CN116410426B - High-adhesion dendritic branched polymer, and synthetic method and application thereof - Google Patents
High-adhesion dendritic branched polymer, and synthetic method and application thereof Download PDFInfo
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Abstract
The invention relates to a high molecular material, a synthesis method and an application technical field, in particular to a high-adhesion dendritic branched polymer, a synthesis method and an application, wherein the high-adhesion dendritic branched polymer is prepared by the following synthesis method: firstly, synthesizing a polymer active chain by adopting an anionic polymerization technology, and adding a halogen-containing styrene compound and an anionic polymerization monomer into the synthesized solution for a plurality of times to synthesize the high-adhesiveness dendritic branched polymer. The high-adhesiveness dendritic branched polymer synthesized by the invention has excellent adhesiveness, can be used in plastic or rubber blending, and is beneficial to improving the adhesiveness of the polymer. The method has mild operation condition, is easy for industrial production, can be directly used or added into other polymers, and can obviously improve the bonding performance between objects.
Description
Technical Field
The invention relates to the technical field of high molecular materials, synthetic methods and applications, and discloses a high-adhesion dendritic branched polymer, a synthetic method and applications.
Background
The tackiness of a polymer is often used to characterize the ease of separation between the polymer or between the polymer and other objects. Good adhesion is required to achieve intermolecular contact between the two, and this requires that the polymer chains on the contact surface flow in a viscous manner, and sufficient contact can be achieved. And when in separation, a strong connecting key is needed, so that the connecting key is not easy to separate. If both objects in contact are polymer melts, sufficient contact requires that the polymer chains can interdiffuse across the interface and entangle with each other. In general, the strength of the polymer linkages can be increased by adding reinforcing agents or crosslinking, but this can affect the viscous flow of the polymer chains, which is detrimental to adequate contact between objects. The addition of the plasticizer facilitates adequate contact but reduces the cohesion of the polymer. Therefore, the development of branched polymers with high adhesion properties is of great importance for its adhesive application.
Although the tackiness of polymers has many applications in life, it is still not clear about the mechanism of tackiness, such as crack propagation mechanism, mechanical action, electrostatic action mechanism, and the like. The adhesion test is mainly divided into two stages, namely the formation of a connecting bond (the contact stage of a probe and pressure-sensitive adhesive) and a separation process (the stretching and separation of the probe), and a complex energy dissipation process exists in the whole process. In general, the adhesiveness of a material is mainly related to the surface properties of the material, the viscoelasticity of the material, the external environment, and the like. When different materials are in contact, this sticking behaviour is called Adhesion (Cohesion), whereas the same material is in adhesive contact, called self-adhesive (Cohesion). In real life, we touch the adhesive material with a finger, and measure its adhesive properties by the movement of the finger. In practical testing, the common polymer adhesion testing methods mainly include probe testing, tearing testing, ball testing, and the like. The probe test is one of the common means for testing the adhesiveness of the polymer, and is convenient and efficient. The method mainly adopts a probe to vertically contact with a sample with a certain thickness, and after a period of contact, the sample is separated at a constant speed, and the adhesive property of the material is measured by using a separation curve. Probe adhesiveness tests can be classified into sphere and plane probe tests according to the probe. The contact surface of the spherical probe is three-dimensional, the contact surface of the probe and the sample is not required to be far greater than the thickness of the sample, and the radius of the contact surface of the planar probe is required to be far greater than the thickness of the sample. In general, the adhesive behavior of polymers tends to exhibit solid-like and liquid-like adhesive behavior. The solid-like adhesion behavior tends to be at a maximum under very small strain, the adhesion energy is relatively small, separation mainly occurs between the probe and the interface of the polymer, while the liquid-like adhesion behavior exhibits a lower maximum tensile force and a very high breaking strain, separation occurs between the polymers, and after stretching is completed, a portion of the polymer remains on the probe.
Disclosure of Invention
The invention provides a high-adhesiveness dendritic branched polymer, a synthesis method and application thereof, overcomes the defects of the prior art, can synthesize a branched polymer with excellent adhesiveness, has a structure similar to a dendritic shape, has mild synthesis conditions and simple operation, and is easy for industrial production.
