CN107011546A - A kind of new modified shoddy/natural rubber vulcanized rubber and preparation method thereof - Google Patents
A kind of new modified shoddy/natural rubber vulcanized rubber and preparation method thereof Download PDFInfo
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- CN107011546A CN107011546A CN201610054645.2A CN201610054645A CN107011546A CN 107011546 A CN107011546 A CN 107011546A CN 201610054645 A CN201610054645 A CN 201610054645A CN 107011546 A CN107011546 A CN 107011546A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
- C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L17/00—Compositions of reclaimed rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2317/00—Characterised by the use of reclaimed rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention provides a kind of new modified shoddy/natural rubber intermingling material and preparation method thereof.This method obtains modified waste rubber powder/natural rubber vulcanized rubber using two sections of mill methods.Vulcanizate has higher tensile strength and good resistance to ag(e)ing, and especially when modified waste rubber powder loading is 50 parts, the tensile strength of the vulcanizate of preparation is suitable with pure natural rubber.Invention significantly improves the added value of shoddy, and processing technology is simple, and production cost is low, has broad application prospects.
Description
Technical field：The present invention relates to the shoddy that graft modification is prepared by desulphurization reaction, and it is related to a kind of modified waste rubber powder/natural rubber vulcanized rubber and preparation method thereof.
Background technology：With developing rapidly for auto industry, the quantity of damaged tire increases year by year with the rising of tire used amount, but junked tire not only causes the waste of resource, and brings serious pollution to our living environment.China's damaged tire quantity in 2013 is up to 2.99 hundred million, and every year still with 5% increasing rate, and China has become one of maximum country of world's scrap rubber yield.And China is about 70% to be to rely on import in the serious deficient country of rubber resource, the rubber sources consumed every year again.Solution is hardly resulted in again in this present situation short time, therefore, the recycling of scrap rubber is just particularly important.
Scrap rubber is crushed the major way that shoddy has become scrap rubber cycling and reutilization is made.But shoddy is that surface is inert, elastic powder body material with three-dimensional net structure, it is difficult to occur diffusion, infiltration with matrix material and chemically reacts, cause the interface compatibility of shoddy and matrix material poor, and with the increase of rubber powder incorporation, the mechanical property of intermingling material can be had a strong impact on.Therefore, shoddy is that surface modification is carried out to it using key, improves the interface binding power of shoddy and matrix material, so as to prepare the composite with compared with high added value, rather than rubber powder simple recycling.
Shoddy surface, which is modified, mainly two methods, and a kind of is the three-dimensional net structure for destroying shoddy, including：Microwave, ultrasonic wave, microorganism, mechanochemical method etc.；Another is that the modified method such as coating, grafting is carried out to shoddy surface, and this method does not destroy the network structure of shoddy.
The present invention makes full use of the advantage of above two method of modifying, by synthetic macromolecule surfactant, the graft modification on shoddy surface is completed during occurring desulphurization reaction with shoddy, this method also finds no reported in literature at present.Active long-chain molecule on the modified waste rubber powder surface grafting of preparation, improve its interface adhesion with natural rubber, so that modified waste rubber powder/the natural rubber prepared has good combination property, improve the added value of shoddy, alleviate me and cross the situation of rubber shortage of resources, reduce the dependence to rubber sources import, the environmental pollution that reduction scrap rubber is brought.
The content of the invention：The invention mainly includes providing, a kind of production cost is low, new modified shoddy/natural rubber vulcanized rubber of high comprehensive performance and preparation method thereof.
The present invention is modified using homemade macromolecular activator to shoddy, the more long-chain molecule to rubber with similar structure of active site on shoddy surface grafting, its interface compatibility with base rubber is improved, the ageing-resistant performance of natural rubber can be obviously improved.
The technical solution adopted in the present invention is as follows：
Scheme one
Modified waste rubber powder preparation method：Load weighted shoddy and homemade molecules surfactant (preparation method is shown in CN103980446A) are added in three-necked flask, reaction is stirred at room temperature, with the hydrogen sulfide gas released during copper-bath absorbing reaction, after question response terminates, product is modified waste rubber powder.
