LIQUID HYDROGENATED NITRILE-BUTADIENE RUBBER, PREPARATION METHOD THEREOF AND USE THEREOF

Abstract

Disclosed are a liquid hydrogenated nitrile-butadiene rubber, a preparation method therefor and the use thereof. In the liquid hydrogenated nitrile-butadiene rubber: the content of acrylonitrile is 15-50%; the hydrogenation saturation is 75-99.5%; the weight-average molecular weight (Mw) is 3,000-60,000; the molecular weight polydispersity index (PDI) is 2.0-8.0; and the glass transition temperature (Tg) is lower than −28° C. The liquid hydrogenated nitrile-butadiene rubber is low in molecular weight and wide in molecular weight polydispersity, simultaneously has an excellent fluidity during processing and excellent mechanical properties after curing and has a unique application value in the field of special rubbers; and the preparation method therefor is simple and feasible in terms of the process.

Claims

1. A liquid hydrogenated nitrile butadiene rubber comprising: acrylonitrile is from 15% to 50%; hydrogenation degree from 75% to 99.5%; weight average molecular weight from 3,000 to 60,000; molecular weight polydispersity index from 2.0 to 8.0; glass transition temperature below −28° C.

2. The liquid hydrogenated nitrile butadiene rubber according to claim 1, wherein, the acrylonitrile is 17-45%, the hydrogenation degree is 80% -99%, the weight average molecular weight is 5,000 - 50,000, the molecular weight polydispersity index is 2.0-6.0; the glass transition temperature is lower than −35° C., an extrapolated glass transition onset temperature is lower than −25° C., wherein the liquid hydrogenated nitrile butadiene rubber is a liquid hydrogenated nitrile butadiene rubber shown in formula IIIa or IIIb. ##STR00016##

