CN105623553A

CN105623553A - Preparation method of auto-vulcanized tire cement

Info

Publication number: CN105623553A
Application number: CN201610037868.8A
Authority: CN
Inventors: 窦伟; 刘伟生; 唐晓亮; 张国林
Original assignee: Lanzhou University
Current assignee: Lanzhou University
Priority date: 2016-01-20
Filing date: 2016-01-20
Publication date: 2016-06-01

Abstract

The invention relates to a preparation method of auto-vulcanized tire cement. The preparation method comprises the following steps: (1) heating 90-95 wt% of solvent to 30-60 DEG C; (2) adding 3-8 wt% of natural rubber into an open mill, compounding, dicing, adding into the solvent, standing to swell for 24 hours, and stirring for 3-5 hours until the rubber is sufficiently dissolved; and (3) adding 1-4 wt% of super super vulcanization accelerator into the system, continuing stirring for 2-3 hours, and adding 0.2-0.5 wt% of N-ethyl cyclohexylamine antioxidant to obtain the product. The tire cement has the advantages of accessible raw materials, simple preparation technique, high vulcanization rate and high bonding firmness, and can reach the maximum bonding strength within 24 hours.

Description

A kind of preparation method of auto-vulcanization tire repair cement

Technical field

The invention belongs to bonding technique field, the preparation method being specifically related to a kind of auto-vulcanization tire repair cement for full capping.

Background technology

Announcing data according to Traffic Administration Bureau of the Ministry of Public Security, by the end of the year 2014, China's vehicle guaranteeding organic quantity reaches 2.64 hundred million, wherein 1.54 hundred million, automobile, becomes the country that vehicle guaranteeding organic quantity in the world is maximum. Annual puncturing because of surface conditions, tire quality, sharp object and the reason such as tire aging causes having a flat tire the phenomenon being to be commonly encountered in life, bring trouble to traveling, severe patient even can cause burst accident. Repairing currently for tire small size cavity mainly includes mushroom nail method, the several methods such as pyrogenic process is repaired, and self-mending liquid for tire is repaired, auto-vulcanization sticking patch repairing. Wherein mushroom nail method, complicated operation, expensive; Pyrogenic process is repaired to be needed repairing area is heated to rubber sulfurizing temp, often the rubber layer of neighboring area is brought injury; Self-mending liquid for tire, in tire, it is filled with all kinds of thixotropic rubber latex that has after being in advance or leaking gas, relies on thixotroping reaction to form rubber deposit at air-leak section, block wound, but the dynamic balancing of tire can be affected largely, usually used as emergency processing not as conventional repair method; Auto-vulcanization method for repairing and mending is due to simple to operate, cheap, the tyre surface damage feature such as little is subject to the favor of repairing personnel and driver, good market prospects.

2000 so far, domestic emerges in large numbers a large amount of tire repair cement, and quality is uneven. Most of product of domestic production is divided into (1) solvent-borne type natural rubber bonding agent, adhering speed is slow, adhesive strength low (2) solvent-borne type neoprene bonding agent, adhering speed is fast, short term strength is high, and tire adstante febre is easy to fall off, and this two classes glue is to improve on the basis to bicycle and motorcycle tyre bonding agent, it is not suitable for load capacity big, the Large vehicle of high-speed cruising. Patent CN103074008A discloses a kind of toluene solution tire repair cement based on butadiene-styrene rubber, adopts butadiene-styrene rubber can strengthen air-tightness, but vulcanization crosslinking does not occur, substantially still falls within solvent-borne type glue. It addition, use the solvent of toluene class to have obvious toxicity. Patent 103289596A discloses a kind of aircraft tyre static balance sticking patch rubber cement glue, with natural rubber and butadiene-styrene rubber for sizing material, sulfenamide type accelerators and thuriam acceserator and sulfur are vulcanizing system, and be equipped with binding agent and reach high-adhesive-strength, the elevated temperature cure but sulfidation needs to pressurize in special vulcanizing equipment, is not belonging to air vulcanizing cement field. Also have been reported that employing natural rubber or synthetic rubber are received with lek and mix use as auto-vulcanization glue, adhering speed is fast, intensity is high, but the reaction that lek is received with rubber occurs only at surface, film is not made to be integrally formed with tire crosslinking, after simultaneously bonding, bonding region easily hardens embrittlement, affects Using Life of Tyre. The high toxicity that additionally lek is received also should be noted that.

