CN112778774B - Environment-friendly plasticizer and preparation method and application thereof - Google Patents
Environment-friendly plasticizer and preparation method and application thereof Download PDFInfo
- Publication number
- CN112778774B CN112778774B CN201911068642.4A CN201911068642A CN112778774B CN 112778774 B CN112778774 B CN 112778774B CN 201911068642 A CN201911068642 A CN 201911068642A CN 112778774 B CN112778774 B CN 112778774B
- Authority
- CN
- China
- Prior art keywords
- parts
- rubber
- plasticizer
- soybean oil
- environment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/06—Sulfur
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to an environment-friendly plasticizer, a preparation method and application thereof, wherein the plasticizer is sulfur-modified soybean oil, and the weight ratio of the soybean oil to sulfur is 100: (1-30), wherein soybean oil and sulfur are mixed, and then the mixture is treated at the temperature of 100-300 ℃ to obtain the environment-friendly plasticizer. The environment-friendly plasticizer can be used for tread rubber, so that the production cost of rubber is reduced, and the processing performance and vulcanized rubber performance of rubber are improved; the use of petroleum raw materials which belong to non-renewable resources in the production process of rubber is reduced, and resources are saved; VOC emission in the rubber production process and the rubber product use process is reduced, and the environment is protected; the double bond content originally contained in the soybean oil is reduced, and the mechanical property of the rubber product is improved.
Description
Technical Field
The invention belongs to the field of high polymer materials, particularly relates to an environment-friendly plasticizer, and particularly relates to an environment-friendly plasticizer.
Background
In the production of tread rubber at present, environment-friendly plasticizers are mainly classified into TDAE, heavy naphthenic oil (HNAP), Residual Aromatic Extract (RAE), light oil pumping (MES) and blending aromatic oil according to the production process and the characteristics of products. TDAE is generally prepared by using DAE as a raw material and refining the DAE by a solvent or hydrogenation, and the aromatic carbon rate (CA) of the TDAE is more than 20 percent; heavy naphthenic oil (HNAP) is generally prepared by using naphthenic distillate oil as a raw material and performing shallow solvent refining or hydrofining, and has high cyclic carbon rate (CN), makes up for the defect of small CA, so that the heavy naphthenic oil has good compatibility with rubber; the residual aromatic hydrocarbon extract (RAE) is prepared by using vacuum residue as a raw material and refining the raw material by using a solvent twice, has high kinematic viscosity and is solid at normal temperature; the blended aromatic oil is prepared by a special blending formula, and the CA of the blended aromatic oil is large.
The plasticizer raw materials are all from petroleum, are non-renewable resources, and generate a large amount of VOC gas emission during processing vulcanization and use of rubber products.
Disclosure of Invention
In order to overcome the problems in the prior art, the inventor conducts a great deal of research, obtains an environment-friendly plasticizer by taking soybean oil and sulfur as raw materials, reduces the production cost of rubber, improves the processing performance of rubber materials and the performance of vulcanized rubber, reduces the use of petroleum raw materials which belong to nonrenewable resources in the production process of the rubber, saves resources, reduces the VOC emission in the production process of the rubber and the use process of rubber products, and protects the environment.
One of the purposes of the invention is to provide an environment-friendly plasticizer which is sulfur-modified soybean oil, wherein the weight ratio of the soybean oil to sulfur is 100: (1-30).
In the invention, the soybean oil is used as the main raw material, so that the production cost of rubber can be effectively reduced, the processing performance of rubber materials and the performance of vulcanized rubber can be improved, and the main raw material is derived from vegetable oil (soybean oil) and belongs to renewable resources. Meanwhile, the soybean oil does not contain aromatic rings, so that the trend of the current international environment-friendly plasticizer is met, the flash point of the soybean oil is higher than that of the current common petroleum environment-friendly plasticizer, less VOC (volatile organic compounds) emission is generated in production, and the soybean oil is more environment-friendly.