3. A method for preparing a liquid hydrogenated nitrile butadiene rubber (NBR) comprising the steps of: adding NBR to a degradation reaction and a hydrogenation reaction, or adding NBR to a hydrogenation reaction, in the presence of Zhan catalyst, under the protection of an inert gas in an organic solvent, to obtain liquid hydrogenated nitrile butadiene rubber; wherein the catalyst comprises one or more of the Zhan catalysts shown in general formula I: ##STR00017## in the general formula I: L is an electron-donating complex ligand; L.sup.1 and L.sup.2 are independently halogen; n=0 or 1; when n=1, Y.sup.1 is independently nitrogen, oxygen, sulphur, CH.sub.2 substituted or unsubstituted C.sub.1-C.sub.20 alkyl, substituted or unsubstituted C.sub.6-C.sub.20 aryl, substituted or unsubstituted C.sub.6-C.sub.20 aryloxy, substituted or unsubstituted C.sub.2-C.sub.20 heterocyclic aryl, carbonyl, carbonyl linked to a substituted or unsubstituted C.sub.1-C.sub.20 alkyl, carbonyl linked to a substituted or unsubstituted C.sub.1-C.sub.20 alkoxy, imino, substituted or unsubstituted C.sub.1-C.sub.20 alkyl imino or amino as shown in R.sub.cR.sub.dN-group; wherein, Rc and Rd are independently hydrogen, substituted or unsubstituted C.sub.6-C.sub.20 aryl, substituted or unsubstituted C.sub.2-C.sub.20 heterocyclic, substituted or unsubstituted C.sub.1-C.sub.20 alkyl, formyl, substituted or unsubstituted C.sub.1-C.sub.20 alkyl formyl, substituted or unsubstituted C.sub.6-C.sub.20 aryl formyl or substituted or unsubstituted C.sub.2-C.sub.20 heterocyclic formyl; or Rc, Rd and the N atom are linked each other to form a ring; X is nitrogen, oxygen, sulphur, CH, CH.sub.2 or carbonyl group; Y is nitrogen, oxygen, CH, methylene, substituted or unsubstituted C.sub.1-C.sub.20 alkoxy, substituted or unsubstituted C.sub.6-C.sub.20 aryl, substituted or unsubstituted C.sub.6-C.sub.20 aryl, substituted or unsubstituted C.sub.2-C.sub.20 heterocyclic aryl, a carbonyl group linked to a substituted or unsubstituted C.sub.1-C.sub.20 alkyl, a carbonyl group linked to a substituted or unsubstituted C.sub.1-C.sub.20 alkoxy, an imino group, a substituted or unsubstituted C.sub.1-C.sub.20 alkyl imino group or a group as shown in R.sub.cR.sub.dN-group; wherein, Rc and Rd are independently hydrogen, substituted or unsubstituted C.sub.6-C.sub.20 aryl, substituted or unsubstituted C.sub.2-C.sub.20 heterocyclic, substituted or unsubstituted C.sub.1-C.sub.20 alkyl, formyl, substituted or unsubstituted C.sub.1-C.sub.20 alkylcarbonyl, substituted or unsubstituted C.sub.6-C.sub.20 arylcarbonyl or substituted or unsubstituted C.sub.2-C.sub.20 heterocycliccarbonyl group; or Rc, Rd and N atoms linked to form a ring; the parent to which the group indicated by X linked is Y, and the parent to which the group indicated by Y linked is X; “XY” between the X and Y is single or double bonds; R.sup.1 is hydrogen, substituted or unsubstituted C.sub.1-C.sub.20 alkyl, substituted or unsubstituted C.sub.1-C.sub.20 alkoxy, substituted or unsubstituted C.sub.6-C.sub.20 aryl, substituted or unsubstituted C.sub.6-C.sub.20 aryloxy or substituted or unsubstituted C.sub.2-C.sub.20 heterocyclic group; R.sup.2 is hydrogen, substituted or unsubstituted C.sub.1-C.sub.20 alkyl, substituted or unsubstituted C.sub.1-C.sub.20 alkoxy, substituted or unsubstituted C.sub.1-C.sub.20 alkylthio, substituted or unsubstituted C.sub.1-C.sub.20 alkylsiloxy, substituted or unsubstituted C.sub.2-C.sub.20 heterocyclic, substituted or unsubstituted C.sub.6-C.sub.20 aryl, C.sub.6-C.sub.20 aryloxy, aldehyde, carbonyl group linked to a substituted or unsubstituted C.sub.1-C.sub.20 alkyl, carbonyl group linked to a substituted or unsubstituted C.sub.6-C.sub.20 aryl, carbonyl group linked to a substituted or unsubstituted C.sub.2-C.sub.20 heterocyclic or a group as shown in R.sub.cR.sub.dN-group; wherein Rc and Rd are independently hydrogen, formyl, substituted or unsubstituted C.sub.1-C.sub.20 alkyl formyl group, substituted or unsubstituted