Patent Description:
The best way of treating waste rubber is recycling and reproduction. However, the existing method of recycling and reproduction has poor quality, bad reproduction factory environment, and high energy consumption. Accordingly, a depolymerization modifier should be developed to reduce the energy used by the recycling process, enhance the rubber's reproduction quality, and increase the applicability of depolymerized rubber.

<CIT> relates to processes for degradation for polymerized plastic products, refuge and plastics in general, to soluble non-toxic products, using mild chemical conditions. Specifically, a cost effective and easy way to prepare degradable compositions of plastics and other polymers containing the amino-sulfenyl, the oxygen-sulfenyl or the disulphide moieties is provided.

<CIT> describes a carbanionic polymer chain that contains polyene mer can be provided with a terminal functionality separated from the polymer chain by a sulfide linkage.

<CIT> describes a functionalized elastomer having the formula I where R1, R2 and R3 are independently selected from a C1 to a C8 alkyl or a C1 to a C8 alkoxy, with the proviso that at least two of R1, R2 and R3 are a C1 to a C8 alkoxy; R4 is a C1 to a C8 alkanediyl, a C1 to a C8 arylene, a C1 to a C8 alkylarylene, a C1 to a C8 arylalkanediyl, or a covalent bond; R5 is a C2 alkanediyl; Si is silicon; X is sulfur or oxygen; P is a diene based elastomer; and n is <NUM> or <NUM>.

Preferred embodiments are defined by the features of the dependent claims.

One embodiment of the disclosure provides recycled rubber, being formed by depolymerizing <NUM> parts by weight of rubber and <NUM> to <NUM> parts by weight of modifier, wherein the modifier is formed by reacting (a) R<NUM>-M, (b) double bond monomer, (c) ethylene sulfide, and (d) polymerization terminator, wherein R<NUM> is C<NUM>-C<NUM> alkyl group, M is Li, Na, K, Ba, or Mg and (b) double bond monomer is <NUM>,<NUM>-butadiene, isoprene, <NUM>,<NUM>-pentadiene, <NUM>,<NUM>-dimethyl-<NUM>,<NUM>-butadiene, <NUM>-methyl-<NUM>,<NUM>-pentadiene, <NUM>,<NUM>-dimethyl-<NUM>,<NUM>-pentadiene, <NUM>-phenyl-<NUM>,<NUM>-butadiene, <NUM>,<NUM>-diethyl-<NUM>,<NUM>-octadiene, styrene, <NUM>-ethylene naphthalene, <NUM>-methylstyrene, <NUM>,<NUM>-diethylstyrene, <NUM>-propylstyrene, <NUM>,<NUM>,<NUM>-trimethylstyrene, <NUM>-dodecylstyrene, <NUM>-methyl-<NUM>-n-hexylstyrene, <NUM>-phenylstyrene, <NUM>-ethyl-<NUM>-benzylstyrene, <NUM>,<NUM>-diphenylstyrene, <NUM>,<NUM>,<NUM>,<NUM>-tetraethyl styrene, <NUM>-ethyl-<NUM>-vinylnaphthalene, <NUM>-isopropyl-<NUM>-vinylnaphthalene, <NUM>-cyclohexyl-<NUM>-vinylnaphthalene, <NUM>-dodecyl-<NUM>-vinylnaphthalene, α-methyl styrene, or a combination thereof.

In some embodiments, (b) double bond monomer and (a) R1-M have a weight ratio of <NUM>:<NUM> to <NUM>:<NUM>.

In some embodiments, (b) double bond monomer and (c) ethylene sulfide have a weight ratio of <NUM>:<NUM> to <NUM>:<NUM>.

In some embodiments, (b) double bond monomer and (d) polymerization terminator have a weight ratio of <NUM>:<NUM> to <NUM>:<NUM>.

In some embodiments, the modifier has a weight average molecular weight of <NUM> to <NUM>,<NUM>.

In some embodiments, the rubber includes poly(cis-<NUM>,<NUM>-butadiene) rubber, polystyrene-butadiene rubber, nitrile rubber, buna rubber, ethylene propylene rubber, butyl rubber, or a combination thereof.

In some embodiments, (b) double bond monomer is styrene.

In some embodiments, (b) double bond monomer is styrene and isoprene, and styrene and the isoprene are arranged in block or random.

