CN109503913B

CN109503913B - Inflation-free micro-foaming manpower vehicle tire raw material, inflation-free micro-foaming manpower vehicle tire and preparation method thereof

Info

Publication number: CN109503913B
Application number: CN201710829165.3A
Authority: CN
Inventors: 张建国; 邢立江; 蒋文英; 周伟平; 姚谅
Original assignee: China Petroleum and Chemical Corp; Sinopec Baling Co
Current assignee: China Petroleum and Chemical Corp; Sinopec Baling Co
Priority date: 2017-09-14
Filing date: 2017-09-14
Publication date: 2021-09-03
Anticipated expiration: 2037-09-14
Also published as: CN109503913A

Abstract

The invention discloses a raw material of an inflation-free micro-foaming human-powered vehicle tire, the inflation-free micro-foaming human-powered vehicle tire and a preparation method thereof, wherein the raw material of the tire comprises SSBR with narrow molecular weight distribution, PSBR with powder containing a spacer in wide distribution, reclaimed rubber powder, filling rubber oil and an auxiliary agent, the auxiliary agent mainly comprises a foaming agent, a pigment, an accelerator, an anti-aging agent, an activating agent, a cross-linking agent and the like, and the raw materials are subjected to extrusion granulation-extrusion injection molding to prepare the inflation-free micro-foaming human-powered vehicle tire which has the characteristics of good rebound resilience and weather resistance, high strength, no deformation at high temperature, no cracking at low temperature, wear resistance, tear resistance, small rolling resistance, long service life and the like.

Description

Inflation-free micro-foaming manpower vehicle tire raw material, inflation-free micro-foaming manpower vehicle tire and preparation method thereof

Technical Field

The invention relates to a tire material, in particular to a tire raw material which takes styrene butadiene rubber such as SSBR, PSBR, SBS, reclaimed rubber powder and the like as main raw materials, and a method for preparing a micro-foamed, high-strength and high-wear-resistant human-powered vehicle tire by using the tire raw material; belongs to the technical field of polymer composite materials.

Background

The conventional tires for non-inflatable rickshaws (including hand trucks, shared bicycles, and the like) are made of thermoplastic elastomers, polyurethanes, polyolefins, thermosetting resins, and the like. For example, Japanese patent applications (JP-A) Nos. N0.2003-104008 and N0.03-143701 disclose pneumatic tires formed by using thermoplastic polymer materials; chinese patent publication No. CN1348878A discloses a solid tire for rickshaw, which is suitable for rickshaw and bicycle. The solid inner tube is made of rubber and plastic materials, wherein the rubber content of the rubber is 15-30 wt%, and the polyurethane content of the rubber is 70-85 wt%. The rubber belt has the characteristics of certain elasticity and wear resistance, simple production process, convenient operation and simple and easy assembly; chinese patent (publication No. CN105295216A) discloses an anti-fatigue, temperature-resistant and non-inflatable tire thermoplastic elastomer material and a preparation method thereof, wherein the anti-fatigue, temperature-resistant and non-inflatable tire thermoplastic elastomer material is prepared by 100-150 parts of an ultrahigh molecular weight hydrogenated styrene elastomer, 80-150 parts of white oil, 10-50 parts of polyphenyl ether, 20-50 parts of polypropylene, 5-15 parts of polyethylene, 5-15 parts of a polyolefin blending toughener, 10-30 parts of mineral powder, 3-8 parts of silicone powder and 0.2-0.5 part of a stabilizer, wherein the ultrahigh molecular weight hydrogenated styrene elastomer and the white oil are fully mixed, then mixed with the rest of materials, placed in a double-screw extruder, and subjected to melt extrusion and granulation, and the anti-fatigue, temperature resistance and high-temperature use of the traditional styrene thermoplastic elastomer material in long-term are overcome. As another example, a chinese patent (publication No. CN105017595A) discloses a method for preparing an inner tire and an outer tire of a microcellular foamed tire, specifically discloses a microcellular foamed tire comprising an outer tire and an inner tire, wherein the inner tire comprises 200 parts of latex reclaimed rubber, 3.45-3.60 parts of an accelerator, 5-6.5 parts of a vulcanizing agent, 24-27 parts of a foaming agent, 20-30 parts of a filler, 5.5-7.5 parts of an activating agent, and 8-15 parts of a softener, and the method for preparing the same is also specifically disclosed, and the microcellular foamed tire provided has the following characteristics: firstly, the pricking resistance and the inflation are not needed; the buffer performance is good, so that the running is safer and more stable; thirdly, the tire is not influenced by weather, and the tire burst caused by overheating in summer weather can be avoided; protecting the outer tire and prolonging the service life of the outer tire; and the replacement is not needed, thereby increasing the recycling value of the old tyre. Chinese patent publication No. CN91106451.6A discloses a non-pneumatic bicycle tire and its molding process, wherein the non-pneumatic bicycle tire is a solid structure formed by processing polyurethane material, and has a cord thread inside to function as a rib and a plurality of wedge holes uniformly arranged in the middle. The structure is simple, the pricking resistance is not needed, the inflation is not needed, and the service performance is good. The forming process comprises the working procedures of material preparation by mixing, pouring, demoulding and forming, curing and the like. The method is characterized in that after pouring, the mold rotates on a centrifugal attachment machine at the speed of 150-450 rpm for 20-80 seconds, and then demolding and molding are carried out, so that the gradient change of bubbles in the tire can be guaranteed, and the elasticity and the wear resistance of the tire are moderate.

