CN111434705B - Modified liquid rubber and preparation method and application thereof - Google Patents
Modified liquid rubber and preparation method and application thereof Download PDFInfo
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- CN111434705B CN111434705B CN201910032984.4A CN201910032984A CN111434705B CN 111434705 B CN111434705 B CN 111434705B CN 201910032984 A CN201910032984 A CN 201910032984A CN 111434705 B CN111434705 B CN 111434705B
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
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Abstract
The invention relates to the field of liquid rubber, and discloses modified liquid rubber and a preparation method and application thereof, wherein the method comprises the following steps: under the condition of illumination, (1) carrying out polymerization reaction on a divinyl ether monomer and a dimercapto monomer to obtain a reaction material containing a dimercapto-terminated linear polythioether telechelic oligomer; (2) contacting said oligomer or said reaction mass comprising dimercapto-terminated linear polythioether telechelic oligomer with a liquid rubber; wherein, the light source with the wavelength of 320-405nm is adopted for the illumination. By adopting the technical scheme, the modified liquid rubber with high grafting rate can be obtained, so that the moving property of the chain segment is stronger, the modified liquid rubber has optical activity, the volume shrinkage rate of the material after photocuring can be obviously reduced when the modified liquid rubber is applied to a photocuring system, the dimensional stability of a product is ensured, and the material after photocuring has the toughness of an elastomer.
Description
Technical Field
The invention relates to the field of liquid rubber, in particular to a method for preparing modified liquid rubber, modified liquid rubber prepared by the method and application thereof.
Background
The functional group liquid rubber is a polymer containing various active functional groups or chain segments at the tail end or the main chain of the molecular chain of the liquid rubber, and the modified liquid rubber not only has the characteristics of the liquid rubber, but also improves the comprehensive performance of the liquid rubber due to the addition of the functional groups.
In recent years, with the proposal of the click reaction concept, the photo-initiated thiol-double bond click reaction is becoming a new research hotspot in the field of polymer materials. The mercapto compound is introduced into the liquid rubber, so that not only can the oxygen inhibition effect of the reaction be reduced, but also the liquid rubber is introduced into a flexible long chain on a side chain while the structure of a main chain of macromolecules of the liquid rubber is not changed, and the application range of the liquid rubber is expanded. For example, the modified rubber phase is introduced into a photocuring reaction system, so that the volume shrinkage rate during curing can be reduced, and the dimensional stability of a product is ensured. The cured material can also be made to have elastomeric properties and be used in the tire, medical, footwear, automotive, and 3D printing fields.
Disclosure of Invention
The invention provides a method for preparing liquid rubber with optical activity, which comprises the step of carrying out polymerization reaction on divinyl ether monomer and dimercapto monomer under the irradiation of a light source with the wavelength of 320-405nm to prepare a reaction material containing dimercapto-terminated linear polythioether telechelic oligomer. The oligomer and the liquid rubber are subjected to contact reaction, so that the defects of odor, micromolecule migration, residue and the like in the obtained product when the micromolecule sulfhydryl compound is directly subjected to contact reaction with the liquid rubber are overcome.
In the invention, under the irradiation of a light source with the wavelength of 320-405nm, the oligomer and the liquid rubber are subjected to contact reaction, so that the modified liquid rubber with high grafting rate can be obtained, the mobility of the chain segment is stronger, the modified liquid rubber has optical activity, and when the modified liquid rubber is applied to a photocuring system, the volume shrinkage rate of a material after photocuring can be obviously reduced, the dimensional stability of a product is ensured, and the material after photocuring has the toughness of an elastomer.
In order to achieve the above object, the present invention provides, in a first aspect, a method for producing a modified liquid rubber, the method comprising: under the condition of light, the light-emitting diode is arranged in a cavity,
(1) carrying out a polymerization reaction on a divinyl ether monomer and a dimercapto monomer to obtain a reaction material containing a dimercapto-terminated linear polythioether telechelic oligomer;
(2) carrying out contact reaction on the oligomer and liquid rubber;
wherein, the light source with the wavelength of 320-405nm is adopted for the illumination.
