CN111607033B - Preparation method of polydiene rubber - Google Patents
Preparation method of polydiene rubber Download PDFInfo
- Publication number
- CN111607033B CN111607033B CN202010517911.7A CN202010517911A CN111607033B CN 111607033 B CN111607033 B CN 111607033B CN 202010517911 A CN202010517911 A CN 202010517911A CN 111607033 B CN111607033 B CN 111607033B
- Authority
- CN
- China
- Prior art keywords
- epoxy
- terminator
- preparation
- reaction
- polydiene rubber
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/06—Butadiene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/08—Isoprene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a preparation method of polydiene rubber, which comprises the following steps: a) carrying out polymerization reaction on diene monomers under an initiation system to obtain a glue solution; the initiation system adopts a Ziegler-Natta catalyst; b) adding an epoxy terminator into the glue solution obtained in the step a) to terminate the reaction, and drying to obtain the polydiene rubber; the epoxy terminator is selected from one or more of epoxy resin, epoxidized soybean oil and ethylene oxide. Compared with the prior art, the preparation method provided by the invention has the advantages that the specific terminator is used for the polymerization reaction of preparing the polydiene rubber by using a Ziegler-Natta system, the termination effect is good, and the function of an antioxidant can be realized, so that the activity of the residual catalyst in the product is stabilized, the stability of the product is improved, and the color generation of the product is improved.
Description
Technical Field
The invention relates to the technical field of synthetic rubber, in particular to a preparation method of polydiene rubber.
Background
The polydiene rubber belongs to synthetic rubber, and main industrial products comprise cis-1, 4-butadiene rubber (butadiene rubber), cis-1, 4-isoprene rubber, high vinyl butadiene rubber, low-intercrystalline isometry-high 1, 2-butadiene rubber, trans-1, 4-isoprene rubber, trans-butadiene rubber and the like, and the polydiene rubber has wide application in various fields.
Synthetic rubbers are generally solution polymerized, and are terminated with water or alcohol, which carry a large amount of water and alcohol when solvents and monomers are recovered in the production process; before the solvent and the monomer are put into use again, the water, alcohol and oxygen are required to be removed, the process is complicated and the energy consumption is increased. Meanwhile, the traditional water and alcohols only can play a role in terminating the reaction, and an antioxidant is required to be additionally added for prolonging the storage time of the diolefin rubber, wherein the most widely applied hindered phenol antioxidant is expensive, and the product cost is directly improved.
With the penetration of green chemistry and energy conservation and consumption reduction concepts in the chemical industry, the bulk polymerization gradually becomes the development direction of synthetic rubber, and has the advantages of no solvent, high viscosity, low energy consumption and the like. However, the addition of a terminator for the polymerization reaction and an antioxidant also troubles the bulk polymerization because the bulk polymerization does not take place without the use of a catalyst. On one hand, under high viscosity, the traditional terminator water and alcohol have poor solubility in glue solution, are difficult to disperse and poor in termination effect, are volatile when monomers are recovered, and enter a circulating system along with the monomers; on the other hand, the catalyst has more residues, the product is unstable, and the product is easy to have color, so that quality accidents occur, and great troubles are brought to production enterprises.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing a polydiene rubber, which has a good termination effect, and can improve the stability and color development of the product.
The invention provides a preparation method of polydiene rubber, which comprises the following steps:
a) carrying out polymerization reaction on diene monomers under an initiation system to obtain a glue solution; the initiation system adopts a Ziegler-Natta catalyst;
b) adding an epoxy terminator into the glue solution obtained in the step a) to terminate the reaction, and drying to obtain the polydiene rubber; the epoxy terminator is selected from one or more of epoxy resin, epoxidized soybean oil and ethylene oxide.
Preferably, the diene monomer in step a) is selected from butadiene and/or isoprene.
Preferably, the Ziegler-Natta catalyst of step a) comprises titanium tetrachloride and an aluminum alkyl.
Preferably, the amount of Ziegler-Natta catalyst added to the initiation system in step a) is between 0.1% and 1% of the mass of the diene monomer.
