue airing groove for airing glue: reacting in a glue drying tank at normal temperature for 3-4 days, then performing wrinkle processing by a crepe machine, performing filter pressing, dewatering, impurity removing and cleaning, fully oxidizing in a shade place, drying, and drying for 1-2 days at day 15;

(4) granulating, drying, briquetting, forming glue and packaging;

the rotating speed of the stirrer in the step 2) is 50-60rmp, and the mixture is in a liquid state; the rotation speed of the stirrer is more than 1000rmp, and the mixture is solidified into gel;

adding 2-5% by mass of lignin-rubber phase solvent aqueous dispersion into natural rubber in the step 2) to produce tread rubber; the anti-slippery low-rolling-resistance rubber can be produced by adding 5-10% of lignin-rubber phase solvent aqueous dispersion into natural rubber; adding 10-15% by mass of lignin-rubber phase solvent aqueous dispersion into natural rubber to produce inner liner rubber; adding 15-20% by mass of lignin-rubber phase solvent aqueous dispersion into natural rubber to produce steel wire rubber; the composite rubber can be produced by adding 20-50% of lignin-rubber phase solvent aqueous dispersion into natural rubber.

2. The wet preparation process of bio-based multifunctional permanent viscose in claim 1, wherein: and 2) the auxiliary agent is two or more of a coupling agent, a surface modifier, a surfactant and an anti-aging agent.

3. The wet process for preparing bio-based multifunctional permanent adhesive according to any one of claims 1-2, wherein: a wet process preparation process for producing bio-based tread rubber, comprising the steps of:

(1) dissolving the lignin rubber phase solvent in water, and uniformly stirring at normal temperature to form a stable dispersion liquid with the mass concentration of 3%;

(2) adding lignin rubber phase solvent aqueous dispersion with the mass fraction of 3 percent relative to the natural rubber into the natural rubber, uniformly mixing, adding silane coupling agent with the mass fraction of 0.1 percent relative to the natural rubber and dodecyl dimethyl betaine with the mass fraction of 0.2 percent relative to the natural rubber, mixing and stirring by adopting a stirrer at normal temperature at the rotating speed of 55rmp, and reacting for 35 minutes;

(3) and (3) introducing the reacted mixture into a glue airing groove for airing glue: reacting in a glue drying tank at normal temperature for 3 days, then performing wrinkle treatment by a crepe machine, performing filter pressing, dewatering, impurity removal, cleaning, fully oxidizing in a shade place, namely drying in the air, and drying in the sun for 1 day at 15 days;

(4) granulating, drying, briquetting, gelatinizing and packaging to obtain the gelatinizing product which is the bio-based tread rubber.

4. The wet process for preparing bio-based multifunctional permanent adhesive according to any one of claims 1-2, wherein: a wet preparation process for producing bio-based anti-slippery low rolling resistance glue comprises the following steps:

(1) dissolving the lignin rubber phase solvent in water, and uniformly stirring at normal temperature to form a stable dispersion liquid with the mass concentration of 2%;

(2) adding 7% of lignin rubber phase solvent aqueous dispersion relative to the mass fraction of natural rubber into the natural rubber, uniformly mixing, adding 0.3% of silane coupling agent, 0.1% of tetradecyl dimethyl betaine and 0.2% of sodium lignosulfonate relative to the mass fraction of the natural rubber, mixing and stirring by using a stirrer at normal temperature at the rotating speed of 50rmp, and reacting for 55 minutes;

(3) and (3) introducing the reacted mixture into a glue airing groove for airing glue: reacting in a glue drying tank at normal temperature for 4 days, then performing wrinkle treatment by using a crepe machine, performing filter pressing, dewatering, impurity removal and cleaning, fully oxidizing in a shade place, namely drying in the air, and drying in the sun for 2 days at the 15 th day;

(4) granulating, drying, briquetting, gelatinizing and packaging, wherein the obtained gelatinizing product is a bio-based anti-slippery low-rolling-resistance adhesive.

