CN107540799B - Hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer and elastomer wire material, and preparation method and application thereof - Google Patents
Hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer and elastomer wire material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer and an elastomer wire material, a preparation method and application thereof; the two ends of the copolymer are polystyrene blocks, the middle of the copolymer is a random copolymerization section of styrene and butadiene, the hydrogenation degree of a butadiene unit is more than 96 percent, and the preparation method comprises the following steps: the preparation method comprises the steps of firstly preparing an S (SB) S triblock copolymer by anionic polymerization, and then hydrogenating the S (SB) S triblock copolymer to obtain an S (SEB) S elastomer, wherein the elastomer is extruded by a single-screw extruder to obtain an elastomer wire, the elastomer wire is very suitable for a desktop-level fused deposition mode 3D printer, the printing stability is good, a product printed by the elastomer wire has a smooth surface, moderate elasticity, sufficient rubber feeling, high bonding strength between layers and excellent comprehensive mechanical properties, can be applied to the fields of toys for children, electronic consumer goods, automotive upholsteries and the like, and has wide market prospect.
Description
Technical Field
The invention relates to a hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer and an elastomer wire material, and a preparation method and application thereof, in particular to a preparation method and application of a hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer wire material suitable for a 3D printing fused deposition mode, and belongs to the field of 3D printing consumable development.
Background
3D printing is a technology for manufacturing a three-dimensional product by adding materials layer by layer through a 3D printing device according to a designed 3D model. This layer-by-layer build-up forming technique is also known as additive manufacturing. The 3D printing integrates advanced technologies in a plurality of fields such as a digital modeling technology, an electromechanical control technology, an information technology, material science and chemistry, is one of rapid prototyping technologies, and is known as a core technology of the third industrial revolution.
The 3D printing technology mainly includes Selective Laser Sintering (SLS), stereo light curing (SLA), Fused Deposition Modeling (FDM), etc., where FDM is the most commonly used technology, and the principle is to utilize thermoplastic polymer material to extrude from a nozzle in a molten state, solidify to form a thin layer with a contour shape, and then stack the thin layers one upon another to finally form a product. At present, the polymer materials used for the FDM forming technology in the market are few in variety and mainly depend on import, acrylonitrile-butadiene-styrene terpolymer (ABS), polylactic acid (PLA), nylon (PA) and the like are commonly used, and most of the materials are hard plastics and have high hardness, so that the requirements of occasions with high toughness requirements cannot be met.
The 3D printing material is an important material basis for the development of the 3D printing technology, and the development of the material determines whether the 3D printing can be widely applied or not to some extent. In recent years, 3D printing technology has been rapidly developed, and the practical application fields thereof have been gradually increased. However, the supply situation of 3D printing materials is not optimistic, and the supply situation becomes a bottleneck that restricts the development of the 3D printing industry. The 3D printing material mainly comprises engineering plastics, photosensitive resin, rubber materials, metal materials, ceramic materials and the like, and besides, food materials such as color gypsum materials, artificial bone powder, cell biological raw materials, granulated sugar and the like are also applied to the field of 3D printing. Among them, the rubber-like materials have the characteristics of various grades of elastic materials, and the hardness, elongation at break, tear strength and tensile strength of these materials make them very suitable for the application fields requiring anti-skid or soft surfaces. According to statistics reported in the industry, more than 200 3D printing consumables are available at present. From a Direct Digital Manufacturing (DDM) perspective, these 200 materials are very limited, especially the variety of flexible consumables.
The development of elastomer materials for 3D printing is still in the beginning, and those developed abroad are called "rubber-like materials, and elastomer materials reported in the prior patents and documents are both acrylate polymers and polyurethane elastomer materials.
It is reported that the flexible wires marketed abroad mainly include NinjaFlex from Fenner Drives and FilaFlex from Recreus, but either NinjaFlex or SemiFlex contains BPA or other toxic gases and cannot be used for manufacturing equipment related to food tableware. In addition, the Tango-series elastomers developed by Objet corporation are suitable for photo-curing molding (SLA), and these materials are mainly applied to the fields of consumer electronics, medical equipment, automotive interior and the like, but generally have problems of low strength and elongation. China is close to the blank in the field of 3D printing flexible material development. Styrenic thermoplastic elastomers (SBC) are currently the highest volume and the fastest growing thermoplastic elastomer worldwide. By virtue of its high strength, softness, rubber elasticity and small permanent deformation, the styrene thermoplastic elastomer has wide application in the aspects of shoe industry, plastic modification, asphalt modification, waterproof coating, liquid sealing material, wires, cables, automobile parts, medical appliance parts, household appliances, office automation, adhesives and the like.