In a second aspect, the present invention provides a process for preparing a modified liquid rubber, the process comprising: under the condition of light, the light-emitting diode is arranged in a cavity,
(1) carrying out a polymerization reaction on a divinyl ether monomer and a dimercapto monomer to obtain a reaction material containing a dimercapto-terminated linear polythioether telechelic oligomer;
(2) carrying out contact reaction on the reaction material containing the dimercapto-terminated linear polythioether telechelic oligomer and liquid rubber;
wherein, the light source with the wavelength of 320-405nm is adopted for the illumination.
In a third aspect, the present invention provides a modified liquid rubber obtained by the method according to the first and second aspects of the present invention.
In a fourth aspect, the present invention provides the use of the modified liquid rubber of the present invention in photocuring.
According to the technical scheme, the grafting rate of the modified liquid rubber prepared by the method can reach 36%, the mobility of the chain segment is enhanced, the volume shrinkage rate of the material after photocuring can be obviously reduced when the modified liquid rubber is applied to a photocuring system, the dimensional stability of the product is ensured, and the material after photocuring has the toughness of an elastomer.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The present invention provides, in a first aspect, a process for preparing a modified liquid rubber, the process comprising: under the condition of light, the light-emitting diode is arranged in a cavity,
(1) carrying out a polymerization reaction on a divinyl ether monomer and a dimercapto monomer to obtain a reaction material containing a dimercapto-terminated linear polythioether telechelic oligomer;
(2) carrying out contact reaction on the oligomer and liquid rubber;
wherein, the light source with the wavelength of 320-405nm is adopted for the illumination.
According to the invention, in order to further improve the grafting rate of the liquid rubber in the prepared modified liquid rubber, a light source with the wavelength of 340-385nm is preferably adopted for the illumination.
Preferably, the oligomer has a number average molecular weight of 1000-3000g/mol and a molecular weight distribution of 1.1-2.0.
In order to better overcome the defects of odor, small molecule migration and residue and the like existing in the obtained product when the small molecule mercapto compound is directly contacted with the liquid rubber, the number average molecular weight of the oligomer is preferably 1600-.
According to the present invention, the polymerization and the contacting are carried out in a solvent, the class of which is conventional in the art and in particular embodiments tetrahydrofuran may be employed.
According to the invention, before the polymerization reaction, a protective gas is introduced into the reaction system to remove oxygen in the reaction system, for example, nitrogen is introduced for 2-15 min.
According to the present invention, both step (1) and step (2) are carried out under illumination conditions, preferably at a power of 50-300mW, more preferably at a power of 200-300 mW.
According to the invention, the illumination power of the step (1) and the illumination power of the step (2) can be the same or different.
In the present invention, preferably, the polymerization reaction and/or the contact reaction is carried out in the presence of a photoinitiator.
In order to avoid the migration of the small-molecule photoinitiator and unnecessary production cost caused by excessive initiator, it is further preferable that the polymerization reaction is carried out without the photoinitiator, and the contact reaction is carried out with the photoinitiator.
In order to enable a better match of the photoinitiator with the light source, preferably the photoinitiator is selected from at least one of 2-Isopropylthioxanthone (ITX), benzoin dimethyl ether (BDK) and (2,4, 6-trimethylbenzoyl chloride) diphenylphosphine oxide (TPO).
In the present invention, when an initiator is used in the polymerization reaction, it is preferable that the photoinitiator is used in an amount of 0.5 to 6% by weight, preferably 0.5 to 2% by weight, based on the total weight of the divinyl ether monomer and the dimercapto monomer in the polymerization reaction.
Preferably, in the contact reaction, the photoinitiator is used in an amount of 0.5 to 6 parts by weight, relative to 100 parts by weight of the liquid rubber. More preferably, the photoinitiator is used in an amount of 1.5 to 3.5 parts by weight, relative to 100 parts by weight of the liquid rubber.