Scheme two
A kind of preparation method of new modified shoddy/natural rubber vulcanized rubber：Natural rubber is added on a mill, after adding shoddy, zinc oxide, stearic acid, carbon black, accelerator, age resistor and sulphur after bag roller, prepares modified waste rubber powder/natural rubber Blend rubber；
By shoddy/natural rubber Blend rubber sulfidization molding on vulcanizing press, curing temperature is 140~150 DEG C, and cure time is 5~25 minutes, prepares modified waste rubber powder/natural rubber vulcanized rubber；
In terms of mass parts, the composition of raw materials of prepared modified waste rubber powder/natural rubber vulcanized rubber is：1~3 part of 100 parts of natural rubber, 50~200 parts of shoddy, 30~70 parts of carbon black, 0~1 part of hexamethylenetetramine, 3~5 parts of zinc oxide, 1~2 part of stearic acid, 0.3~1 part of Vulcanization accelerator TMTD, 1~3 part of altax, 0.5~2 part of antioxidant 4010NA and sulphur；
In order to further realize the present invention, used shoddy particle diameter is 40~80 mesh, and melting temperature is 30~50 DEG C, and mixing time is 10~20 minutes.
Scheme three
A kind of preparation method of new modified shoddy/natural rubber vulcanized rubber：Natural rubber is added on a mill, after adding modified waste rubber powder, zinc oxide, stearic acid, carbon black, accelerator, age resistor and sulphur after bag roller, prepares modified waste rubber powder/natural rubber Blend rubber；
By modified waste rubber powder/natural rubber Blend rubber sulfidization molding on vulcanizing press, curing temperature is 140~150 DEG C, and cure time is 5~25 minutes, prepares modified waste rubber powder/natural rubber vulcanized rubber；
In terms of mass parts, the composition of raw materials of prepared modified waste rubber powder/natural rubber vulcanized rubber is：1~3 part of 100 parts of natural rubber, 50~200 parts of modified waste rubber powder, 30~70 parts of carbon black, 0~1 part of hexamethylenetetramine, 3~5 parts of zinc oxide, 1~2 part of stearic acid, 0.3~1 part of Vulcanization accelerator TMTD, 1~3 part of altax, 0.5~2 part of antioxidant 4010NA and sulphur；
In order to further realize the present invention, used shoddy particle diameter is 40~80 mesh, and melting temperature is 30~50 DEG C, and mixing time is 10~20 minutes.
A kind of new modified shoddy/natural rubber vulcanized rubber is made by above-mentioned preparation method.
New modified shoddy/natural rubber vulcanized rubber prepared by the present invention has high tensile strength and good ageing-resistant performance.The present invention is blended using modified waste rubber powder with natural rubber, and processing technology is simple, and production cost is low, it is possible to achieve the recycling of resource.
The present invention has advantages below：
1) present invention has expanded the approach of scrap rubber resources circulation recycling, fully combine the advantage of desulfurization modification and graft modification, self-control high molecular weight surface activator is grafted to shoddy surface by the desulphurization reaction with shoddy, the physical and chemical performance on shoddy surface is improved, its surface inactive shortcoming is overcome.This method the advantage is that the sulphur sulfide linkage in selectively destruction cross-linked network, do not interrupt the carbon-carbon bond of rubber backbone in shoddy compared with conventional sulfur method；Compared with conventional graft modification method, its is simple to operate, and grafting rate is not influenceed by factors such as initiators, and reaction is carried out at room temperature.
2) long-chain molecule similar to rubber structure on modified waste rubber powder surface grafting prepared by the present invention, its long-chain molecule can be together with natural rubber molecular entanglement, interface binding power between raising modified waste rubber powder and natural rubber matrix is (as shown in Figure 1B, interfacial adhesion it is more close, do not occur such as the clear gap in Figure 1A), so as to significantly improve the mechanical property of modified waste rubber powder/natural rubber vulcanized rubber.
3) self-crosslinking can occur at high temperature for the macromolecular surface activator employed in the present invention, further improve the crosslink density of modified waste rubber powder/natural rubber vulcanized rubber, improve the resistance to ag(e)ing of material, overcome the shortcoming of natural rubber resistance to ag(e)ing difference.Therefore, new modified shoddy/natural rubber vulcanized rubber excellent combination property, is with a wide range of applications.
4) hexamethylenetetramine is added in modified waste rubber powder/natural rubber in the present invention, further increase the crosslink density of vulcanizate, because the heated formaldehyde decomposited of hexamethylenetetramine can react with unreacted active site in sizing material, form methyl key bridge, so as to improve intermingling material tensile strength, and obvious change does not occur for interface, as shown in Figure 1 C.
Brief description of the drawings
Figure 1A is unmodified shoddy/natural rubber intermingling material scanning electron microscope (SEM) photograph
Figure 1B is modified waste rubber powder/natural rubber intermingling material scanning electron microscope (SEM) photograph
Fig. 1 C are the modified waste rubber powder/natural rubber intermingling material scanning electron microscope (SEM) photographs for adding hexamethylenetetramine
Embodiment
The following examples are that the present invention is further illustrated, are not limitation the scope of the present invention.