In some embodiments, (b) double bond monomer is isoprene.

In some embodiments, the recycled rubber is further vulcanization crosslinked.

A detailed description is given in the following embodiments.

It will be apparent, however, that one or more embodiments may be practised without these specific details.

One embodiment of the disclosure provides recycled rubber being formed by depolymerizing <NUM> parts by weight of rubber and <NUM> to <NUM> parts by weight of modifier. If the amount of the modifier is too low, the depolymerization quality cannot be improved. If the amount of the modifier is too high, the depolymerization quality is good, but the depolymerization quality cannot be further enhanced after the modifier amount achieves a certain degree. For example, the waste rubber and the depolymerization agent (e.g. the modifier) can be mixed by any known method in this field, such as thermo-mechanical mixing. The thermo-mechanical mixing steps often include a mechanical process at a depolymerization temperature in a mixer or an extruder for a suitable period of time. The suitable period of time of the thermo-mechanical work may vary based on the operation conditions and volume and properties of the components. For example, the thermo-mechanical work period can be from <NUM> minute to <NUM> minutes. In one embodiment, the depolymerization temperature can be <NUM> to <NUM>. If the depolymerization temperature is too low, the depolymerization period will be longer or even fail to depolymerize the rubber. If the depolymerization temperature is too high, over-depolymerization may occurr, degrading the recycled rubber quality and thereby lowering the tensile strength and elongation rate of the recycled rubber.

In one embodiment, the modifier is formed by reacting (a) R<NUM>-M, (b) double bond monomer, (c) ethylene sulfide, and (d) polymerization terminator. (a) R<NUM>-M serves as initiator to polymerize (b) double bond monomer. R<NUM> is C<NUM>-C<NUM> alkyl group, and M is Li, Na, K, Ba, or Mg. In one embodiment, (b) double bond monomer is <NUM>,<NUM>-butadiene, isoprene, <NUM>,<NUM>-pentadiene, <NUM>,<NUM>-dimethyl-<NUM>,<NUM>-butadiene, <NUM>-methyl-<NUM>,<NUM>-pentadiene, <NUM>,<NUM>-dimethyl-<NUM>,<NUM>-pentadiene, <NUM>-phenyl-<NUM>,<NUM>-butadiene, <NUM>,<NUM>-diethyl-<NUM>,<NUM>-octadiene, styrene, <NUM>-ethylene naphthalene, <NUM>-methylstyrene, <NUM>,<NUM>-diethylstyrene, <NUM>-propylstyrene, <NUM>,<NUM>,<NUM>-trimethylstyrene, <NUM>-dodecylstyrene, <NUM>-methyl-<NUM>-n-hexylstyrene, <NUM>-phenylstyrene, <NUM>-ethyl-<NUM>-benzylstyrene, <NUM>,<NUM>-diphenylstyrene, <NUM>,<NUM>,<NUM>,<NUM>-tetraethyl styrene, <NUM>-ethyl-<NUM>-vinylnaphthalene, <NUM>-isopropyl-<NUM>-vinylnaphthalene, <NUM>-cyclohexyl-<NUM>-vinylnaphthalene, <NUM>-dodecyl-<NUM>-vinylnaphthalene, α-methyl styrene, or a combination thereof. After the polymerization is performed for a period, (c) ethylene sulfide can be added to react. Finally, (d) polymerization terminator can be added to terminate the reaction to obtain the so-called modifier. In one embodiment, (d) polymerization terminator can be butylated hydroxytoluene (BHT), butylated hydroxy anisole (BHA), tert-butylhydroquinone (TBHQ), propyl gallate (PG), ethoxyquinoline (EQ), hydroxymethyldibutylphenol (HMBP), Trihydroxybutyrophenone (THBP), octyl gallate (OG), dodecyl gallate (DG), hexyl resorcinol (<NUM>-HR), or n-dihydroguaiac acid (NDGA). In some embodiments, (b) double bond monomer is styrene. In some embodiments, (b) double bond monomer is styrene and isoprene, and styrene and the isoprene are arranged in block or random. In some embodiments, (b) double bond monomer is isoprene.