In the invention, preferably, the liquid rubber is diene liquid rubber, the number average molecular weight of the diene liquid rubber is 1000-30000g/mol, and the molecular weight distribution is 1.1-2.0; in order to impart better processability to the liquid rubber, it is more preferable that the diene-based liquid rubber has a number average molecular weight of 20000-28000 g/mol.
Preferably, the diene-based liquid rubber is selected from polybutadiene liquid rubber (LBR) and/or polyisoprene-butadiene liquid rubber (LIBR).
According to the present invention, it is preferable that the content of the 1, 2-vinyl structural unit in the diene-based liquid rubber is not less than 20% by weight based on the total weight of the diene-based liquid rubber.
In order to further improve the graft ratio of the liquid rubber, it is further preferable that the content of the 1, 2-vinyl structural unit in the diene-based liquid rubber is 35 to 50% by weight based on the total weight of the diene-based liquid rubber.
In the present invention, it is preferable that the oligomer and the diene-based liquid rubber are used in a molar ratio of 1: (1-10), more preferably 1: (1-5).
In order to prepare a dimercapto-terminated linear polythioether telechelic oligomer according to the present invention, the divinyl ether monomer and the dimercapto monomer are preferably used in a molar ratio of 1: (1.2-2), in order to further increase the graft ratio of the liquid rubber, it is preferable that the divinyl ether monomer and the dimercapto monomer are used in a molar ratio of 1: (1.2-1.5).
In the present invention, preferably, the divinyl ether monomer is selected from at least one of diethylene glycol divinyl ether, triethylene glycol divinyl ether, and divinyl-1, 4-butanediol ether.
In order to further improve the properties of the liquid rubber, it is preferable that the dimercapto monomer is selected from the group consisting of dimercapto monomers containing a benzene ring structure, for example, 1, 4-benzenedimethylthiol, 1, 4-benzenedithiol. The inventor of the invention finds that when the method of the invention is carried out by using the dimercapto monomer containing a benzene ring structure, the benzene ring has volume effect, large steric hindrance and difficult crystallization. Thereby expanding the application range of the liquid rubber. According to the present invention, preferably, the method comprises: and (c) carrying out contact reaction on the reaction material containing the dimercapto-terminated linear polythioether telechelic oligomer and the liquid rubber.
In the present invention, the polymerization reaction time is preferably 5 to 120min, more preferably 20 to 40 min.
Preferably, the contact reaction time is 5-120min, more preferably 15-40 min.
In a second aspect, the present invention provides a process for preparing a modified liquid rubber, the process comprising: under the condition of light, the light-emitting diode is arranged in a cavity,
(1) carrying out a polymerization reaction on a divinyl ether monomer and a dimercapto monomer to obtain a reaction material containing a dimercapto-terminated linear polythioether telechelic oligomer;
(2) carrying out contact reaction on the reaction material containing the dimercapto-terminated linear polythioether telechelic oligomer and liquid rubber;
wherein, the light source with the wavelength of 320-405nm is adopted for the illumination.
The relevant operating and reaction conditions involved in the process according to the second aspect of the invention can be the same as the corresponding operating and reaction conditions of the process according to the first aspect of the invention, and the invention is not described in detail here.
According to a particularly preferred embodiment, the process for preparing a modified liquid rubber comprises:
(1) under the irradiation of a light source with the wavelength of 340-385nm, carrying out polymerization reaction on a divinyl ether monomer and a dimercapto monomer under the condition of no initiator to obtain a reaction material containing a dimercapto-terminated linear polythioether telechelic oligomer;
(2) and (3) carrying out contact reaction on the reaction material containing the dimercapto-terminated linear polythioether telechelic oligomer, a photoinitiator and liquid rubber.
That is, in the above embodiment, after the polymerization reaction is completed, the photoinitiator and the liquid rubber are directly added to the reaction mass without post-treatment, and the modified liquid rubber is prepared by the "one-pot method", so that the process of separating and dissolving the polythioether oligomer is omitted, and the preparation process is simpler and more efficient. The modified liquid rubber has higher grafting rate under the same material condition because the loss of the oligomer in post treatment is avoided.