C.sub.6-C.sub.20 aryl formyl group, substituted or unsubstituted C.sub.2-C.sub.2 heterocyclic formyl group; or wherein Rc, Rd and the N atom are linked each other to form a ring; E is hydrogen, halogen, nitro, nitrile, sulfinyl, sulfone, aldehyde, C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 alkoxy, C.sub.1-C.sub.20 alkylthio, C.sub.1-C.sub.20 alkyl silyl, C.sub.1-C.sub.20 alkyl siloxy, C.sub.2-C.sub.20 heterocyclic, C.sub.6-C.sub.20 aryl, C.sub.6-C.sub.20 aryloxy, carbonyl linked to C.sub.1-C.sub.20 alkyl, carbonyl linked to C.sub.6-C.sub.20 aryl C6-C20 heterocyclic, carbonyl linked to C.sub.2-C.sub.20 heterocyclic, carbonyl linked to C.sub.1-C.sub.20 alkoxy, carbonyl linked to C.sub.6-C.sub.20 aryloxy, carbonyl linked to C.sub.6-C.sub.20 heterocyclic oxy, aminoacyl, carbonyl linked to C.sub.1-C.sub.20 alkylamino, carbonyl linked to C.sub.6-C.sub.20 arylamino, carbonyl linked to C.sub.2-C.sub.20 heterocyclic amino, ureido, substituted or unsubstituted C.sub.1-C.sub.20 alkyl ureido, substituted or unsubstituted C.sub.6-C.sub.20 aryl ureido, substituted or unsubstituted C.sub.2-C.sub.20 heterocyclic ureido, sulfonyl group linked to a C.sub.1-C.sub.20 alkyl amino group, sulfonyl group linked to a C.sub.6-C.sub.20 aryl amino group, sulfonyl group linked to a C.sub.2-C.sub.20 heterocyclic amino group, or a group as shown in R.sub.cR.sub.dN-group; wherein Rc and Rd are independently hydrogen, substituted or unsubstituted C.sub.6-C.sub.20 aryl, substituted or unsubstituted C.sub.2-C.sub.20 heterocyclic, substituted or unsubstituted C.sub.1-C.sub.20 alkyl, formyl, substituted or unsubstituted C.sub.1-C.sub.20 alkyl formyl, substituted or unsubstituted C.sub.6-C.sub.20 aryl formyl, substituted or unsubstituted C.sub.2-C.sub.20 heterocyclic formyl, substituted or unsubstituted C.sub.1-C.sub.20 alkyl sulfonyl, substituted or unsubstituted C.sub.6-C.sub.20 aryl sulfonyl, or substituted or unsubstituted C.sub.2-C.sub.20 heterocyclic sulfonyl group; or Rc, Rd and the N atom are linked each other to form a ring; E.sup.1 is hydrogen, halogen, nitro, nitrile, C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 alkoxy, C.sub.1-C.sub.20 alkylthio, C.sub.1-C.sub.20 alkasilyl, C.sub.1-C.sub.20 alkasiloxy, C.sub.2-C.sub.20 heterocyclic, substituted or unsubstituted amino, aminoacyl, carbonyl linked to C.sub.1-C.sub.20 alkylamino, C.sub.6-C.sub.20 aryl, C.sub.6-C.sub.20 aryloxy, sulfinyl, sulfone group, aldehyde group, carbonyl group linked to a C.sub.1-C.sub.20 alkyl group, carbonyl group linked to a substituted or unsubstituted C.sub.6-C.sub.20 aryl group, carbonyl group linked to a substituted or unsubstituted C.sub.2-C.sub.20 heterocyclic group, carbonyl group linked to a C.sub.1-C.sub.20 alkoxy group, carbonyl group linked to a C.sub.6-C.sub.20 aryloxy group, carbonyl group linked to a C.sub.2-C.sub.20 heterocyclic oxy group, urea group, substituted or unsubstituted C.sub.1-C.sub.20 alkyl urea group , substituted or unsubstituted C.sub.6-C.sub.20 aryl ureido group, substituted or unsubstituted C.sub.2-C.sub.20 heterocyclic ureido group; E.sup.2 is hydrogen, halogen, C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 alkoxy, C.sub.1-C.sub.20 alkylthio, C.sub.1-C.sub.20 alkyl silyl, C.sub.1-C.sub.20 alkyl siloxy, aminoacyl, carbonyl linked to C.sub.1-C.sub.20 alkylamino, carbonyl linked to C.sub.6-C.sub.20 arylamino, carbonyl linked to C.sub.2-C.sub.20 heterocyclic amino, C.sub.6-C.sub.20 aryl, C.sub.6-C.sub.20 aryl oxy, C.sub.2-C.sub.20 heterocyclic aryl, aldehyde, a carbonyl group linked to a C.sub.1-C.sub.20 alkyl group, a carbonyl group linked to a C.sub.6-C.sub.20 aryl group, a carbonyl group linked to a C.sub.2-C.sub.20 heterocyclic group, a carbonyl group linked to a C.sub.1-C.sub.20 alkoxy group, a carbonyl group linked to a C.sub.6-C.sub.20 aryloxy group, a carbonyl group linked to a C.sub.2-C.sub.20 heterocyclic oxy group or a group as shown in R.sub.cR.sub.dN-group; wherein Rc and Rd are independently hydrogen, substituted or unsubstituted