Disclosure of Invention
Aiming at the problem of poor flexibility of the conventional Fused Deposition Mode (FDM)3D printing consumables, the first object of the invention is to provide a flexible hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer with excellent comprehensive mechanical properties.
The second purpose of the invention is to provide a method for preparing the hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer, which has simple operation, low cost and mild conditions.
The third purpose of the invention is to provide the SBC elastomer wire material which has low melt viscosity, low die-release expansion rate, good melt fluidity and excellent comprehensive mechanical property and is particularly suitable for the fused deposition mode 3D printer.
The fourth purpose of the invention is to provide an application of the SBC elastomer filament, the comprehensive performance of the elastomer filament meets the requirements of the FDM mode 3D printer on the filament, the phenomenon of interruption or material piling cannot occur in the printing process, and the printing stability is good.
In order to achieve the above technical objects, the present invention provides a hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer having the structure of formula 1:
wherein the content of the first and second substances,
n is 42 to 78; x is 85-156; y is 292-367; z is 125-244; m is 42 to 78.
In a preferred embodiment, the modified styrene-b-styrene/butadiene-b-polystyrene copolymer is obtained by hydrogenation modification.
The styrene-b-styrene/butadiene-b-polystyrene copolymer has polystyrene blocks at two ends and a random copolymer block of styrene and butadiene in the middle. The randomization degree of the random copolymer block of styrene and butadiene is very high and is basically close to a completely random structure, and the randomization degree is characterized by the nuclear magnetic resonance hydrogen spectrum of the polymer, and the characterization method is the ratio of the chemical shift value on the benzene ring to the ortho-position hydrogen with 6.56 and the absorption peak value of the para-position hydrogen with 7.12.
In a more preferable scheme, the hydrogenation degree of butadiene units in the polystyrene-b-styrene/butadiene random copolymer-b-polystyrene triblock copolymer is more than or equal to 96 percent, and the hydrogenation degree of styrene units is less than or equal to 5 percent. The butadiene unit has higher selective hydrogenation degree, and can endow the polymer with better flexibility and better processing performance.
In a more preferable scheme, the number average molecular weight of the styrene-b-styrene/butadiene-b-styrene copolymer is 4.5-5.5 ten thousand, and the molecular weight distribution index is less than or equal to 1.04.
The invention also provides a method for preparing the hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer, which comprises the steps of firstly adding a styrene monomer into an anionic polymerization system in a polymerization kettle under the condition of maintaining the pressure in the polymerization kettle to be 0.1-0.5 MPa, and carrying out primary polymerization at the temperature of 60-70 ℃; then adding a mixed monomer of butadiene and styrene, and carrying out second-stage polymerization at 60-80 ℃; then adding styrene monomer, and carrying out three-stage polymerization at 60-70 ℃; and after the polymerization is finished, transferring the glue solution into a hydrogenation kettle, introducing hydrogen into the hydrogenation kettle at the temperature of 70-75 ℃ in the presence of a hydrogenation catalyst, and carrying out hydrogenation reaction to obtain the catalyst.
In the preferred scheme, the butadiene monomer and the styrene monomer are uniformly mixed and then added into an anionic polymerization system for secondary polymerization.
In a more preferred embodiment, the butadiene monomer and the styrene monomer are uniformly mixed by the following method: 1) pumping the inside of a sealing tank I to negative pressure, and pumping a styrene monomer into the sealing tank I; 2) pumping the inside of a sealing tank II into negative pressure, and pumping a butadiene monomer into the sealing tank II; 3) and pressing the styrene monomer in the seal pot I into the seal pot II by using nitrogen, and fully and uniformly mixing the styrene monomer and the butadiene monomer by using the pressure action of the nitrogen in the seal pot II, or pressing the butadiene monomer in the seal pot II into the seal pot I by using the nitrogen, and fully and uniformly mixing the butadiene monomer and the styrene monomer by using the pressure action of the nitrogen in the seal pot I.
In a further preferable scheme, the nitrogen pressure of the seal tank I or the seal tank II is maintained at 0.4-0.6 MPa.
In a preferred embodiment, the mixed monomers of butadiene and styrene are added in a single step, in portions or continuously.