In a third aspect, the present invention provides a modified liquid rubber obtained by the method according to the first and second aspects of the present invention.
In a fourth aspect, the present invention provides the use of the modified liquid rubber of the present invention in photocuring.
Preferably, when the modified liquid rubber is applied to an acrylic light curing system, the volume shrinkage of the material after light curing can be obviously reduced, and the material after light curing has the characteristics of an elastomer.
The present invention will be described in detail below by way of examples.
In the following examples, the starting materials are all commercially available unless otherwise specified;
the polymer structure was determined using a Switzerland Bruker AVANCE400 NMR spectrometer (400Hz), a magnetic field strength of 9.40 Tesla, CDC13As solvent, TMS as internal standard, testing at 25 deg.C;
the grafting ratio (% by mole of 1, 2-vinyl structural unit in the liquid rubber before grafting-the mole of 1, 2-vinyl structural unit in the modified liquid rubber after grafting)/(the mole of 1, 2-vinyl structural unit in the liquid rubber before grafting) × 100%.
Example 1
(1) Mixing diethylene glycol divinyl ether and 1, 4-benzenedimethylmercaptan according to a molar ratio of 1: 1.5, dissolving in a tetrahydrofuran solvent, uniformly mixing under the stirring condition, then introducing nitrogen to remove oxygen for 10min, then turning on a light source, carrying out polymerization reaction under the light source with the illumination power of 300mW and the wavelength of 365nm, obtaining a reaction material containing the dimercapto-terminated linear polythioether telechelic oligomer after 20min of reaction, and measuring the number average molecular weight of the oligomer to be 1600g/mol and the molecular weight distribution to be 1.32.
(2) Adding polybutadiene liquid rubber (LBR) with the content of a1, 2-vinyl structural unit of 50 weight percent (the number average molecular weight is 22100g/mol, the molecular weight distribution is 1.07) and a photoinitiator TPO into the reaction material containing the dimercapto-terminated linear polythioether telechelic oligomer in the step (1) to carry out contact reaction, so that the molar ratio of the oligomer to the 1, 2-vinyl structural unit in the LBR in the reaction system is 1: 1, the amount of TPO is 1.5 percent of the weight of the liquid rubber, the reaction is carried out for 15min, and the light source is turned off, thus obtaining the modified rubber A1 prepared by the 'one-pot method'.
The structure of the modified rubber A1 was analyzed by nuclear magnetic analysis, and the grafting ratio of LBR was calculated to be 35.8%.
Example 2
(1) Divinyl-1, 4-butanediol ether and 1, 4-xylylene thiol are mixed according to a molar ratio of 1: 1.3, dissolving in a tetrahydrofuran solvent, uniformly mixing under the stirring condition, then introducing nitrogen to remove oxygen for 10min, then turning on a light source, carrying out polymerization reaction under the light source with the illumination power of 150mW and the wavelength of 385nm, obtaining a reaction material containing the dimercapto-terminated linear polythioether telechelic oligomer after 30min of reaction, and measuring the number average molecular weight of the oligomer to be 2500g/mol and the molecular weight distribution to be 1.8.
(2) Adjusting the illumination power to 180mW, and then adding polyisoprene-butadiene liquid rubber (LIBR) (the number average molecular weight is 28000g/mol, the molecular weight distribution is 1.6) with the content of a1, 2-vinyl structural unit of 43 weight percent and 2-Isopropyl Thioxanthone (ITX) into the reaction material containing the dimercapto-terminated linear polythioether telechelic oligomer in the step (1) to carry out contact reaction, so that the molar ratio of the oligomer to the 1, 2-vinyl structural unit in the LIBR in the reaction system is 1: 2, the ITX is 3.5 parts by weight of the liquid rubber, the reaction is carried out for 40min, and the light source is turned off, thus obtaining the modified rubber A2 prepared by the 'one-pot method'.