Unless otherwise stated, all experimental raw numbers are all mass fractions in embodiment.
Natural rubber (SCRWF) used in embodiment, manufacturer is hainan rubber limited company.
Shoddy mesh number used in embodiment is 40~80 mesh, is provided by Suzhou Zhong Jiao resource regenerations Co., Ltd.
Surfactant used in embodiment is the high-molecular compound (synthetic method is shown in CN103980446A) of oneself synthesis, with acidity.
The raw material of other in embodiment is rubber industry auxiliary agent.
Embodiment 1
In the formula of embodiment 1, first natural rubber is plasticated on a mill, then zinc oxide, stearic acid and carbon black N234 are added, after carbon black mixing is uniform, a period of time is placed, then carry out mill, sequentially add accelerator and age resistor, sulphur is eventually adding, melting temperature control is at 30~50 DEG C, and mixing time is 10~15 minutes.Blend is finally placed in sulfidization molding on vulcanizing press, curing temperature is 150 DEG C, and cure time is 10 minutes.The performance of prepared natural rubber elastomeric compound is shown in Table 1.
Embodiment 2
In the formula of embodiment 2, after after natural rubber bag roller, sequentially add shoddy, zinc oxide, stearic acid and carbon black N234, after carbon black mixing is uniform, a period of time is placed, then carry out mill, sequentially add accelerator and age resistor, sulphur is eventually adding, melting temperature control is at 30~50 DEG C, and mixing time is 15 minutes.Blend is finally placed in sulfidization molding on vulcanizing press, curing temperature is 150 DEG C, and cure time is 10 minutes.The performance of prepared natural rubber elastomeric compound is shown in Table 1.
Embodiment 3
In the formula of embodiment 3, after after natural rubber bag roller, sequentially add shoddy, zinc oxide, stearic acid and carbon black N234, after carbon black mixing is uniform, a period of time is placed, then carry out mill, sequentially add accelerator and age resistor, sulphur is eventually adding, melting temperature control is at 30~50 DEG C, and mixing time is 15 minutes.Blend is finally placed in sulfidization molding on vulcanizing press, curing temperature is 150 DEG C, and cure time is 10 minutes.The performance of prepared natural rubber elastomeric compound is shown in Table 1.
Embodiment 4
In the formula of embodiment 4, after after natural rubber bag roller, sequentially add shoddy, zinc oxide, stearic acid and carbon black N234, after carbon black mixing is uniform, a period of time is placed, then carry out mill, sequentially add accelerator and age resistor, sulphur is eventually adding, melting temperature control is at 30~50 DEG C, and mixing time is 15 minutes.Blend is finally placed in sulfidization molding on vulcanizing press, curing temperature is 150 DEG C, and cure time is 10 minutes.The performance of prepared natural rubber elastomeric compound is shown in Table 1.
Embodiment 5
In the formula of embodiment 5, in terms of mass parts, first the shoddy of 50 part of 80 mesh is mixed with 2.5 parts of macromolecular surface activators, reaction is stirred at room temperature, with the hydrogen sulfide gas released during copper-bath absorbing reaction, after question response terminates, product is modified waste rubber powder.
First natural rubber is plasticated on a mill, then modified waste rubber powder, zinc oxide, stearic acid and carbon black N234 are sequentially added, after carbon black mixing is uniform, place a period of time, mill is carried out again, accelerator and age resistor is sequentially added, and is eventually adding sulphur, melting temperature control is at 30~50 DEG C, and mixing time is 15 minutes.Blend is finally placed in sulfidization molding on vulcanizing press, curing temperature is 150 DEG C, and cure time is 10 minutes.The performance of prepared natural rubber elastomeric compound is shown in Table 1.
Embodiment 6
In the formula of embodiment 6, in terms of mass parts, first the shoddy of 100 part of 80 mesh is mixed with 5 parts of macromolecular surface activators, reaction is stirred at room temperature, with the hydrogen sulfide gas released during copper-bath absorbing reaction, after question response terminates, product is modified waste rubber powder.
First natural rubber is plasticated on a mill, then modified waste rubber powder, zinc oxide, stearic acid and carbon black N234 are sequentially added, after carbon black mixing is uniform, place a period of time, mill is carried out again, accelerator and age resistor is sequentially added, and is eventually adding sulphur, melting temperature control is at 30~50 DEG C, and mixing time is 15 minutes.Blend is finally placed in sulfidization molding on vulcanizing press, curing temperature is 150 DEG C, and cure time is 10 minutes.The performance of prepared natural rubber elastomeric compound is shown in Table 1.