Preferably, the polymerization in step a) is carried out in bulk or solution.
Preferably, the temperature of the polymerization reaction in the step a) is 40-50 ℃ and the time is 10-40 min.
Preferably, the epoxy value of the epoxy terminator in the step b) is 2-10%.
Preferably, the adding amount of the epoxy terminator in the step b) is 0.5-10% of the mass of the glue solution.
Preferably, the mode of terminating the reaction in the step b) is stirring; the stirring time is 10 min-30 min.
Preferably, the drying process in step b) is specifically:
and cooling the product after the reaction is ended to 15-25 ℃, and then drying the product in vacuum at 40-80 ℃ for 1-5 h to constant weight to obtain the polydiene rubber.
The invention provides a preparation method of polydiene rubber, which comprises the following steps: a) carrying out polymerization reaction on diene monomers under an initiation system to obtain a glue solution; the initiation system adopts a Ziegler-Natta catalyst; b) adding an epoxy terminator into the glue solution obtained in the step a) to terminate the reaction, and drying to obtain the polydiene rubber; the epoxy terminator is selected from one or more of epoxy resin, epoxidized soybean oil and ethylene oxide. Compared with the prior art, the preparation method provided by the invention has the advantages that the specific terminator is used for the polymerization reaction of preparing the polydiene rubber by using a Ziegler-Natta system, the termination effect is good, and the function of an antioxidant can be realized, so that the activity of the residual catalyst in the product is stabilized, the stability of the product is improved, and the color generation of the product is improved.
In addition, the preparation method provided by the invention simplifies the synthesis process, reduces the energy consumption and the cost, and simultaneously, the used specific terminator is an environment-friendly terminator, is food-grade, nontoxic and high in safety performance, and meets the requirement of environmental protection.
Drawings
FIG. 1 shows the yellowing resistance of the polydiene rubber prepared by the preparation method provided in example 4 of the present invention;
FIG. 2 shows the yellowing resistance of the polydiene-based rubber prepared by the preparation method of comparative example 3;
FIG. 3 shows the yellowing resistance of the polydiene-based rubber prepared by the preparation method of comparative example 4;
FIG. 4 is a graph comparing results of thermal oxygen aging resistance of the polydiene-based rubbers prepared by the preparation methods provided in example 4 and comparative examples 3 to 4.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of polydiene rubber, which comprises the following steps:
a) carrying out polymerization reaction on diene monomers under an initiation system to obtain a glue solution; the initiation system adopts a Ziegler-Natta catalyst;
b) adding an epoxy terminator into the glue solution obtained in the step a) to terminate the reaction, and drying to obtain the polydiene rubber; the epoxy terminator is selected from one or more of epoxy resin, epoxidized soybean oil and ethylene oxide.
The invention firstly carries out polymerization reaction on diene monomer under an initiating system to obtain glue solution. In the present invention, the diene monomer is preferably selected from butadiene and/or isoprene, more preferably butadiene and isoprene. The source of the diene monomer in the present invention is not particularly limited, and commercially available products of the above-mentioned butadiene and isoprene known to those skilled in the art may be used.
In the present invention, the initiation system employs a Ziegler-Natta catalyst; said Ziegler-Natta catalyst preferably comprises titanium tetrachloride and an aluminum alkyl; wherein, the titanium tetrachloride is a main catalyst. In a preferred embodiment of the invention, the Ziegler-Natta catalyst is titanium tetrachloride and triisobutylaluminium. The present invention is not particularly limited with respect to the source of the Ziegler-Natta catalyst, and any commercially available product of the above titanium tetrachloride and aluminum alkyl known to those skilled in the art may be used.
In the present invention, the amount of Ziegler-Natta catalyst added to the initiation system is preferably 0.1% to 1% by mass of the diene monomer, more preferably 0.5% to 0.6% by mass of the diene monomer. In the preferred embodiment of the invention, the addition amount of the Ziegler-Natta catalyst in the initiation system is 0.5-0.6% of the mass of the diene monomer; on this basis, the ratio of the molar amounts of Ziegler-Natta catalyst to diene monomer in the initiating system is 1X 10-5。
In the present invention, the mode of the polymerization reaction is preferably bulk polymerization or solution polymerization, and more preferably bulk polymerization. The apparatus for the polymerization reaction is not particularly limited in the present invention, and a reaction vessel with a circulating water bath, which is well known to those skilled in the art, may be used.