The invention discloses a method for synthesizing a high-adhesiveness dendritic branched polymer, which comprises the following steps of:
(1) Under the anhydrous and anaerobic condition, adding an anionic polymerization monomer into an organic solvent, initiating polymerization by using an initiator, and adding a structure regulator to prepare a polymer active chain;
(2) Adding a small amount of a halogen-containing styrene compound into the reaction solution in the step (1), and adding an anionic polymerization monomer again to continue polymerization;
(3) And (3) repeating the step (2) for a plurality of times after the reaction is finished, finally adding a terminator and an anti-aging agent, and carrying out precipitation washing, filtering and vacuumizing drying to obtain the high-adhesion dendritic branched polymer.
The following are further optimizations and/or improvements to one of the above-described inventive solutions:
In the step (1), the initiator can be alkyl lithium or alkoxy alkali metal or alkali metal amino compound or sodium naphthalene, the anionic polymerization monomer can be one or more of conjugated diolefin and benzene olefin derivatives, the concentration of the initiator is 0.01mol/L to 10.00mol/L,
Preferably, the initiator concentration is from 0.01mol/L to 2mol/L.
The alkyl lithium is one or more of n-butyl lithium, sec-butyl lithium, tert-butyl lithium and isobutyl lithium, the alkali metal amino compound is sodium amide or lithium amide, and the alkali metal amino compound can be a secondary amine compound and an alkyl lithium initiator react to form an amine lithium initiator, such as a cyclohexylimine lithium initiator.
The structure regulator is 2, 2-di (2-furyl) propane, and the addition amount of the 2, 2-di (2-furyl) propane is 0.5 times of the mole number of the initiator.
The conjugated diene may be at least one of isoprene and butadiene, and the styrene derivative may be at least one of styrene and 1-phenyl-1, 3-butadiene.
In the step (1), the organic solvent is one or more of linear or cyclic organic solvents, the linear organic solvent is one or more of n-hexane, pentane, heptane and octane, the cyclic organic solvent is one or more of cyclic long molecular chains or epoxy hydrocarbon organic solvents, and the cyclic long molecular chain organic solvent is one or more of cyclohexane, cyclopentane and cycloheptane, and the epoxy hydrocarbon organic solvent is tetrahydrofuran.
In the above step (1), the conditions for the anionic polymerization are such that the reaction is carried out at 10 to 80℃for 1 to 400 minutes, and at the same time, the solid content of the anionic polymerized monomer in the polymerization reaction liquid is not more than 50% because the greater the danger due to the heat effect of the polymerization reaction as the solid content of the monomer in the reaction liquid increases.
In the above step (1), the conditions for the anionic polymerization are preferably 30 to 70℃and the solid content of the anionic polymerization monomer in the polymerization reaction liquid is preferably 15%.
In the step (2), the halogen-containing styrene compound is one of 3-chlorostyrene, 2-bromostyrene, trans-4-bromostilbene, 4-bromostyrene, 2-chlorostyrene and 4-chloromethylstyrene.
Preferably, the molar ratio of the total addition amount of the halogen-containing styrene compound to the addition amount of the initiator is 0.1 to 10.
In the step (3), the terminator is one of carbon dioxide, organic acid, water and isopropanol, and the antioxidant is one or more of 2, 6-di-tert-butylphenol, ketoamine antioxidant, diphenylamine derivative, p-phenylenediamine derivative, 2, 6-di-tert-butyl-p-cresol, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate and phenol-free phosphite.
The addition amount of the anti-aging agent is 1 to 2 percent of the mass of the high-adhesion dendritic branched polymer.
The second technical scheme of the invention is realized by the following measures that the high-adhesion dendritic branched polymer is prepared by the synthesis method of the high-adhesion dendritic branched polymer according to the first technical scheme.
The third technical scheme of the invention is realized by the following measures that the second technical scheme is the application of the high-adhesion dendritic branched polymer in the aspect of high-adhesion polymer materials.
The high-adhesiveness dendritic branched polymer synthesized by the invention has excellent adhesiveness, can be used in plastic or rubber blending, and is beneficial to improving the adhesiveness of the polymer. The method has mild operation condition and is easy for industrial production, or the method is directly used or added into other polymers, and the bonding performance between objects can be obviously improved.
Drawings
FIG. 1 is a schematic representation of the synthetic route to branched polymer I of example 1.
FIG. 2 is a nuclear magnetic resonance spectrum of the branched polymer I synthesized in example 1.
FIG. 3 is a rheological profile of branched polymer I synthesized in example 1.
