1. A method for producing a rubber adhesive, which is characterized in that the rubber adhesive is a double-end hydroxyl-group polymerized styrene-butadiene liquid rubber adhesive, and the production method comprises the following steps:

s1 lithium initiator synthesis:

s1-1: continuously vacuumizing the reaction container, filling argon, baking for 3 times, discharging water and air, then filling argon to maintain the argon atmosphere, and keeping the temperature at 22-25 ℃;

s1-2: adding 1 part by weight of tert-butyldimethylsilyl chloride, 1.25-1.7 parts by weight of imidazole and 2.3-2.75 parts by weight of cyclohexane into a reaction vessel, mixing and stirring for 1h, then dropwise adding 0.5-0.6 part by weight of 3-chloro-1-propanol into the reaction vessel, continuously dropwise adding for 1h, heating to 42-47 ℃, stirring and reacting for 2-4h, then standing for 6-8h, filtering out insoluble substances to obtain an intermediate solution, and filling argon for sealing;

s1-3: adding 3.3-3.5 parts by weight of lithium sheets into the intermediate solution, heating to 75-85 ℃, carrying out ultrasonic oscillation reaction for 1.5-2h, then cooling to 30-33 ℃, carrying out stirring reaction for 4-5h, then cooling to 2 +/-2 ℃, standing for 6-8h, and filtering out insoluble substances to obtain a lithium initiator;

polymerization of S2: weighing 2 parts of styrene, 4.6-5 parts of tetrahydrofuran, 1.1-1.3 parts of butadiene and 0.015-0.03 part of lithium initiator according to parts by weight, continuously vacuumizing a reaction container, filling argon, baking for 3 times to discharge water and air, adding the styrene and the tetrahydrofuran into the reaction container, then dropwise adding the butadiene, controlling the temperature at 10-20 ℃, stirring for reaction for 3-4h, then adding the lithium initiator, and continuously stirring for reaction for 0.5-1h to obtain a polymerization solution;

and (3) end capping reaction of S3: dripping 0.05-0.06 weight part of ethylene oxide-cyclohexane solution into the polymerization solution, cooling to-5-8 ℃, stirring for reaction for 1-2h, and then pouring 8-10 weight parts of absolute ethyl alcohol or dilute hydrochloric acid into a reaction container to terminate the end-capping reaction to obtain glue solution;

and S4 post-processing: spin-steaming the glue solution for 1h to remove the residual ethylene oxide-cyclohexane solution in the glue solution, washing the glue solution with sodium bicarbonate solution for 1h, pouring the glue solution into absolute ethyl alcohol for precipitation, collecting the lower glue solution, and drying under a vacuum condition to obtain the double-end hydroxyl poly-styrene-butadiene liquid rubber adhesive;

s5 ultraviolet light curing: and (4) dropwise adding a photoinitiator accounting for 2-4% of the total mass of the liquid rubber adhesive obtained in the step S4, uniformly stirring, placing in a production device, vacuumizing, and carrying out ultraviolet irradiation to obtain the cured and tackified double-end hydroxyl polymerized styrene butadiene liquid rubber adhesive.

2. The method as claimed in claim 1, wherein the stirring speed in steps S1-2 and S1-3 is 200rpm, the stirring speed in step S2 is 400rpm, the stirring speed in step S3 is 260rpm, and the stirring modes are magnetic stirring.

3. The method for producing a rubber adhesive according to claim 1, wherein the baking temperature in step S1-1 is 55-60 ℃, and the lithium flakes are soaked in cyclohexane in advance for 1-2h in step S1-3.

4. The method for producing a rubber adhesive according to claim 1, wherein the dilute hydrochloric acid in the step S3 has a mass concentration of 0.2 to 0.3mol/L, the rotary evaporation temperature in the step S4 is 40 to 45 ℃, the degree of vacuum is 0.01Pa, and the sodium bicarbonate solution has a mass concentration of 0.5 mol/L.

5. The method for producing a rubber adhesive as defined in claim 1, wherein the ultraviolet light in step S5 has a luminous power of 300W, a wavelength of 355 and 365nm, a light distance of 80-120cm and a light time of 3-5 min.

6. The production device for producing the rubber adhesive according to any one of the claims 1 to 5, which comprises a stirring barrel (1), an ultraviolet irradiation bin (2), an ultraviolet generating device (3) and a feeding device (4), wherein the ultraviolet irradiation bin (2) is arranged in a hollow circular ring shape, an ultraviolet lamp (31) of the ultraviolet generating device (3) is arranged in the middle of the ultraviolet irradiation bin (2), the bottom of the stirring barrel (1) is connected with the annular space of the ultraviolet irradiation bin (2) through two groups of guide pipes (11) provided with electromagnetic valves (8), and the tail end of the ultraviolet irradiation bin (2) is connected with the feeding device (4) through one group of conveying pipes (21) provided with the electromagnetic valves (8);

a stirring telescopic rod (5) and a lifting plate (6) are arranged inside the stirring barrel (1), the stirring telescopic rod (5) is located at the center of the top of the stirring barrel (1), the telescopic stirring rod (5) comprises an inner loop bar (51) which is located at the upper part and an outer loop bar (52) which is located at the lower part in a sliding connection mode, a combined motor (7) used for controlling the telescopic stirring rod (5) to stretch and rotate is arranged on the outer top surface of the stirring barrel (1), a plurality of stirring blades (53) are arranged on the outer periphery of the outer loop bar (52) from top to bottom, a screw buckle head (54) is arranged at the bottom of the outer loop bar (52), a group of pressing plates (55) are arranged on the outer periphery of the outer loop bar (52) above the;

