Thermoplastic elastic resin / elastomer and preparation method thereof

Abstract

The invention discloses thermoplastic elastic resin / elastomer and a preparation method thereof. The thermoplastic elastic resin / elastomer is an elastic alloy obtained by modifying polyolefin resin with a polyethylene-butylene rubber (E-B / E-E) transparent elastomer, has proper hardness, tensile strength, modulus, impact toughness, rebound resilience, oil resistance, wear resistance, low compression set and good processability, and is economical and environment-friendly; the preparation method can adopt the existing mature equipment and process for preparation, and is easy to industrialize.

Description

Technical Field

[0001] The invention relates to a thermoplastic elastic resin / elastomer and a preparation method thereof, in particular to an elastic alloy of polyethylene-butylene rubber (EB / EE) transparent elastomer modified polyolefin resin, belonging to the technical field of new rubber materials. Background Art

[0002] Traditional polyethylene and polypropylene resins on the market have defects such as low impact strength, especially low-temperature brittleness, easy aging, poor toughness, and easy cracking. Usually, they are blended with ethylene propylene rubber (EPDM) or polyolefin elastomer (POE) or dynamically vulcanized to improve their tensile strength and low impact toughness, and are widely used in automobile bumpers, door panels, interior trims, home appliance housings, office appliances, and plastic accessories for two-wheeled motor vehicles. The "2013-2018 China EPDM Market Research and Development Prospects Consulting Report" predicts that the total domestic demand for EPDM will reach about 320,000 tons in 2015, of which automobiles and polymer modification will still be the two main consumer areas. The use of EPDM in the global automotive industry accounts for 42% to 44% of the total use.

[0003] The ratio of ethylene to propylene in the EPDM molecule can be changed during the polymerization stage. When the ethylene-propylene ratio changes from 50 / 50 to 80 / 20, the positive effects are: higher green strength, higher tensile strength, higher crystallization, higher glass transition temperature, the ability to convert the raw polymer into pellets, and better extrusion characteristics. The negative effects are poor calendering mixing, poor low temperature properties, and poor compression set. When the propylene ratio is higher, the benefits are better processing performance, better low temperature properties, and better compression set. The molecular weight of EPDM is usually expressed as Mooney viscosity. The Mooney viscosity value of EPDM is obtained at a high temperature of 125°C. The main reason is to eliminate the crystallization caused by the high ethylene content, which will mask the true molecular weight of the polymer. The Mooney viscosity of EPDM ranges from 20 to 100. Its molecular weight distribution index varies from 2 to 5. As the molecular weight distribution increases, the mixing and milling processability increases. However, a narrower molecular weight distribution can improve the vulcanization rate, the vulcanization state and the injection molding behavior. EPDM can be vulcanized with peroxide or sulfur, showing higher temperature resistance, lower compression set and improved vulcanization characteristics.

[0004] In "Thermoplastic Elastomers", 99 rubber / plastic blends prepared from 11 rubbers and 9 plastics were reviewed. The study found that in order to obtain the best performance of the rubber / thermoplastic dynamic vulcanization blend, the surface energy of the two polymers of plastic and rubber must be matched; the length of the rubber entanglement molecular chain is low, and the crystallinity of the plastic is greater than 15%. When the polarity or surface energy difference between the plastic and the rubber is relatively large, adding a suitable compatibilizer and then dynamically vulcanizing can also obtain a blend with excellent performance. Commercially available PP / PE / EPDM and PP / EPDM can form dynamically vulcanized thermoplastic elastomers (TPV), accounting for 90% of the total TPV, mainly because PP and EPDM materials have better compatibility, the vulcanization system that EPDM can use is relatively mature, and EPDM has very good weather resistance, and ultimately has a medium raw material cost. Thermoplastic ethylene propylene rubber (EPDM / PP) is a product in which EPDM is mixed with PP based on EPDM as the main body. At the same time, the EPDM reaches the expected degree of crosslinking. It not only retains the inherent properties of EPDM, but also has significant thermoplastic injection, extrusion, blow molding and calendering processing properties.