C.sub.6-C.sub.20 aryl, substituted or unsubstituted C.sub.2-C.sub.20 heterocyclic, substituted or unsubstituted C.sub.1-C.sub.20 alkyl, formyl, substituted or unsubstituted C.sub.1-C.sub.20 alkyl formyl, substituted or unsubstituted C.sub.6-C.sub.20 aryl formyl, substituted or unsubstituted C.sub.2-C.sub.20 heterocyclic formyl, substituted or unsubstituted C.sub.1-C.sub.20 alkyl sulfonyl, substituted or unsubstituted C.sub.6-C.sub.20 aryl sulfonyl, or substituted or unsubstituted C.sub.2-C.sub.20 heterocyclic sulfonyl group; or Rc, Rd and the N atom are linked each other to form a ring; E.sup.3 is hydrogen, halogen, C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 alkoxy, C.sub.1-C.sub.20 alkylthio, C.sub.1-C.sub.20 alkyl siloxy, C.sub.6-C.sub.20 aryloxy, C.sub.6-C.sub.20 aryl, C.sub.2-C.sub.20 heterocyclic aryl, a carbonyl group linked to a C.sub.1-C.sub.20 alkoxy, a carbonyl group linked to a substituted or unsubstituted C.sub.6-C.sub.20 aryloxy, a carbonyl group linked to a substituted or unsubstituted C.sub.6-C.sub.20 heterocyclic aryloxy or a group as shown in R.sub.cR.sub.dN-group; wherein, Rc and Rd are independently hydrogen, substituted or unsubstituted C.sub.6-C.sub.20 aryl, substituted or unsubstituted C.sub.2-C.sub.20 heterocyclic, substituted or unsubstituted C.sub.1-C.sub.20 alkyl, formyl, substituted or unsubstituted C.sub.1-C.sub.20 alkyl formyl, substituted or unsubstituted C.sub.6-C.sub.20 aryl formyl, substituted or unsubstituted C.sub.2-C.sub.20 heterocyclic formyl, substituted or unsubstituted C.sub.1-C.sub.20 alkyl sulfonyl, substituted or unsubstituted C.sub.6-C.sub.20 aryl sulfonyl, or substituted or unsubstituted C.sub.2-C.sub.20 heterocyclic sulfonyl group; or Rc, Rd and the N atom are linked each other to form a ring; E.sup.4, E.sup.5, E.sup.6 and E.sup.7 are independently hydrogen, halogen, nitro, nitrile, sulfinyl, sulfonyl, aldehyde, substituted or unsubstituted C.sub.1-C.sub.20 alkyl, substituted or unsubstituted C.sub.1-C.sub.20 alkoxy, C.sub.1-C.sub.20 alkylthio, C.sub.1-C.sub.20 alkasilyl, C.sub.1-C.sub.20 alkasiloxy, substituted or unsubstituted C.sub.2-C.sub.20 heterocyclic, substituted or unsubstituted amino, amino acyl, carbonyl groups linked to substituted or unsubstituted C.sub.1-C.sub.20 alkylamino groups, carbonyl groups linked to substituted or unsubstituted C.sub.6-C.sub.20 arylamino groups, carbonyl groups linked to substituted or unsubstituted C.sub.2-C.sub.20 heterocyclic amino groups, carbonyl groups linked to substituted or unsubstituted C.sub.1-C.sub.20 alkyl groups, carbonyl groups linked to substituted or unsubstituted C.sub.6-C.sub.20 aryl groups, carbonyl groups linked to substituted or unsubstituted C.sub.2-C.sub.20 heterocyclic group, carbonyl group linked to substituted or unsubstituted C.sub.1-C.sub.20 alkoxy, carbonyl group linked to substituted or unsubstituted C.sub.6-C.sub.20 aryloxy, carbonyl group linked to substituted or unsubstituted C.sub.6-C.sub.20 heterocyclic oxy, ureido, substituted or unsubstituted C.sub.1-C.sub.20 alkyl ureido, substituted or unsubstituted C.sub.6-C.sub.20 aryl ureido, substituted or unsubstituted C.sub.2-C.sub.20 heterocyclic based ureido, substituted or unsubstituted C.sub.6-C.sub.20 aryl, substituted or unsubstituted C.sub.6-C.sub.20 aryloxy, or a group as shown in R.sub.cR.sub.dN-group; wherein, Rc and Rd are independently hydrogen, substituted or unsubstituted C.sub.6-C.sub.20 aryl, substituted or unsubstituted C.sub.2-C.sub.20 heterocyclic, substituted or unsubstituted C.sub.1-C.sub.20 alkyl, formyl, substituted or unsubstituted C.sub.1-C.sub.20 alkyl formyl, substituted or unsubstituted C.sub.6-C.sub.20 aryl formyl, substituted or unsubstituted C.sub.2-C.sub.20 heterocyclic formyl, substituted or unsubstituted C.sub.1-C.sub.20 alkyl sulfonyl, substituted or unsubstituted C.sub.6-C.sub.20 aryl sulfonyl, substituted or unsubstituted C.sub.2-C.sub.20 heterocyclic sulfonyl group; or Rc, Rd and the N atom are linked each other to form a ring.