In a preferred embodiment, the anionic polymerization system comprises a non-polar alkane solvent, an initiator and a randomizer.
In a more preferable scheme, the nonpolar alkane solvent is cyclohexane, and the dosage of the cyclohexane maintains the mass percentage concentration of the polymerized monomers in the anionic polymer system within the range of 5-15%.
In a more preferred embodiment, the initiator is n-butyllithium, and the amount of n-butyllithium used is determined based on the molecular weight of the polymer being designed, as is well known to those skilled in the art.
In a more preferable scheme, the randomizing agent is at least one of ditetrahydrofurfurylpropane, tetramethylethylenediamine, tetrahydrofurfuryl alcohol ethyl ether and tetrahydrofuran; the dosage of the randomizer relative to the nonpolar alkane solvent is 70-110 mg/kg.
Preferably, the period of polymerization is 25-35 min.
In a preferred scheme, the second-stage polymerization time is more than or equal to 50 min.
In a preferred scheme, the three-stage polymerization time is 25-35 min.
In the preferable scheme, the hydrogen pressure in the hydrogenation reaction process is 1.0-2 MPa, and the hydrogenation reaction time is 1.5-2.5 h.
In a preferable scheme, the hydrogenation catalyst is a dicyclopentadiene titanium dichloride/dimethyl phthalate combined hydrogenation catalyst.
The invention adopts dicyclopentadiene titanium dichloride/dimethyl phthalate combined catalyst, which takes dimethyl phthalate as a cocatalyst and dicyclopentadiene titanium dichloride as a main catalyst. In the hydrogenation reaction process, the glue solution is pressed into a hydrogenation kettle which is replaced by nitrogen, the temperature is raised to 70-75 ℃, a cocatalyst dimethyl phthalate is firstly added for passivation reaction for 5-15 min, a main catalyst dicyclopentadiene titanium dichloride is then added, hydrogenation reaction is carried out under the hydrogen pressure of 1.0-2.0 MPa, the hydrogenation reaction lasts for 1.5-2.5 h, the hydrogenation degree of a polymer polybutadiene section is more than or equal to 98%, and the hydrogenation degree of a benzene ring is less than or equal to 5%.
The hydrogenated styrene-styrene/butadiene-styrene copolymer (S (SEB)) prepared by the invention needs to remove metal ions, and the main process comprises the following steps: terminating the hydrogenated glue solution by using a small amount of soft water for 15min, acidifying the hydrogenated glue solution by using tertiary decanoic acid for 30min, finally adding soft water with the volume being 10 percent of the volume of the glue solution, emulsifying and extracting the mixture for 15min, centrifuging the mixture, standing the mixture, separating out a water phase, and adding the n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (1076) or the mixture of the n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and tris [2, 4-di-tert-butylphenyl ] phosphite ester (168) into the residual glue solution. Condensing with water vapor, and drying in a forced air drying oven for 8 hr.
The invention provides an SBC elastomer wire which is obtained by extruding a hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer by a double-screw extruder.
In the preferred scheme, the process parameters of the single-screw extruder in the extrusion process are as follows: the diameter of a mouth mold of the single-screw extruder is 1.5-1.7 mm, and the rotating speed of a screw is 120-150 revolutions per minute; the cavity comprises five regions from the feeding end to the discharging end in sequence, and the temperature and pressure conditions of each region are as follows in sequence: 175-185 ℃ and 14-16 bar; and a second zone: 185-195 ℃; 12-14 bar; and (3) three zones: 195-205 ℃; 11-13 bar; and (4) four areas: 195-205 ℃; 11-13 bar; and a fifth zone: 195-205 ℃; 11 to 13 bar. Further preferably, the temperature and pressure conditions in each zone of the twin-screw extruder are, in order, zone: 15bar at 180 ℃; and a second zone: 190 ℃; 13 bar; and (3) three zones: 200 ℃; 12 bar; and (4) four areas: 200 ℃; 12 bar; and a fifth zone: 200 ℃; 12 bar.
The invention also provides an application of the SBC elastomer wire, which is to apply the SBC elastomer wire as a 3D printing material to a 3D printing preparation device.
Preferably, the 3D printing adopts a desktop-level fused deposition mode 3D printer.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1. the hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer provided by the invention has a special molecular structure, wherein the two ends of the copolymer are styrene blocks, the middle of the copolymer is a styrene butadiene block, the butadiene block contains a 1,2 structure with a high proportion, and butadiene units are highly hydrogenated.