the lifting plate (6) and the inner wall of the stirring barrel (1) are sealed and slide relatively, a screw thread hole (61) which is rotatably and threadedly connected with the screw thread head (54) is formed in the center of the lifting plate (6), a flat groove (62) with the same area as the pressing plate (55) is formed in the upper surface of the lifting plate (6), a plurality of water through holes (63) penetrating through the lifting plate (6) are formed in the circumferential direction of the flat groove (62), two ends of the upper surface of the lifting plate (6) at the outer side of the flat groove (62) are respectively provided with a group of limiting blocks (64) capable of sliding along the surface of the lifting plate (6), the limit block (64) is meshed and connected with a gear set (65) arranged on the upper surface of the lifting plate (6) through teeth arranged on the side edge of the limit block, the gear sets (65) are meshed with teeth arranged on the periphery of the pressure plate (55), and the two groups of gear sets (65) are arranged in a central symmetry mode relative to the lifting plate (6);

agitator (1) inner wall upper portion be equipped with spacing groove (12) of stopper (64) joint, spacing groove (12) top is equipped with limiting plate (13), and agitator (1) inner wall lower part is equipped with spacing ring (14), spacing ring (14) upper surface is equipped with pressure sensor (15), pressure sensor (15) extend to agitator (1) outside and with three groups solenoid valve (8) are through infrared sensor (9) induction connection.

7. The production apparatus for producing rubber adhesive according to claim 6, wherein said combined motor (7) comprises a set of electric push rod (71) and a set of rotating motor (72), said ultraviolet irradiation chamber (2) is provided with a circle of rotating portion (22) at the outside, a support seat (23) is provided below the ultraviolet irradiation chamber (2) at both sides of said rotating portion (22), said support seat (23) is provided with a rotating wheel (24) for engaging with the rotating portion (22) to rotate, one set of said support seat (23) is provided with a driving motor (25) for driving said rotating wheel (24) to rotate, the ultraviolet irradiation chamber (2) is rotatably connected with said conveying pipe (21), and the ultraviolet irradiation chamber (2) is rotatably connected with an annular sleeve (17) provided at the end of said guiding pipe (11).

8. The apparatus for producing rubber cement as claimed in claim 6, wherein said screw head (54) has a set of stirring blades (53) extending through said screw hole (61) and below said lifting plate (6) at the bottom, said gear set (65) includes a driving wheel (651) engaged with said pressing plate (55) and a driven wheel (652) engaged with said stopper (64), and the sides of said teeth are all arc-shaped.

9. A device for producing rubber adhesives as defined in claim 6, wherein a stirring and conveying rod (26) is provided in said conveying pipe (21), said feeding device (4) comprises a conveying belt (41) and a plurality of collecting barrels (42) disposed on said conveying belt (41), and said pressure sensor (15) is disposed on a support (16) provided outside said stirring barrel (1).

Background

The rubber adhesive is an adhesive prepared by using chloroprene rubber, butyronitrile, butyl silicone rubber, polysulfide and other synthetic rubbers or natural rubbers as main materials, has excellent viscoelasticity, is suitable for bonding soft materials or materials with greatly different thermal expansion coefficients, such as bonding between rubber and rubber, between rubber and metal, between plastic, between leather, between wood and other materials, and has wide application in the departments of aircraft manufacturing, automobile manufacturing, building, light industry, rubber product processing and the like. Rubber adhesives are mainly classified into two categories: structural adhesive and non-structural adhesive, the structural adhesive is divided into solvent glue solution type and adhesive film adhesive tape type, and most of them are composite systems (except polyurethane adhesive), and the non-structural rubber adhesive can be divided into two categories of solution type and emulsion type, wherein the solution type rubber adhesive (rubber glue solution for short) is used as the main type.

When the performance of a rubber adhesive is evaluated, the bonding performance is not only considered but also the heat resistance, the impact resistance, the environmental protection performance and the like of the rubber adhesive are considered, and the rubber with stronger comprehensive performance has stronger practicability and wider application range. The existing rubber adhesives and preparation processes thereof are various, and most of the rubber adhesives are used outdoors and need to be influenced by weather conditions, so that the stability of the rubber adhesives needs to meet the use requirements, and some rubber adhesives are easy to deteriorate or emit harmful substances under the conditions of high temperature and the like, or have short service life due to defects of technological means, so that the practicability needs to be improved by using more stable and harmless rubber adhesives.

Patent CN112321896A discloses a rubber modifier, a rubber material, a preparation method and an application, wherein the rubber modifier is obtained by modifying with a rubber modifier, and the preparation method of the rubber modifier comprises the following steps: stirring and dispersing graphite powder and hexadecyl trimethyl ammonium bromide in water to modify graphite to obtain a mixed solution; carrying out surface modification treatment on the polytetrafluoroethylene microspheres by using a sodium naphthalene solution; adding the polytetrafluoroethylene microspheres into the mixed solution, stirring for reaction, and performing aftertreatment to obtain the rubber modifier. The rubber material prepared by the invention has good high temperature resistance, corrosion resistance, solvent resistance, aging resistance and radiation resistance, and simultaneously has self-lubricating property and air impermeability. However, naphthalene, a carcinogen contained therein, may cause a health hazard.

Disclosure of Invention

In view of the above-mentioned problems, the present invention provides a method and an apparatus for producing a rubber adhesive.