In some embodiments, (b) double bond monomer and (a) R<NUM>-M have a weight ratio of <NUM>:<NUM> to <NUM>:<NUM>. In one embodiment, (b) double bond monomer and (a) R<NUM>-M have a weight ratio of <NUM>:<NUM> to <NUM>:<NUM>. The amount of (a) R<NUM>-M is varied on the basis of the required molecular weight of the synthesized rubber polymer and the precise polymerization temperature used to synthesize the rubber. One skilled in the art can easily determine the precise amount of (a) R<NUM>-M for a polymer with an expected molecular weight. If the (a) R<NUM>-M amount is too low, the reaction condition will be more rigorous, such as well-anhydrous solvent or reactor to prevent overly low yield (or even no reaction). If the (a) R<NUM>-M amount is too high, the polymerization will produce a lot of heat, so that the reaction will be very dangerous due to the reaction temperature being out of control. In some embodiments, (b) double bond monomer and (c) ethylene sulfide have a weight ratio of <NUM>:<NUM> to <NUM>:<NUM>. If the (c) ethylene sulfide amount is over the stoichiometry amount, it may increase the cost. However, (c) ethylene sulfide amount can be over the stoichiometry amount a bit in many conditions to ensure that each of the modifier molecules is functionalized without being influenced by water molecule. In some embodiments, (b) double bond monomer and (d) polymerization terminator have a weight ratio of <NUM>:<NUM> to <NUM>:<NUM>. If the (d) polymerization terminator amount is too low, the reaction will not be terminated. If the (d) polymerization terminator amount is too high, the residual polymerization terminator will have a negative influence on the recycled rubber quality when the rubber is depolymerized thereafter.

In some embodiments, the modifier has a weight average molecular weight (Mw) of <NUM> to <NUM>. In some embodiments, the modifier has a number average molecular weight (Mn) of <NUM> to <NUM>. If the molecular weight of the rubber is higher, the molecular weight of modifier should be higher. If Mw or Mn of the modifier is too low, the depolymerization of the vulcanized rubber will be very smelly. If Mw or Mn of the modifier is too high, the sulfur group content of the modifier will be too low, and the quality of the recycled rubber will be poor. In some embodiments, the modifier has polymer dispersity index (PDI, Mw/Mn) of <NUM> to <NUM>. If the PDI of the modifier is too low, the processability of the recycled rubber will be poor, and the recycled rubber will be smelly. If the PDI of the modifier is too high, the quality of the recycled rubber will be poor.

In some embodiments, the recycled rubber can be further vulcanization crosslinked. For example, sulfur or other crosslinker can be added as needed to crosslink the recycled rubber, such that the properties of the recycled rubber are further adjusted to meet product specifications.

Below, exemplary embodiments will be described in detail so as to be easily realized by a person having ordinary knowledge in the art. The inventive concept may be embodied in various forms without being limited to the exemplary embodiments set forth herein. Descriptions of well-known parts are omitted for clarity, and like reference numerals refer to like elements throughout.

<NUM> of styrene was dissolved in <NUM> of toluene, and <NUM> of n-butyl lithium (C<NUM>H<NUM>Li) was then added into the toluene solution to initiate polymerization at room temperature for <NUM> minutes. Subsequently, <NUM> of isoprene was added into the above reaction, and reacted at room temperature for <NUM> minutes to form poly(styrene-b-isoprene) block copolymer. <NUM> of ethylene sulfide was added into the above reaction, and reacted at room temperature for <NUM> minutes. Finally, an isopropyl alcohol solution of butylated hydroxytoluene (BHT) (<NUM>/<NUM>) serving as polymerization terminator was added into the above reaction, and reacted at room temperature for <NUM> minutes to terminate the reaction.

The crude product was added into a lot of distilled water, stirred for <NUM> hour, and then stood to separate into two layers. The upper layer was extracted, and distilled water was added to the upper layer to perform extraction <NUM> times to ensure that the salt in the upper layer was completely removed. The upper layer was dropwisely added into a lot of ethanol to precipitate solid. The solid was collected and put into a vacuum oven at <NUM> for <NUM> hours, thereby obtaining a pale yellow modifier. The modifier was analyzed by gel permeation chromatography (GPC) to measure its weight average molecular weight (Mw) of <NUM>, number average molecular weight (Mn) of <NUM>, and polymer dispersity index (PDI, Mw/Mn) of <NUM>.