[0005] In addition, the existing commercially available polyolefin elastomer (POE) is copolymerized by ethylene and comonomer butene or octene, and the comonomer content in its molecular structure is 20-30%. The presence of 1-butene or 1-octene chain segments in the molecule at room temperature destroys the polyethylene chain, but also gives the copolymer excellent transparency and good elasticity. The crystallization of the polyethylene chain at room temperature serves as a physical crosslinking point, and the amorphous region of the random copolymer chain of ethylene-comonomer makes the copolymer plastic. The insufficient molecular weight distribution makes POE have higher tensile strength and impact resistance, and also reflects good processing performance, but the disadvantages are high modulus, high hardness, poor resilience, incompatibility with white oil, poor oil resistance, wear resistance and compression permanent deformation. It has been widely used when blended with polyolefin resins, but it has large usage, increased cost and large price fluctuations when used together with polyolefin resins.

[0006] However, the existing EPDM pellet products of DOW Chemical Company are all low-crystallinity polymers with a crystallization temperature (Tc) of 30-46°C. When the temperature rises, the crystallinity of the polymer decreases, the physical and mechanical properties decrease, and the tensile deformation is higher than 140%, which has the behavior of rubber and is not completely a thermoplastic elastomer. The PP / EPDM dynamically vulcanized thermoplastic elastic materials all have large compression deformation, hairy surface and tiny defects, are not scratch-resistant and easy to scratch.

[0007] To sum up, how to improve and overcome such defects, select a polymer with small dosage, economy and good comprehensive performance to modify the existing PP resin, and overcome the shortcomings of the existing EPDM and POE modified PP, is the current development direction of civil and industrial products. Summary of the invention

[0008] In view of the defects of the existing composite materials of EPDM or POE combined with PP, the first object of the present invention is to provide an elastic alloy obtained by modifying a polyolefin resin with a polyethylene-butylene rubber (EB / EE) transparent elastomer, which has suitable hardness, tensile strength, modulus, impact toughness, resilience, oil resistance, wear resistance, low compression permanent deformation and good processing performance, and is economical and environmentally friendly.

[0009] The second object of the present invention is to provide a method for preparing a thermoplastic elastic resin / elastomer, which is simple, low-cost, can be produced using existing mature equipment and processes, and is easy to industrialize.

[0010] In order to achieve the above technical purpose, the present invention provides a thermoplastic elastic resin / elastomer, which comprises raw materials including EB / EE rubber, polyolefin resin and auxiliary materials;

[0011] The EB / EE rubber has a structure of Formula 1:

[0012]

[0013] in,

[0014] n, m, x, y, n1, m1, x1, y1, n2, m2, x2 and y2 are degrees of polymerization;

[0015] (x+y) / (x+y+n+m)﹤0.14;

[0016] (x1+y1) / (x1+y1+n1+m1)=0.35~0.60;

[0017] (x2+y2) / (x2+y2+n2+m2)﹤0.14;

[0018] (x+y+x1+y1+x2+y2) / (n+m+n1+m1+n2+m2+x+y+x1+y1+x2+y2)=0.20~0.40;

[0019] The double bond hydrogenation rate is 99.50-99.75%.

[0020] The double bond hydrogenation rate of the present invention refers to the molar percentage of hydrogenated butadiene units in the total butadiene units.

[0021] The key to the thermoplastic elastic resin / elastomer of the present invention is to use EB / EE rubber to modify the polyolefin resin. After the two are compounded, they produce good flexibility, high resilience, high elastic modulus, low compression deformation and anti-aging properties. EB / EE rubber is obtained by hydrogenating polybutadiene obtained by anionic polymerization, and its hydrogenation rate reaches 99.5% to 99.75%. The small amount of double bonds remaining can be used for crosslinking and vulcanization. EB / EE rubber has a three-block structure, and its two ends are polybutadiene with a very high 1,4-polymerization ratio. After hydrogenation, it mainly forms a polyethylene block, that is, an E block, which has a relatively high crystallinity, while the middle segment is a polybutadiene with a high 1,2-polymerization ratio. After hydrogenation, it mainly forms a polyethylene / poly-1-butene random block, that is, a B / E block, which has a very low crystallinity and has soft segment properties. The E block in the EB / EE rubber molecule can provide physical cross-linking points, giving the polymer high tensile strength, and has the same polyethylene main chain as polyolefin resin, with good compatibility. The B / E block in the EB / EE rubber molecule gives the polymer good flexibility, high resilience and other properties, and the trace double bonds provide chemical vulcanization cross-linking points for the polymer. After blending with polyolefins, it can form a homogeneous composite similar to an island-like distribution through vulcanization cross-linking, thereby improving the comprehensive physical properties of the composite material.