In addition, the following documents are reported about solid tires and manufacturing processes:

the raw materials and synthesis principle of polyurethane microcellular elastomer solid tires are disclosed in the text of ("manufacturing method of polyurethane microcellular elastomer solid tires", rubber industry, 2010 05), and the raw materials for synthesizing microcellular elastomer comprise polyol, diisocyanate, chain extender, catalyst, foaming agent, foam stabilizer and other additives. The polyhydric alcohols include polyester polyols (such as polyethylene glycol propylene glycol adipate) and the like, polyether polyols (such as polytetrahydrofuran ether glycol) and the like; TDI, MDI and the like commonly used for diisocyanate; chain extenders such as 1, 4-butanediol; the foaming agent comprises water, dichloromethane and the like; catalysts are triethylenediamine and dibutyltin dilaurate; foam stabilizers L-520, etc.; other auxiliaries include flame retardants, antioxidants, colorants, and the like. Through research and practice, the centrifugal casting adopted in the forming process of the polyurethane microporous elastomer solid tire has the following advantages compared with other processing methods that the polyurethane microporous elastomer solid tire is manufactured by adopting a static method in the past, namely, materials are directly injected into a mold and centrifugal casting is adopted in the horizontal direction, so that homogeneous layers with uniform density change and no obvious layering phenomenon among the layers and integrated with each other can be obtained. Meanwhile, the solid tire is manufactured by adopting a horizontal centrifugal casting method, so that the advantages of the polyurethane material and the processing convenience of the polyurethane material are fully embodied, the defects that the matching of the tire tread and the internal vulcanization degree of the tire can be ensured only by long-time vulcanization of the traditional solid tire, the tire tread is over-vulcanized, the tire core is under-vulcanized and the like are easily caused are overcome, and the production efficiency is greatly improved.

In the research of polyurethane elastomer filled solid tire formula and process written by Zhaofie in International rubber conference Collection (C) in 2004, the synthesis process of polyurethane elastomer filler comprises adding polyether polyol and filling oil into a reaction kettle in proportion, and adding measured TD l to obtain prepolymer (component A). And adding the polyol, the chain extender, the catalyst and the filling oil into the reaction kettle according to the proportion, performing dehydration and degassing reaction lh, and sealing to obtain the component B. The A, B components are mixed in a static mixer by a metering pump according to the proportion of 1:1, and then are injected into the inner cavity of the tire through an inflating valve after being mixed, and the injection is stopped after reaching a certain pressure, and the injection port is sealed. And vulcanizing the tire in a drying room at 5 ℃ of 60 ℃ for 24h, and performing post vulcanization at room temperature for 24h to obtain the tire. The physical and mechanical properties of the filler are tested after the AB components are mixed and molded into a standard test piece on a flat vulcanizing machine.

The Tannus TIRE company introduced a non-pneumatic solid bicycle TIRE using a special material called a micro-closed cell micro-foamed polymeric resin which provides puncture, corrosion and aging resistance, a light weight and a stylish appearance, a three durometer TIRE, and a combination of black, yellow, red, white, etc. colors, but the chemical name of the resin is not described. In addition, some companies use styrene-butadiene elastomer and its hydride to cooperate with PP, white oil, etc., solid bicycle (or sharing bicycle) tires made by extrusion injection molding process, only the uniform circular holes 6-8mm away are equally spaced in the horizontal circumferential direction of the tire, the purpose of reducing material consumption and tire quality is called as perforated solid tire.

In general, the characteristic behavior of the existing solid tire is as follows.

The first is injection molding of a solid tire with holes using a thermoplastic elastomer, polyolefin, mineral oil, or the like as a base material. The tyre has the disadvantages of large material consumption, heavy tyre body, high cost, easy bursting, large deformation, poor elasticity and fatigue resistance, large rolling resistance, poor weather resistance and wear resistance, high aging speed, easy loose deformation or cracking and tyre release and short service life of less than one year.