In the present invention, the temperature of the polymerization reaction is preferably 40 to 50 ℃, more preferably 45 ℃; the time for the polymerization reaction is preferably 10 to 40min, more preferably 20 to 30 min.
After the glue solution is obtained, the epoxy terminator is added into the obtained glue solution to terminate the reaction, and the polydiene rubber is obtained after drying. In the present invention, the epoxy terminator is selected from one or more of epoxy resin, epoxidized soybean oil and ethylene oxide, and more preferably epoxidized soybean oil. The source of the epoxy terminator in the present invention is not particularly limited, and commercially available products of the above epoxy resin, epoxidized soybean oil and ethylene oxide, which are well known to those skilled in the art, may be used. In the present invention, the epoxy terminator contains an epoxy structure; the epoxy value of the epoxy terminator is preferably 2% to 10%, more preferably 6%.
In the invention, the addition amount of the epoxy terminator is preferably 0.5-10% of the mass of the glue solution, and more preferably 0.5-5% of the mass of the glue solution. In a preferred embodiment of the present invention, the addition amount of the epoxy terminating agent is 0.5% of the mass of the glue solution, and on the basis of the addition amount, the ratio (O/Ti) of the molar amount of the epoxy structure in the epoxy terminating agent to the molar amount of the main catalyst is 10: 1; in another preferred embodiment of the present invention, the addition amount of the epoxy terminating agent is 2.5% of the mass of the glue solution, and on the basis of the addition amount, the ratio (O/Ti) of the molar amount of the epoxy structure in the epoxy terminating agent to the molar amount of the main catalyst is 50: 1; in another preferred embodiment of the present invention, the addition amount of the epoxy terminating agent is 5% of the mass of the glue solution, and on the basis, the ratio (O/Ti) of the molar amount of the epoxy structure in the epoxy terminating agent to the molar amount of the main catalyst is 100: 1.
in the present invention, the manner of terminating the reaction is preferably stirring; the stirring time is preferably 10 to 30min, and more preferably 20 min.
The specific terminator can effectively terminate the polymerization of the diene monomer catalyzed by the Ziegler-Natta catalyst, has good termination effect, and plays roles in stabilizing the activity of the residual catalyst, improving the stability of the product and improving the color generation of the product; but also can solve the problems that the traditional terminator is easy to volatilize (the terminator is prevented from returning to a circulating system along with a solvent or a monomer), and has poor compatibility with glue solution; meanwhile, the double functions of the terminating agent and the antioxidant are taken into consideration, and the traditional terminating agent (such as water or ethanol) and the traditional antioxidant (such as phenol antioxidants 1135, 264 and the like) can be directly replaced, so that the synthesis process is simplified, the energy consumption is reduced, and the cost is reduced; and the used specific terminator is an environment-friendly terminator, is food-grade, nontoxic and high in safety performance, and meets the requirement of environmental protection.
In the present invention, the drying process preferably includes:
cooling the product after the reaction is stopped to 15-25 ℃, and then drying the product in vacuum at 40-80 ℃ for 1-5 h to constant weight to obtain the polydiene rubber;
more preferably:
and cooling the product after the reaction is ended to 20 ℃, and then drying the product in vacuum at the temperature of between 40 and 80 ℃ for 1 to 5 hours until the weight is constant to obtain the polydiene rubber.
The invention provides a preparation method of polydiene rubber, which comprises the following steps: a) carrying out polymerization reaction on diene monomers under an initiation system to obtain a glue solution; the initiation system adopts a Ziegler-Natta catalyst; b) adding an epoxy terminator into the glue solution obtained in the step a) to terminate the reaction, and drying to obtain the polydiene rubber; the epoxy terminator is selected from one or more of epoxy resin, epoxidized soybean oil and ethylene oxide. Compared with the prior art, the preparation method provided by the invention has the advantages that the specific terminator is used for the polymerization reaction of preparing the polydiene rubber by using a Ziegler-Natta system, the termination effect is good, and the function of an antioxidant can be realized, so that the activity of the residual catalyst in the product is stabilized, the heat resistance and the chemical stability of the product are greatly improved, and the color generation of the product is improved.