The technical scheme of the invention is as follows:

a method for producing a rubber adhesive, wherein the rubber adhesive is a double-end hydroxyl-group polymerized styrene-butadiene liquid rubber adhesive, and the production method comprises the following steps:

s1 lithium initiator synthesis:

s1-1: continuously vacuumizing the reaction container, filling argon, baking for 3 times, discharging water and air, then filling argon to maintain the argon atmosphere, and keeping the temperature at 22-25 ℃;

s1-2: adding 1 part by weight of tert-butyldimethylsilyl chloride, 1.25-1.7 parts by weight of imidazole and 2.3-2.75 parts by weight of cyclohexane into a reaction vessel, mixing and stirring for 1h, then dropwise adding 0.5-0.6 part by weight of 3-chloro-1-propanol into the reaction vessel, continuously dropwise adding for 1h, heating to 42-47 ℃, stirring and reacting for 2-4h, then standing for 6-8h, filtering out insoluble substances to obtain an intermediate solution, and filling argon for sealing;

s1-3: adding 3.3-3.5 parts by weight of lithium sheets into the intermediate solution, heating to 75-85 ℃, carrying out ultrasonic oscillation reaction for 1.5-2h, then cooling to 30-33 ℃, carrying out stirring reaction for 4-5h, then cooling to 2 +/-2 ℃, standing for 6-8h, and filtering out insoluble substances to obtain a lithium initiator;

polymerization of S2: weighing 2 parts of styrene, 4.6-5 parts of tetrahydrofuran, 1.1-1.3 parts of butadiene and 0.015-0.03 part of lithium initiator according to parts by weight, continuously vacuumizing a reaction container, filling argon, baking for 3 times to discharge water and air, adding the styrene and the tetrahydrofuran into the reaction container, then dropwise adding the butadiene, controlling the temperature at 10-20 ℃, stirring for reaction for 3-4h, then adding the lithium initiator, and continuously stirring for reaction for 0.5-1h to obtain a polymerization solution;

and (3) end capping reaction of S3: dripping 0.05-0.06 weight part of ethylene oxide-cyclohexane solution into the polymerization solution, cooling to-5-8 ℃, stirring for reaction for 1-2h, and then pouring 8-10 weight parts of absolute ethyl alcohol or dilute hydrochloric acid into a reaction container to terminate the end-capping reaction to obtain glue solution;

and S4 post-processing: spin-steaming the glue solution for 1h to remove the residual ethylene oxide-cyclohexane solution in the glue solution, washing the glue solution with sodium bicarbonate solution for 1h, pouring the glue solution into absolute ethyl alcohol for precipitation, collecting the lower glue solution, and drying under a vacuum condition to obtain the double-end hydroxyl poly-styrene-butadiene liquid rubber adhesive;

s5 ultraviolet light curing: and (4) dropwise adding a photoinitiator accounting for 2-4% of the total mass of the liquid rubber adhesive obtained in the step S4, uniformly stirring, placing in a production device, vacuumizing, and carrying out ultraviolet irradiation to obtain the cured and tackified double-end hydroxyl polymerized styrene butadiene liquid rubber adhesive.

Further, the stirring speed in the steps S1-2 and S1-3 is 100-200rpm, the stirring speed in the step S2 is 350-400rpm, the stirring speed in the step S3 is 230-260rpm, and the stirring modes are magnetic stirring, and different stirring speeds are set according to the properties of the solution required in different stages.

Furthermore, the baking temperature in the step S1-1 is 55-60 ℃, and the lithium sheet is soaked in cyclohexane for 1-2 hours in advance in the step S1-3, so that oxides on the surface of the lithium sheet can be effectively removed.

Furthermore, the mass concentration of the dilute hydrochloric acid in the step S3 is 0.2-0.3mol/L, the temperature of rotary evaporation in the step S4 is 40-45 ℃, the vacuum degree is 0.01Pa, and the mass concentration of the sodium bicarbonate solution is 0.5mol/L, so that the boiling point of the organic solvent can be reduced by using the rotary evaporation method, and the evaporation efficiency is higher.

Further, in the step S5, the light emitting power of the ultraviolet light is 300W, the wavelength of the ultraviolet light is 355-365nm, the illumination distance is 80-120cm, the illumination time is 3-5min, and the viscosity of the rubber adhesive can be improved by the appropriate amount of ultraviolet light irradiation.

The production device for producing the rubber adhesive by any one of the methods comprises a stirring barrel, an ultraviolet irradiation bin, an ultraviolet generating device and a feeding device, wherein the ultraviolet irradiation bin is arranged in a hollow circular ring shape, an ultraviolet lamp of the ultraviolet generating device is arranged in the middle of the ultraviolet irradiation bin, the bottom of the stirring barrel is connected with an annular space of the ultraviolet irradiation bin through two groups of guide pipes provided with electromagnetic valves, and the tail end of the ultraviolet irradiation bin is connected with the feeding device through a group of conveying pipes provided with electromagnetic valves;

the stirring device comprises a stirring barrel, a stirring telescopic rod and a lifting plate, wherein the stirring telescopic rod is arranged in the center of the top of the stirring barrel, the telescopic stirring rod comprises an inner loop bar and an outer loop bar, the inner loop bar is arranged at the upper part of the stirring barrel in a sliding connection mode, the outer loop bar is arranged at the lower part of the stirring barrel, a combined motor used for controlling the telescopic stirring rod to stretch and rotate is arranged on the outer top surface of the stirring barrel, a plurality of stirring blades are arranged on the outer periphery of the outer loop bar from top to bottom, a screw buckle head is arranged at the bottom of the outer loop bar, a group of pressing plates are arranged on the outer periphery of the outer loop bar above the screw buckle head, and teeth are arranged on the outer periphery of the pressing plates;