The structure of the modified rubber A2 was analyzed by nuclear magnetic analysis, and the grafting ratio of LBR was calculated to be 32.7%.
Example 3
The process of example 1 was followed except that: in steps (1) and (2), a light source with a wavelength of 320nm is used. Modified liquid rubber A3 was prepared. In the modified liquid rubber A3, the LBR graft ratio was 28.7%.
Example 4
According to the raw material ratio of the embodiment 1, the difference is as follows: in the steps (1) and (2), a light source with the illumination power of 50mW and the wavelength of 365nm is adopted. Modified liquid rubber A5 was prepared. Because the illumination power is obviously reduced, the illumination time needs to be prolonged to 120min in the preparation process of the oligomer, so that the effect equivalent to that of the embodiment 1 can be achieved; in the process of contact reaction, the reaction time reaches 80min, and the modified rubber A4 is prepared. In the modified liquid rubber A4, the grafting ratio of LBR was 25.6%.
Example 5
The process of example 1 was followed except that: in the step (1), triethylene glycol divinyl ether and 1, 4-xylylene thiol are mixed according to a molar ratio of 1: 2 and mixing. Modified liquid rubber A5 was prepared. In the modified liquid rubber A5, the grafting ratio of LBR was 19.7%.
Example 6
The process of example 1 was followed except that: in step (2), the molar ratio of oligomer to 1, 2-vinyl structural unit in LBR in the reaction system is 1: 10, modified liquid rubber A6 was prepared. In the modified liquid rubber A6, the grafting ratio of LBR was 21.3%.
Example 7
The process of example 1 was followed except that: in the step (1), during the addition reaction, a photoinitiator TPO corresponding to 1% of the total mass of the triethylene glycol divinyl ether and the 1, 4-benzenedimethylmercaptan is added to prepare a modified liquid rubber A7. In the modified liquid rubber A7, the grafting ratio of LBR was 35.5%.
Example 8
The process of example 1 was followed except that: in the step (2), during the contact reaction, no initiator TPO was added to prepare a modified liquid rubber A8. In the modified liquid rubber A8, the grafting ratio of LBR was 16.3%.
Example 9
(1) Mixing triethylene glycol divinyl ether and 1, 4-xylylene thiol according to a molar ratio of 1: 1.5, dissolving in a tetrahydrofuran solvent, uniformly mixing under the stirring condition, then introducing nitrogen to remove oxygen for 10min, then turning on a light source, carrying out polymerization reaction under the light source with the illumination power of 300mW and the wavelength of 365nm, after 20min of reaction, turning off the light source to obtain a reaction material containing the dithiol-terminated linear polythioether telechelic oligomer, and then washing and drying the oligomer in the reaction material by using methanol.
(2) Adding LBR and TPO which are the same in amount as those in example 1 into the washed and dried sample, then turning on a light source, carrying out reaction under the light source with the illumination power of 300mW and the wavelength of 365nm, and turning off the light source after reacting for 15min to obtain the modified rubber A9 prepared by the two-pot method.
The modified rubber A9 had a grafting yield of LBR of 15.7% due to the loss of the oligomer upon the post-treatment.
Test example 1
The glass transition temperatures (T) of the modified liquid rubbers A1-A9 were measured by thermogravimetric analysis (TGA)g) And temperature at 5% of thermal weight loss (T)d 5％) Wherein the operating conditions of the TGA comprise: n is a radical of2The atmosphere and the temperature rise rate were 10K/min, and the results are shown in Table 1.
TABLE 1
| Sample (I) | Percent of grafting% | Tg/℃ | Td 5％/℃ |
| A1 | 35.8 | -84.6 | 398.4 |
| A2 | 32.7 | -86.4 | 398.8 |
| A3 | 28.7 | -82.3 | 397.5 |
| A4 | 25.6 | -79.6 | 396.9 |
| A5 | 19.7 | -75.7 | 396.2 |
| A6 | 21.3 | -74.8 | 396.6 |
| A7 | 35.5 | -84.1 | 398.1 |
| A8 | 16.3 | -71.2 | 396.7 |
| A9 | 15.7 | -70.3 | 396.3 |
As can be seen from Table 1, T increases with the graft ratiogThe reason why the modified liquid rubber is improved in elastic properties is that the higher the mobility of the segment is as the graft ratio is increased, and the liquid rubber is left at 0 ℃ without causing crystallization or the like, so that the modified liquid rubber can be used under low temperature conditions.