2. The SBC elastomer filament prepared by the flexible hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer has three outstanding advantages: one of the advantages is that the middle section of S (SEB) S is a special structure of random copolymerization section of styrene and butadiene to endow the elastomer with lower melt viscosity, the prepared filament material has low die release expansion rate, and the die release expansion coefficient is less than or equal to 1.05. Secondly, the melt fluidity of the wire is excellent, and the melt index under the conditions of 200 ℃ and 5Kg load is as follows: 15-20 g/10 min. Thirdly, the Shore A hardness of the wire is 78-82 degrees, the elasticity is moderate, and the wire can meet application occasions with high requirements on flexibility. Therefore, the developed S (SEB) S elastomer wire can completely meet the requirements of the FDM mode 3D printer on the wire.
3. The elastomer wire provided by the invention is used for 3D printing of desktop FDM printing equipment, the phenomenon of printing interruption or material bet of most commercialized flexible wires can not occur in the printing process, and the printing stability is good. In addition, the elastomer wire has good thermal stability, no peculiar smell is smelled in the whole printing process, and the elastomer wire is safer and more environment-friendly compared with ABS and PLA wires. The printed product has smooth surface, excellent physical property and sufficient rubber feeling, is very suitable for the fields of children toys, electronic consumer goods, automotive upholstery and the like, and has wide market prospect. The development of the elastomer wire not only enriches the types of FDM mode 3D printing consumables, but also promotes the development of Styrene (SBC) thermoplastic elastomers in China to a higher end direction.
4. The hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer has the advantages of simple preparation method, low cost and mild process conditions, and meets the requirements of industrial production and application.
Drawings
FIG. 1 shows the nuclear magnetic hydrogen spectrum of the S (SB) S base gum prepared in example 1.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Example 1
Adding 3000 mL of pure cyclohexane (water value is less than 20ppm) and 2.0mL of bistetrahydrofurfuryl propane (prepared into a cyclohexane solution with the concentration of 0.5mol/L and the dosage is equivalent to 80mg/kg of solvent) into a 5-liter polymerization kettle replaced by high-purity nitrogen, starting stirring, heating to 60 ℃, then respectively adding 49mL of styrene monomer and 6.0mmol of n-butyl lithium, carrying out polymerization reaction for 30 minutes, then adding 242mL of mixed monomer of butadiene and 65mL of styrene, adding the mixed monomer into the polymerization kettle in a one-time adding manner, controlling the reaction temperature to be below 80 ℃, adding 49mL of styrene monomer after reacting for 50 minutes, and carrying out reaction for 30 minutes at the temperature of 60-65 ℃. And introducing the glue solution into a 10L hydrogenation kettle after the polymerization reaction is finished, heating to 70 ℃, supplementing 8mmol of n-butyl lithium, and terminating the reaction for 10 minutes by using hydrogen. Adding 4mL (0.2mol/L) of dibutyl phthalate serving as a cocatalyst and 0.2g of dicyclopentadiene titanium dichloride serving as a main catalyst, controlling the hydrogenation pressure to be 1.0-1.5 Mpa, carrying out hydrogenation reaction for two hours, and supplementing the cocatalyst 2-3 times in the middle, wherein the amount of the cocatalyst is 2mL each time. And after the hydrogenation reaction is finished, transferring the hydrogenated glue solution to a washing kettle, heating to 60-65 ℃, stopping the reaction of the hydrogenated glue solution for 15min by using 10mL of soft water, acidifying for 30min by using 2mL of tert-decanoic acid (dissolved in 200mL of cyclohexane), emulsifying and extracting for 15min by using 300mL of soft water, centrifuging, standing, separating out a water phase, condensing the residual glue solution by using water vapor, and drying to obtain the hydrogenated styrene-styrene/butadiene-styrene copolymer.
The hydrogenated styrene-styrene/butadiene-styrene copolymer thus obtained was uniformly mixed with n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (1076) or tris [ 2.4-di-tert-butylphenyl ] phosphite (168) in a high-speed mixer in such a manner that the oxygen resistance was 99.7: 0.3 by mass. The mixture is melted and extruded on a small single screw extruder, and the extrusion process comprises the following steps: the rotating speed of the screw is 270-350 revolutions per minute; the temperature of each zone of the injection molding machine screw is respectively as follows: a first area: 180 ℃; and a second zone: 190 ℃; and (3) three zones: 200 ℃; and (4) four areas: 200 ℃; and a fifth zone: 200 ℃; the corresponding pressure in each zone is: a first area: 15 bar; and a second zone: 13 bar; and (3) three zones: 12 bar; and (4) four areas: 12 bar; and a fifth zone: 12 bar.