As the glue connecting sticking patch and repaired tyre surface, the autohension and the cohesiveness that rely solely on rubber in bonding do not reach bonding efficiently, in tire motion, along with the deformation of the rising of temperature and tire, it is easy to bubbling, floating and obscission occur. In order to strengthen adhesive strength, it is necessary to both relied on the initial cohesiveness of rubber, more to rely on generation sulfurization in bonding rear certain time, it is ensured that sticking patch is integrally formed with tire crosslinking. In actual production, it is necessary to select suitable vulcanization accelerator, at short notice the sulfur generation sulfurization in sticking patch should be cross-linked, prevent curingprocess rate too fast again, recovery or over cure phenomenon occur. The accelerator being presently used in the vulcanization of rubber has tens kinds more than, but is applicable to room temperature-vulcanized accelerator and is mostly super vulcanization accelerator and super vulcanization accelerator. In rubber cement, by certain chemical stability and heat stability, there is the autovulcanization phenomenon of glue in vulcanization accelerator to ensure glue will not decompose in production process, shipping storage; Meanwhile, such accelerator is when contacting with the sulfur in sticking patch and repaired tire, it is necessary to inspiring vulcanization reaction at normal temperatures and carry out, response speed is steady; The selection of solvent is also intended to the factor considered, first, it should select non-toluene solvent as far as possible, to alleviate the pollution to operator and environment and injury, Petroleum series of products are best selections, but consider dissolubility and fire resistance, also optional trichloro ethylene, dichloroethylene equal solvent; Secondly, solvent must have suitable evaporation rate, solubility property: dissolving rubber and accelerator can form uniform rubber cement on the one hand, on the one hand, in glue use procedure, solvent also acts as swelling sticking patch and surface of tyre rubber, accelerator and sulfurization are penetrated into the full extent in the top layer of tire, reach maximum bonding degree.

Summary of the invention

The technical problem to be solved in the present invention is the above-mentioned deficiency for prior art, preferably suitable vulcanization accelerator, rubber and accelerator ratio and suitable solvent provide a kind of technique simple, glue steady quality, not easily degumming, sulfuration is fully, adhesive strength is big, the preparation method of the auto-vulcanization glue of environment-protecting asepsis.

For solving above-mentioned technical problem, the preparation method that the technical scheme is that a kind of tire repair cement for full capping, its preparation process includes: the solvent of weight ratio 85%-95% is heated to 30-60 DEG C by (1); (2) it is the natural rubber of 3-8% by weight ratio, put into and mill is opened refining, cut into the fritter of 5 centimeter square, join in above-mentioned solvent, after standing swelling 24 hours, stirring 3-5 hour, make rubber fully dissolve (3) and the super vulcanization accelerator that weight ratio is 1%-4% is joined in above-mentioned system, after continuing stirring 2-3 hour, add weight ratio 0.2-1%N-ethyl cyclohexylamine antioxidant, mix homogeneously, namely obtains product. Tire repair cement provided by the invention, raw material is easy to get, and preparation technology is simple, curingprocess rate fast (3-5 minute), bonding firmly, within 24 hours, reach maximum adhesive strength.

Further, above-mentioned raw material is by weight being preferably: solvent 90-95%, opens refining natural rubber 4-6%, accelerator 2-3, and antioxidant N-ethyl cyclohexylamine is 0.3%-0.8%

Above-mentioned raw material by weight optimum is: solvent 92%, natural rubber 5%, accelerator is 2.5%, and antioxidant is 0.5%.

Solvent preferred 120# solvent naphtha and the mixture (requiring product suitable in halogen-free benzene-free) of hexamethylene, trichloro ethylene (requiring product suitable in benzene-free fire-retarded) in above-mentioned raw material

In above-mentioned solvent, it is preferable that the admixture solvent weight ratio of 120# solvent naphtha and hexamethylene is 1:1-5:1, it is preferable that 3:1.

Above-mentioned opening refining rubber, it is preferable that one-level or good fair average quality ribbed smokedsheet glue, must not use recovery rubber and inferior substandard products rubber, opening refining number of times is 5-20 time, it is preferable that 10-15 time.

In above-mentioned raw materials, the super vulcanization accelerator of accelerator preferred dithiocar-bamate system or super vulcanization accelerator, including N, N-PZ is (also known as accelerator ZDMC or accelerator PZ, CAS is numbered 137-30-4), N, N-(DDC)2Zn is (also known as accelerator EZ or accelerator ZDC, CAS is numbered 14324-55-1), N, N-zinc dibutyl dithiocarbamate (is numbered 136-23-2 also known as accelerant B Z or accelerator ZDBCCAS), N-zinc-ethylphenyl dithiocarbamate is (also known as accelerator ZEPC or accelerator PX, No. CAS: 14634-93-6), N, N-zinc dibenzyl dithiocarbamate is (also known as accelerator ZBEC, No. CAS: 14726-36-4).

Preferred N, N-PZ is (also known as accelerator ZDMC or accelerator PZ, CAS is numbered 137-30-4), N, N-zinc dibutyl dithiocarbamate (is numbered 136-23-2 also known as accelerant B Z or accelerator ZDBCCAS), N-zinc-ethylphenyl dithiocarbamate is (also known as accelerator ZEPC or accelerator PX, No. CAS: 14634-93-6), the curingprocess rate of three kinds of preferred accelerators is PZ>BZ>PX, the shelf stability PZ<BZ<PX. of the glue made

Advantages of the present invention and beneficial effect:

(1) glue relies on the sulfurization of rubber, and by crosslinked together to tire and sticking patch, bond strength is big, will not fall off phenomenon; Sulfurization strengthens with motion gradually along with the raw heat of tire, and 24 hours up to maximum adhesive strength.