the lifting plate and the inner wall of the stirring barrel are sealed and slide relatively, a screw thread hole for being in rotary threaded connection with the screw thread head is formed in the center of the lifting plate, a flat groove with the same area as the pressing plate is formed in the upper surface of the lifting plate, a plurality of water through holes penetrating through the lifting plate are formed in the circumferential direction of the flat groove, a group of limiting blocks capable of sliding along the surface of the lifting plate are arranged at two ends of the upper surface of the lifting plate outside the flat groove respectively, the limiting blocks are in meshed connection with gear sets arranged on the upper surface of the lifting plate through teeth arranged on the side edges of the limiting blocks, the gear sets are in meshed connection with teeth arranged on the periphery of the pressing plate, and the two groups of gear sets are symmetrically arranged about the center of the lifting plate;

a limiting groove clamped with the limiting block is arranged at the upper part of the inner wall of the stirring barrel, a limiting plate is arranged above the limiting groove, a limiting ring is arranged at the lower part of the inner wall of the stirring barrel, a pressure sensor is arranged on the upper surface of the limiting ring, the pressure sensor extends to the outside of the stirring barrel and is connected with the three groups of electromagnetic valves in an induction way through infrared sensors,

further, the combination motor includes a set of electric putter and a set of rotation motor, the ultraviolet irradiation storehouse outside is equipped with round rotation portion, is located the ultraviolet irradiation storehouse below of rotation portion both sides is equipped with the supporting seat, be equipped with on the supporting seat and be used for rotating the runner of being connected with rotation portion meshing, wherein a set of the supporting seat is equipped with and is used for the drive runner pivoted driving motor, the ultraviolet irradiation storehouse with the conveyer pipe rotates to be connected, the ultraviolet irradiation storehouse with the ring cover that the pipe end was equipped with rotates to be connected, can make the ultraviolet irradiation storehouse rotate to make and shine more evenly.

Further, the bottom of the screw thread head is provided with a group of stirring blades which penetrate through the screw thread hole and extend to the lower side of the lifting plate, the gear set comprises a driving wheel connected with the pressing plate in a meshed mode, a driven wheel connected with the limiting block in a meshed mode, the side edge of each tooth is arc-shaped, the phenomenon that the pressing plate is clamped due to the fact that the tooth of the pressing plate and the tooth of the driving wheel are not in butt joint in the descending process is prevented, and the tooth of the pressing plate can be in butt joint with the driving wheel through the relative sliding of the arc-shaped edge.

Further, be equipped with stirring transfer bar in the conveyer pipe, material feeding unit includes the conveyer belt and is located a plurality of collecting vessel on the conveyer belt, pressure sensor sets up on the support that the agitator outside was equipped with, can carry the rubber adhesive stirring through ultraviolet irradiation and prevent solidifying.

The invention has the beneficial effects that:

(1) the rubber adhesive is a double-end hydroxyl-based poly-styrene-butadiene liquid rubber adhesive, has strong adhesive force and strong water resistance and corrosion resistance, does not use carcinogen naphthalene in an initiator, has good environmental protection effect, improves the compatibility of a lithium initiator and a cyclohexane solvent by adding butadiene and a lithium initiator using specific components, promotes the polymerization reaction, generates an oligomer active short chain with active double ends, and has good heat resistance and impact resistance, good comprehensive performance and good stability.

(2) The rubber adhesive production device can realize ultraviolet irradiation on the rubber adhesive to improve the adhesion degree, and can finish extrusion conveying on the rubber adhesive through the telescopic stirring rod and the lifting plate arranged in the stirring barrel, so that the subpackaging operation is convenient, the production device is matched with the limiting block and the pressure sensor for use through the electromagnetic valve and the infrared sensing device, the high degree of intellectualization is realized, the structure is reasonable, and the working efficiency is greatly improved.

Drawings

FIG. 1 is a schematic view showing the overall construction of a production apparatus of the present invention;

FIG. 2 is a schematic view of the internal structure of a mixing tank of the production apparatus of the present invention;

FIG. 3 is a schematic diagram of the construction of the elevator plate of the production apparatus of the present invention;

FIG. 4 is a schematic view of the structure of the driving wheel of the production apparatus of the present invention;

FIG. 5 is a schematic view of the structure of the end of the catheter of the production apparatus of the present invention;

FIG. 6 is a sectional view of an ultraviolet irradiation chamber of the production apparatus of the present invention;

FIG. 7 is a schematic view showing the internal structure of a transport pipe of the production apparatus of the present invention.

Wherein, 1-a stirring barrel, 11-a guide pipe, 12-a limiting groove, 13-a limiting plate, 14-a limiting ring, 15-a pressure sensor, 16-a bracket, 17-a ring sleeve, 2-an ultraviolet irradiation cabin, 21-a conveying pipe, 22-a rotating part, 23-a supporting seat, 24-a rotating wheel, 25-a driving motor, 26-a stirring conveying rod, 3-an ultraviolet generating device, 31-an ultraviolet lamp, 4-a feeding device, 41-a conveying belt, 42-a collecting barrel, 5-a stirring telescopic rod, 51-an inner sleeve rod, 52-an outer sleeve rod, 53-a stirring blade, 54-a thread head, 55-a pressing plate, 6-a lifting plate, 61-a thread hole, 62-a flat groove, 63-a water through hole and 64-a limiting block, 65-gear group, 651-driving wheel, 652-driven wheel, 7-combined motor, 71-electric push rod, 72-rotating motor, 8-electromagnetic valve and 9-infrared sensor.