Selecting a printing model, printing the prepared elastomer wire on a desktop printer with the model of makerbot regenerator 2, and setting the software printing temperature to be 230 ℃.
And respectively carrying out corresponding performance tests. The results of each test are as follows:
GPC analysis results: the number average molecular weight of the base rubber is 5.1 ten thousand, the molecular weight distribution is 1.03, and the test standard is carried out according to ISO16014-1: 2003;
HNMR analysis results: s (SB) the PB segment 1, 2-structure content of the S base glue is 35.4%, the randomness of the random copolymerization segment of the styrene and the butadiene is 99.5, the nuclear magnetic hydrogen spectrum diagram is shown in the attached figure 1, and the test standard is executed according to JJF 1448-2014;
iodine value analysis results: the degree of hydrogenation was 98.2%;
results of S (SEB) S elastomer performance tests are shown in Table 1, and the test standards are performed according to GB/T3354-1999:
TABLE 1 results of performance tests on S (SEB) S elastomer obtained in example 1
Note: die diameter divided by die expansion coefficient
Description of the printing situation: the printing stability is good without wire clamping. The product has smooth surface, good elasticity, high bonding strength between layers and excellent comprehensive mechanical property.
Example 2
The procedure of example 1 was repeated, except that the amount of n-butyllithium as an initiator (6.6mmol) was changed to synthesize a hydrogenated styrene-styrene/butadiene-styrene copolymer having a base gum molecular weight of 4.6 ten thousand. The results are shown in Table 2:
TABLE 2 results of S (SEB) S elastomer structures and performance tests obtained in example 2
Description of the printing situation: the printing stability is good because the wire is not clamped; the apparent quality of the product is excellent.
Example 3
The procedure of example 1 was repeated to change the amounts of the first and third styrene units (39mL) and the third styrene unit (85mL) to synthesize a hydrogenated styrene-styrene/butadiene-styrene copolymer having a styrene block content of 12% in the first and third styrene units and a styrene content of 26% in the random styrene unit. The results are shown in Table 3:
TABLE 3 results of testing the S (SEB) S elastomer structure and properties obtained in example 3
Description of the printing situation: the printing stability is good because the wire is not clamped; the apparent quality of the product is excellent.
Example 4
The procedure is as in example 1 except that the randomizer is replaced by tetrahydrofurfuryl alcohol ethyl ether, which is added in the same amount as ditetrahydrofurkanopropane. The results are shown in Table 4:
TABLE 4 results of performance tests on S (SEB) S elastomer obtained in example 4
The above table shows that tetrahydrofurfuryl alcohol ethyl ether is slightly less randomizing than ditetrahydrofurfuryl propane.
Description of the printing situation: the printing stability is good because the wire is not clamped; the apparent quality of the product is excellent.
Example 5
The procedure of example 1 was followed to synthesize a hydrogenated styrene-styrene/butadiene-styrene copolymer having a higher 1, 2-structure content and a higher degree of randomization while changing the amount of ditetrahydrofurfuryl propane (2.6mL, equivalent to 100mg/kg of solvent), and the experimental results are shown in Table 5:
TABLE 5 results of S (SEB) S elastomer structures and Performance tests obtained in example 5
Description of the printing situation: the printing stability is good because the wire is not clamped; the apparent quality of the product is excellent.
Example 6
The addition of the mixed monomers in example 1 was changed from one addition to ten additions to synthesize hydrogenated styrene-styrene/butadiene-styrene copolymers having a higher degree of randomization, and the experimental results are shown in Table 6:
TABLE 6 results of S (SEB) S elastomer structure and performance testing obtained in example 6
This indicates that the addition of the mixed monomer in ten times is not very significant in improving the degree of randomization.
Description of the printing situation: the printing stability is good because the wire is not clamped; the apparent quality of the product is excellent.