[0022] As a preferred scheme, (x+y+x1+y1+x2+y2) / (n+m+n1+m1+n2+m2+x+y+x1+y1+x2+y2)=0.25~0.30.

[0023] As a preferred solution, (x+y+n+m):(x1+y1+n1+m1):(x2+y2+n2+m2)=(0.50-2.5):(3.5-5.0):(0.50-2.5). The number average molecular weight M of the E blocks at both ends of the EB / EE rubber of the present invention is n (0.50~2.5)×10 4 If the molecular weight is too low, the crystallinity is too low and the tensile strength of the polymer is too low. If the molecular weight is too high, the B / E molecular chain presents a disordered distribution of random segments. If the molecular weight is too low, the modulus of the polymer increases and the elasticity decreases. The molecular weight M of the middle B / E block is too high. n (3.5~5.0)×10 4 .

[0024] As a preferred solution, the Mooney viscosity ML of the EB / EE rubber is 125℃The Mooney viscosity of the rubber is usually measured at 100°C / (1+4min). The EB / EE molecules of the present invention contain highly isotactic E blocks and have relatively high crystallinity. The polymer molecules are not completely randomly distributed and cannot accurately reflect the molecular weight of the polymer (the Mooney viscosity and the molecular weight present a corresponding relationship). Therefore, the Mooney viscosity of the polymer of the present invention is measured at 125°C / (1+4min), which can eliminate the crystallization and cohesive energy of the polymer. If the Mooney viscosity is too large, melt fracture will occur when it is blended and extruded with polyolefin resin, and defects will occur in the product. That is, it is more suitable that the melting temperatures of the polymer and the polyolefin are not much different.

[0025] As a preferred solution, the number average molecular weight M of the EB / EE rubber is n =(6.0~8.0)×10 4 , molecular mass distribution M w / M n =1.05 to 1.20. The molecular weight distribution of the E-BEB-E rubber of the present invention is a medium narrow distribution.

[0026] As a more preferred solution, the polyolefin resin includes polypropylene and / or polyethylene. The most preferred polyolefin resin is PP with a melt index (MFR) of 3 to 15 g / min, such as PP T30.

[0027] As a more preferred solution, the auxiliary materials include rubber filling oil, inorganic filler, organic peroxide, antioxidant, colorant and light stabilizer.

[0028] As a more preferred solution, the rubber filler oil includes cycloalkyl rubber filler oil and / or paraffin-based rubber filler oil. The preferred rubber filler oil is at least one of the commercially available KN4010, KN4006, 150N and 32# white oil. The greater the amount of rubber filler oil, the modified polyolefin resin exhibits the behavior of a thermoplastic elastomer; the smaller the amount of white oil, the composite exhibits the behavior of a cemented carbide with high toughness and low elasticity. The amount of rubber filler oil is 10 to 200 g / 100 g rubber, and the further preferred amount is 10 to 100 g / 100 g rubber.

[0029] As a more preferred solution, the inorganic filler includes light calcium carbonate and / or talcum powder. The amount of the inorganic filler is 30-80 g / 100 g rubber, and the more preferred amount is (30-60) g / 100 g rubber resin.

[0030] As a more preferred solution, the organic peroxide includes di-tert-butyl diisopropylbenzene peroxide and / or diisopropylbenzene peroxide. The amount of the organic peroxide is (0.03-1.20) g / 100 g rubber, and the further preferred amount is (0.30-0.60) g / 100 g rubber. The EB / EE rubber in the composite material is cross-linked under the high temperature of 150°C or above by the peroxide, and the molecular weight is improved, which can better reflect the anti-aging property and comprehensive physical properties.

[0031] As a more preferred solution, the antioxidant includes at least one of 3114, 1010, and 1076. A further preferred antioxidant is 3114 or 1010, because such antioxidants have good suction resistance and low migration in resins or rubbers composed of hydrocarbon elements. The amount of the antioxidant is 0.03-2.5 g / 100 g of rubber resin, and a further preferred amount is 0.2-1.5 g / 100 g of rubber resin.

[0032] As a more preferred solution, the colorant includes inorganic pigments and / or organic pigments; the preferred colorant is commercially available inorganic pigments or organic pigments such as carbon black and scarlet, and the further preferred amount thereof is 5 to 10 g / 100 g of rubber resin.