FIG. 4 is a graph of the adhesion properties of branched polymer I synthesized in example 1.
FIG. 5 is a block diagram of branched polymer I synthesized in example 1.
FIG. 6 is a nuclear magnetic resonance spectrum of branched polymer II synthesized in example 2.
FIG. 7 is a rheological profile of branched polymer II synthesized in example 2.
FIG. 8 is a graph of the adhesion properties of branched polymer II synthesized in example 2.
FIG. 9 is a block diagram of branched polymer II synthesized in example 2.
FIG. 10 is a rheological profile of branched polymer III synthesized in example 3.
In FIG. 1, n-BuLi represents butyllithium.
In the rheogram, G' represents storage modulus and G "represents loss modulus on the ordinate.
Detailed Description
The present invention is not limited by the following examples, and specific embodiments can be determined according to the technical scheme and practical situations of the present invention. The chemical reagents and chemical supplies mentioned in the invention are all commonly used chemical reagents and chemical supplies known in the prior art unless specified otherwise, the percentages in the invention are all mass percentages unless specified otherwise, the solutions in the invention are all aqueous solutions with water as solvents, for example, hydrochloric acid solution is hydrochloric acid aqueous solution, and the room temperature in the invention generally refers to the temperature of 15 ℃ to 25 ℃ and is generally defined as 25 ℃.
The invention is further described below with reference to examples:
example 1 the high adhesion dendritic branched polymer was prepared by the following synthesis method:
In a 850ml reaction flask which had been pretreated with a positive pressure of nitrogen-filled, 400ml of an n-hexane solution and 8ml of isoprene monomer were introduced with a double-ended needle, 2.18ml of n-butyllithium (molar concentration: 1 mmol/ml) which had been calibrated was added, respectively, to initiate polymerization, and 2, 2-bis (2-furyl) propane (structure-controlling agent) corresponding to half the number of moles of n-butyllithium was added. After 2h of reaction in a 60℃water bath, 0.04ml of 4-chloromethylstyrene (halogen-containing styrene compound) and 7ml of isoprene monomer were added, the reaction was continued for 1h, and the operation was repeated 6 times until the reaction was completed, and the specific synthetic route was shown in FIG. 1. After cooling to room temperature, 6ml of an isopropanol solution containing 3wt.% of 2, 6-di-t-butyl-p-cresol was added to terminate the reaction. And then washing by isopropanol precipitation, filtering, vacuumizing and drying to prepare the high-adhesion dendritic branched polymer (branched polymer I).
The branched polymer I has a weight average molecular weight of 57230 and M w/Mn of 2.688, as measured by Gel Permeation Chromatography (GPC) from Malvern.
The microstructure of the branched polymer I was analyzed by nuclear magnetic resonance (see FIG. 2 in particular), and it had a1, 2-structure polyisoprene content of 5.21%, a 3, 4-structure polyisoprene content of 59.27%, a cis 1, 4-structure polyisoprene content of 13.33%, a trans 1, 4-structure polyisoprene content of 21.50% and a styrene structure content of 0.68%. The synthesized branched polymer I was subjected to rheological frequency sweep, specifically to a test thickness of 1mm, and the sample was subjected to frequency sweep test of 0.01Hz to 100Hz using a 25mm plate (see FIG. 3).
The synthesized branched polymer I was tested for adhesion properties using a stainless steel probe adhesion test method (probe diameter of 12mm, surface roughness Ra of 0.12um, sample thickness of 1 mm) using different molecular speeds, and a graph of the maximum separation force of the probe versus speed at different separation speeds is shown in FIG. 4. Wherein, when the probe separation speed is 5mm/s, the maximum separation force in the separation process is up to 40N.
The structure of the synthesized branched polymer I is shown in FIG. 5, and it can be seen from FIG. 5 that the branched polymer I is dendritic.
Comparative example 1:
In a 850ml reaction flask which had been pretreated with nitrogen-filled positive pressure, 400ml of n-hexane solution and 60ml of isoprene monomer were introduced with a double-ended needle, and 0.71ml of n-butyllithium (molar concentration: 1 mmol/ml) which had been calibrated was added, respectively, to initiate polymerization, and the resulting polymer (linear polyisoprene) was prepared by washing and drying the precipitate in a 60℃water bath for 2 hours, and had a weight average molecular weight of 61860 and an M w/Mn of 1.12. The linear polyisoprene of the same molecular weight has little tackiness and is so susceptible to viscous flow that probe tackiness testing is not possible.