In a preferred embodiment, the weight ratio of soybean oil to sulfur is 100: (2-15), preferably 100: (3-10).
Wherein, the soybean oil contains excessive double bonds, and the mechanical property of the rubber product is reduced only by taking the soybean oil as the raw material as the plasticizer. In the invention, a small amount of sulfur is adopted to modify the soybean oil, so that the double bond content in the soybean oil can be reduced, and the mechanical property of the rubber product can be improved.
The second purpose of the invention is to provide a preparation method of the environment-friendly plasticizer, which comprises the following steps: and mixing the soybean oil and the sulfur, and then treating at 100-300 ℃ to obtain the environment-friendly plasticizer.
In a preferred embodiment, the ratio of soybean oil to sulfur is 100: (1 to 30), preferably 100: (3-15), more preferably 100: (5-10).
In a preferred embodiment, the treatment is carried out at 120 to 250 ℃, preferably at 140 to 200 ℃.
The invention also aims to provide tread rubber which is prepared from the following raw materials in parts by weight:
wherein the plasticizer is the plasticizer for one purpose of the invention or the plasticizer obtained by the preparation method for the other purpose of the invention.
In a preferred embodiment, the raw rubber is selected from one or more of raw natural rubber, raw styrene-butadiene rubber and raw butadiene rubber.
In a preferred embodiment, the reinforcing aid comprises carbon black, and preferably further comprises white carbon black and a coupling agent.
Wherein the coupling agent is selected from silicon 69 and/or (triethoxysilylpropyl) disulfide [ TESPB ].
In a further preferred embodiment, the reinforcing aid is used in the following amounts by weight, based on 100 parts by weight of raw rubber:
20-60 parts of carbon black, preferably 30-50 parts;
0-50 parts of white carbon black, preferably 20-40 parts;
0-6 parts of coupling agent, preferably 1-4 parts.
In a preferred embodiment, the processing aid comprises zinc oxide and stearic acid.
In a further preferred embodiment, the processing aid further comprises an anti-aging agent and microcrystalline paraffin.
In a further preferred embodiment, the processing aid is used in the following amounts by weight, based on 100 parts by weight of raw rubber:
the fourth purpose of the invention is to provide a preparation method of the tread rubber of the third purpose of the invention, which comprises the following steps:
step 1, plasticating raw rubber;
step 3, carrying out banburying treatment on the raw rubber plasticated in the step 1, adding the raw rubber into the filling system in the step 2 for banburying treatment for 2-5 times, preferably carrying out banburying treatment after each addition, and more preferably carrying out banburying treatment in a banbury mixer;
and 4, heating to carry out banburying treatment, then adding a vulcanizing agent and an accelerator to carry out open mixing treatment, preferably in an open mixer, and obtaining the tread rubber.
In a preferred embodiment, in step 1, when two or more raw rubbers are used, after the raw rubbers are plasticated, the plasticated raw rubbers are mixed, and then subjected to open mixing, preferably 3 to 5 passes on a roll mill.
In a preferred embodiment, in step 3, the banburying treatment is performed for 0.5 to 10 minutes, preferably 1 to 5 minutes, and more preferably 1 to 2 minutes.
In a preferred embodiment, in the step 4, the temperature is raised to 120 to 180 ℃ for banburying treatment for 2 to 20 minutes.
In a further preferred embodiment, in the step 4, the temperature is raised to 140 to 160 ℃ for banburying treatment for 6 to 10 minutes.
Compared with the prior art, the invention has the following beneficial effects:
(1) the environment-friendly plasticizer reduces the production cost of rubber, and improves the processing performance of rubber and the performance of vulcanized rubber;
(2) the environment-friendly plasticizer reduces the use of petroleum raw materials which belong to non-renewable resources in the production process of rubber, and saves resources;
(3) the environment-friendly plasticizer reduces VOC emission in the rubber production process and the rubber product use process, and protects the environment;
(4) the environment-friendly plasticizer reduces the double bond content originally contained in the soybean oil and improves the mechanical property of rubber products.