Detailed Description

Example 1

A method for producing a rubber adhesive, wherein the rubber adhesive is double-end hydroxyl poly-styrene-butadiene liquid rubber adhesive, and the production method comprises the following steps:

s1 lithium initiator synthesis:

s1-1: continuously vacuumizing the reaction container, filling argon, baking for 3 times, discharging water and air, wherein the baking temperature is 55 ℃, then filling argon to keep the argon atmosphere, and keeping the temperature at 22 ℃;

s1-2: adding 1 part of tert-butyldimethylsilyl chloride, 1.25 parts of imidazole and 2.75 parts of cyclohexane into a reaction vessel by weight, mixing and stirring for 1h at the stirring speed of 100rpm in a magnetic stirring manner, then dropwise adding 0.5 part of 3-chloro-1-propanol into the reaction vessel, continuously dropwise adding for 1h, heating to 42 ℃, stirring and reacting for 2h, then standing for 6h, filtering out insoluble substances to obtain an intermediate solution, and filling argon for sealing;

s1-3: adding 3.3 parts by weight of lithium sheets into the intermediate solution, soaking the lithium sheets in cyclohexane in advance for 1h, heating to 75 ℃, carrying out ultrasonic oscillation reaction for 1.5h, then cooling to 30 ℃, carrying out stirring reaction for 4h at the stirring speed of 100rpm, then cooling to 0 ℃, standing for 6h, and filtering out insoluble substances to obtain a lithium initiator;

polymerization of S2: weighing 2 parts of styrene, 4.6 parts of tetrahydrofuran, 1.1 parts of butadiene and 0.03 part of lithium initiator according to parts by weight, continuously vacuumizing a reaction container, filling argon, baking for 3 times to discharge water and air, adding the styrene and the tetrahydrofuran into the reaction container, then dropwise adding the butadiene, controlling the temperature at 10 ℃, stirring for 3 hours at a stirring speed of 350rpm, and then adding the lithium initiator to continue stirring for 0.5 hour to obtain a polymerization solution;

and (3) end capping reaction of S3: dripping 0.05 weight part of ethylene oxide-cyclohexane solution into the polymerization solution, cooling to-5 ℃, stirring for 1 hour at the stirring speed of 230rpm, and then pouring 8 weight parts of absolute ethyl alcohol into a reaction container to terminate the end-capping reaction to obtain glue solution;

and S4 post-processing: carrying out rotary evaporation on the glue solution for 1h to remove the residual ethylene oxide-cyclohexane solution in the glue solution, wherein the rotary evaporation temperature is 40 ℃, the vacuum degree is 0.01Pa, washing the glue solution for 1h by using a sodium bicarbonate solution, the mass concentration of the sodium bicarbonate solution is 0.5mol/L, then pouring the glue solution into absolute ethyl alcohol for precipitation, collecting the lower glue solution, and drying under the vacuum condition to obtain the double-end hydroxyl-group polymerized styrene-butadiene liquid rubber adhesive;

s5 ultraviolet light curing: and (4) dropwise adding a photoinitiator accounting for 2% of the total mass of the liquid rubber adhesive obtained in the step (S4), uniformly stirring, placing in a production device, vacuumizing, and performing ultraviolet irradiation to obtain the cured and tackified double-end hydroxy-polymerized styrene-butadiene liquid rubber adhesive, wherein the luminous power of ultraviolet light is 300W, the wavelength of the ultraviolet light is 355nm, the irradiation distance is 80cm, and the irradiation time is 3 min.

Example 2

This embodiment is substantially the same as embodiment 1, except that: the temperature control in step S1-1 is different.

S1 lithium initiator synthesis:

s1-1: continuously vacuumizing the reaction container, filling argon, baking for 3 times, discharging water and air, wherein the baking temperature is 60 ℃, then filling argon to maintain the argon atmosphere, and maintaining the temperature at 25 ℃.

Example 3

This embodiment is substantially the same as embodiment 1, except that: the intermediate solution in step S1-2 has different composition ratios.

S1-2: adding 1 part of tert-butyldimethylsilyl chloride, 1.5 parts of imidazole and 2.5 parts of cyclohexane into a reaction vessel by weight, mixing and stirring for 1h at the stirring speed of 150rpm in a magnetic stirring manner, then dropwise adding 0.5 part of 3-chloro-1-propanol into the reaction vessel, continuously dropwise adding for 1h, heating to 45 ℃, stirring and reacting for 3h, then standing for 7h, filtering insoluble substances to obtain an intermediate solution, and filling argon for sealing.

Example 4

This embodiment is substantially the same as embodiment 1, except that: the intermediate solution in step S1-2 has different composition ratios.

S1-2: adding 1 part of tert-butyldimethylsilyl chloride, 1.7 parts of imidazole and 2.3 parts of cyclohexane into a reaction vessel by weight, mixing and stirring for 1h at the stirring speed of 200rpm in a magnetic stirring manner, then dropwise adding 0.6 part of 3-chloro-1-propanol into the reaction vessel, continuously dropwise adding for 1h, heating to 47 ℃, stirring and reacting for 4h, then standing for 8h, filtering insoluble substances to obtain an intermediate solution, and filling argon for sealing.

Example 5

This embodiment is substantially the same as embodiment 1, except that: the step of adding the lithium sheet in step S1-3 is different in parameters.