Example 2 the high adhesion dendritic branched polymer was prepared by the following synthesis method:
In 850ml of a reaction flask which had been pretreated with a positive pressure of nitrogen-filled, 400ml of an n-hexane solution and 8ml of isoprene monomer were introduced with a double-ended needle, and polymerization was initiated by adding 1.08ml of n-butyllithium (1 mmol/ml in molar concentration) which had been calibrated, respectively, and by adding 2, 2-bis (2-furyl) propane corresponding to half the number of moles of n-butyllithium. After 2h reaction in a 60℃water bath, 0.02ml of 4-chloromethylstyrene and 7ml of isoprene monomer were added, the reaction was continued for 1h, and the operation was repeated 6 times until the reaction was completed, and the specific synthetic route was shown in FIG. 1. After cooling to room temperature, 6ml of an isopropanol solution containing 3wt.% of 2, 6-di-t-butyl-p-cresol was added to terminate the reaction. And then washing by isopropanol precipitation, filtering, and vacuumizing and drying to obtain a final sample (branched polymer II). The molecular weight was measured by Gel Permeation Chromatography (GPC) from Malvern, and the weight average molecular weight of the branched polymer II was 98480 and M w/Mn was 1.930.
The microstructure of the branched polymer II was analyzed by nuclear magnetic resonance (see FIG. 6 in particular), the 1, 2-structure polyisoprene content was 2.86%, the 3, 4-structure polyisoprene content was 49.79%, the cis 1,4 structure polyisoprene content was 23.10%, the trans 1,4 structure polyisoprene content was 23.97%, and the styrene structure polyisoprene content was 0.28%. The synthesized polymer was subjected to a rheological frequency sweep, specifically 1mm in thickness, and the sample was subjected to a frequency sweep test of 0.01Hz to 100Hz using a 25mm plate (see FIG. 7).
The structure of the synthesized branched polymer II is shown in FIG. 9, and it can be seen from FIG. 9 that the branched polymer II is dendritic.
Comparative example 2:
In a 850ml reaction flask filled with positive pressure of nitrogen gas, 400ml of n-hexane solution and 90ml of isoprene monomer were introduced with a double-ended needle, and 0.61ml of n-butyllithium (molar concentration: 1 mmol/ml) was added to initiate polymerization, and after 2 hours of reaction in a 60℃water bath, linear polyisoprene was prepared. Finally, stopping with isopropanol, precipitating, washing, filtering and vacuumizing. The molecular weight was measured by Gel Permeation Chromatography (GPC) of Malvern, the weight average molecular weight of the linear polymer was 98900 and M w/Mn was 1.180.
The adhesion properties of the synthesized branched polymer II and the linear polymer of comparative example 2 were each tested by using a stainless steel probe adhesion test method (probe diameter of 12mm, surface roughness Ra of 0.12 μm, sample thickness of 1 mm), with different molecular speeds, and a graph of the maximum separation force of the probe versus speed at different separation speeds is shown in FIG. 8. As can be seen from FIG. 8, the adhesive properties of the branched polymer are significantly higher than those of the linear polymer of the same molecular weight, wherein the maximum separation force during separation increases directly from 43N to 54N when the probe separation speed is 5 mm/s.
Example 3 the high adhesion dendritic branched polymer was prepared by the following synthesis method:
Into 850ml of a reaction flask which had been pretreated with a positive pressure of nitrogen-filled, 400ml of an n-hexane solution and 8ml of isoprene monomer were introduced with a double-ended needle, and polymerization was initiated by adding 0.73ml of n-butyllithium (1 mmol/ml in molar concentration) which had been calibrated, and by adding 2, 2-bis (2-furyl) propane corresponding to half the number of moles of n-butyllithium. After 2h reaction in a 60℃water bath, 0.015ml of 4-chloromethylstyrene and 7ml of isoprene monomer were added, the reaction was continued for 1h, and the operation was repeated 7 times until the reaction was completed, and the specific synthetic route was shown in FIG. 1. After cooling to room temperature, 6ml of an isopropanol solution containing 3wt.% of 2, 6-di-t-butyl-p-cresol was added to terminate the reaction. And then washing by isopropanol precipitation, filtering, and vacuumizing and drying to obtain a final sample (branched polymer III). The molecular weight was measured by Gel Permeation Chromatography (GPC) of Malvern company, and the weight average molecular weight of the polymer was 137480 and m w/Mn was 2.070.