Example 7
The addition of the mixed monomers in example 1 was changed from one addition to ten additions to synthesize hydrogenated styrene-styrene/butadiene-styrene copolymers having a higher degree of randomization, and the experimental results are shown in Table 7:
TABLE 7 results of S (SEB) S elastomer structure and performance testing obtained in example 7
The mixed monomers are continuously added to obtain the hydrogenated styrene-styrene/butadiene-styrene copolymer which is basically nearly random.
Description of the printing situation: the printing stability is good because the wire is not clamped; the apparent quality of the product is excellent.
Claims (20)
1. A hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer characterized by: has the structure of formula 1:
wherein the content of the first and second substances,
n is 42 to 78;
x is 85-156;
y is 292-367;
z is 125-244;
m is 42 to 78.
2. The hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer according to claim 1, wherein: obtained by hydrogenating and modifying a styrene-b-styrene/butadiene-b-styrene copolymer.
3. The hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer according to claim 2, wherein: the hydrogenation degree of a butadiene unit in the styrene-b-styrene/butadiene-b-styrene copolymer is more than or equal to 96 percent, and the hydrogenation degree of a styrene unit is less than or equal to 5 percent.
4. The hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer according to claim 2, wherein: the number average molecular weight of the styrene-b-styrene/butadiene-b-styrene copolymer is 4.5-5.5 ten thousand, and the molecular weight distribution index is less than or equal to 1.04.
5. A process for producing the hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer according to any one of claims 1 to 4, wherein: under the condition of maintaining the pressure in the polymerization kettle to be 0.1 MPa-0.5 MPa, firstly adding styrene monomer into an anionic polymerization system in the polymerization kettle, and carrying out first-stage polymerization at the temperature of 60-70 ℃; then adding a mixed monomer of butadiene and styrene, and carrying out second-stage polymerization at 60-80 ℃; then adding styrene monomer, and carrying out three-stage polymerization at 60-70 ℃; and after the polymerization is finished, transferring the glue solution into a hydrogenation kettle, introducing hydrogen into the hydrogenation kettle at the temperature of 70-75 ℃ in the presence of a hydrogenation catalyst, and carrying out hydrogenation reaction to obtain the catalyst.
6. The process for producing a hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer according to claim 5, wherein: after the butadiene monomer and the styrene monomer are uniformly mixed, the mixture is added into an anionic polymerization system for secondary polymerization.
7. The process for producing a hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer according to claim 6, wherein: the butadiene monomer and the styrene monomer are uniformly mixed by the following method: 1) will seal the jar
Is internally pumped into negative pressure, and is arranged in the sealed tank
Adding styrene monomer; 2) will seal the jar
Is internally pumped into negative pressure, and is arranged in the sealed tank
A butadiene monomer is added into the mixture; 3) sealing the tank with nitrogen
The styrene monomer in the sealing tank is pressed into the sealing tank
In, utilize a sealed tank
The pressure of the nitrogen inside the reactor is used for fully and uniformly mixing the styrene monomer and the butadiene monomer; alternatively, the sealed tank is filled with nitrogen gas
The butadiene monomer in the rubber is pressed into the sealing tank
In, utilize a sealed tank
The pressure of the nitrogen inside the reactor is used for fully and uniformly mixing the butadiene monomer and the styrene monomer.
8. The process for producing a hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer according to claim 7, wherein: the sealing tank
Or sealed cans
The nitrogen pressure is maintained at 0.4 to 0.6 MPa.
9. The process for producing a hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer according to claim 5, wherein: the addition mode of the mixed monomer of butadiene and styrene is one-time addition, batch addition or continuous addition.
10. The process for producing a hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer according to claim 5, wherein: the anionic polymerization system comprises a non-polar alkane solvent, an initiator and a randomizer.
11. The process for producing a hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer according to claim 10, wherein: the nonpolar alkane solvent is cyclohexane, and the dosage of the cyclohexane maintains the mass percentage concentration of the polymer monomer in the anionic polymer system within the range of 5-15%.
12. The process for producing a hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer according to claim 10, wherein: the initiator is n-butyl lithium.
13. The process for producing a hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer according to claim 10, wherein: the randomizing agent is at least one of ditetrahydrofurfurylpropane, tetramethylethylenediamine, tetrahydrofurfuryl alcohol ethyl ether and tetrahydrofuran; the dosage of the randomizer relative to the nonpolar alkane solvent is 70-110 mg/kg.
14. The process for producing a hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer according to claim 5, wherein: the first-stage polymerization time is 25-35 min, the second-stage polymerization time is more than or equal to 50min, and the third-stage polymerization time is 25-35 min.