Drawings
FIG. 1 shows vulcanization performance curves of tread rubbers obtained in examples 6 to 8 and comparative examples 4 to 5;
FIG. 2 shows stress-strain curves of tread rubbers obtained in examples 6 to 8 and comparative examples 4 to 5;
FIG. 3 is a graph showing vulcanization performance curves of tread rubbers obtained in examples 9 to 12;
FIG. 4 shows stress-strain curves of tread rubbers obtained in examples 9 to 12;
FIG. 5 is a graph showing vulcanization performance curves of tread rubbers obtained in examples 13 to 14;
FIG. 6 is a graph showing stress-strain curves of tread rubbers obtained in examples 13 to 14;
fig. 7 shows stress-strain curves of the tread rubbers obtained in example 8 and comparative example 3.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The starting materials used in the examples and comparative examples are either commercially available or prepared by themselves by methods disclosed in the prior art.
EXAMPLE 1 preparation of environmentally friendly plasticizer
Adding soybean oil and sulfur into a three-neck flask according to the weight ratio of 100:3, stirring and heating in an oil bath kettle, starting timing after the temperature rises to 160 ℃, continuously reacting for one hour, stopping heating, and waiting for the product to be cooled to obtain the environment-friendly plasticizer.
Example 2 preparation of Environment-friendly plasticizer
Adding soybean oil and sulfur into a three-neck flask according to the ratio of 100:6, stirring and heating in an oil bath kettle, starting timing after the temperature rises to 160 ℃, continuously reacting for one hour, stopping heating, and waiting for the product to be cooled to obtain the environment-friendly plasticizer.
EXAMPLE 3 preparation of Environment-friendly plasticizer
Adding soybean oil and sulfur into a three-neck flask according to the ratio of 100:9, stirring and heating in an oil bath kettle, starting timing after the temperature rises to 160 ℃, continuously reacting for one hour, stopping heating, and waiting for the product to be cooled to obtain the environment-friendly plasticizer.
Example 4 preparation of Environment-friendly plasticizer
Adding soybean oil and sulfur into a three-neck flask according to the ratio of 100:2, stirring and heating in an oil bath kettle, starting timing after the temperature rises to 160 ℃, continuously reacting for one hour, stopping heating, and waiting for the product to be cooled to obtain the environment-friendly plasticizer.
EXAMPLE 5 preparation of Environment-friendly plasticizer
Adding soybean oil and sulfur into a three-neck flask according to the ratio of 100:15, stirring and heating in an oil bath kettle, starting timing after the temperature rises to 160 ℃, continuously reacting for one hour, stopping heating, and waiting for the product to be cooled to obtain the environment-friendly plasticizer.
Comparative example 1
The procedure of example 1 was repeated except that sulfur was not added.
Comparative example 2
Adding soybean oil and vulcanizing agent DCP into a three-neck flask according to the weight ratio of 100:6, stirring and heating in an oil bath kettle, starting timing after the temperature rises to 160 ℃, continuously reacting for one hour, stopping heating, and waiting for the product to be cooled to obtain a pretreated product;
and placing the pretreated product in ethanol, separating liquid after shaking, reserving an oil layer, repeatedly washing with alcohol for several times, and performing rotary evaporation at 50-80 ℃ until the liquid is not turbid.
In comparative example 2, soybean oil was modified using a vulcanizing agent DCP which polymerizes soybean oil without consuming double bonds in soybean oil, unlike sulfur which was used in the example in which soybean oil was modified by consuming double bonds in soybean oil. In addition, when the vulcanizing agent DCP is used for modifying the soybean oil to prepare the plasticizer, the generated micromolecule alcohol by-products have certain influence on the mechanical property, and the micromolecule by-products need to be removed by alcohol washing, while the sulfur modification of the embodiment does not need post-treatment such as alcohol washing.