S1-3: and adding 3.4 parts by weight of lithium sheets into the intermediate solution, soaking the lithium sheets in cyclohexane in advance for 1.5h, heating to 80 ℃, carrying out ultrasonic oscillation reaction for 1.6h, then cooling to 32 ℃, carrying out stirring reaction for 4.5h at the stirring speed of 150rpm, then cooling to 2 ℃, standing for 7h, and filtering insoluble substances to obtain the lithium initiator.

Example 6

This embodiment is substantially the same as embodiment 1, except that: the step of adding the lithium sheet in step S1-3 is different in parameters.

S1-3: adding 3.5 parts by weight of lithium sheets into the intermediate solution, soaking the lithium sheets in cyclohexane in advance for 2 hours, heating to 85 ℃, carrying out ultrasonic oscillation reaction for 2 hours, then cooling to 33 ℃, carrying out stirring reaction for 5 hours at the stirring speed of 200rpm, then cooling to 4 ℃, standing for 8 hours, and filtering out insoluble substances to obtain the lithium initiator.

Example 7

This embodiment is substantially the same as embodiment 1, except that: the polymerization solution in step S2 has different composition ratios and reaction parameters.

Polymerization of S2: weighing 2 parts of styrene, 4.7 parts of tetrahydrofuran, 1.2 parts of butadiene and 0.02 part of lithium initiator according to parts by weight, continuously vacuumizing a reaction container, filling argon, baking for 3 times to discharge water and air, adding the styrene and the tetrahydrofuran into the reaction container, then dropwise adding the butadiene, controlling the temperature at 15 ℃, stirring for reaction for 3.5 hours at the stirring speed of 370rpm, then adding the lithium initiator, and continuously stirring for reaction for 0.8 hour to obtain a polymerization solution.

Example 8

This embodiment is substantially the same as embodiment 1, except that: the polymerization solution in step S2 has different composition ratios and reaction parameters.

Polymerization of S2: weighing 2 parts of styrene, 5 parts of tetrahydrofuran, 1.3 parts of butadiene and 0.015 part of lithium initiator according to parts by weight, continuously vacuumizing a reaction container, filling argon, baking for 3 times to discharge water and air, adding the styrene and the tetrahydrofuran into the reaction container, then dropwise adding the butadiene, controlling the temperature at 20 ℃, stirring for reaction for 4 hours at the stirring speed of 400rpm, then adding the lithium initiator, and continuing to stir for reaction for 1 hour to obtain a polymerization solution.

Example 9

This embodiment is substantially the same as embodiment 1, except that: the parameters of the capping reaction in step S3 are different.

And (3) end capping reaction of S3: and (3) dropwise adding 0.055 part by weight of ethylene oxide-cyclohexane solution into the polymerization solution, cooling to-6 ℃, stirring for reacting for 1.5 hours at the stirring speed of 255rpm, and then pouring 9 parts by weight of dilute hydrochloric acid into the reaction container to terminate the end-capping reaction, wherein the mass concentration of the dilute hydrochloric acid is 0.2mol/L, so as to obtain a glue solution.

Example 10

This embodiment is substantially the same as embodiment 1, except that: the parameters of the capping reaction in step S3 are different.

And (3) end capping reaction of S3: and (2) dropwise adding 0.06 part by weight of ethylene oxide-cyclohexane solution into the polymerization solution, cooling to-8 ℃, stirring for 2 hours at the stirring speed of 260rpm, and then pouring 10 parts by weight of dilute hydrochloric acid into the reaction container to terminate the end-capping reaction, wherein the mass concentration of the dilute hydrochloric acid is 0.3mol/L, so as to obtain a glue solution.

Example 11

This embodiment is substantially the same as embodiment 1, except that: the temperature of the rotary evaporation in step S4 is different.

And S4 post-processing: and (3) carrying out rotary evaporation on the glue solution for 1 hour to remove the residual ethylene oxide-cyclohexane solution in the glue solution, wherein the rotary evaporation temperature is 45 ℃ and the vacuum degree is 0.01 Pa.

Example 12

This embodiment is substantially the same as embodiment 1, except that: the parameters of the ultraviolet curing in step S5 are different.

S5 ultraviolet light curing: and (4) dropwise adding a photoinitiator accounting for 3% of the total mass of the liquid rubber adhesive obtained in the step (S4), uniformly stirring, placing in a production device, vacuumizing, and performing ultraviolet illumination to obtain the cured and tackified double-end hydroxy-polymerized styrene-butadiene liquid rubber adhesive, wherein the luminous power of ultraviolet light is 300W, the wavelength of the ultraviolet light is 360nm, the illumination distance is 100cm, and the illumination time is 4 min.

Example 13

This embodiment is substantially the same as embodiment 1, except that: the parameters of the ultraviolet curing in step S5 are different.

S5 ultraviolet light curing: and (4) dropwise adding a photoinitiator accounting for 4% of the total mass of the liquid rubber adhesive obtained in the step S4, uniformly stirring, placing in a production device, vacuumizing, and performing ultraviolet illumination to obtain the cured and tackified double-end hydroxy-polymerized styrene-butadiene liquid rubber adhesive, wherein the luminous power of ultraviolet light is 300W, the wavelength of the ultraviolet light is 365nm, the illumination distance is 120cm, and the illumination time is 5 min.

Example 14

This embodiment is substantially the same as embodiment 1, except that: also provided with a production device for producing the rubber adhesive.