In addition, the preparation method provided by the invention simplifies the synthesis process, reduces the energy consumption and the cost, and simultaneously, the used specific terminator is an environment-friendly terminator, is food-grade, non-toxic, high in boiling point and high in safety performance, and meets the requirement of environmental protection.
To further illustrate the present invention, the following examples are provided for illustration.
Example 1
Heating the reaction kettle to 45 ℃ by using a circulating water bath, vacuumizing, and drying the reaction kettle; then taking butadiene and isoprene as monomers, adopting titanium tetrachloride and triisobutylaluminum as an initiation system (the addition amount is 0.5-0.6 percent of the mass of the monomers), and the molar weight ratio of the catalyst to the monomers in the initiation system is 1 x 10-5Carrying out bulk polymerization; monitoring the conversion rate in the kettle after the reaction starts, when the conversion rate reaches 10 percent, adding 0.5 weight percent of epoxidized soybean oil with the epoxy value of 6.0 percent into the glue solution, and continuously stirring for 20min to prepare a sample with the ratio (O/Ti) of the molar weight of the epoxy structure to the molar weight of the main catalyst being 10; cooling to about 20 ℃, deflating, opening the kettle, drying in a vacuum drying oven at 40-80 ℃ for 1-5 h to constant weight to obtain the polydiene rubber, and calculating the conversion rate.
According to calculation, the polydiene rubber prepared by the preparation method provided by the embodiment 1 of the invention has the compound conversion rate of 12.9 percent and the Mn of 26.1 multiplied by 104，Mw＝107.8×104，PDI＝3.9。
Example 2
The preparation process provided in example 1 was used, with the difference that: O/Ti of 50 (2.5 wt% of epoxidized soybean oil with an epoxy value of 6.0% was added to the glue solution); and obtaining the polydiene rubber, and calculating the conversion rate.
According to calculation, the polydiene rubber prepared by the preparation method provided by the embodiment 2 of the invention has the compound conversion rate of 12.2 percent and the Mn of 25.4 multiplied by 104，Mw＝96.5×104，PDI＝3.8。
Example 3
The preparation process provided in example 1 was used, with the difference that: O/Ti is 100 (5.0 wt% of epoxidized soybean oil with an epoxy value of 6.0% is added to the glue solution); and obtaining the polydiene rubber, and calculating the conversion rate.
According to calculation, the polydiene rubber prepared by the preparation method provided by the embodiment 3 of the invention has the compound conversion rate of 11.8 percent and the Mn of 25.2 multiplied by 104，Mw＝93.2×104，PDI＝3.7。
From examples 1 to 3, it is known that when epoxidized soybean oil is used as the epoxy terminator and the conversion rate is 10%, different amounts of the epoxy terminator are added, the polymerization conversion rate decreases and the molecular weight decreases with the increase of O/Ti, i.e., the terminating effect gradually increases with the increase of the amount of the epoxy terminator.
Example 4
Heating the reaction kettle to 45 ℃ by using a circulating water bath, vacuumizing, and drying the reaction kettle; then taking butadiene and isoprene as monomers, adopting titanium tetrachloride and triisobutylaluminum as an initiation system (the addition amount is 0.5-0.6 percent of the mass of the monomers), and the molar weight ratio of the catalyst to the monomers in the initiation system is 1 x 10-5Carrying out bulk polymerization; after 30min of polymerization, 0.5 wt% of epoxidized soybean oil with the epoxy value of 6.0% is added into the glue solution, and the mixture is continuously stirred for 20min to prepare a sample with the ratio (O/Ti) of the molar weight of the epoxy structure to the molar weight of the main catalyst being 10; and (3) cooling to about 20 ℃, deflating, opening the kettle, and drying in a vacuum drying oven at 40-80 ℃ for 1-5 h to constant weight to obtain the polydiene rubber.