5. The wet process for preparing bio-based multifunctional permanent adhesive according to any one of claims 1-2, wherein: a wet process for producing bio-based air barrier adhesives, comprising the steps of:

(1) dissolving the lignin rubber phase solvent in water, and uniformly stirring at normal temperature to form a stable dispersion liquid with the mass concentration of 1.5%;

(2) adding 12% of lignin rubber phase solvent aqueous dispersion relative to the mass fraction of natural rubber into the natural rubber, uniformly mixing, adding 0.1% of silane coupling agent, 0.2% of tetradecyl dimethyl betaine and 0.1% of sodium dodecyl benzene sulfonate relative to the mass fraction of the natural rubber, mixing and stirring by adopting a stirrer at normal temperature at the rotating speed of 60rmp, and reacting for 70 minutes;

(3) and (3) introducing the reacted mixture into a glue airing groove for airing glue: reacting in a glue drying tank at normal temperature for 3 days, then performing wrinkle treatment by a crepe machine, performing filter pressing, dewatering, impurity removal, cleaning, fully oxidizing in a shade place, namely drying in the air, and drying in the sun for 1 day at 15 days;

(4) granulating, drying, briquetting, gelatinizing and packaging, wherein the obtained gelatinizing product is the bio-based inner liner rubber.

6. The wet process for preparing bio-based multifunctional permanent adhesive according to any one of claims 1-2, wherein: a wet preparation process for producing bio-based steel sericin, comprising the following steps:

(1) dissolving the lignin rubber phase solvent in water, and uniformly stirring at normal temperature to form a stable dispersion liquid with the mass concentration of 2.5%;

(2) adding the lignin rubber phase solvent aqueous dispersion with the mass percent of 18 percent relative to the natural rubber into the natural rubber, uniformly mixing, adding 0.2 percent of silane coupling agent, 0.3 percent of tetradecyl dimethyl betaine and 0.15 percent of sodium dodecyl benzene sulfonate relative to the mass percent of the natural rubber, mixing and stirring by a stirrer at normal temperature at the rotating speed of 1100rmp, and reacting for 80 minutes;

(3) and (3) introducing the reacted mixture into a glue airing groove for airing glue: reacting in a glue drying tank at normal temperature for 3 days, then performing wrinkle treatment by a crepe machine, performing filter pressing, dewatering, impurity removal, cleaning, fully oxidizing in a shade place, namely drying in the air, and drying in the sun for 2 days at 15 days;

(4) granulating, drying, briquetting, gelatinizing and packaging, wherein the obtained gelatinizing product is the bio-based steel wire glue.

7. The wet process for preparing bio-based multifunctional permanent adhesive according to any one of claims 1-2, wherein: a wet preparation process for producing bio-based composite adhesive comprises the following steps:

(1) dissolving the lignin rubber phase solvent in water, and uniformly stirring at normal temperature to form a stable dispersion liquid with the mass concentration of 5.5%;

(2) adding 25% of lignin rubber phase solvent aqueous dispersion relative to the mass fraction of natural rubber into the natural rubber, uniformly mixing, adding 0.3% of silane coupling agent, 0.1% of dodecyl dihydroxy ethyl betaine and 0.5% of sodium dodecyl benzene sulfonate relative to the mass fraction of the natural rubber, mixing and stirring by adopting a stirrer at normal temperature at the rotating speed of 1300rmp, and reacting for 70 minutes;

(3) and (3) introducing the reacted mixture into a glue airing groove for airing glue: reacting in a glue drying tank at normal temperature for 3 days, then performing wrinkle treatment by a crepe machine, performing filter pressing, dewatering, impurity removal, cleaning, fully oxidizing in a shade place, namely drying in the air, and drying in the sun for 1 day at 15 days;

(4) granulating, drying, briquetting, gelatinizing and packaging to obtain the product of the gelatinizing being the bio-based composite adhesive.