Preparation of tread rubber of examples 6 to 18 and comparative examples 3 to 5
(1) Plasticating raw rubber (natural rubber NR, styrene butadiene rubber SBR, and butadiene rubber BR, green natural rubber formula), mixing 3 raw rubbers, and rolling for 4 times on an open mill;
(2) mixing a plasticizer, carbon black, white carbon black and a coupling agent (silicon 69) to obtain a filling system;
(3) adding the raw rubber obtained in the step 1 into a Haake internal mixer for internal mixing for 2 minutes, then adding zinc oxide, stearic acid, an anti-aging agent and microcrystalline wax, stirring for 1 minute and half minutes in the Haake internal mixer, then adding 1/2 mixed filling system, stirring for one minute and half minutes, then adding 1/4 mixed filling system, stirring for one minute and half minutes, then adding 1/4 mixed filling system, and then stirring for one minute and half minutes.
(4) The haake mixer is heated to 150 ℃ for 8 minutes.
(5) Adding sulfur S and an accelerator into the open mill.
The specific raw material dosage is shown in tables 1-5, wherein the three raw rubbers SBR-1739, NR and BR which are adopted are oil-filled raw rubbers, the sum of the weight of the three raw rubbers is 107.5 parts, the pure weight of the raw rubber after oil removal is 100 parts, and the adopted environment-friendly oil is Hansheng V700 environment-friendly aromatic oil. In tables 1 to 5 below, one table is one preparation lot.
Table 1:
table 2:
table 3:
table 4:
table 5:
experimental example 1 vulcanization Performance test
1. The tread rubbers obtained in examples 6 to 8 and comparative examples 4 to 5 in Table 1 were subjected to a vulcanization performance test, and the results are shown in FIG. 1 and Table 6.
Table 6:
| MH(dNm) | ML(dNm) | MH-ML(dNm) | T90(min：sec) | |
| example 6 | 34.52 | 8.75 | 25.77 | 10:03 |
| Example 7 | 36.00 | 10.36 | 25.64 | 6:23 |
| Example 8 | 36.28 | 12.45 | 23.83 | 6:53 |
| Comparative example 4 | 29.86 | 9.92 | 19.94 | 6:07 |
| Comparative example 5 | 35.54 | 9.48 | 26.06 | 10:03 |
In Table 6, MHDenotes the highest torque, MLDenotes the lowest torque, MH-MLRepresenting the torque difference, and T90 representing the cure time.
As can be seen from table 6:
(1) compared with the comparative example 4(DCP modified soybean oil), the torque difference of the embodiment 7 (same plasticizer dosage) of the invention is obviously larger, which indicates that the crosslinking degree of the tread rubber is larger, and the analysis reason is that when the soybean oil is modified by the vulcanizing agent DCP, the principle of the modified soybean oil is different from that of sulfur, and the vulcanizing agent DCP polymerizes the soybean oil under the condition of not consuming double bonds in the soybean oil, so the DCP modified soybean oil still contains double bonds which consume the vulcanizing agent in the vulcanization treatment process of the tread rubber, so that the vulcanization effect is lower than the theoretical condition, and the crosslinking degree of the tread rubber is further reduced.
(2) Compared with the comparative example 5 (environment-friendly oil), the torque difference of the example 7 (with the same plasticizer dosage) is not very large, but T90 is obviously reduced, T90 represents vulcanization time, and the longer the vulcanization time is, the lower the energy consumption is, so the sulfur modified soybean oil (plasticizer) of the example of the invention has better effect compared with the environment-friendly oil disclosed in the prior art. Meanwhile, the environment-friendly oil is environment-friendly aromatic oil, is not environment-friendly in nature and harmful to human bodies, is made of petroleum, and is high in price.
2. The tread rubbers obtained in examples 9 to 12 in Table 2 were subjected to a vulcanization performance test, and the results are shown in FIG. 3.