[0033] As a more preferred solution, the light stabilizer includes a UV-327 compound. The light stabilizer is further preferably a UV-327 compound, and its further preferred dosage is 0.05-0.07 g / 100 g rubber resin. It is worth mentioning that antioxidants and light stabilizers are both highly polar organic compounds, which have poor compatibility with non-polar hydrocarbon polymers. Excessive dosage is prone to migration and the product will produce blooming.

[0034] As a preferred solution, the thermoplastic elastic resin / elastomer includes the following mass component raw materials: 100 parts of polyolefin resin, 10-200 parts of EB / EE rubber, 30-80 parts of inorganic filler, 10-200 parts of rubber filler oil, 0.03-1.20 parts of organic peroxide, 0.03-0.70 parts of antioxidant, 0.15-0.20 parts of light stabilizer, and 5-20 parts of colorant.

[0035] The present invention also provides a method for preparing a thermoplastic elastic resin / elastomer, which comprises the following steps:

[0036] 1) polyolefin resin, EB / EE rubber and auxiliary materials including inorganic fillers, antioxidants and light stabilizers are mixed and granulated by screw extrusion at high speed to obtain masterbatch;

[0037] 2) The masterbatch is mixed with auxiliary materials including organic peroxide and filler oil and granulated by twin-screw extrusion to obtain a thermoplastic elastic resin / elastomer.

[0038] As a more preferred solution, in step 1), during the high-speed mixing process, the mixer speed is not less than 1500 rpm / min, and the time is not less than 3 minutes.

[0039] As a more preferred solution, in step 2), the speed of the mixer during the mixing process is 500 to 800 rpm / min, and the mixing time is 3 to 5 minutes.

[0040] As a more preferred solution, in step 1) and step 2), the melting temperature of the screw extrusion granulation is 180-230°C.

[0041] The preparation method of the thermoplastic tough resin and the thermoplastic elastomer provided by the present invention is specifically as follows:

[0042] In the first step, polyolefin resin, EB / EE, inorganic filler, antioxidant and UV-327 are mixed by a high-speed mixer at a speed of not less than 1500 rpm / min for not less than 3 minutes, and then the mixture is put into a screw extruder for melt mixing and granulation at 180-230°C to form a masterbatch.

[0043] In the second step, the organic peroxide vulcanizer is evenly dissolved in white oil, and then mixed with the masterbatch prepared in the first step in a mixer at a speed of 500-800 rpm / min for 3-5 minutes to evenly coat the white oil-containing vulcanizer on the surface of the masterbatch, and then placed in a twin-screw extruder at 180-230° C. for extrusion granulation, which is a dynamically vulcanized thermoplastic elastic resin or elastomer.

[0044] Among them, the preferred dynamic vulcanization (residence time of the material in the twin-screw extruder) time is not less than 30 seconds, the cross-linking temperature is not lower than 180°C, the preferred EB / EE cross-linking particle size is 1-5 microns, and it is distributed in the polyolefin resin continuous phase in an island shape to form an ideal physical cross-linking point for the entire composite.

[0045] The PP / EB / EE dynamically vulcanized thermoplastic elastic resin or elastomer granules of the present invention can be used for automotive interior decoration parts, such as bumpers, sealing strips, fenders, instrument panels, pipes and home appliance housings, and the production method can adopt conventional screw injection or extrusion molding known to technicians in the field.

[0046] The EB / EE provided by the present invention is prepared by a stepwise polymerization temperature control method:

[0047] Step 1: In an anionic polymerization solvent system containing an activator and a hindered amine molecular weight distribution broadening regulator, the cyclohexane solvent is heated to 80-90°C, and then a certain amount of n-butyl lithium (NBL) is added, followed by a certain amount of butadiene for homopolymerization for 20-25 minutes to form B1-Li + The active polymer B1 is mainly composed of 1,4-polymerized units of butadiene, and also contains a small amount of 1,2-polymerized units, among which the number of 1,4-polymerized units is much greater than that of 1,2-polymerized units;

[0048] Step 2: Cool the above polymerization solution, add a certain amount of butadiene and react at 50-60°C for not less than 30 minutes. The resulting polymer exhibits a B1-B2-Li + The active polymer (BR original rubber) in the B2 segment still contains more 1,4-polymer units than 1,2-polymer units, but the content of 1,2-polymer units in the B2 segment is greater than that in the B1 segment.