The synthesized polymer was subjected to a rheological frequency sweep, specifically 1mm in thickness, and the sample was subjected to a frequency sweep test of 0.01Hz to 100Hz using a 25mm plate (see FIG. 10). The adhesive property test of the stainless steel probe shows that the synthesized branched polymer III has good adhesive behavior and is very suitable for increasing the adhesive property of the polymer.
Example 4 the high adhesion dendritic branched polymer was prepared by the following synthesis method:
In 850ml of a reaction flask which had been pretreated with a positive pressure of nitrogen-filled, 400ml of pentane solution and 8ml of styrene monomer were introduced with a double-ended needle, and polymerization was initiated by adding 1.56ml of the calibrated isobutyl lithium (molar concentration: 1 mmol/ml) and 2, 2-bis (2-furyl) propane corresponding to half the molar number of the isobutyl lithium, respectively. After 1.5h of reaction in a water bath at 68 ℃,0.04 ml of 2-bromostyrene and 7ml of styrene monomer were added, the reaction was continued for 1h, and the operation was repeated 5 times until the reaction was completed. After cooling to room temperature, 7ml of an isopropanol solution containing 3wt.% of phenol-free phosphite were added to terminate the reaction. And then washing by isopropanol precipitation, filtering, vacuumizing and drying to prepare the high-adhesion dendritic branched polymer.
Example 5 the high adhesion dendritic branched polymer was prepared by the following synthesis method:
In 850ml of a reaction flask pretreated with nitrogen-filled positive pressure, 400ml of pentane solution and 8ml of 1-phenyl-1, 3-butadiene monomer were introduced with a double-ended needle, 2.40ml of calibrated lithium amide (molar concentration: 1 mmol/ml) were each added to initiate polymerization, and 2, 2-bis (2-furyl) propane corresponding to half the molar number of lithium amide was added. After 2h of reaction in a 40℃water bath, 0.04ml of 4-chloromethylstyrene and 7ml of 1-phenyl-1, 3-butadiene monomer were added, the reaction was continued for 1h, and the operation was repeated 4 times until the reaction was completed. After cooling to room temperature, 6ml of an isopropanol solution containing 3wt.% of 2, 6-di-t-butyl-p-cresol was added to terminate the reaction. And then washing by isopropanol precipitation, filtering, vacuumizing and drying to prepare the high-adhesion dendritic branched polymer.
Example 6 the high adhesion dendritic branched polymer was prepared by the following synthesis method:
In a 10L reaction kettle, 4000g of cyclopentane and 60g of butadiene monomer are added, under the action of 2, 2-di (2-furyl) propane (OOPS, the ratio of the OOPS to the amount of the initiator at the stage is 1:2), 12mmol of n-butyllithium is added to initiate polymerization, the whole reaction system is reacted for 2 hours at 60 ℃, and stirring is continuously carried out in the middle. After the reaction was completed, 2mmol of 4-chloromethylstyrene was added, and after the reaction was continued for 1 hour by continuously adding 60g of butadiene monomer, the operation was repeated 6 times, and the subsequent operation was the same as in example 3, to obtain a branched structure polymer having high adhesion property, which can significantly improve the adhesion behavior of rubber.
From the above, the high-adhesion dendritic branched polymer synthesized by the synthesis method has excellent adhesion performance, can be used in plastics or rubber blending, and is beneficial to improving the adhesion performance of the polymer. The method has mild operation condition and is easy for industrial production, or the method is directly used or added into other polymers, and the bonding performance between objects can be obviously improved.
The technical characteristics form the embodiment of the invention, have stronger adaptability and implementation effect, and can increase or decrease unnecessary technical characteristics according to actual needs so as to meet the requirements of different situations.