3. The tread rubbers obtained in examples 13 to 14 in Table 3 were subjected to a vulcanization performance test, and the results are shown in FIG. 5.
Experimental example 2 mechanical Property test
1. The tread rubbers obtained in examples 6 to 8 and comparative examples 4 to 5 in Table 1 were subjected to mechanical property tests, and the results are shown in FIG. 2 and Table 7.
Table 7:
as can be seen from table 7:
(1) compared with comparative example 4(DCP modified soybean oil), the mechanical property parameters of example 7 (same plasticizer dosage) of the invention are all higher than those of comparative example 4, and it should be noted that the DCP modified soybean oil adopted in comparative example 4 needs repeated alcohol washing in the later stage of preparation to remove small molecular alcohol byproducts which have influence on the mechanical property of tread rubber, in this case, the mechanical property of comparative example 4 is inferior to that of the invention, and if the post-treatment is not carried out as in the preparation of sulfur modified soybean oil of the invention, the mechanical property of comparative example 4 is worse;
(2) the elongation at break is significantly higher for example 7 (same plasticizer level) compared to comparative example 5 (environmental oil), 30% higher than comparative example 5.
2. The mechanical properties of the tread rubbers obtained in examples 9 to 12 in Table 2 were measured, and the results are shown in FIG. 4.
3. The mechanical properties of the tread rubbers obtained in examples 13 to 14 in Table 3 were measured, and the results are shown in FIG. 6.
4. The tread rubber obtained from example 8 and comparative example 3 in table 4 was subjected to mechanical property test, and the result is shown in fig. 7, and it can be seen from fig. 7 that the mechanical property of example 8 is significantly better than that of comparative example 3.
5. The tread rubber obtained in the examples 15-18 in the table 5 is subjected to mechanical property test, and the result shows that the tread rubber also has excellent mechanical property.
Claims (14)
1. The environment-friendly plasticizer is sulfur-modified soybean oil, wherein the weight ratio of the soybean oil to sulfur is 100: (1-30), mixing the soybean oil and the sulfur, and then treating at 100-300 ℃ to obtain the environment-friendly plasticizer.
2. The environment-friendly plasticizer according to claim 1, wherein the weight ratio of soybean oil to sulfur is 100: (2-15).
3. The method for preparing the environment-friendly plasticizer according to claim 1 or 2, comprising: and mixing the soybean oil and the sulfur, and then treating at 100-300 ℃ to obtain the environment-friendly plasticizer.
4. The production method according to claim 3,
the dosage ratio of the soybean oil to the sulfur is 100: (1-30); and/or
The treatment is carried out at 120-250 ℃.
5. The production method according to claim 4,
the dosage ratio of the soybean oil to the sulfur is 100: (3-15); and/or
The treatment is carried out at 140-200 ℃.
6. Use of the plasticizer according to any one of claims 1 to 2 or the environmentally friendly plasticizer obtained by the preparation method according to any one of claims 3 to 5 in tread rubber.
7. The tread rubber is prepared from the following raw materials in parts by weight:
100 parts of raw rubber;
2-35 parts of a plasticizer;
60-90 parts of a reinforcing auxiliary agent;
3-20 parts of a processing aid;
0.5-5 parts of a vulcanizing agent;
1-8 parts of an accelerator;
wherein the plasticizer is the plasticizer according to any one of claims 1 to 2 or the plasticizer obtained by the preparation method according to any one of claims 3 to 5.
8. The tread band of claim 7,
the raw rubber is one or more selected from raw natural rubber, raw styrene-butadiene rubber and raw cis-butadiene rubber; and/or
The reinforcing aid comprises carbon black; and/or
The processing aid comprises zinc oxide and stearic acid.
9. The tread band of claim 8,
the reinforcing auxiliary agent further comprises white carbon black and a coupling agent, wherein the coupling agent is selected from silicon 69 and/or (triethoxysilylpropyl) disulfide; and/or
The processing aid further comprises an anti-aging agent and microcrystalline paraffin.