[0049] Step 3: The above polymerization solution is heated, and then a certain amount of butadiene is added to react at 75-85°C for 25-35 minutes. The resulting polymer exhibits a B1-B2-B3-Li + The active polymer (BR original rubber) contains 1,4-polymer units in the B3 segment which are much larger than 1,2-polymer units.

[0050] Step 4: Add a certain amount of NBL and titanium catalyst system to the BR original rubber solution and react at a certain temperature and hydrogen pressure for no less than 90 minutes to obtain EB / EE rubber solution;

[0051] Step 5: Terminate the EB / EE glue solution with a small amount of water, then use dry method to devolatilize the solvent in the glue solution, and obtain EB / EE transparent material through pelletizing.

[0052] In the preparation process of the polyethylene-butene rubber of the present invention, high-temperature polymerization is adopted in the first stage polymerization and the third stage polymerization to produce more 1,4-polymer structures, which is convenient for producing longer polyethylene blocks after hydrogenation. Low-temperature polymerization is adopted in the second stage polymerization to produce more 1,2-polymer structures, which is convenient for producing more ethyl side chains after hydrogenation, thereby increasing the disordered distribution of the hydrogenated polyethylene and poly-1-butene and the elasticity of the entire polymer.

[0053] In the preparation process of the polyethylene-butene rubber of the present invention, the activator used is tetrahydrofuran; the concentration of the activator in the anionic polymerization solution system is 50-100 mg / kg. Tetrahydrofuran (THF) is a commonly used activator in the anionic polymerization process of styrene-butadiene polymers (SBS), such as the 1,2-polymerization structure in the butadiene chain segments in the commercially available SBS molecules is not higher than 14%. The higher the amount of THF used, the higher the content of 1,2-polymerization structure; the lower the amount of THF used, the lower the content of 1,2-polymerization structure. In addition, the higher the polymerization temperature, the lower the content of 1,2-polymerization structure, and the lower the polymerization temperature content, the higher the content of 1,2-polymerization structure. The polymerization mechanism of the Lewis base used in the anionic polymerization process, such as the regulator or activator, is the same, only the regulating ability of different Lewis bases is different. Among the Lewis bases, THF has the worst regulating ability, but it is beneficial for preparing a higher content of 1,4-adducts such as SBS. This is why the present invention uses high-temperature polymerization in the first and third stage polymerizations to produce more 1,4-polymer structures, which is convenient for producing longer polyethylene blocks after hydrogenation, and uses low-temperature polymerization in the second stage polymerization to produce more 1,2-polymer structures, which is convenient for producing more ethyl side chains after hydrogenation, and increase the disordered distribution of hydride polyethylene and poly-1-butene and the elasticity of the entire polymer. In addition, hindered amine molecules are also a kind of Lewis base and have a regulating function. They can slow down the polymerization rate and widen the molecular weight distribution of the polymer, which is described in (US4451576A). The present invention uses THF as an activating agent for initiation, so that the probability of 1,2-polymerization of butadiene is less than 14%, so that butadiene can be 1,4-polymerized to the maximum extent, and an E block containing more than 86% polyethylene can be formed after hydrogenation.

[0054] In the preparation process of the polyethylene-butene rubber of the present invention, the hindered amine molecules include at least one of 1,5-diazabicyclo[5.4.0]-undec-5-ene and 1,5-diazabicyclo[4.3.0]-5-nonene; the concentration of the hindered amine molecules in the anionic polymerization solution system is 100-150 mg / kg.

[0055] In the preparation process of the polyethylene-butene rubber of the present invention, the total molar ratio of the alkyl lithium to butadiene is 1:(6.0-8.0)×10 4 .

[0056] In the preparation process of the polyethylene-butene rubber of the present invention, the conditions of the catalytic hydrogenation reaction are: using active lithium as an activator, adopting a titanium-based catalyst system, a hydrogen pressure of 13-16 bar, a temperature of 75-110° C., and a time of not less than 120 minutes.

[0057] In the preparation process of the polyethylene-butene rubber of the present invention, the titanium-based catalyst system includes a dicyclopentadiene titanium dichloride main catalyst and dimethyl phthalate and / or methyl o-toluate co-catalysts; the molar ratio of the main catalyst to the co-catalyst is (3-8):1.

[0058] In the preparation process of the polyethylene-butene rubber of the present invention, the molar ratio of the active lithium to the main catalyst is (6-12): 1. The active lithium is an alkyl lithium, such as n-butyl lithium.

[0059] In the preparation process of the polyethylene-butene rubber of the present invention, the amount of the titanium-based catalyst system added is measured as 0.01-0.05 g / 100 g of the polymer based on the amount of the main catalyst.

[0060] Compared with the prior art, the technical solution of the present invention has the following beneficial effects:

[0061] Aiming at the defects of existing EPDM and POE modified PP,

[0062] The existing POE has high tensile strength and impact resistance, and also shows good processing performance, but its disadvantages are high modulus, high hardness, poor resilience, incompatibility with white oil, poor wear resistance and compression permanent deformation. It has been widely used when blended with polyolefin resins, but sharing with polyolefin resins has the advantages of large usage, increased cost and large price fluctuations.

[0063] The existing EPDM granular products of DOW Chemical Company are all low-crystallinity polymers with a crystallization temperature (Tc) of 30-46°C. When the temperature rises, the crystallinity of the polymer decreases, the physical and mechanical properties decrease, and the tensile deformation is higher than 140%, which has the behavior of rubber and is not completely a thermoplastic elastomer. The PP / EPDM dynamically vulcanized thermoplastic elastic materials all have large compression deformation, hairy surface and tiny defects, are not scratch-resistant and easy to scratch.

[0064] To sum up, how to improve and overcome such defects, select a polymer with small dosage, economy and good comprehensive performance to modify the existing PP resin, and overcome the shortcomings of the existing EPDM and POE modified PP, is the current development direction of civil and industrial products.

[0065] The EB / EE hydrocarbon rubber selected in the present invention can be prepared by existing anionic polymerization and titanocene catalytic hydrogenation process technology, and has the advantages of short polymerization time, controllable molecular weight and distribution and crystallization block, and EB / EE has the behavior of thermoplastic elastomer and vulcanizable rubber.

[0066] The present invention unexpectedly discovered that EB / EE has excellent compatibility with polyethylene and polypropylene resins. The surface energy of the two can be maximized after melt mixing, and a homogeneous composite similar to an island distribution can be formed after cross-linking. According to different PP / EB / EE ratios, hard and high-toughness thermoplastic resins or thermoplastic elastomers can be made with good processing performance. Compared with the general styrene-diene elastomer and polyolefin resin, PP / EB / EE shows complete compatibility, higher heat resistance, anti-aging performance, and filling properties, and the comprehensive physical properties of the composite material are improved. Compared with TPE, EB / EE dynamically vulcanized thermoplastic elastomer has better oil locking performance and anti-aging performance, and the product has small compression deformation, smooth surface and scratch resistance.

[0067] The polyolefin / EB / EE composite material of the present invention has a simple preparation process, can be prepared by utilizing existing mature processes, and is easy to control and industrialize. BRIEF DESCRIPTION OF THE DRAWINGS

[0068] Figure 1 This is the GPC spectrum of hydrogenated polymer EB / EE-1# raw rubber BR.

[0069] Figure 2 H of hydrogenated polymer EB / EE-1# original rubber BR 1 -NMR.

[0070] Figure 3 H of hydrogenated polymer EB / EE-1# 1 -NMR. DETAILED DESCRIPTION

[0071] The following examples are intended to further illustrate the present invention in detail and are not intended to limit the scope of protection of the claims of the present invention.

[0072] In the following examples, the number average molecular weight and molecular weight distribution index of the polymers were determined by gel permeation chromatography (GPC); 1 -NMR spectroscopy is used to quantitatively determine the microstructure of the polymer; the mechanical properties of raw rubber and dynamically vulcanized blended granules are tested according to the GB / T36089-2018 method.

[0073] Example 1

[0074] Under nitrogen protection, add 3500mL of cyclohexane and 1.30mL of tetrahydrofuran (THF) to a 5-liter polymerization kettle, heat it to 78°C with hot water, then add 10mL of 0.35mol / L NBL and 130mL of butadiene, and polymerize for 25min at a maximum polymerization temperature of no more than 90°C under a nitrogen pressure of 4.0bar; then cool the polymerization kettle to 52°C, add 200mL of butadiene, and carry out polymerization for no less than 25min, during which the polymerization temperature is maintained at no more than 65°C. Then heat the polymerization solution to 80°C, and add 100mL of butadiene for the third time to the polymerization kettle, maintain the polymerization time for no less than 25min, and the maximum polymerization temperature is no more than 90°C, to obtain BR raw rubber. 1 -NMR and GPC spectra are attached Figure 1 and attached Figure 2 .

[0075] The glue liquid was pressed into a hydrogenation kettle with nitrogen, and 4 mL of 0.35 mol / L NBL, 4 mL of 0.02 mol / L cyclohexane solution of dimethyl phthalate and methyl o-toluate (co-catalyst), and 0.08 g of dicyclopentadiene titanium dichloride were added, and the mixture was stirred and hydrogenated for 120 min at a hydrogen pressure of 14 bar and a temperature of 75-110° C. to obtain EB / EE glue liquid. The hydrogenated glue liquid was then terminated with a small amount of water, and the solvent and a small amount of water were removed by dry method at 165° C. by a twin-screw extruder, and underwater pelletization was performed to obtain EB / EE transparent pellets (labeled as EB / EE-1). The H NMR spectrum was shown as follows: Figure 3 , the characteristic behaviors of the polymers are shown in Tables 1 and 2.

[0076] Example 2

[0077] The relevant process conditions in Example 1 remain unchanged, except that THF is changed to 0.8 mL, the total amount of NBL is changed to 12 mL, and the butadiene used for the first, second and third times is 100, 230 and 100 mL respectively.

[0078] Results The prepared polymer was designated as EB / EE-2, and its behavior parameters are shown in Tables 1 and 2.

[0079] Example 3

[0080] The relevant process conditions in Example 2 were kept unchanged, except that THF was changed to 0.6 mL, the total amount of NBL was changed to 8 mL, and the butadiene used for the first, second and third times was 80, 240 and 100 mL respectively.

[0081] Results The prepared polymer was designated as EB / EE-3, and its behavior parameters are shown in Tables 1 and 2.

[0082] Example 4

[0083] The relevant process conditions in Example 2 were kept unchanged, and only THF 0.3 mL was changed.

[0084] Results The prepared polymer was designated as EB / EE-4, and its behavior parameters are shown in Tables 1 and 2.

[0085] Table 1 Characteristic analysis of original BR and hydrogenated rubber in E-B / EE source example

[0086]

[0087]

[0088] Example 5

[0089] The EB / EE prepared in Examples 1 to 4, the commercially available DOW3745P and the polyolefin elastomer POE 6202 produced by Exxon were statically pressed at 170°C, stored at 25°C for 24 hours, and then tested. The results are shown in Table 2.

[0090] Table 2 Physical and mechanical properties of EB / EE in the examples

[0091]

[0092] Note: DOW3745P is DOW Chemical EPDM rubber.

[0093] Example 6

[0094] Rubber samples 1#, 2#, 3#, 4#, DOW3745P and POE 6202 in Table 1 were blended with PP respectively, and master batches were prepared by extruding a single screw extruder with a diameter of 30 mm at 195-230° C. and a residence time of 30 seconds; then the master batches were blended with a white oil solution containing 5% by mass of BIPB, and the master batches whose surfaces were moistened with a vulcanizing agent white oil were dynamically vulcanized in a twin screw extruder with a diameter of 35 mm at 190-220° C. and a residence time of 40 seconds to prepare corresponding modified PP resin or elastomer pellets. The corresponding formula is shown in Table 3, and the physical properties of the prepared modified PP resin or elastomer pellets are shown in Table 4.

[0095] Table 3 Modified PP resin or elastomer formula (mass fraction)

[0096]

[0097] Note: (1) Add 0.15 parts of UV-327, 1.2 parts of antioxidant 3114, and 20 parts of carbon black 330 to the formula.

[0098] (2) FHC 7260 is a commercially available high-density polyethylene resin.

[0099] Table 4 Physical and mechanical properties of modified PP resin or elastomer

[0100]

[0101] Note: (1) Hardness A is Shore A and hardness D is Rockwell D.

[0102] (2) The modified pellets were pressed into tablets at 175°C and tested at 25°C.

[0103] As can be seen from Table 4, the EB / EE modified polyolefin resin used in the present invention can obtain a modified hard resin or elastomer with better comprehensive physical and mechanical properties, mainly showing higher tensile strength and lower deformation; in addition, compared with POE, under the condition of lower dosage, it can still have lower deformation and higher impact strength.

Claims

1. A thermoplastic elastic resin / elastomer, characterized in that: Raw materials including EB / EE rubber, polyolefin resin and auxiliary materials; The EB / EE rubber has a structure of Formula 1: in, n, m, x, y, n1, m1, x1, y1, n2, m2, x2 and y2 are degrees of polymerization; (x+y) / (x+y+n+m)﹤0.14; (x1+y1) / (x1+y1+n1+m1)=0.35~0.60; (x2+y2) / (x2+y2+n2+m2)﹤0.14; (x+y+x1+y1+x2+y2) / (n+m+n1+m1+n2+m2+x+y+x1+y1+x2+y2)=0.20~0.40; The double bond hydrogenation rate is 99.50-99.75%.

2. The polyethylene-butene rubber according to claim 1, characterized in that: (x+y+x1+y1+x2+y2) / (n+m+n1+m1+n2+m2+x+y+x1+y1+x2+y2)=0.25~0.

30.

3. The polyethylene-butene rubber according to claim 1, characterized in that: (x+y+n+m):(x1+y1+n1+m1):(x2+y2+n2+m2)=(0.50~2.5):(3.5~5.0):(0.50~2.5).

4. A thermoplastic elastic resin / elastomer according to claim 1 or 2, characterized in that: Mooney viscosity ML of the EB / EE rubber 125 ℃ is 20-30, and the crystallinity is 12-26%.

5. A thermoplastic elastic resin / elastomer according to claim 1 or 2, characterized in that: The number average molecular weight M of the EB / EE rubber n =(6.0~8.0)×10 4 , molecular mass distribution M w / M n =1.05~1.

20.

6. A thermoplastic elastic resin / elastomer according to claim 1, characterized in that: The polyolefin resin includes polypropylene and / or polyethylene.

7. A thermoplastic elastic resin / elastomer according to claim 1, characterized in that: The auxiliary materials include rubber filling oil, inorganic filler, organic peroxide, antioxidant, colorant and light stabilizer.

8. A thermoplastic elastic resin / elastomer according to claim 7, characterized in that: The rubber extending oil includes naphthenic rubber extending oil and / or paraffinic rubber extending oil; The inorganic filler includes light calcium carbonate and / or talc; The organic peroxide includes di-tert-butyl dicumyl peroxide and / or dicumyl peroxide; The antioxidant includes at least one of 3114, 1010, and 1076. The colorant includes inorganic pigments and / or organic pigments; The light stabilizer includes UV-327 compounds.

9. A thermoplastic elastic resin / elastomer according to claim 1, 2, 6, 7 or 8, characterized in that: It comprises the following components by mass: 100 parts of polyolefin resin, 10-200 parts of EB / EE rubber, 30-80 parts of inorganic filler, 10-200 parts of rubber filling oil, 0.03-1.20 parts of organic peroxide, 0.03-2.50 parts of antioxidant, 0.15-0.20 parts of light stabilizer and 5-20 parts of colorant.

10. A method for preparing a thermoplastic elastic resin / elastomer according to any one of claims 1 to 9, characterized in that: The following steps are involved: 1) polyolefin resin, EB / EE rubber and auxiliary materials including inorganic fillers, antioxidants, light stabilizers and colorants are mixed and granulated by screw extrusion at high speed to obtain masterbatch; 2) The masterbatch is mixed with auxiliary materials including organic peroxide and filler oil and granulated by twin-screw extrusion to obtain a thermoplastic elastic resin / elastomer.

11. The method for preparing a thermoplastic elastic resin / elastomer according to claim 10, characterized in that: In step 1), during the high-speed mixing process, the mixer speed is not less than 1500 rpm / min, and the time is not less than 3 minutes.

12. The method for preparing a thermoplastic elastic resin / elastomer according to claim 10, characterized in that: In step 2), during the mixing process, the mixer speed is 500 to 800 rpm / min and the mixing time is 3 to 5 min.

13. The method for preparing a thermoplastic elastic resin / elastomer according to claim 10, characterized in that: In step 1) and step 2), the melting temperature of the screw extrusion granulation is 180-230°C.

Images