The second type is a solid foam tire made of polyurethane, plastic or rubber and recycled vulcanized rubber powder. The tyre has the disadvantages that the tyre body is formed by foaming plastic, so that the foam part of the tyre core is quickly softened and then cracked to be incapable of use particularly when the tyre body continuously runs at a high speed, the tyre body is easy to harden, the tyre body is hardened to lose elasticity, the tearing resistance is poor, the bearing capacity and the heat dissipation are poor, the rolling resistance is high, the tyre body is easy to soften when the air temperature is high, and the tyre body is easy to fall off and is not wear-resistant.

Disclosure of Invention

The tyre aims at the defects and disadvantages of large consumption of materials, heavy tyre body, high cost, easy burst, poor elasticity and weather resistance, large rolling resistance, high aging speed, easy relaxation, deformation or fragmentation and tyre release, easy hardening, hardening and elasticity loss, poor tearing resistance, poor bearing capacity and heat dissipation, easy softening and tyre release at high temperature, no wear resistance, short service life, long vulcanization time and the like of the tyre for the non-inflatable manpower vehicle in the prior art.

The invention aims to provide a rubber raw material which takes a styrene-butadiene copolymer and reclaimed rubber powder as main components, and the manpower vehicle tire which has the advantages of good rebound resilience and weather resistance, high strength, no deformation at high temperature, no cracking at low temperature, wear resistance and tear resistance, small rolling resistance, long service life and the like can be obtained by simple extrusion granulation and extrusion injection molding processes.

The second purpose of the invention is to provide a micro-foaming manpower vehicle tire which has the advantages of good rebound resilience and weather resistance, high strength, no deformation at high temperature, no cracking at low temperature, good wear resistance, tear resistance and fatigue resistance, small rolling resistance, long service life and the like.

The third purpose of the invention is to provide a method for preparing the micro-foamed tyre for the manpower vehicle, which has simple process, short production period and low cost.

In order to achieve the technical purpose, the invention provides an inflation-free micro-foaming tire material for a rickshaw, which comprises the following components in parts by mass: 10-60 parts of SSBR; 10-60 parts of PSBR (PSBR, P is abbreviated as Powder); 20-60 parts of SBS; 40-60 parts of reclaimed rubber powder; 20-50 parts of softened and filled rubber oil; 20.5-31 parts of an auxiliary agent.

The raw materials for the inflation-free micro-foaming rickshaw tire are styrene-butadiene copolymer and reclaimed rubber powder which are used as main raw materials, and the raw materials can be subjected to micro-crosslinking through a crosslinking agent, so that the tire has the characteristics of good rebound resilience and weather resistance, high strength, high temperature resistance, no deformation, no cracking at low temperature, wear resistance, tear resistance, fatigue resistance, small rolling resistance, long service life and the like.

In a preferred scheme, the SSBR is solution polymerized styrene-butadiene rubber with narrow molecular weight distribution, and the molecular weight distribution index is less than or equal to 1.15. More preferably, SSBR has a number average molecular mass Mn of 120000 to 150000 and a Mooney viscosity ML of 55 to 70. Further preferably, the SSBR comprises 15 to 20 mass percent of a polystyrene block, and the block mass ratio S/B is (25 to 35)/(65 to 75). The SSBR polymer can be easily crushed into particles by a mixer or a crusher, is convenient for mixing and granulating, can be mixed at low temperature and injection-molded at high temperature, and can easily absorb rubber oil at low-high temperature (SSBR with briquette viscosity and large-flow and wide-molecular-weight distribution, such as 2557S or VSL5025, and the like, cannot be granulated). The present invention may be used with existing SSBR1205 or Dynasol 1205 as commercially available.

In a preferable scheme, the PSBR is powdered emulsion styrene-butadiene rubber with wide molecular weight distribution and containing a spacer, and the molecular weight distribution index is more than or equal to 2.5. The PSBR has a more preferable number average molecular weight Mn of 200000 to 300000 and a Mooney viscosity ML of 40 to 80. More preferably, the PSBR is in the form of powder, and the particle size of the PSBR is 20-80 meshes. The PSBR polymer has the advantages of easy mixing at low temperature, proper elasticity, good viscosity and fluidity, high oil absorption rate and good processability at low temperature or high temperature. The PSBR 1502 or PSBR 1588 may be used.

Preferably, the SBS has a block mass ratio S/B of (25-35)/(65-75). More preferably, SBS has a linear or star structure, and has a number average molecular weight Mn of 80000 to 200000. The SBS selected in the tire formula not only contains a large number of vulcanized double bond crosslinking points, but also has the functions that the granulating material formed by mixing the SBS and the SSBR with narrow molecular weight distribution is firm and does not flow cold, and the granules are not adhered and agglomerated, so that the subsequent injection molding of the tire is facilitated. Most preferably, the SBS is at least one of the commercially available Basil brand YH-796, YH-791, YH-803, YH-805 and the like or SBS produced by other companies.