After the polydiene type rubber prepared by the preparation method provided by the embodiment 4 is placed in an oven at 130 ℃ and subjected to thermo-oxidative aging for 4 hours, the color is observed to be basically unchanged, and the yellowing phenomenon does not occur (see figure 1); namely, the epoxidized soybean oil with the addition of 0.5 wt% is used as a terminator, and the prepared polydiene rubber has a good yellowing resistant effect.
Before and after the polydiene-based rubber prepared by the preparation method provided in example 4 was subjected to thermo-oxidative aging (thermo-oxidative aging in an oven at 130 ℃ for 4 hours), the modulus test was performed by using MDR under the test conditions of 140 ℃, 1.67Hz, 14% strain and a scan time of 120 min. The MDR result shows that the torque before the product is subjected to thermo-oxidative aging is stable to 4.7 dN.m; after thermo-oxidative ageing, the torque increases from 3.2 dN.m to 3.4 dN.m; namely, the epoxidized soybean oil with the addition of 0.5 weight percent is used as a terminator, and the prepared polydiene rubber has better thermal-oxidative aging resistance.
Comparative example 1
The preparation process provided in example 1 was used, with the difference that: adding 0.5 wt% of water into the glue solution; and obtaining the polydiene rubber, and calculating the conversion rate.
As a result of calculation, the polydiene-based rubber prepared by the preparation method provided in comparative example 1 had a stock conversion of 13.9%, and Mn of 27.3X 104，Mw＝109.2×104PDI is 4.0; compared with example 1, the termination effect is significantly deteriorated by using water as a terminator in an amount of 0.5 wt%.
Comparative example 2
The preparation method provided in comparative example 1 was used, with the only difference that: when the conversion rate reaches 10%, continuing to stir for 20min, and then adding 0.5 wt% of water into the glue solution; and obtaining the polydiene rubber, and calculating the conversion rate.
As a result of calculation, the polydiene-based rubber prepared by the preparation method provided in comparative example 2 had a stock conversion of 20.8%, and Mn of 35.0X 104，Mw＝147.0×104PDI is 4.2; compared with the comparative example 1, the addition of water as a terminating agent when the conversion rate reaches 10% does have a terminating effect on the polymerization reaction, and further shows that the terminating effect of epoxidized soybean oil is better than that of water.
Comparative example 3
The preparation process provided in example 4 was used, with the only difference that: adding 0.5 wt% of water into the glue solution; thus obtaining the polydiene rubber.
Placing the polydiene rubber prepared by the preparation method provided by the comparative example 3 in a 130 ℃ oven for thermo-oxidative aging for 4h, and observing the yellowing phenomenon of the color; that is, compared with example 4, the yellowing resistance of the prepared polydiene rubber is significantly reduced by using 0.5 wt% of water as a terminator.
Before and after the polydiene-based rubber prepared by the preparation method provided in comparative example 3 was subjected to thermo-oxidative aging (thermo-oxidative aging in an oven at 130 ℃ for 4 hours), modulus test was performed using MDR under test conditions of 140 ℃, 1.67Hz, 14% strain and scan time of 120 min. The MDR results show that the torque of the product before thermo-oxidative aging is reduced from 5.5dN m to 5.3dN m; after thermo-oxidative aging, the torque is reduced from 2.9dN m to 2.7dN m; that is, compared with example 4, the heat-resistant oxygen aging resistance of the polydiene type rubber prepared by using water as a terminator in an amount of 0.5 wt% was remarkably lowered.
Comparative example 4
The preparation process provided in example 4 was used, with the only difference that: adding 0.5 wt% of water and 1.0 wt% of anti-aging agent 264 into the glue solution; thus obtaining the polydiene rubber.