<NUM> of styrene was dissolved in <NUM> of toluene, and <NUM> of n-butyl lithium (C<NUM>H<NUM>Li) was then added into the toluene solution to initiate polymerization at room temperature for <NUM> minutes. Subsequently, <NUM> of isoprene was added into the above reaction, and reacted at room temperature for <NUM> minutes to form poly(styrene-b-isoprene) block copolymer. <NUM> of ethylene sulfide was added into the above reaction, and reacted at room temperature for <NUM> minutes. Finally, an isopropyl alcohol solution of BHT (<NUM>/<NUM>) serving as polymerization terminator was added into the above reaction, and reacted at room temperature for <NUM> minutes to terminate the reaction.

The crude product was added into a lot of distilled water, stirred for <NUM> hour, and then stood to separate into two layers. The upper layer was extracted, and distilled water was added to the upper layer to perform extraction <NUM> times to ensure that the salt in the upper layer was completely removed. The upper layer was dropwisely added into a lot of ethanol to precipitate solid. The solid was collected and put into a vacuum oven at <NUM> for <NUM> hours, thereby obtaining a pale yellow modifier. The modifier was analyzed by GPC to measure its Mw of <NUM>, Mn of <NUM>, and PDI of <NUM>.

<NUM> of styrene and <NUM> of isoprene were dissolved in <NUM> of toluene, and <NUM> of n-butyl lithium (C<NUM>H<NUM>Li) was then added into the mixture solution of styrene and isoprene to initiate polymerization in ice bath for <NUM> minutes to form poly(styrene-isoprene) random copolymer. <NUM> of ethylene sulfide was added into the above reaction, and reacted at room temperature for <NUM> minutes. Finally, an isopropyl alcohol solution of BHT (<NUM>/<NUM>) serving as polymerization terminator was added into the above reaction, and reacted at room temperature for <NUM> minutes to terminate the reaction.

<NUM> of styrene was dissolved in <NUM> of toluene, and <NUM> of n-butyl lithium (C<NUM>H<NUM>Li) was then added into the solution of styrene to initiate polymerization at room temperature for <NUM> minutes to form polystyrene. <NUM> of ethylene sulfide was added into the above reaction, and reacted at room temperature for <NUM> hours. Finally, an isopropyl alcohol solution of BHT (<NUM>/<NUM>) serving as polymerization terminator was added into the above reaction, and reacted at room temperature for <NUM> minutes to terminate the reaction.

The crude product was added into a lot of distilled water, stirred for <NUM> hour, and then stood to separate into two layers. The upper layer was extracted, and distilled water was added to the upper layer to perform extraction <NUM> times to ensure that the salt in the upper layer was completely removed. The upper layer was dropwisely added into a lot of ethanol to precipitate solid. The solid was collected and put into a vacuum oven at <NUM> for <NUM> hours, thereby obtaining a white modifier. The modifier was analyzed by GPC to measure its Mw of <NUM>, Mn of <NUM>, and PDI of <NUM>.

<NUM> of isoprene was added into a anhydrous rounded bottom bottle, and <NUM> of n-butyl lithium (C<NUM>H<NUM>Li) was then added into isoprene to initiate polymerization in a water bath for <NUM> minutes to form a polyisoprene random copolymer. <NUM> of ethylene sulfide was added into the above reaction, and reacted at room temperature for <NUM> minutes. Finally, an isopropyl alcohol solution of BHT (<NUM>/<NUM>) serving as polymerization terminator was added into the above reaction, and reacted at room temperature for <NUM> minutes to terminate the reaction.

<NUM> of waste rubber (recycled from batch A of whole tire from minibus) was added to a plastometer (plasti-corder PL2000) for depolymerization at <NUM> and 70rpm to obtain recycled rubber. The depolymerization was repeated <NUM> times to obtain about <NUM> of the recycled rubber. The recycled rubber was refined by double rollers at <NUM> and 30rpm for <NUM> minutes to obtain a sheet. <NUM> of the sheet was sampled to measure its solute content of <NUM>% (according to ASTM5667) and crosslink degree of <NUM> (according to ASTM <NUM>-<NUM>). <NUM> of the sheet was vulcanization crosslinked according to JIS standard (JIS K6313-<NUM>), and the vulcanization crosslinked sheet was analyzed to measure its tensile strength of <NUM>. 01MPa and elongation rate of <NUM>%.