Test example 2
And respectively mixing the photocuring formula with the modified liquid rubber A1-A9, carrying out photocuring to respectively obtain photocured materials B1-B9, and then measuring the volume shrinkage, tensile strength and elongation at break of the photocured materials B1-B9. Specifically, the operation is as follows:
epoxy acrylate (brand HS9103), modified liquid rubber (A1-A9), isobornyl acrylate, tripropylene glycol diacrylate and photoinitiator TPO are mixed according to the weight ratio of 41:6:30:20:3
Placing the mixture into a beaker, uniformly mixing the mixture by magnetic stirring under the condition of keeping out of the sun, standing and defoaming, uniformly coating the liquid material on a glass plate, placing the glass plate into a 1000W ultraviolet lamp box, and irradiating the glass plate for 60s at a lamp distance of 20cm to obtain a light solid material B1-B9; wherein the density rho of the material before and after solidification is measured by using a ZMD-2 type electronic densitometer1And ρ2The material volume shrinkage rate is (ρ)2-ρ1)/ρ2；
According to type I samples of GB/T1042-92, 5 samples of 60X 10X 4mm size were prepared3And testing the tensile strength and the average elongation at break of the cured material by using a universal mechanical testing machine. The loading speed was 5mm/min, and the results are shown in Table 2.
TABLE 2
| Sample (I) | Volume shrinkage/% | Tensile strength/MPa | Average elongation at break% |
| B1 | 4.9 | 20.7 | 201.3 |
| B2 | 5.5 | 20.3 | 195.7 |
| B3 | 6.5 | 19.1 | 176.3 |
| B4 | 6.3 | 17.9 | 175.2 |
| B5 | 7.1 | 16.7 | 152.5 |
| B6 | 6.8 | 17.1 | 165.7 |
| B7 | 5.8 | 20.1 | 193.7 |
| B8 | 7.5 | 14.3 | 137.8 |
| B9 | 7.3 | 15.1 | 131.6 |
| Rubber without modified liquid | 8.2 | 12.2 | 95.5 |
As can be seen from table 2, compared with a photocuring system without liquid rubber, the addition of the modified liquid rubber a1-a9 significantly improves the properties of the photocured material, specifically, the volume shrinkage of the photocured material can be reduced to 4.9%, the tensile strength can reach 20.7MPa, and the average elongation at break can reach 201.3%.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (25)
1. A process for preparing a modified liquid rubber, the process comprising: under the condition of light, the light-emitting diode is arranged in a cavity,
(1) carrying out a polymerization reaction on a divinyl ether monomer and a dimercapto monomer to obtain a reaction material containing a dimercapto-terminated linear polythioether telechelic oligomer;
(2) carrying out contact reaction on the oligomer and liquid rubber;
wherein, the light source with the wavelength of 320-405nm is adopted for illumination;
the liquid rubber is diene liquid rubber, the number average molecular weight of the oligomer is 1000-3000g/mol, and the molecular weight distribution is 1.1-2.0.
2. The method as claimed in claim 1, wherein the illumination is performed by a light source with a wavelength of 340-385 nm.
3. The method according to claim 1, wherein the power of the illumination is 50-300 mW.
4. The method as claimed in claim 1, wherein the power of the illumination is 200-300 mW.
5. The process according to any one of claims 1 to 4, wherein the polymerization reaction and/or the contact reaction is carried out in the presence of a photoinitiator.
6. The method of claim 5, wherein the photoinitiator is selected from at least one of 2-isopropylthioxanthone, benzoin bis methyl ether, and (2,4, 6-trimethylbenzoyl chloride) diphenylphosphine oxide.