10. The tread rubber according to claim 9, wherein the reinforcing aid is used in the following amounts by weight based on 100 parts by weight of the raw rubber:
20-60 parts of carbon black;
0-50 parts of white carbon black;
0-6 parts of a coupling agent.
11. The tread rubber according to claim 9, wherein the reinforcing aid is used in the following amounts by weight based on 100 parts by weight of the raw rubber:
30-50 parts of carbon black;
20-40 parts of white carbon black;
1-4 parts of a coupling agent.
12. The tread rubber according to any one of claims 9 to 11, wherein the processing aid is used in the following amounts by weight based on 100 parts by weight of the raw rubber:
1-8 parts of zinc oxide;
0.5-5 parts of stearic acid;
0-6 parts of an anti-aging agent;
0-6 parts of microcrystalline paraffin.
13. The tread rubber according to any one of claims 9 to 11, wherein the processing aid is used in the following amounts by weight based on 100 parts by weight of the raw rubber:
2-5 parts of zinc oxide;
1-3 parts of stearic acid;
1-4 parts of an anti-aging agent;
1-4 parts of microcrystalline paraffin.
14. A method for preparing the tread rubber of any one of claims 7 to 13, comprising the following steps:
step 1, plasticating raw rubber;
step 2, mixing the plasticizer and the reinforcing additive to obtain a filling system;
step 3, carrying out banburying treatment on the raw rubber plasticated in the step 1, and then adding the raw rubber into the filling system in the step 2 for banburying treatment for 2-5 times;
and 4, heating to carry out banburying treatment, and then adding a vulcanizing agent and an accelerator to carry out open mixing treatment to obtain the tread rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911068642.4A CN112778774B (en) | 2019-11-05 | 2019-11-05 | Environment-friendly plasticizer and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911068642.4A CN112778774B (en) | 2019-11-05 | 2019-11-05 | Environment-friendly plasticizer and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112778774A CN112778774A (en) | 2021-05-11 |
| CN112778774B true CN112778774B (en) | 2022-04-01 |
Family
ID=75748840
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911068642.4A Active CN112778774B (en) | 2019-11-05 | 2019-11-05 | Environment-friendly plasticizer and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112778774B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113736154A (en) * | 2021-07-27 | 2021-12-03 | 中策橡胶集团有限公司 | Application of modified rice bran oil in preparation of tire rubber material, rubber composition and tire |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1064295A (en) * | 1992-03-03 | 1992-09-09 | 曹群 | Roof waterproof leak stopping glue and preparation technology thereof |
| WO1996010601A1 (en) * | 1994-10-03 | 1996-04-11 | Cabot Corporation | Epdm compositions and process for producing same |
| CN102964641A (en) * | 2012-11-14 | 2013-03-13 | 沈阳化工大学 | Method for preparing rubber by using illegal cooking oil as plasticizer |
| CN103435870A (en) * | 2013-09-04 | 2013-12-11 | 沈阳化工大学 | Method for preparing rubber plasticizing agent by using waste cooking oil |
| CN103642079A (en) * | 2013-12-04 | 2014-03-19 | 沈阳化工大学 | Method for preparing rubber plasticizer by using illegal cooking oil |
| CN110092949A (en) * | 2018-06-07 | 2019-08-06 | 北京化工大学 | A kind of rubber composition and preparation method thereof containing hydrogenated vegetable oil |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050145312A1 (en) * | 2003-12-18 | 2005-07-07 | Herberger James R.Sr. | Tire component, and tire with such component, of rubber composition which contains combination of soybean oil and starch/plasticizer composite |
| WO2017123877A1 (en) * | 2016-01-15 | 2017-07-20 | Ndsu Research Foundation | Modified plant oils and rubber containing compositions containing the same |
-
2019