<NUM> of waste rubber (similar to the waste rubber in Comparative Example <NUM>-<NUM>) and 1phr of BHT (serving as anti-oxidant) were added to a plastometer (plasti-corder PL2000) for depolymerization at <NUM> and 70rpm to obtain recycled rubber. The depolymerization was repeated <NUM> times to obtain about <NUM> of the recycled rubber. The recycled rubber was refined by double rollers at <NUM> and 30rpm for <NUM> minutes to obtain a sheet. <NUM> of the sheet was sampled to measure its solute content of <NUM>% (according to ASTM5667) and crosslink degree of <NUM> (according to ASTM <NUM>-<NUM>). <NUM> of the sheet was vulcanization crosslinked according to JIS standard (JIS K6313-<NUM>), and the vulcanization crosslinked sheet was analyzed to measure its tensile strength of <NUM>. 63MPa and elongation rate of <NUM>%.

<NUM> of waste rubber (similar to the waste rubber in Comparative Example <NUM>-<NUM>), 1phr of BHT (serving as anti-oxidant), and 1phr of <NUM>-mercaptobenzimidazole (MMBI, <NUM>%, commercially available from Aldrich, serving as a vulcanization retarder) were added to a plastometer (plasti-corder PL2000) for depolymerization at <NUM> and 70rpm to obtain recycled rubber. The depolymerization was repeated <NUM> times to obtain about <NUM> of the recycled rubber. The recycled rubber was refined by double rollers at <NUM> and 30rpm for <NUM> minutes to obtain a sheet. <NUM> of the sheet was sampled to measure its solute content of <NUM>% (according to ASTM5667) and crosslink degree of <NUM> (according to ASTM <NUM>-<NUM>). <NUM> of the sheet was vulcanization crosslinked according to JIS standard (JIS K6313-<NUM>), and the vulcanization crosslinked sheet was analyzed to measure its tensile strength of <NUM>. 18MPa and elongation rate of <NUM>%.

<NUM> of waste rubber (similar to the waste rubber in Comparative Example <NUM>-<NUM>), 1phr of the modifier of Synthesis Example <NUM>, 1phr of BHT (serving as anti-oxidant), and 1phr of MMBI (serving as a vulcanization retarder) were added to a plastometer (plasti-corder PL2000) for depolymerization at <NUM> and 70rpm to obtain recycled rubber. The depolymerization was repeated <NUM> times to obtain about <NUM> of the recycled rubber. The recycled rubber was refined by double rollers at <NUM> and 30rpm for <NUM> minutes to obtain a sheet. <NUM> of the sheet was sampled to measure its solute content of <NUM>% (according to ASTM5667) and crosslink degree of <NUM> (according to ASTM <NUM>-<NUM>). <NUM> of the sheet was vulcanization crosslinked according to JIS standard (JIS K6313-<NUM>), and the vulcanization crosslinked sheet was analyzed to measure its tensile strength of <NUM>. 02MPa and elongation rate of <NUM>%.

<NUM> of waste rubber (similar to the waste rubber in Comparative Example <NUM>-<NUM>), 1phr of the modifier of Synthesis Example <NUM>, 1phr of BHT (serving as anti-oxidant), and 1phr of MMBI (serving as a vulcanization retarder) were added to a plastometer (plasti-corder PL2000) for depolymerization at <NUM> and 70rpm to obtain recycled rubber. The depolymerization was repeated <NUM> times to obtain about <NUM> of the recycled rubber. The recycled rubber was refined by double rollers at <NUM> and 30rpm for <NUM> minutes to obtain a sheet. <NUM> of the sheet was sampled to measure its solute content of <NUM>% (according to ASTM5667) and crosslink degree of <NUM> (according to ASTM <NUM>-<NUM>). <NUM> of the sheet was vulcanization crosslinked according to JIS standard (JIS K6313-<NUM>), and the vulcanization crosslinked sheet was analyzed to measure its tensile strength of <NUM>. 22MPa and elongation rate of <NUM>%.