In the preferable scheme, the fineness of the reclaimed rubber powder is 80-120 meshes. The regenerated rubber powder is rubber powder obtained by crushing waste or waste tires. The invention adopts the reclaimed rubber powder as the aggregate, has elasticity, can participate in vulcanization and has certain oil absorption rate, the wear resistance of the tire can be obviously improved, the service life of the tire is prolonged, and the wear resistance is improved to the maximum.

Preferably, the softening filling rubber oil comprises at least one of white oil, naphthenic oil, paraffin oil, environment-friendly rubber oil and high aromatic oil. The preferred softening filled rubber oils are naphthenic or environmentally friendly aromatic oils. Such as at least one of commercially available NAP-10, mediterranean oil 322# and TDAE oil.

In a preferred scheme, the auxiliary agents comprise a foaming agent, a pigment, an accelerator, an anti-aging agent, an activating agent and a crosslinking agent. In the more preferable auxiliary agent, the mass ratio of the foaming agent to the pigment to the accelerator to the anti-aging agent to the activator to the crosslinking agent is 1.5-2: 8-10: 2-4: 2-3: 5-9: 2 to 3.

The preferable foaming agent is an organic compound capable of releasing small molecular compounds at the temperature of 120-200 ℃. Further preferred blowing agents include at least one of azodicarbonamide, blowing agent H, ADC, DNTA, DAB, AIBN. Most preferred is where the blowing agent is Azodicarbonamide (AC).

Preferred accelerators include at least one of accelerator TBBS, accelerator D, accelerator CZ, ultrarapid dithiocarbamate, xanthate accelerators, thiuram accelerators. Further preferred accelerators are at least one of zinc dithiocarbamates, PZ, ZDC, BZ, tetraethylthiuram disulfide, tetrabutylthiuram disulfide. The accelerator can be at least one of an accelerator TBBS, an accelerator D, an accelerator CZ and an overspeed-level dithiocarbamate or xanthate accelerator and a thiuram accelerator which are commonly used in the tire industry; further preferred are high-speed accelerators for rapid vulcanization and low-temperature vulcanization, such as dithiocarbamates, e.g., zinc dithiocarbamate, PZ, ZDC, BZ, and at least one of tetraethylthiuram disulfide (TETD), tetrabutylthiuram disulfide (TBTD) having high activity.

The preferred anti-aging agent is an amine anti-aging agent. Since the amine-based antioxidants have better aging resistance than hindered phenols, aldehydes, heterocycles and the like in terms of aging resistance such as heat aging, weather aging resistance, ozone aging, light aging, yield, and the like, the amine-based antioxidants are preferably used, and include at least one of antioxidants D, A, OD, 405, DFL, DNPA, RD, AW, DD, and the like.

The preferred pigment is carbon black. The pigment is not limited to carbon black, and may be other pigments, and may be appropriately selected depending on the color of the tire. The present invention selects the most conventional carbon black as the starting material.

The preferred cross-linking agent is sulfur.

Preferred activators include inorganic activators and organic activators; wherein the mass ratio of the inorganic activator to the organic activator is 2-8: 2-6. A preferred inorganic activator is zinc oxide. A preferred organic activator is stearic acid.

The raw materials of the inflation-free micro-foaming human-powered vehicle tire adopt the rapid vulcanization accelerator, so that the vulcanization time of a tire blank in an injection mold is shortened, the yield of the tire in unit time is accelerated, and the amine antioxidant is selected to replace the traditional hindered phenol antioxidant to realize the anti-aging performance and the weather resistance of the tire for the human-powered vehicle; the foaming agent is selected to decompose the tire blank in the injection mold into micromolecular gas under the influence of temperature during vulcanization so as to slightly foam vulcanized rubber, so that the weight of the tire is reduced and the cost is reduced.

The preferable raw materials of the inflation-free micro-foaming manpower vehicle tire comprise the following components in parts by mass: 20-30 parts of SSBR; 20-30 parts of PSBR; 30-40 parts of SBS; 40-60 parts of reclaimed rubber powder; 20-50 parts of softened and filled rubber oil; 1.5-2 parts of a foaming agent; 8-10 parts of pigment; 2-4 parts of an accelerator; 2-3 parts of an anti-aging agent; 3-5 parts of an inorganic activating agent; 2-4 parts of an organic activating agent; 2-3 parts of a crosslinking agent.

The invention also provides an inflation-free micro-foaming rickshaw tire which is prepared from the raw materials through extrusion granulation and extrusion injection molding.