As shown in fig. 1 and 7, the apparatus for producing rubber adhesives by the above method comprises a mixing tank 1, an ultraviolet irradiation bin 2, an ultraviolet ray generating device 3 and a feeding device 4, wherein the ultraviolet irradiation bin 2 is arranged in a hollow circular ring shape, an ultraviolet lamp 31 of the ultraviolet ray generating device 3 is arranged in the middle of the ultraviolet irradiation bin 2, the ultraviolet ray generating device 3 and the ultraviolet lamp 31 are both of commercial products and have a structure matched with the ultraviolet irradiation bin 2 after being adjusted in shape, the bottom of the mixing tank 1 is connected with the annular space of the ultraviolet irradiation bin 2 through two groups of guide pipes 11 provided with electromagnetic valves 8, the tail end of the ultraviolet irradiation bin 2 is connected with the feeding device 4 through a group of conveying pipes 21 provided with electromagnetic valves 8, a stirring conveying rod 26 is arranged in the conveying pipe 21, and the feeding device 4 comprises a transfer belt 41 and a plurality of collecting tanks 42 positioned on the transfer belt 41;

as shown in figure 1 of the drawings, in which, 2, a stirring telescopic rod 5 and a lifting plate 6 are arranged inside a stirring barrel 1, the stirring telescopic rod 5 is located at the center of the top of the stirring barrel 1, the telescopic stirring rod 5 comprises an inner loop bar 51 located at the upper part and an outer loop bar 52 located at the lower part which are in sliding connection, a combined motor 7 used for controlling the telescopic stirring rod 5 to stretch and rotate is arranged on the outer top surface of the stirring barrel 1, the combined motor 7 comprises a group of electric push rods 71 and a group of rotating motors 72, the electric push rods 71 are commercially available electric push rods, the rotating motors 72 are commercially available gear reduction motors, a plurality of stirring blades 53 are arranged on the outer periphery of the outer loop bar 52 from top to bottom, a screw head 54 is arranged at the bottom of the outer loop bar 52, a group of pressing plates 55 are arranged on the outer periphery of the outer loop bar 52 above the screw head 54, teeth are arranged on the outer periphery of the pressing plates 55, and a group of stirring blades 53 penetrating through a screw hole 61 and extending to the lower part of the lifting plate 6 are arranged at the bottom of the screw head 54;

as shown in fig. 2-4, the lifting plate 6 and the inner wall of the stirring barrel 1 are sealed and slide relatively, a screw thread hole 61 for connecting with a screw thread head 54 in a rotating and threaded manner is formed in the center of the lifting plate 6, a flat groove 62 having the same area as the pressure plate 55 is formed in the upper surface of the lifting plate 6, a plurality of water through holes 63 penetrating through the lifting plate 6 are formed in the circumferential direction of the flat groove 62, a set of limit blocks 64 capable of sliding along the surface of the lifting plate 6 are respectively arranged at two ends of the upper surface of the lifting plate 6 outside the flat groove 62, the limit blocks 64 are meshed and connected with gear sets 65 arranged on the upper surface of the lifting plate 6 through teeth arranged on the side edges of the limit blocks, the gear sets 65 are meshed and connected with teeth arranged on the periphery of the pressure plate 55, the two sets of gear sets 65 are symmetrically arranged with respect to the center of the lifting plate 6, each gear set 65 includes a driving wheel 651 meshed and connected with the pressure plate 55 and a driven wheel 652 meshed and connected with the limit blocks 64, and the side edges of the teeth are both arranged in an arc shape;

as shown in fig. 1 and 2, a limiting groove 12 clamped with a limiting block 64 is arranged at the upper part of the inner wall of the stirring barrel 1, a limiting plate 13 is arranged above the limiting groove 12, a limiting ring 14 is arranged at the lower part of the inner wall of the stirring barrel 1, a pressure sensor 15 is arranged on the upper surface of the limiting ring 14, the pressure sensor 15 extends to the outside of the stirring barrel 1 and is in induction connection with three groups of electromagnetic valves 8 through an infrared sensor 9, the pressure sensor 15 is arranged on a bracket 16 arranged at the outside of the stirring barrel 1, and the pressure sensor 15 and the infrared sensor 9 are both structures which are commercially available products and are adapted to the stirring barrel 1 after being subjected to shape adjustment;

as shown in fig. 1, 5 and 6, a circle of rotating part 22 is arranged outside the ultraviolet irradiation bin 2, supporting seats 23 are arranged below the ultraviolet irradiation bin 2 at two sides of the rotating part 22, rotating wheels 24 which are meshed with the rotating part 22 and are rotatably connected with the rotating part are arranged on the supporting seats 23, one group of the supporting seats 23 is provided with a driving motor 25 which is used for driving the rotating wheels 24 to rotate, the driving motor 25 is a commercially available driving motor, the ultraviolet irradiation bin 2 is rotatably connected with the conveying pipe 21, and the ultraviolet irradiation bin 2 is rotatably connected with an annular sleeve 17 arranged at the tail end of the guide pipe 11.