<NUM> of waste rubber (similar to the waste rubber in Comparative Example <NUM>-<NUM>), 1phr of the modifier of Synthesis Example <NUM>, 1phr of BHT (serving as anti-oxidant), and 1phr of MMBI (serving as a vulcanization retarder) were added to a plastometer (plasti-corder PL2000) for depolymerization at <NUM> and 70rpm to obtain recycled rubber. The depolymerization was repeated <NUM> times to obtain about <NUM> of the recycled rubber. The recycled rubber was refined by double rollers at <NUM> and 30rpm for <NUM> minutes to obtain a sheet. <NUM> of the sheet was sampled to measure its solute content of <NUM>% (according to ASTM5667) and crosslink degree of <NUM> (according to ASTM <NUM>-<NUM>). <NUM> of the sheet was vulcanization crosslinked according to JIS standard (JIS K6313-<NUM>), and the vulcanization crosslinked sheet was analyzed to measure its tensile strength of <NUM>. 37MPa and elongation rate of <NUM>%.

<NUM> of waste rubber (similar to the waste rubber in Comparative Example <NUM>-<NUM>), 1phr of the modifier of Synthesis Example <NUM>, 1phr of BHT (serving as anti-oxidant), and 1phr of MMBI (serving as a vulcanization retarder) were added to a plastometer (plasti-corder PL2000) for depolymerization at <NUM> and 70rpm to obtain recycled rubber. The depolymerization was repeated <NUM> times to obtain about <NUM> of the recycled rubber. The recycled rubber was refined by double rollers at <NUM> and 30rpm for <NUM> minutes to obtain a sheet. <NUM> of the sheet was sampled to measure its solute content of <NUM>% (according to ASTM5667) and crosslink degree of <NUM> (according to ASTM <NUM>-<NUM>). <NUM> of the sheet was vulcanization crosslinked according to JIS standard (JIS K6313-<NUM>), and the vulcanization crosslinked sheet was analyzed to measure its tensile strength of <NUM>. 29MPa and elongation rate of <NUM>%.

<NUM> of waste rubber (similar to the waste rubber in Comparative Example <NUM>-<NUM>), 1phr of the modifier of Synthesis Example <NUM>, 1phr of BHT (serving as anti-oxidant), and 1phr of MMBI (serving as a vulcanization retarder) were added to a plastometer (plasti-corder PL2000) for depolymerization at <NUM> and 70rpm to obtain recycled rubber. The depolymerization was repeated <NUM> times to obtain about <NUM> of the recycled rubber. The recycled rubber was refined by double rollers at <NUM> and 30rpm for <NUM> minutes to obtain a sheet. <NUM> of the sheet was sampled to measure its solute content of <NUM>% (according to ASTM5667) and crosslink degree of <NUM> (according to ASTM <NUM>-<NUM>). <NUM> of the sheet was vulcanization crosslinked according to JIS standard (JIS K6313-<NUM>), and the vulcanization crosslinked sheet was analyzed to measure its tensile strength of <NUM>. 77MPa and elongation rate of <NUM>%.

The properties of Comparative Examples <NUM>-<NUM> to <NUM>-<NUM> and Examples <NUM> to <NUM> are shown in Table <NUM>.

As shown in Comparison of Table <NUM>, the modifier in Example <NUM> may greatly enhance the tensile strength of the recycled rubber.

<NUM> of waste rubber (recycled from batch B of whole tire from minibus), 1phr of diphenyl disulfide (DPDS, <NUM>%, commercially available from Aldrich, serving as modifier), 1phr of BHT (serving as anti-oxidant), and 1phr of MMBI (serving as a vulcanization retarder) were added to a plastometer (plasti-corder PL2000) for depolymerization at <NUM> and 70rpm to obtain recycled rubber. The depolymerization was repeated <NUM> times to obtain about <NUM> of the recycled rubber. The recycled rubber was refined by double rollers at <NUM> and 30rpm for <NUM> minutes to obtain a sheet. <NUM> of the sheet was sampled to measure its solute content of <NUM>% (according to ASTM5667), crosslink degree of <NUM> (according to ASTM <NUM>-<NUM>), and decrosslink degree of <NUM>% (according to ASTM <NUM>-<NUM>). <NUM> of the sheet was vulcanization crosslinked according to JIS standard (JIS K6313-<NUM>), and the vulcanization crosslinked sheet was analyzed to measure its tensile strength of <NUM>. 06MPa and elongation rate of <NUM>%.