The preferred micro-foamed tire molding compound for the manpower vehicle has the 300% stress at definite elongation of 4-5 MPa, the Shaoxing A hardness of 60-70, the permanent deformation of 16-24%, the elongation at break of 280-320%, the elasticity of 30-40%, and the density of 0.60-0.65 g/cm³。

The invention also provides a preparation method of the inflation-free micro-foaming manpower vehicle tire, which comprises the following steps:

1) uniformly stirring SSBR powder, SBS, reclaimed rubber powder, softened filling rubber oil, pigment, an anti-aging agent, an activating agent and a crosslinking agent at room temperature to obtain a bulk rubber material; (note: PSBR should not be made, otherwise would stick the pellet, release agent failure);

2) extruding and granulating the bulk rubber material through a screw to obtain a granulated rubber material;

3) uniformly stirring the granulation rubber material, the PSBR, the accelerator, the foaming agent and the softened and filled rubber oil to obtain a mixture;

4) and (3) performing injection molding and curing on the mixture to obtain the composite material.

Preferably, in the step 1), the amount of the softening filling rubber oil is 3/4-4/5 of the total amount of the softening filling oil.

In a preferable scheme, in the step 1), the stirring and mixing time is 5-8 min.

In a preferable scheme, in the step 2), the granulation temperature is 190-210 ℃.

Preferably, the granulation rubber is phi (3-6) х (3-6) columnar particles.

Preferably, in the step 3), the amount of the softened filling rubber oil is 1/5-1/4 (note: the addition of a small amount of oil can uniformly adhere the auxiliary agent and the granular material-powder material, and the addition of more oil can easily adhere the PSBR).

In a preferable scheme, in the step 3), the stirring and mixing time is 3-6 min.

In the preferable scheme, in the step 4), in the injection molding process, the melting temperature is 190-210 ℃, the temperature in the mold is maintained at 120-180 ℃, and the heat preservation time is 8-12 min.

In the preferable scheme, in the step 4), in the curing process, the curing temperature is 80-100 ℃, and the curing time is 10-15 min.

The manufacturing method of the inflation-free micro-foaming tire for the manpower vehicle comprises the following specific steps:

the first step is as follows: putting the weighed SSBR, SBS, reclaimed rubber powder, 3/4-4/5 of total dosage of filled rubber oil, carbon black and an anti-aging agent, ZnO, stearic acid, sulfur and the like into a mixer, and stirring at high speed for 5-8 min at room temperature, wherein the materials are considered to be uniformly mixed for later use;

the second step is that: putting the uniformly mixed bulk rubber material in the first step into a hopper bin in a screw extruder, extruding and granulating at 190-210 ℃, and cutting into phi (3-6) х (3-6) columnar particles for later use;

the third step: feeding the second-step granulation rubber material, the accelerant and the foaming agent in equal proportion and 1/5-1/4 of the total amount of the filling rubber oil (the powdery accelerant and the foaming agent can be uniformly adhered to the surface of the granular cut material when the oil product is mixed) into a mixer to be stirred at high speed for 3-6 min at room temperature, and uniformly mixing the materials; (note: the mixed and homogenized material obtained in the third step is mixed and pressed into a mixed rubber sheet at the temperature of 70-80 ℃ by a two-roll rubber mixing mill, and then the mixed rubber sheet is vulcanized and formed on a tablet press at the temperature of 145 ℃/8min to carry out performance measurement)

The fourth step: and (3) putting the mixture obtained in the third step into a hopper bin of an injection molding machine, injecting a rubber material melt into a tire molding mold at an injection molding temperature of 190-210 ℃, maintaining the temperature of the melt in the tire molding mold at 120-180 ℃, and keeping the time (injection: vulcanization and foaming molding time) for 8-12 min, wherein the longer the vulcanization molding time is, the greater the crosslinking density is, the strength of the styrene-butadiene rubber is guaranteed only after the vulcanization crosslinking degree is completely achieved, otherwise, the strength of the tire blank is not enough, then opening the mold for demolding, taking out the vulcanized tire, performing injection molding-vulcanization foaming-demolding, and performing cyclic repeated preparation, and taking out the vulcanized tire to continue to cure for 10-15 min at 80-100 ℃.

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

the raw material formula of the inflation-free micro-foaming tire for the manpower vehicle adopts granular or powdery SSBR, PSBR and SBS with good melt flowability as main materials, and gives good processing performance to the mixture in the process of easy injection molding; in the formula, triblock styrene-butadiene (S-B-S) molecules contain a large number of double bonds, can form a cross-linked network under the action of sulfur, and can be connected with regenerated rubber powder by chemical bonds, so that the strength, wear resistance and resilience of the injection-molded tire after vulcanization are provided, the deformation of a tire body is reduced, and the service life is prolonged. The softened rubber filling oil can ensure that the cross-linked body formed by the S-B or vulcanized micro-cross-linked body and the reclaimed rubber powder has better filling compatibility, adjust the hardness of a tire body, increase the elasticity and reduce the rolling resistance of the tire. The ultra-high-speed vulcanization accelerator and the sulfur are used, so that the vulcanization speed is accelerated, the processing and forming time is shortened, and scorching of an injection molding vulcanized tire blank is avoided; the foaming agent is used, so that the density of the micro-crosslinked matrix is reduced, and materials are saved; the use of amine anti-aging agent increases the service life of the tire.