The working principle of using the production device to produce the rubber adhesive is as follows:

injecting the double-end hydroxyl-polymerized butadiene styrene liquid rubber adhesive obtained in the step S4 into the stirring barrel 1, after the ultraviolet curing treatment of the step S5 is carried out, after the stirring barrel 1 is filled with the rubber adhesive, opening the rotating motor 72 to continuously stir the stirring blade 53 to prevent the rubber adhesive from solidifying, at this time, the limit blocks 64 of the lifting plate 6 are clamped in the limit grooves 12, then opening the electric push rod 71 to make the outer sleeve rod 52 descend and continuously rotate, when the screw head 54 enters the screw hole 61, the screw head 54 and the screw hole 61 start to be screwed tightly together along with the rotation, simultaneously, the teeth of the pressing plate 55 and the teeth of the driving wheel 651 are meshed in the descending process, simultaneously, the driving wheel 651 drives the driven wheel 652 to rotate synchronously in the rotating process, the driven wheel 652 drives the limit blocks 64 to move, the two groups of limit blocks 64 slide out from the limit grooves 12, and when the limit blocks 64 completely move out of the limit grooves 12, the screw thread head 54 is tightly clamped with the screw thread hole 61, the pressure plate 55 is tightly clamped with the flat groove 62 to prevent the water through hole 63 from passing through, at the moment, the outer loop bar 52 drives the lifting plate 6 to descend when the outer loop bar continues descending, the rubber adhesive is extruded into the conduit 11 and enters the annular space of the ultraviolet irradiation bin 2;

when the pressure sensor 15 is lowered to the bottom of the lifting plate 6 and contacts with the pressure sensor 15, the pressure sensor 15 transmits signals through the infrared sensor 9, 3 groups of electromagnetic valves 8 are all closed, the annular space of the ultraviolet irradiation bin 2 is filled with rubber adhesive, the ultraviolet lamp 31 is started for irradiation treatment, meanwhile, the electric push rod drives the outer sleeve rod 52 to drive the lifting plate 6 to ascend until the lifting plate contacts with the limiting plate 13, the rotating motor 72 rotates reversely, the limiting block 64 slides into the limiting groove 12 again in the same way to complete clamping, the outer sleeve rod 52 continuously moves upwards, the screw thread head 54 is loosely buckled with the screw thread hole 61, the pressure plate 55 leaves the surface of the flat groove 62, the rubber adhesive fills the lower space of the stirring barrel 1 again through the water through hole 63 and is continuously stirred, after the irradiation time of the ultraviolet lamp 31 reaches, the electromagnetic valve 8 is started to irradiate the next group in the same way, the irradiated rubber adhesive is stirred and conveyed into the collecting barrel 42 through the conveying pipe 21 by the stirring conveying rod 26 and is output by the conveying belt 41, and the sub-packaging production is completed.

In addition, in the irradiation process of the ultraviolet lamp 31, the driving motor 25 is simultaneously started to drive the rotating wheel 24 to rotate, and simultaneously, the rotating part 22 and the whole ultraviolet irradiation bin 2 are driven to rotate, the front end of the ultraviolet irradiation bin 2 and the annular sleeve 17 rotate relatively, and the tail end of the ultraviolet irradiation bin 2 and the conveying pipe 21 rotate relatively, so that the irradiation effect is better.

Examples of the experiments

The rubber adhesives prepared in examples 1-13 were tested for their properties and compared to conventional rubber adhesives, and the results are shown in the following table:

TABLE 1 EXAMPLES 1-6 rubber adhesive Properties

It can be seen from this that the rubber adhesive produced by the rubber adhesive production method of the present invention is higher in adhesive strength than that of the conventional rubber adhesive; the drying temperature in step S1-1 in example 2 does not greatly affect the bonding strength of the rubber adhesive, and may be within the scope of the present invention; the bonding strength in example 3 is slightly greater than that in examples 1 and 4, wherein the main influencing factor is the content of the intermediate solution component of the lithium initiator, and the bonding strength of the rubber adhesive with moderate component ratio is optimal; in examples 5 and 6, the bonding strength is slightly greater than 1, and the content of lithium in the lithium initiator is increased to extremely increase the performance of the lithium initiator and promote the improvement of the bonding strength of the rubber adhesive, but the content of lithium is not more than 3.5 parts by weight in consideration of the cost and other factors.

Table 2 examples 1, 7, 8 rubber adhesive properties

It can be seen that the rubber adhesive produced by the rubber adhesive preparation method of the present invention has higher adhesive strength at high temperature than the conventional rubber adhesive; changing the composition ratio in the polymerization reaction has an effect on the bonding strength at high temperature, wherein the rubber adhesive obtained by the parameter ratio in example 7 has the best performance.

Table 3 examples 1, 9, 10 rubber adhesive properties

It can be seen that the rubber adhesive produced by the rubber adhesive preparation method of the present invention has a smaller decrease in bonding strength at low temperatures, while the conventional rubber adhesive has a larger decrease in bonding strength at low temperatures; it can be seen from comparison of examples 1, 9 and 10 that examples 9 and 10 have a smaller difference in bonding strength at normal temperature than example 1, but have a higher bonding strength at low temperature than example 1, and therefore capping with dilute hydrochloric acid has a positive effect on the cold resistance of the rubber adhesive compared to absolute ethanol.

Example 11 the rubber adhesive obtained in example 1 performed identically, so the roto-steaming temperature was selected within the specified range of the invention;

table 4 examples 1, 12, 13 rubber adhesive properties

It can be seen that the rubber adhesive produced by the preparation method of the rubber adhesive can still maintain a certain bonding strength under the strong acid corrosion condition, while the conventional rubber adhesive is separated under the strong acid corrosion condition; it is understood from comparison of examples 1, 12 and 13 that the use of longer-term ultraviolet irradiation can improve the adhesive strength of the rubber adhesive under the strong acid corrosion condition, but the ultraviolet irradiation parameters in example 1 are selected to be optimum because the adhesive strength under the normal temperature condition is affected to some extent.