<NUM> of waste rubber (recycled from batch B of whole tire from minibus), 1phr of bis(<NUM>-benzamidophenyl) disulfide (PiTong <NUM>, commercially available from ShunLi, serving as modifier), 1phr of BHT (serving as anti-oxidant), and 1phr of MMBI (serving as a vulcanization retarder) were added to a plastometer (plasti-corder PL2000) for depolymerization at <NUM> and 70rpm to obtain recycled rubber. The depolymerization was repeated <NUM> times to obtain about <NUM> of the recycled rubber. The recycled rubber was refined by double rollers at <NUM> and 30rpm for <NUM> minutes to obtain a sheet. <NUM> of the sheet was sampled to measure its solute content of <NUM>% (according to ASTM5667), crosslink degree of <NUM> (according to ASTM <NUM>-<NUM>), and decrosslink degree of <NUM>% (according to ASTM <NUM>-<NUM>). <NUM> of the sheet was vulcanization crosslinked according to JIS standard (JIS K6313-<NUM>), and the vulcanization crosslinked sheet was analyzed to measure its tensile strength of <NUM>. 73MPa and elongation rate of <NUM>%.

<NUM> of waste rubber (recycled from batch B of whole tire from minibus), 1phr of the modifier of Synthesis Example <NUM>, 1phr of BHT (serving as anti-oxidant), and 1phr of MMBI (serving as a vulcanization retarder) were added to a plastometer (plasti-corder PL2000) for depolymerization at <NUM> and 70rpm to obtain recycled rubber. The depolymerization was repeated <NUM> times to obtain about <NUM> of the recycled rubber. The recycled rubber was refined by double rollers at <NUM> and 30rpm for <NUM> minutes to obtain a sheet. <NUM> of the sheet was sampled to measure its solute content of <NUM>% (according to ASTM5667), crosslink degree of <NUM> (according to ASTM <NUM>-<NUM>), and decrosslink degree of <NUM>% (according to ASTM <NUM>-<NUM>). <NUM> of the sheet was vulcanization crosslinked according to JIS standard (JIS K6313-<NUM>), and the vulcanization crosslinked sheet was analyzed to measure its tensile strength of <NUM>. 81MPa and elongation rate of <NUM>%.

The properties of Comparative Examples <NUM>-<NUM> and <NUM>-<NUM> and Example <NUM> are shown in Table <NUM>.

As shown in Comparison of Table <NUM>, the modifier in Example <NUM> may greatly enhance the tensile strength and elongation rate of the recycled rubber compared to the commercially available modifiers.

<NUM> of waste rubber (recycled from cover tire from trunk) was added to a plastometer (plasti-corder PL2000) for depolymerization at <NUM> and 70rpm to obtain recycled rubber. The depolymerization was repeated <NUM> times to obtain about <NUM> of the recycled rubber. The recycled rubber was refined by double rollers at <NUM> and 30rpm for <NUM> minutes to obtain a sheet. <NUM> of the sheet was sampled to measure its solute content of <NUM>% (according to ASTM5667), crosslink degree of <NUM> (according to ASTM <NUM>-<NUM>), and decrosslink degree of <NUM>% (according to ASTM <NUM>-<NUM>). <NUM> of the sheet was vulcanization crosslinked according to JIS standard (JIS K6313-<NUM>), and the vulcanization crosslinked sheet was analyzed to measure its tensile strength of <NUM>. 99MPa and elongation rate of <NUM>%.

<NUM> of waste rubber (recycled from cover tire from trunk) and 1phr of MMBI (serving as a vulcanization retarder) were added to a plastometer (plasti-corder PL2000) for depolymerization at <NUM> and 70rpm to obtain recycled rubber. The depolymerization was repeated <NUM> times to obtain about <NUM> of the recycled rubber. The recycled rubber was refined by double rollers at <NUM> and 30rpm for <NUM> minutes to obtain a sheet. <NUM> of the sheet was sampled to measure its solute content of <NUM>% (according to ASTM5667), crosslink degree of <NUM> (according to ASTM <NUM>-<NUM>), and decrosslink degree of <NUM>% (according to ASTM <NUM>-<NUM>). <NUM> of the sheet was vulcanization crosslinked according to JIS standard (JIS K6313-<NUM>), and the vulcanization crosslinked sheet was analyzed to measure its tensile strength of <NUM>. 65MPa and elongation rate of <NUM>%.