7. The method of claim 5, wherein the photoinitiator is used in an amount of 0.5 to 6 wt% based on the total weight of the divinyl ether monomer and dimercapto monomer in the polymerization reaction.
8. The method of claim 5, wherein the photoinitiator is used in an amount of 0.5 to 2 wt% based on the total weight of the divinyl ether monomer and dimercapto monomer in the polymerization reaction.
9. The method according to claim 5, wherein the photoinitiator is used in an amount of 0.5 to 6 parts by weight relative to 100 parts by weight of the liquid rubber in the contact reaction.
10. The method according to claim 5, wherein the photoinitiator is used in an amount of 1.5 to 3.5 parts by weight, relative to 100 parts by weight of the liquid rubber, in the contact reaction.
11. The process as claimed in any one of claims 1 to 4, wherein the diene-based liquid rubber has a number average molecular weight of 1000-30000g/mol and a molecular weight distribution of 1.1-2.0.
12. The method according to any one of claims 1 to 4, wherein the diene-based liquid rubber is selected from polybutadiene liquid rubber and/or polyisoprene-butadiene liquid rubber.
13. The method according to claim 11, wherein the content of the 1, 2-vinyl structural unit in the diene-based liquid rubber is not less than 20% by weight based on the total weight of the diene-based liquid rubber.
14. The method according to claim 11, wherein the content of the 1, 2-vinyl structural unit in the diene-based liquid rubber is 35 to 50% by weight based on the total weight of the diene-based liquid rubber.
15. The method according to claim 13, wherein the oligomer is used in a molar ratio to the diene-based liquid rubber based on the 1, 2-vinyl structural unit contained therein of 1: (1-10).
16. The method according to claim 13, wherein the oligomer is used in a molar ratio to the diene-based liquid rubber based on the 1, 2-vinyl structural unit contained therein of 1: (1-5).
17. The process of any of claims 1-4, wherein the divinyl ether monomer and dimercaptomonomer are used in a molar ratio of 1: (1.2-2).
18. The process of any of claims 1-4, wherein the divinyl ether monomer and dimercaptomonomer are used in a molar ratio of 1: (1.2-1.5).
19. The process of any of claims 1-4, wherein the divinyl ether monomer is selected from at least one of diethylene glycol divinyl ether, triethylene glycol divinyl ether, and divinyl-1, 4-butanediol ether.
20. The method of any one of claims 1-4, wherein the dimercaptomonomer is selected from 1, 4-benzenedimethylthiol and/or 1, 4-benzenemethanethiol.
21. The method of any one of claims 1-4, wherein the polymerization reaction time is 5-120min and the contact reaction time is 5-120 min.
22. The method according to any one of claims 1 to 4, wherein the polymerization reaction time is 20 to 40min and the contact reaction time is 15 to 40 min.
23. A process for preparing a modified liquid rubber, the process comprising: under the condition of light, the light-emitting diode is arranged in a cavity,
(1) carrying out a polymerization reaction on a divinyl ether monomer and a dimercapto monomer to obtain a reaction material containing a dimercapto-terminated linear polythioether telechelic oligomer;
(2) carrying out contact reaction on the reaction material containing the dimercapto-terminated linear polythioether telechelic oligomer and liquid rubber;
wherein, the light source with the wavelength of 320-405nm is adopted for illumination;
the liquid rubber is diene liquid rubber, the number average molecular weight of the oligomer is 1000-3000g/mol, and the molecular weight distribution is 1.1-2.0.
24. A modified liquid rubber prepared by the process of any one of claims 1 to 23.
25. Use of the modified liquid rubber of claim 24 in photocuring.
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| CN201910032984.4A CN111434705B (en) | 2019-01-14 | 2019-01-14 | Modified liquid rubber and preparation method and application thereof |
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| CN201910032984.4A CN111434705B (en) | 2019-01-14 | 2019-01-14 | Modified liquid rubber and preparation method and application thereof |
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