Placing the polydiene rubber prepared by the preparation method provided by the comparative example 4 in a 130 ℃ oven for thermo-oxidative aging for 4h, and observing the severe yellowing phenomenon of the color; compared with comparative example 3 and example 4, the prepared polydiene rubber has the worst yellowing resistance effect by adopting 0.5 wt% of water as a terminator and 1.0 wt% of antioxidant 264 as an antioxidant; the reason is that the epoxidized soybean oil is heated to open the ring, and the O free radical is exposed to be combined with Ti in the catalyst, so that the condition that the sample is yellowed due to the reaction of the Ti and the antioxidant is avoided.
Before and after the polydiene-based rubber prepared by the preparation method provided in comparative example 4 was subjected to thermo-oxidative aging (thermo-oxidative aging in an oven at 130 ℃ for 4 hours), modulus test was performed using MDR under test conditions of 140 ℃, 1.67Hz, 14% strain, and scan time of 120 min. The MDR results show that the torque of the product before thermo-oxidative aging is reduced from 5.3dN m to 5.2dN m; after thermo-oxidative aging, the torque is reduced from 3.1 dN.m to 3.0 dN.m; that is, compared with comparative example 3 and example 4, the heat-oxygen aging resistance of the polydiene rubber prepared by using water as a terminator in an amount of 0.5 wt% and antioxidant 264 in an amount of 1.0 wt% is superior to that of comparative example 3, but is obviously inferior to that of example 4.
The results of the thermal oxygen aging resistance of the polydiene rubber prepared by the preparation method provided in example 4 and comparative examples 3 to 4 are shown in the comparative figure 4.
In addition, the epoxy terminator adopted by the invention (less than 1 ten thousand yuan/t) can directly replace the traditional terminator and antioxidant (3-3.5 ten thousand yuan/t), so that the raw material cost can be reduced, the synthesis process can be simplified, and the polymerization efficiency can be improved; in addition, a charging opening can be reduced in industrial production, so that the energy consumption is greatly reduced, and the enterprise benefit is improved; meanwhile, the phenomenon that the trans-form polydiene rubber is degraded due to the fact that residual titanium in the glue solution and a terminator ethanol generate titanium ethoxide and the titanium ethoxide and a thioether-type hindered phenol antioxidant synergistically release free radicals is avoided, and therefore the anti-aging performance of the trans-form polydiene rubber is improved.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of polydiene rubber comprises the following steps:
a) carrying out polymerization reaction on diene monomers under an initiation system to obtain a glue solution; the initiation system adopts a Ziegler-Natta catalyst;
b) adding an epoxy terminator into the glue solution obtained in the step a) to terminate the reaction, and drying to obtain the polydiene rubber; the epoxy terminator is selected from one or more of epoxy resin, epoxidized soybean oil and ethylene oxide.
2. The process according to claim 1, wherein in step a) the diene monomer is selected from butadiene and/or isoprene.
3. The method of claim 1, wherein the Ziegler-Natta catalyst of step a) comprises titanium tetrachloride and an aluminum alkyl.
4. The process according to claim 1, wherein the amount of Ziegler-Natta catalyst added to the initiating system in step a) is between 0.5% and 1% by mass of the diene monomer.
5. The method according to claim 1, wherein the polymerization in step a) is carried out by bulk polymerization or solution polymerization.
6. The method according to claim 1, wherein the polymerization reaction in step a) is carried out at a temperature of 40 ℃ to 50 ℃ for a time of 10min to 40 min.
7. The method according to claim 1, wherein the epoxy value of the epoxy terminator in step b) is 2 to 10%.
8. The preparation method according to claim 1, wherein the addition amount of the epoxy terminator in the step b) is 0.1-10% of the mass of the glue solution.
9. The method according to claim 1, wherein the means for terminating the reaction in step b) is stirring; the stirring time is 10 min-30 min.