The inflation-free micro-foaming manpower vehicle tire disclosed by the invention has excellent comprehensive performance, and has the characteristics of good rebound resilience and weather resistance, high strength, no deformation at high temperature, no cracking at low temperature, wear resistance, tear resistance, small rolling resistance, long service life and the like. For example, the micro-foaming tire forming rubber material for a manpower vehicle has the advantages of 300% stress at definite elongation of 4-5 MPa, Shaoxing A hardness of 60-70, permanent deformation of 16-24%, elongation at break of 280-320%, elasticity of 30-40%, and density of 0.60-0.65 g/cm³。

The inner tire and the outer tire of the inflation-free micro-foaming tire for the manpower vehicle are integrated, and inflation is not needed.

The preparation method of the inflation-free micro-foaming tire for the manpower vehicle is simple, short in preparation period and low in cost, and is beneficial to industrial production.

Detailed Description

The present invention is illustrated by the following examples, which are not intended to limit the scope or practice of the invention.

The mixed pellets in the fourth step of the production process of the present invention were vulcanized by a YXE-50 type pressure molding machine under a vulcanization condition of х 8min at 145 ℃.

The physical properties of the vulcanized rubber sheet are measured by an INSTRON5565 type tensile machine.

The abrasion of the vulcanized foam sheet was measured by using a LAT100 indoor abrasion machine manufactured by VIM.

The rolling resistance of the vulcanizate was determined using a DUNLOP power loss meter from POLYSAR corporation.

Examples 1 to 7 and comparative examples 1 to 2:

examples 1 to 7 and comparative examples 1 to 2 were each prepared by the first to third steps of the method for producing a tire for a human powered vehicle of the present invention, and the produced pellets were subjected to the fourth step of vulcanization molding;

the first step is as follows: and (3) putting the weighed SSBR1205, SBS, reclaimed rubber powder, 3/4-4/5 of the total using amount of the filled rubber oil, carbon black, an anti-aging agent, ZnO, stearic acid, sulfur and the like into a mixer, and stirring at a high speed for 5-8 min at room temperature, wherein the materials are considered to be uniformly mixed for later use.

The second step is that: adding the uniformly mixed rubber material in the first step into a funnel in a screw extruder, extruding and granulating at 200 ℃, and cutting into phi (3-5) х (3-5) columnar particles for later use.

The third step: and (3) putting the second-step granulation rubber material, the PSBR, the accelerator, the foaming agent and 1/5-1/4 of total used amount of the filled rubber oil into a mixer, stirring at high speed for 5min at room temperature, and uniformly mixing the materials.

The fourth step: and (3) putting the mixture in the third step into a hopper in an injection molding machine, injecting a rubber material melt into a tire molding mold at the injection molding temperature of 200 ℃, keeping the melt temperature in the tire molding mold at 160 ℃ for 8-12 min, then opening the mold for demolding, taking out the vulcanized tire, performing injection molding, vulcanization foaming and demolding, preparing repeatedly in a circulating manner, taking out the vulcanized tire, and continuously curing the vulcanized tire in a hot air oven at 80-100 ℃ for 10-15 min.

The manufacturing process of the detection sample wafers of the embodiments 1 to 7 and the comparative examples 1 to 2 is as follows: and (3) preparing materials according to the first step to the third step, mixing the prepared materials, and carrying out hot press molding on a flat vulcanizing machine. Finally, physical properties of each molded sample were measured, and the physical properties of each comparative sample in examples are shown in Table 2.

Examples 1-7 and comparative examples 1-2 were formulated as in Table 1:

TABLE 1

Example 1

YH-805 as SBS, H as foaming agent, PZ as accelerator, D as antiager, and other components as shown in Table 1.

Example 2

YH-791 as SBS, AC as foaming agent, ZDC as accelerator, OD as anti-aging agent, and other components as shown in Table 1.

Example 3

YH-796 as SBS, AC as foaming agent, PZ as accelerator, A as anti-aging agent, and other components as shown in Table 1.

Example 4

YH-801 for SBS, AC for foaming agent, BZ for accelerator, 405 for anti-aging agent, and the other components are shown in Table 1.

Example 5

YH-791H as SBS, DNTA as foaming agent, TETD as accelerator, D as anti-aging agent, and the other components are shown in Table 1.

Example 6

LG411 is adopted as SBS, DAB is adopted as foaming agent, TBTD is adopted as accelerator, RD is adopted as anti-aging agent, and other components are shown in Table 1.