<NUM> of waste rubber (recycled from cover tire from trunk), 1phr of BHT (serving as anti-oxidant), and 1phr of MMBI (serving as a vulcanization retarder) were added to a plastometer (plasti-corder PL2000) for depolymerization at <NUM> and 70rpm to obtain recycled rubber. The depolymerization was repeated <NUM> times to obtain about <NUM> of the recycled rubber. The recycled rubber was refined by double rollers at <NUM> and 30rpm for <NUM> minutes to obtain a sheet. <NUM> of the sheet was sampled to measure its solute content of <NUM>% (according to ASTM5667), crosslink degree of <NUM> (according to ASTM <NUM>-<NUM>), and decrosslink degree of <NUM>% (according to ASTM <NUM>-<NUM>). <NUM> of the sheet was vulcanization crosslinked according to JIS standard (JIS K6313-<NUM>), and the vulcanization crosslinked sheet was analyzed to measure its tensile strength of <NUM>. 93MPa and elongation rate of <NUM>%.

<NUM> of waste rubber (recycled from cover tire from trunk), 1phr of the modifier of Synthesis Example <NUM>, 1phr of BHT (serving as anti-oxidant), and 1phr of MMBI (serving as a vulcanization retarder) were added to a plastometer (plasti-corder PL2000) for depolymerization at <NUM> and 70rpm to obtain recycled rubber. The depolymerization was repeated <NUM> times to obtain about <NUM> of the recycled rubber. The recycled rubber was refined by double rollers at <NUM> and 30rpm for <NUM> minutes to obtain a sheet. <NUM> of the sheet was sampled to measure its solute content of <NUM>% (according to ASTM5667), crosslink degree of <NUM> (according to ASTM <NUM>-<NUM>), and decrosslink degree of <NUM>% (according to ASTM <NUM>-<NUM>). <NUM> of the sheet was vulcanization crosslinked according to JIS standard (JIS K6313-<NUM>), and the vulcanization crosslinked sheet was analyzed to measure its tensile strength of <NUM>. 66MPa and elongation rate of <NUM>%.

The properties of Comparative Examples <NUM>-<NUM> to <NUM>-<NUM> and Example <NUM> are shown in Table <NUM>.

As shown in Comparison of Table <NUM>, the modifier in Example <NUM> may greatly enhance the tensile strength of the recycled rubber compared to the commercially available modifiers.

As shown in Examples <NUM>, <NUM>, and <NUM>, the modifier can be used in the same rubber type from different sources (Examples <NUM> and <NUM>), and can be used in different rubber types (Examples <NUM> and <NUM>).

Claim 1:
Recycled rubber, being formed by
depolymerizing <NUM> parts by weight of rubber and <NUM> to <NUM> parts by weight of modifier,
wherein the modifier is formed by reacting (a) R<NUM>-M, (b) double bond monomer, (c) ethylene sulfide, and (d) polymerization terminator,
wherein R<NUM> is C<NUM>-C<NUM> alkyl group, M is Li, Na, K, Ba, or Mg and (b) double bond monomer is <NUM>,<NUM>-butadiene, isoprene, <NUM>,<NUM>-pentadiene, <NUM>,<NUM>-dimethyl-<NUM>,<NUM>-butadiene, <NUM>-methyl-<NUM>,<NUM>-pentadiene, <NUM>,<NUM>-dimethyl-<NUM>,<NUM>-pentadiene, <NUM>-phenyl-<NUM>,<NUM>-butadiene, <NUM>,<NUM>-diethyl-<NUM>,<NUM>-octadiene, styrene, <NUM>-ethylene naphthalene, <NUM>-methylstyrene, <NUM>,<NUM>-diethylstyrene, <NUM>-propylstyrene, <NUM>,<NUM>,<NUM>-trimethylstyrene, <NUM>-dodecylstyrene, <NUM>-methyl-<NUM>-n-hexylstyrene, <NUM>-phenylstyrene, <NUM>-ethyl-<NUM>-benzylstyrene, <NUM>,<NUM>-diphenylstyrene, <NUM>,<NUM>,<NUM>,<NUM>-tetraethyl styrene, <NUM>-ethyl-<NUM>-vinylnaphthalene, <NUM>-isopropyl-<NUM>-vinylnaphthalene, <NUM>-cyclohexyl-<NUM>-vinylnaphthalene, <NUM>-dodecyl-<NUM>-vinylnaphthalene, α-methyl styrene, or a combination thereof.