10. The preparation method according to claim 1, wherein the drying process in step b) is specifically:
and cooling the product after the reaction is ended to 15-25 ℃, and then drying the product in vacuum at 40-80 ℃ for 1-5 h to constant weight to obtain the polydiene rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010517911.7A CN111607033B (en) | 2020-06-09 | 2020-06-09 | Preparation method of polydiene rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010517911.7A CN111607033B (en) | 2020-06-09 | 2020-06-09 | Preparation method of polydiene rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111607033A CN111607033A (en) | 2020-09-01 |
| CN111607033B true CN111607033B (en) | 2022-03-29 |
Family
ID=72198522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010517911.7A Active CN111607033B (en) | 2020-06-09 | 2020-06-09 | Preparation method of polydiene rubber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111607033B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050968A (en) * | 2009-11-06 | 2011-05-11 | 青岛科技大学 | Trans-1,4-polydialkene composite rubber and preparation methods thereof |
| CN103204973A (en) * | 2012-01-12 | 2013-07-17 | 青岛科技大学 | Trans-1,4-polydiene copolymer having low molecular weight, and preparation method and use thereof |
| CN106750637A (en) * | 2017-01-24 | 2017-05-31 | 山东华聚高分子材料有限公司 | A kind of trans copolymerized rubber of Isosorbide-5-Nitrae butadiene-isoprene of nano-carbon material filling and preparation method thereof |
-
2020
- 2020-06-09 CN CN202010517911.7A patent/CN111607033B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050968A (en) * | 2009-11-06 | 2011-05-11 | 青岛科技大学 | Trans-1,4-polydialkene composite rubber and preparation methods thereof |
| CN103204973A (en) * | 2012-01-12 | 2013-07-17 | 青岛科技大学 | Trans-1,4-polydiene copolymer having low molecular weight, and preparation method and use thereof |
| CN106750637A (en) * | 2017-01-24 | 2017-05-31 | 山东华聚高分子材料有限公司 | A kind of trans copolymerized rubber of Isosorbide-5-Nitrae butadiene-isoprene of nano-carbon material filling and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111607033A (en) | 2020-09-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH04266908A (en) | Catalyst for synthesis of crystalline 3,4- polyisoprene | |
| US5491230A (en) | Anionic polymerization initiators containing adducts of cyclic secondary amines and conjugated dienes, and products therefrom | |
| CN107722402B (en) | Toughening agent composition, ABS resin and preparation method thereof | |
| JP3630502B2 (en) | Rubber composition for tire | |
| CN111607033B (en) | Preparation method of polydiene rubber | |
| CN106188356A (en) | A kind of Tetraheteropoly rare earth catalyst system and catalyzing and its preparation method and application | |
| US3409604A (en) | Polymerization of butadiene | |
| CN109251263B (en) | Low cis-polybutadiene rubber and preparation method thereof, and HIPS resin and preparation method thereof | |
| JP2017132955A (en) | Vinyl-cis-polybutadiene rubber and method for producing the same | |
| US20030134999A1 (en) | Method for polymerizing conjugated diolefins (dienes) with rare earth catalysts in the presence of vinylaromatic solvents | |
| CN110305240B (en) | Preparation method of polybutadiene oligomer, grafting modifier and rare earth isoprene rubber | |
| WO2020160000A1 (en) | Method for producing polydienes with reduced cold flow | |
| US4430487A (en) | Shortstop for synthetic cis-1,4-polyisoprene | |
| CN107722179B (en) | Preparation method of butadiene-isoprene homopolymer and copolymer | |
| CN108610451A (en) | A kind of preparation method of high trans -1,4- isoprene-butadiene copolymers | |
| JP2007031568A (en) | Method for manufacturing vinyl-cis-polybutadiene | |
| EP0702034A1 (en) | Process for preparing (co)polychloroprene rubber | |
| CN114874374B (en) | Ethylene propylene diene monomer rubber and preparation method and application thereof | |
| JP2017132954A (en) | Vinyl-cis-polybutadiene rubber and method for producing the same | |
| CN105732868B (en) | The continuous solution polymerization method and rare-earth isoprene rubber and vulcanization rubber of rare-earth isoprene rubber | |
| CN106977656B (en) | Dendritic polydiene rubber and preparation method thereof | |
| CA1065993A (en) | Two-step polymerization process and product thereof | |
| CN104693519A (en) | Preparation method for butadiene rubber composite | |
| CN113896894B (en) | Branched cross-linking agent, and preparation method and application thereof | |
| CN114874394A (en) | Ethylene propylene diene monomer and preparation method and application thereof |
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 |