Example 7

LG411 is adopted as SBS, AIBN is adopted as foaming agent, BZ is adopted as accelerator, DD is adopted as anti-aging agent, and other components are shown in Table 1.

Comparative example 1

The formula and the composition are the same as those of example 6, except that 2.0 parts of TBBS and 1.5 parts of CZ accelerator are used instead.

Comparative example 2

The formula and the composition are the same as those of example 5, except that the accelerator is changed into an accelerator D2.0 parts and an accelerator CZ 1.8 parts.

The YH series SBS products are produced by synthetic rubber division of the country petrochemical company, the Barring petrochemical company, and can be purchased directly through the market.

LG411 is SBS produced by LG chem.

TABLE 2

Note that:

compared with the micro-foaming composite material prepared by the mild or medium-speed vulcanization accelerator D, TBBS and CZ which are commonly used in the tire industry, the micro-foaming composite material prepared by the overspeed vulcanization accelerator has the advantages that the vulcanized composite material in the comparative examples 1-2 is relatively high in abrasion, relatively high in rolling resistance and density, and relatively low in elasticity, hardness, strength and elongation at break. The results show that the invention obtains obvious beneficial effects. (higher end tires cannot be overvulcanized or overvulcanized to avoid scorching when vulcanized, and lower end tires are required to be rapidly vulcanized mainly to improve the yield per unit.)

The vulcanized molding rubber samples of the invention in examples 1 to 3 and the test pieces prepared in comparative examples 1 to 2 were respectively put into a thermal aging oven for thermal aging. The aging conditions were 150 ℃ for х 72h, and the results are shown in Table 3.

TABLE 3

Description of the drawings:

after thermal aging, the composite material has relatively high strength retention rate, small deformation rate loss, large elasticity retention degree and small abrasion rise rate. Namely, the tire composite material for the manpower vehicle has better ageing resistance.

Claims

1. The inflation-free micro-foaming rickshaw tire raw material is characterized in that: the adhesive comprises the following components in parts by mass:

10-60 parts of SSBR;

10-60 parts of PSBR;

20-60 parts of SBS;

40-60 parts of reclaimed rubber powder;

20-50 parts of softened and filled rubber oil;

20.5-31 parts of an auxiliary agent;

the auxiliary agent comprises a foaming agent, a pigment, an accelerator, an anti-aging agent, an activating agent and a crosslinking agent;

the accelerator comprises at least one of overspeed-grade dithiocarbamates and thiuram accelerators.

2. The inflation-free micro-foaming human-powered vehicle tire raw material as claimed in claim 1, wherein: the SSBR is solution polymerized styrene butadiene rubber with narrow molecular weight distribution, and the molecular weight distribution index is less than or equal to 1.15.

3. The inflation-free micro-foaming human-powered vehicle tire raw material as claimed in claim 2, wherein: the SSBR has a number average molecular mass Mn = 120000-150000 and a Mooney viscosity ML = 55-70.

4. The raw material for non-pneumatic micro-foaming rickshaw tires according to claim 1, 2 or 3, wherein: the SSBR comprises 15-20% of polystyrene block mass percentage and S/B = (25-35)/(65-75) block mass percentage.

5. The inflation-free micro-foaming human-powered vehicle tire raw material as claimed in claim 1, wherein: the PSBR is powdered emulsion styrene butadiene rubber with wide molecular weight distribution and containing a separant, and the molecular weight distribution index is more than or equal to 2.5.

6. The inflation-free micro-foaming human-powered vehicle tire raw material as claimed in claim 5, wherein:

the PSBR has a number average molecular weight Mn = 200000-300000 and a Mooney viscosity ML = 40-80.

7. The raw material for non-pneumatic micro-foaming rickshaw tires according to claim 1, 5 or 6, wherein: the particle size of the PSBR is 20-80 meshes.

8. The inflation-free micro-foaming human-powered vehicle tire raw material as claimed in claim 1, wherein: the SBS has a block mass ratio S/B = (25-35)/(65-75).

9. The raw material for non-pneumatic micro-foaming rickshaw tires according to claim 1 or 8, wherein: the SBS is in a linear or star structure, and the number average molecular weight Mn = 80000-200000.

10. The inflation-free micro-foaming human-powered vehicle tire raw material as claimed in claim 1, wherein: the fineness of the reclaimed rubber powder is 80-120 meshes.

11. The inflation-free micro-foaming human-powered vehicle tire raw material as claimed in claim 1, wherein: the softening filling rubber oil comprises at least one of environment-friendly rubber oil and high aromatic oil.

12. The raw material for the inflation-free micro-foaming rickshaw tire as claimed in claim 11, wherein:

the softening filling rubber oil is naphthenic oil or environment-friendly aromatic oil.