15. The process for producing a hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer according to claim 5, wherein: in the hydrogenation reaction process, the hydrogen pressure is 1.0-2 MPa, and the hydrogenation reaction time is 1.5-2.5 h.
16. The process for producing a hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer according to claim 5, wherein: the hydrogenation catalyst is a dicyclopentadiene titanium dichloride/dimethyl phthalate combined hydrogenation catalyst.
17. An SBC elastomer filament, characterized in that: the hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer according to any one of claims 1 to 4, which is obtained by a twin-screw extruder extrusion process.
18. The SBC elastomer filament of claim 17, wherein: the process parameters of the single-screw extruder in the extrusion process are as follows: the diameter of a mouth mold of the single-screw extruder is 1.5-1.7 mm, and the rotating speed of a screw is 120-150 revolutions per minute; the cavity comprises five regions from the feeding end to the discharging end in sequence, and the temperature and pressure conditions of each region are as follows in sequence: 175-185 ℃ and 14-16 bar; and a second zone: 185-195 ℃ and 12-14 bar; and (3) three zones: 195-205 ℃ and 11-13 bar; and (4) four areas: 195-205 ℃ and 11-13 bar; and a fifth zone: 195-205 ℃ and 11-13 bar.
19. The use of the SBC elastomer filament of claim 18, wherein: the material is applied to 3D printing preparation devices as a 3D printing material.
20. The use of the SBC elastomer filament of claim 19, wherein: the 3D printing adopts a desktop-level fused deposition mode 3D printer.
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| CN113736041A (en) * | 2020-05-28 | 2021-12-03 | 中国石油化工股份有限公司 | Styrene elastomer, preparation method thereof and application of styrene elastomer as wear-resistant and slip-resistant sole material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1865294A (en) * | 2005-05-17 | 2006-11-22 | 北京化工大学 | Hydrogenated styrene analog thermoplastic elastomer and its preparation method |
| DE102011017310A1 (en) * | 2011-04-16 | 2012-10-18 | Kai Parthy | Three dimensional printing head for melting and depositing layers of wire-shaped materials, has various types of wire feeders and feed channels for wires, where soft wire is made of thermoplastic elastomers |
| CN103756236A (en) * | 2014-01-06 | 2014-04-30 | 朱叶周 | Thermoplastic elastomer composition for preparing flexible printing material for three-dimensional printing rapid prototyping |
| CN104945559A (en) * | 2014-03-26 | 2015-09-30 | 中国石油化工股份有限公司 | Hydrogenated polystyrene-b-styrene/butadiene/isoprene random copolymer as well as preparation method and application thereof |
| CN105199178A (en) * | 2015-09-21 | 2015-12-30 | 江苏科技大学 | Three-dimensional printing photosensitive resin material containing modified butadiene rubber and preparation method |
| CN105504174A (en) * | 2015-12-29 | 2016-04-20 | 成都新柯力化工科技有限公司 | Spherical styrene-butadiene rubber for 3D printing and preparation method thereof |
-
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- 2016-06-28 CN CN201610490953.XA patent/CN107540799B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1865294A (en) * | 2005-05-17 | 2006-11-22 | 北京化工大学 | Hydrogenated styrene analog thermoplastic elastomer and its preparation method |
| DE102011017310A1 (en) * | 2011-04-16 | 2012-10-18 | Kai Parthy | Three dimensional printing head for melting and depositing layers of wire-shaped materials, has various types of wire feeders and feed channels for wires, where soft wire is made of thermoplastic elastomers |
| CN103756236A (en) * | 2014-01-06 | 2014-04-30 | 朱叶周 | Thermoplastic elastomer composition for preparing flexible printing material for three-dimensional printing rapid prototyping |
| CN104945559A (en) * | 2014-03-26 | 2015-09-30 | 中国石油化工股份有限公司 | Hydrogenated polystyrene-b-styrene/butadiene/isoprene random copolymer as well as preparation method and application thereof |
| CN105199178A (en) * | 2015-09-21 | 2015-12-30 | 江苏科技大学 | Three-dimensional printing photosensitive resin material containing modified butadiene rubber and preparation method |
| CN105504174A (en) * | 2015-12-29 | 2016-04-20 | 成都新柯力化工科技有限公司 | Spherical styrene-butadiene rubber for 3D printing and preparation method thereof |
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