Claims (10)
1. A synthesis method of a high-adhesion dendritic branched polymer is characterized by comprising the following steps:
(1) Under the anhydrous and anaerobic condition, adding an anionic polymerization monomer into an organic solvent, initiating polymerization by using an initiator, and adding a structure regulator to prepare a polymer active chain;
(2) Adding a small amount of a halogen-containing styrene compound into the reaction solution in the step (1), and adding an anionic polymerization monomer again to continue polymerization;
(3) Repeating the step (2) for a plurality of times after the reaction is finished, finally adding a terminator and an anti-aging agent, and carrying out precipitation washing, filtering and vacuumizing drying to obtain the high-adhesion dendritic branched polymer;
Wherein the structure regulator is 2, 2-di (2-furyl) propane, and the addition amount of the 2, 2-di (2-furyl) propane is 0.5 times of the mole number of the initiator;
The halogen-containing styrene compound is 4-chloromethyl styrene, and the molar ratio of the total addition amount of the halogen-containing styrene compound to the addition amount of the initiator is 0.1 to 10;
The initiator is alkyl lithium or alkoxy alkali metal or alkali metal amino compound or sodium naphthalene;
The anionic polymeric monomer is one or more of conjugated dienes.
2. The method for synthesizing a high-adhesion dendritic branched polymer according to claim 1, wherein the initiator concentration is 0.01 mol/L to 10.00 mol/L.
3. The method for synthesizing the high-adhesion dendritic branched polymer according to claim 2, wherein the alkyl lithium is one or more of n-butyl lithium, sec-butyl lithium, tert-butyl lithium and isobutyl lithium, or/and the alkali metal amino compound is sodium amide or lithium amide, or/and the initiator concentration is 0.01 mol/L to 2 mol/L, or/and the conjugated diene is one or more of isoprene and butadiene, or/and the benzene olefin derivative is one or more of styrene and 1-phenyl-1, 3-butadiene.
4. The method for synthesizing the high-adhesion dendritic branched polymer according to claim 1,2 or 3, wherein in the step (1), the organic solvent is one or more of linear or cyclic organic solvents, the linear organic solvent is one or more of n-hexane, pentane, heptane and octane, the cyclic organic solvent is one or more of cyclic long molecular chains or epoxy hydrocarbon organic solvents, and the cyclic long molecular chains are one or more of cyclohexane, cyclopentane and cycloheptane, and the epoxy hydrocarbon organic solvent is tetrahydrofuran.
5. The method for synthesizing a highly adhesive dendritic branched polymer according to claim 4, wherein in the step (1), the anionic polymerization is carried out at a temperature of 10 to 80℃for 1 to 400 minutes, and at the same time, the solid content of the anionic polymerization monomer in the polymerization reaction liquid is not more than 50%.
6. The method for synthesizing a high-adhesion dendritic branched polymer according to claim 5, wherein the anionic polymerization condition is 30 ℃ to 70 ℃, and the solid content of the anionic polymerization monomer in the polymerization reaction liquid is 15%.
7. The method for synthesizing the high-adhesion dendritic branched polymer according to claim 1,2, 3 or 5, wherein in the step (3), the terminating agent is one of carbon dioxide, organic acid, water and isopropanol, or/and the antioxidant is one or more of 2, 6-di-tert-butylphenol, ketoamine antioxidant, diphenylamine derivative, p-phenylenediamine derivative, 2, 6-di-tert-butyl-p-cresol, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate and phenol-free phosphite.
8. The method for synthesizing a high-adhesion dendritic-like branched polymer according to claim 7, wherein the addition amount of the anti-aging agent is 1% to 2% of the mass of the high-adhesion dendritic-like branched polymer.
9. A high-adhesion dendritic-like branched polymer obtained by the synthesis method of a high-adhesion dendritic-like branched polymer according to any one of claims 1 to 8.
10. Use of a high adhesion dendritic branched polymer according to claim 9 in a high adhesion performance polymeric material.
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| US6255424B1 (en) * | 1997-11-25 | 2001-07-03 | Colorado School Of Mines | Dendritic polymers and convergent method of synthesis |
| US6518383B1 (en) * | 1997-07-17 | 2003-02-11 | E.I. Du Pont De Nemours And Company | Branched polyolefin synthesis |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6518383B1 (en) * | 1997-07-17 | 2003-02-11 | E.I. Du Pont De Nemours And Company | Branched polyolefin synthesis |
| US6255424B1 (en) * | 1997-11-25 | 2001-07-03 | Colorado School Of Mines | Dendritic polymers and convergent method of synthesis |
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| 结构调节剂双四氢糠丙烷对苯乙烯-异戊二烯橡胶微观结构的影响;王旭 等;《橡胶工业》;20191125;第66卷(第11期);第803-808页 * |
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