13. The raw material for the inflation-free micro-foaming rickshaw tire as claimed in claim 11, wherein: the mass ratio of the foaming agent to the pigment to the accelerator to the anti-aging agent to the activator to the crosslinking agent is 1.5-2: 8-10: 2-4: 2-3: 5-9: 2 to 3.

14. The raw material for the inflation-free micro-foaming rickshaw tire as claimed in claim 13, wherein:

the foaming agent is an organic compound capable of releasing small molecular compounds at the temperature of 120-200 ℃.

15. The raw material for non-pneumatic micro-foaming rickshaw tires according to claim 14, wherein:

the foaming agent comprises at least one of azodicarbonamide, foaming agent H, DNTA, DAB and AIBN.

16. The raw material for the inflation-free micro-foaming rickshaw tire as claimed in claim 13, wherein:

the anti-aging agent is an amine anti-aging agent.

17. The raw material for the inflation-free micro-foaming rickshaw tire as claimed in claim 13, wherein:

the pigment is carbon black.

18. The raw material for the inflation-free micro-foaming rickshaw tire as claimed in claim 13, wherein: the cross-linking agent is sulfur.

19. The raw material for the inflation-free micro-foaming rickshaw tire as claimed in claim 13, wherein:

the activator comprises an inorganic activator and an organic activator; wherein the mass ratio of the inorganic activator to the organic activator is 2-8: 2-6.

20. The raw material for non-pneumatic micro-foaming rickshaw tires according to claim 19, wherein:

the inorganic activator is zinc oxide.

21. The raw material for non-pneumatic micro-foaming rickshaw tires according to claim 19, wherein:

the organic activator is stearic acid.

22. The inflation-free micro-foaming human-powered vehicle tire raw material as claimed in claim 1, wherein: the adhesive comprises the following components in parts by mass:

20-30 parts of SSBR;

20-30 parts of PSBR;

SBS 30~40；

40-60 parts of reclaimed rubber powder;

20-50 parts of softened and filled rubber oil;

1.5-2 parts of a foaming agent;

8-10 parts of pigment;

2-4 parts of an accelerator;

2-3 parts of an anti-aging agent;

3-5 parts of an inorganic activating agent;

2-4 parts of an organic activating agent;

2-3 parts of a crosslinking agent.

23. The utility model provides an exempt from to aerify little foaming rickshaw tire which characterized in that: prepared from the raw material of claim 22 by extrusion granulation and extrusion injection molding.

24. The non-pneumatic microfoaming human powered vehicle tire of claim 23, wherein: the micro-foaming tire forming rubber material for the manpower vehicle has the advantages of 300% stress at definite elongation of 4-5 MPa, Shaoxing A hardness of 60-70, permanent deformation of 16-24%, elongation at break of 280-320%, elasticity of 30-40%, and density of 0.60-0.65 g/cm³。

25. A method for manufacturing an inflation-free microcellular foamed human-powered vehicle tire according to claim 23 or 24, wherein: the method comprises the following steps:

1) uniformly stirring SSBR powder, SBS, reclaimed rubber powder, softened filling rubber oil, pigment, an anti-aging agent, an activating agent and a crosslinking agent at room temperature to obtain a bulk rubber material;

26. The method for preparing the non-pneumatic microcellular foamed human-powered vehicle tire according to claim 25, wherein the method comprises the following steps: in the step 1), the dosage of the softened filling rubber oil is 3/4-4/5 of the total amount of the softened filling oil; the stirring and mixing time is 5-8 min.

27. The method for preparing the non-pneumatic microcellular foamed human-powered vehicle tire according to claim 25, wherein the method comprises the following steps: in the step 2), the granulation temperature is 190-210 ℃.

28. The method for preparing the non-pneumatic microcellular foamed human-powered vehicle tire according to claim 25, wherein the method comprises the following steps: the granulation rubber is phi (3-6) х (3-6) columnar particles.

29. The method for preparing the non-pneumatic microcellular foamed human-powered vehicle tire according to claim 25, wherein the method comprises the following steps: in the step 3), the using amount of the softened filling rubber oil is 1/5-1/4 of the total amount of the softened filling oil; the stirring and mixing time is 3-6 min.

30. The method for preparing the non-pneumatic microcellular foamed human-powered vehicle tire according to claim 25, wherein the method comprises the following steps: in the step 4), in the injection molding process, the melting temperature is 190-210 ℃, the temperature in the mold is maintained at 120-180 ℃, and the heat preservation time is 8-12 min.

31. The method for preparing the non-pneumatic microcellular foamed human-powered vehicle tire according to claim 25, wherein the method comprises the following steps: in the step 4), in the curing process, the curing temperature is 80-100 ℃, and the curing time is 10-15 min.