- 2019-11-05 CN CN201911068642.4A patent/CN112778774B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1064295A (en) * | 1992-03-03 | 1992-09-09 | 曹群 | Roof waterproof leak stopping glue and preparation technology thereof |
| WO1996010601A1 (en) * | 1994-10-03 | 1996-04-11 | Cabot Corporation | Epdm compositions and process for producing same |
| CN102964641A (en) * | 2012-11-14 | 2013-03-13 | 沈阳化工大学 | Method for preparing rubber by using illegal cooking oil as plasticizer |
| CN103435870A (en) * | 2013-09-04 | 2013-12-11 | 沈阳化工大学 | Method for preparing rubber plasticizing agent by using waste cooking oil |
| CN103642079A (en) * | 2013-12-04 | 2014-03-19 | 沈阳化工大学 | Method for preparing rubber plasticizer by using illegal cooking oil |
| CN110092949A (en) * | 2018-06-07 | 2019-08-06 | 北京化工大学 | A kind of rubber composition and preparation method thereof containing hydrogenated vegetable oil |
Non-Patent Citations (2)
| Title |
|---|
| EPDM crosslinking from bio-based vegetable oil and DielseAlder reactions;Cyrille Betron et al.;《Materials Chemistry and Physics》;20180223;第211卷;第361-374页 * |
| 大豆作为橡胶用环保生物基增塑剂的研究;韩悦;《中国优秀博硕士学位论文全文数据库（硕士） 工程科技Ι辑》;20121015(第10期);第2.1.2.2节、2.1.4节、2.1.2.3节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112778774A (en) | 2021-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2015109792A1 (en) | Method for improving elasticity and heat build-up performance of rubber product | |
| CN103435858B (en) | Tyre inner liner rubber and preparation method thereof | |
| EP3083276B1 (en) | A rubber compound for tyre production | |
| JP5567401B2 (en) | Tire rubber composition and heavy duty tire | |
| CN107641228B (en) | Use of organosilanes and rubber compositions and vulcanizates and process for their preparation | |
| CN112778774B (en) | Environment-friendly plasticizer and preparation method and application thereof | |
| CN109929160B (en) | Application of organosilane coupling agent, rubber composition, vulcanized rubber and preparation method and application thereof | |
| CN109929149B (en) | Rubber composition for tire side wall of tire, vulcanized rubber, and preparation method and application thereof | |
| CN109929159B (en) | Rubber composition and vulcanized rubber for tire tread as well as preparation method and application of rubber composition and vulcanized rubber | |
| CN103483706B (en) | A kind of halogenated butyl rubber air retaining wall rubber and calendering process thereof | |
| CN104530414B (en) | Preparation and application of silica white dispersing agent for rubber products | |
| KR20110071606A (en) | Rubber composition for tire and tire manufactured by using the same | |
| KR102332844B1 (en) | Rubber composition for tire tread and tire manufactured by using the same | |
| CN109485932B (en) | Rubber material | |
| CN101314651B (en) | Ozone resistant rubber composition | |
| JP2009013195A (en) | Rubber composition for breaker cushion and tire with breaker cushion using the same | |
| CN104961940B (en) | Four-season semisteel tire tread rubber material and preparation method and application thereof | |
| CN109929155B (en) | Rubber composition for shoe sole, vulcanized rubber, and preparation method and application thereof | |
| CN114437422B (en) | Rubber composition for shoe soles and application thereof, vulcanized rubber and preparation method and application thereof | |
| JP2017149864A (en) | Tire rubber composition and pneumatic tire | |
| CN106170513B (en) | Rubber compound with high impermeability to oxygen for tire components | |
| CN109929148B (en) | Rubber composition for tire side wall of tire, vulcanized rubber, and preparation method and application thereof | |
| KR101142551B1 (en) | Tread rubber composition for retreading bustruck tire and tire retreaded by using the same | |
| KR101884271B1 (en) | Rubber composition for shoes sole with improved fluidity | |
| KR101299945B1 (en) | Rubber composition for tire tread and tire manufactured by using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |