COPOLYMER, METHOD OF ITS PRODUCTION, VULCANIZED RUBBER AND ITS APPLICATION

Claims

1. A copolymer wherein the copolymer is a block copolymer and the copolymer comprises a polyethylene segment and a butadiene rubber segment; based on the total weight of the copolymer, the weight ratio of the polyethylene chain segment to the butadiene rubber chain segment is in the range from 0.1:99.9 to 80:20; in the butadiene rubber chain segment, based on the total amount of the butadiene rubber chain segment, the content of the cis-1,4-structural unit is 90-98.5 mol.%; the content of the trans-1,4-structural unit is 0.9-5.7 mol.%, and the content of the 1,2-structural unit is 0.6-4.3 mol.%; the length of the continuous methylene sequence in the copolymer is at least 165.

2. The copolymer according to claim 1, wherein the weight ratio of the polyethylene chain segment to the butadiene rubber chain segment is in the range from 1:99 to 75:25; preferably, the length of the continuous methylene sequence in the copolymer is in the range of 250-1800.

3. The copolymer according to claim 1 or 2, wherein the content of the cis-1,4-structural unit in the butadiene rubber chain segment is in the range of 92-98 mol.% based on the total amount of the butadiene rubber segment.

4. The copolymer according to any one of claims 1-3, wherein the copolymer has a melting temperature Tm in the range of 120-150°C and a crystallinity in the range of 0.2-80%; preferably Tm is in the range of 125-145°C and the crystallinity is in the range of 0.5-65%.

5. The copolymer of any one of claims 1 to 4, wherein the copolymer has a number average molecular weight in the range of 50,000 to 800,000 g / mol and a molecular weight distribution in the range of 2 to 7; preferably the copolymer has a number average molecular weight in the range of 100,000 to 700,000 g / mol and a molecular weight distribution in the range of 2.5 to 6.

5.

6. A method for producing a copolymer, comprising: (1) subjecting ethylene to a polymerization reaction in the presence of an organic solvent, a catalyst, and an aluminum-containing cocatalyst-1 to obtain a polyethylene product; wherein the polymerization reaction temperature is in the range of 20-70°C, the ethylene pressure is maintained at 1-70 bar, and the polymerization reaction time is in the range of 1-80 min; (2) feeding 1,3-butadiene monomers into the polyethylene product and removing unreacted ethylene monomers; (3) adding an aluminum chloride-containing cocatalyst-2 to the polymerization system obtained in step (2) to initiate a copolymerization reaction between the 1,3-butadiene monomers and the active segment of the polyethylene chain in the polyethylene product to obtain a copolymer; wherein the catalyst is at least one catalyst selected from the group consisting of compounds represented by formula 1, formula 2 and formula 3; where X is chlorine or bromine; R1 is a substituent which is mono-substituted at the 2- or 4-position of the benzene ring, or the same or different substituents which are di-substituted at the 2-, 4-positions or 2-, 6-positions of the benzene ring, or the same or different substituents which are tri-substituted at the 2-, 4-, 6-positions of the benzene ring, where the substituent is -F, -CH3, -CH2CH3, -CH(CH3)2, -C(CH3)3, -C6H5 or -CH(C6H5)2; R3 is -CH3, -CH2CH3, -CH(CH3)2, -C(CH3)3, -C6H5, or -CH(C6H5)2, which is mono-substituted at the 6-position of the pyridine ring, or -CH3, -N(CH3)2, or -CF3, which is mono-substituted at the 4-position of the pyridine ring, or the same or different -CH3, -CH2CH3, -C6H5, -CH(C6H5)2, -N(CH3)2, or -CF3, which are di-substituted at the 4- and 6-positions of the pyridine ring; R5 is -CH3, -CH2CH3, -CH(CH3)2, -C(CH3)3, -C6H5, or -CH(C6H5)2, which is mono-substituted at the 4-position of the dihydrooxazole ring; R2, R4, and R6 are each independently H or -Cl, -F, -CH3, -OCH3, -N(CH3)2, or -CF3, which are mono-substituted at the 4-position of the pyridine ring; R7 is H, -CH3, -CH2CH3, -CH(CH3)2, -C(CH3)3, -Cl, -C6H5, or -CH(C6H5)2.

7. The method according to claim 6, wherein in step (1) the polymerization reaction temperature is in the range of 30-60°C, the ethylene pressure is maintained at 2.5-50 bar, and the polymerization reaction time is in the range of 2-60 min; Preferably, the organic solvent is at least one solvent selected from the group consisting of n-pentane, neopentane, n-hexane, cyclohexane, n-heptane, n-octane, isooctane, benzene, toluene, decalin, dodecane and hydrogenated gasoline, more preferably toluene.

8. The method according to claim 6 or 7, wherein the molar ratio of catalyst: aluminum-containing cocatalyst-1: cocatalyst-2 containing aluminum chloride is 1: (15-1000): (20-1000), preferably 1: (20-900): (40-900); preferably cocatalyst-2 containing aluminum chloride is added in step (3).

9. The method according to any of paragraphs. 6-8, wherein the aluminum-containing cocatalyst-1 is at least one cocatalyst-1 selected from the group consisting of methylaluminoxane, methylaluminoxane modified with triisobutylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, di-n-propylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-tert-butylaluminum chloride, di-n-octylaluminum chloride, ethylaluminum dichloride, n-propylaluminum dichloride, isopropylaluminum dichloride, n-butylaluminum dichloride, isobutylaluminum dichloride and n-octylaluminum dichloride, preferably at least one cocatalyst selected from the group consisting of methylaluminoxane, methylaluminoxane modified with triisobutylaluminum, diethylaluminum chloride, di-tert-butylaluminum chloride, ethylaluminum dichloride and ethylaluminum sesquichloride.

10. The method according to any one of claims 6 to 9, wherein the cocatalyst 2 containing aluminum chloride is at least one cocatalyst selected from the group consisting of diethyl aluminum chloride, ethyl aluminum sesquichloride, di-n-propyl aluminum chloride, diisopropyl aluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-n-octylaluminum chloride, ethyl aluminum dichloride, n-propyl aluminum dichloride, isopropyl aluminum dichloride, n-butylaluminum dichloride, isobutylaluminum dichloride and n-octylaluminum dichloride, preferably at least one cocatalyst selected from the group consisting of diethyl aluminum chloride, ethyl aluminum dichloride and ethyl aluminum sesquichloride.

11. The method according to any one of claims 6 to 10, wherein in step (3) the concentration of 1,3-butadiene in the polymerization system obtained in step (2) is in the range of 0.4-12 mol / l, preferably in the range of 0.6-9 mol / l; preferably, the molar ratio of catalyst to 1,3-butadiene is 1: (1000-10000); more preferably 1: (1200-8000); Preferably, the copolymerization reaction temperature is in the range of 30-70°C, more preferably in the range of 40-60°C; the copolymerization reaction pressure is in the range of 1-10 bar, more preferably in the range of 2-5 bar; the copolymerization reaction time is in the range of 0.5-5 hours, more preferably in the range of 1-4 hours.

12. A copolymer obtained by the method according to any of paragraphs 6-11.

13. Vulcanized rubber obtained with a copolymer according to any one of paragraphs 1-5 and 12.

14. A method of using vulcanized rubber according to claim 13 in a tire, shoe sole, conveyor belt, hose or sealing gasket.