(2) auto-vulcanization tire repair cement preparation technology provided by the invention is simple, and raw material is easy to get, and is suitable for industrialized production.

Detailed description of the invention:

Embodiment 1:

5 kilograms of natural rubbers are cut into fritter, opens after refining 5 times that to be cut into small pieces standby on a mill until; Rubber cement machine adds 92 kilograms of No. 120 solvent naphthas, adds the sheet rubber sheared above, soak 24 hours, middle every 6 hours, stir 5-10 minute. After immersion terminates, open stirring, stir 3-4 hour uniform to rubber cement. After adding 2.5 kilograms of accelerator PZ, continue stirring 1-2 hour, be subsequently adding 0.5 kilogram of N-ethyl cyclohexylamine, after continuing stirring 1h, stop stirring, canned.

Embodiment 2:

5 kilograms of natural rubbers are cut into fritter, opens after refining 5 times that to be cut into small pieces standby on a mill until; Rubber cement machine adds the mass ratio 1:1 mixed solvent of 92 kilograms of No. 120 solvent naphthas and hexamethylene, adds the sheet rubber sheared above, soak 24 hours, middle every 6 hours, stir 5-10 minute. After immersion terminates, open stirring, stir 3-4 hour uniform to rubber cement. After adding 2.5 kilograms of accelerant B Z, continue stirring 1-2 hour, be subsequently adding 0.3 kilogram of N-ethyl cyclohexylamine, after continuing stirring 1h, stop stirring, canned.

Embodiment 3:

5 kilograms of natural rubbers are cut into fritter, opens after refining 5 times that to be cut into small pieces standby on a mill until; Rubber cement machine adds 92 kilograms of trichloroethylene solvents, adds the sheet rubber sheared above, soak 24 hours, middle every 6 hours, stir 5-10 minute. After immersion terminates, be warming up to 50 degree, open stirring, stir 3-4 hour uniform to rubber cement. After adding 2.5 kilograms of accelerator PX, continue insulated and stirred 1-2 hour, be subsequently adding 0.3 kilogram of N-ethyl cyclohexylamine, after continuing stirring 1h, stop stirring, canned.

Above-described embodiment use mill is, Jiangsu 16 cun of machines of beginning to pratise of Hua Yuan XK-400 type.

Bonding example:

Vacuum tyre artificial destruction is gone out the aperture about 5mm diameter, after polishing with polisher in wound, smear the sulfuration rubber cement of the embodiment of the present invention 1 preparation, after drying solvent, tear commercially available auto-vulcanization film off surface plastic materials protecting film and be affixed on wound circumference, rush bubble with compact wheel, after placing 1 hour, test adhesive strength; Contrast test selects the rubber cement of commercially available brand A and brand B, uses identical test method test. After within 80Km/ hour, speed per hour travels 2 hours, test adhesive strength, contrast adhesive effect.

Glue stability test:

Preventing from glue sealing in test tube, be positioned in calorstat and heat, temperature is set to 30-70 DEG C, observes glue state:

Claims

1. an auto-vulcanization tire repair cement, it is characterised in that: the formula of auto-vulcanization tire repair cement is, solvent 85%-95%, natural rubber 3-8%, super vulcanization accelerator 1%-4%. Antioxidant 0.2-0.5%.

2. the preparation method of a kind of auto-vulcanization tire repair cement according to claim 1, it is characterised in that preparation process includes: the solvent that weight ratio is 85%-95% is heated to 30-60 DEG C by (1); (2) it is the natural rubber of 3-8% by weight ratio, cuts into the square fritter of 5cm, join in above-mentioned solvent, after standing swelling 24 hours, stirring 3-5 hour, make rubber fully dissolve; (3) the super vulcanization accelerator that weight ratio is 1%-4% is joined in above-mentioned system, after continuing stirring 2-3 hour, add weight ratio 0.2-0.5% antioxidant, obtain product.

3. a kind of auto-vulcanization tire repair cement according to claim 1 and 2, it is characterised in that the percentage by weight of each raw material is solvent 92%, natural rubber 5%, and accelerator is 2.5%, and antioxidant is 0.5%.

4. according to claim 1 and 2 for a kind of auto-vulcanization tire repair cement, it is characterised in that natural rubber used is one-level smoke sheet rubber, good fair average quality ribbed smokedsheet glue, and number of times of beginning to pratise on a mill until is 5-20 time.

5. according to claim 1 and 2 for a kind of auto-vulcanization tire repair cement, it is characterised in that the super ultras used is zinc dithiocarbamate.

6. a kind of auto-vulcanization tire repair cement according to claim 1 and 2, it is characterised in that solvent includes No. 120 solvent naphthas, naphthenic oil, trichloro ethylene, or the mixture of the 1:1-5:1 of two or three in three of the above solvent.

7. a kind of auto-vulcanization tire repair cement according to claim 3, it is characterised in that the admixture solvent weight ratio of 120# solvent naphtha and hexamethylene is 3:1.