Embodiment 7
In the formula of embodiment 7, in terms of mass parts, first the shoddy of 150 part of 80 mesh is mixed with 7.5 parts of macromolecular surface activators, reaction is stirred at room temperature, with the hydrogen sulfide gas released during copper-bath absorbing reaction, after question response terminates, product is modified waste rubber powder.
First natural rubber is plasticated on a mill, then modified waste rubber powder, zinc oxide, stearic acid and carbon black N234 are sequentially added, after carbon black mixing is uniform, place a period of time, mill is carried out again, accelerator and age resistor is sequentially added, and is eventually adding sulphur, melting temperature control is at 30~50 DEG C, and mixing time is 15 minutes.Blend is finally placed in sulfidization molding on vulcanizing press, curing temperature is 150 DEG C, and cure time is 10 minutes.The performance of prepared natural rubber elastomeric compound is shown in Table 1.
Embodiment 8
In the formula of embodiment 8, in terms of mass parts, first the shoddy of 50 part of 80 mesh is mixed with 2.5 parts of macromolecular surface activators, reaction is stirred at room temperature, with the hydrogen sulfide gas released during copper-bath absorbing reaction, after question response terminates, product is modified waste rubber powder.Then hexamethylenetetramine is well mixed with modified waste rubber powder.
First natural rubber is plasticated on a mill, then modified waste rubber powder, zinc oxide, stearic acid and the carbon black N234 of addition hexamethylenetetramine are sequentially added, after carbon black mixing is uniform, place a period of time, mill is carried out again, accelerator and age resistor is sequentially added, and is eventually adding sulphur, melting temperature control is at 30~50 DEG C, and mixing time is 15 minutes.Blend is finally placed in sulfidization molding on vulcanizing press, curing temperature is 150 DEG C, and cure time is 10 minutes.The performance of prepared natural rubber elastomeric compound is shown in Table 1.
Embodiment 9
In the formula of embodiment 9, in terms of mass parts, first the shoddy of 100 part of 80 mesh is mixed with 5 parts of macromolecular surface activators, reaction is stirred at room temperature, with the hydrogen sulfide gas released during copper-bath absorbing reaction, after question response terminates, product is modified waste rubber powder.Then hexamethylenetetramine is well mixed with modified waste rubber powder.
First natural rubber is plasticated on a mill, then modified waste rubber powder, zinc oxide, stearic acid and the carbon black N234 of addition hexamethylenetetramine are sequentially added, after carbon black mixing is uniform, place a period of time, mill is carried out again, accelerator and age resistor is sequentially added, and is eventually adding sulphur, melting temperature control is at 30~50 DEG C, and mixing time is 15 minutes.Blend is finally placed in sulfidization molding on vulcanizing press, curing temperature is 150 DEG C, and cure time is 10 minutes.The performance of prepared natural rubber elastomeric compound is shown in Table 1.
Embodiment 10
In the formula of embodiment 9, in terms of mass parts, first the shoddy of 150 part of 80 mesh is mixed with 7.5 parts of macromolecular surface activators, reaction is stirred at room temperature, with the hydrogen sulfide gas released during copper-bath absorbing reaction, after question response terminates, product is modified waste rubber powder.Then hexamethylenetetramine is well mixed with modified waste rubber powder.
First natural rubber is plasticated on a mill, then modified waste rubber powder, zinc oxide, stearic acid and the carbon black N234 of addition hexamethylenetetramine are sequentially added, after carbon black mixing is uniform, place a period of time, mill is carried out again, accelerator and age resistor is sequentially added, and is eventually adding sulphur, melting temperature control is at 30~50 DEG C, and mixing time is 15 minutes.Blend is finally placed in sulfidization molding on vulcanizing press, curing temperature is 150 DEG C, and cure time is 10 minutes.The performance of prepared natural rubber elastomeric compound is shown in Table 1.
The new modified shoddy of table 1/natural rubber intermingling material formula and its performance
Senile experiment presses standard GB/T 3512-2001 in above-described embodiment 1-10, and sample is carried out into hot air aging and heat-resistant experiment.Aging condition is 100 DEG C × 24h.
Tensile strength and elongation at break measurement are determined according to standard GB/T 528-2009 in above-described embodiment 1-10, and the length of tensile bars is 75mm, and gauge length is 20mm, and the rate of extension of puller system is 500mm/min.Every group of sample at least measures 3 samples, averages as test value.
Standard GB/T 23651-2009 are pressed in the test of Shao Er A type hardness testers in above-described embodiment 1-10, and the hardness of sample is measured using TH200 types durometer.
The mechanical property of modified waste rubber powder/natural rubber intermingling material prepared by above-described embodiment is as shown in table 1, as it can be seen from table 1 the tensile strength and elongation at break of (1) modified waste rubber powder/natural rubber intermingling material are substantially better than unmodified shoddy/natural rubber intermingling material；(2) in modified waste rubber powder/natural rubber intermingling material formula after addition hexamethylenetetramine, the tensile strength of intermingling material is further improved；Especially when modified waste rubber powder loading is 50 parts, now the tensile strength of intermingling material is substantially suitable with the tensile strength of pure natural rubber；(3) intermingling material is after aging, and its tensile strength is all higher than the tensile strength after pure natural rubber aging；(4) intermingling material is after aging, and the tensile strength of modified waste rubber powder/natural rubber intermingling material is higher than unmodified shoddy/natural rubber intermingling material.In summary, modified waste rubber powder has higher tensile strength and good ageing-resistant performance.
Claims (5)
1. a kind of preparation method of new modified shoddy/natural rubber Blend rubber, it is characterised in that prepare modified waste rubber powder first；Then modified waste rubber powder/natural rubber Blend rubber is prepared using two sections of mill methods；Again by modified waste rubber powder/natural rubber Blend rubber sulfidization molding on vulcanizing press, curing temperature is 140~150 DEG C, and cure time is 5~25 minutes, prepares modified waste rubber powder/natural rubber vulcanized rubber；
In terms of mass parts, the composition of raw materials of prepared modified waste rubber powder/natural rubber vulcanized rubber is：1~3 part of 100 parts of natural rubber, 50~200 parts of modified waste rubber powder, 30~70 parts of carbon black, 0~1 part of hexamethylenetetramine, 3~5 parts of zinc oxide, 1~2 part of stearic acid, 0.3~1 part of Vulcanization accelerator TMTD, 1~3 part of altax, 0.5~2 part of antioxidant 4010NA and sulphur.
2. the preparation method of modified waste rubber powder according to claim 1/natural rubber intermingling material, it is characterised in that modified waste rubber powder preparation method used：The surfactant for the HMW that the method being related in load weighted shoddy and Chinese patent application publication number CN103980446A is synthesized is added in three-necked flask, reaction is stirred at room temperature, with the hydrogen sulfide gas released during copper-bath absorbing reaction, after question response terminates, product is modified waste rubber powder.
3. the preparation method of modified waste rubber powder according to claim 1/natural rubber intermingling material, it is characterised in that prepared modified waste rubber powder is a kind of graft modification shoddy prepared by desulphurization reaction.
4. the preparation method of modified waste rubber powder according to claim 1/natural rubber intermingling material, it is characterised in that used shoddy particle diameter is 40~80 mesh.
5. a kind of new modified shoddy/natural rubber vulcanized rubber, it is characterised in that it is prepared as described in claim 1-5, with high tensile strength and good resistance to ag(e)ing.
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| CN109957156A (en) * | 2019-04-15 | 2019-07-02 | 莆田学院 | A kind of sole for recycling rubber powder filled rubber material and preparation method thereof and being prepared by the material |
| RU2730857C1 (en) * | 2020-04-20 | 2020-08-26 | Андрей Леонидович Воробьев | Low-temperature method of producing modified rubber crumbs |
| CN111675835A (en) * | 2020-06-30 | 2020-09-18 | 重庆凌峰橡塑制品股份有限公司 | Formula of high-adhesion natural rubber |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109456514A (en) * | 2018-10-17 | 2019-03-12 | 沈阳化工大学 | A kind of natural rubber material and preparation method thereof containing natural rubber powder |
| CN109957156A (en) * | 2019-04-15 | 2019-07-02 | 莆田学院 | A kind of sole for recycling rubber powder filled rubber material and preparation method thereof and being prepared by the material |
| RU2730857C1 (en) * | 2020-04-20 | 2020-08-26 | Андрей Леонидович Воробьев | Low-temperature method of producing modified rubber crumbs |
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| CN111675835B (en) * | 2020-06-30 | 2023-01-31 | 重庆凌峰橡塑制品股份有限公司 | Formula of high-adhesion natural rubber |
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Application publication date: 20170804 |