4. The method according to claim 3, wherein the general formula I comprises one or more of the following compounds: ##STR00018## ##STR00019## ##STR00020## ##STR00021## ##STR00022## ##STR00023## wherein the NBR has a structure as shown in formula II, IIa or IIb as follows: ##STR00024## wherein the amount of Zhan catalyst is 0.005%-0.1%, wherein the degradation reaction is at a temperature of 60-100° C. for 0.5-10 hours, wherein a pressure within the hydrogenation reaction is contributed by a hydrogen gas, and wherein said pressure reaches 2 to 15 MPa, wherein the temperature of the hydrogenation reaction is 80 to 200° C. and the time of the hydrogenation reaction is 2 to 6 hours; wherein the organic solvent is one or more of trichloromethane, dichloroethane, acetone and chlorobenzene in an amount of 100 to 300 g of NBR/1 L of organic solvent, wherein the inert gas is argon or nitrogen; and conducting a post-treatment at a temperature of 100-150° C. when the hydrogenation reaction is completed, wherein the post-treatment comprises removing the organic solvent under negative pressure.

5. The method according to claim 3, comprising reactions presented in route-1 and/or route-2 as shown below ##STR00025## ##STR00026##

6. (canceled)

7. A method for degradating NBR comprising the steps of: adding the NBR to a degradation reaction in an organic solvent under the protection of an inert gas in the presence of Zhan catalyst of the general formula I to obtain a NBR degradation product; ##STR00027## wherein the Zhan catalyst and the amount thereof are recited in claim 4; wherein the NBR is recited in claim 4; wherein the temperature and time of degradation reaction are recited in claim 4; wherein the organic solvent and the amount thereof are recited in claim 4; wherein the inert gas is recited in claim 4; and further comprising a reaction process shown in Route-3: ##STR00028##

8. An rubber compound comprising the liquid hydrogenated nitrile butadiene rubber of claim 1, a filler and a vulcanizing agent.

9. A vulcanized rubber comprising rubber compound of claim 8 vulcanized by a vulcanized agent.

10. (canceled)

11. The rubber compound of claim 8, wherein the filler is carbon black selected from the group consisting of carbon black N220, carbon black N-330, carbon black N550, and carbon black N774.

12. The rubber compound of claim 8, wherein the filler is silica selected from the group consisting of precipitated silica, fumed silica, and alkaline silica.

13. The rubber compound of claim 12, wherein the alkaline silica is alkaline silica AS-70.

14. The rubber compound of claim 8, wherein the vulcanizing agent is 1,4-bis(tert-butylperoxyisopropyl)benzene.

15. The rubber compound of claim 8 further comprising one or more rubber compounding agent, wherein said rubber compounding agent is selected from the group consisting of a co-sulfurizing agent, stearic acid, magnesium oxide, accelerator and antioxidant.

16. The rubber compound of claim 15, wherein the co-sulfurizing agent is N,N′-m-phenylenebismaleimide.

17. The rubber compound of claim 15, wherein the accelerator is zinc salt of 2-mercaptobenzimidazole.

18. The rubber compound of claim 15, wherein the antioxidant is 4,4′-bis(dimethylbenzyl)diphenylamine.

19. The rubber compound of claim 8, wherein said rubber compound comprises, in parts by weight: 100 parts of liquid hydrogenated nitrile butadiene rubber, 50 parts of carbon black N-330, 10 parts of silica AS-70, 14 parts of 1,4-bis(tert-butylperoxyisopropyl)benzene, 0.5 parts of N,N′-m-phenylene braced bismaleimide, 0.5 parts of stearic acid, 6 parts of magnesium oxide, 0.5 parts of zinc salt of 2-mercaptobenzimidazole and 1.0 parts of 4,4′-bis(dimethylbenzyl)diphenylamine.

20. An rubber compound comprising the liquid hydrogenated nitrile butadiene rubber of claim 2, a filler and a vulcanizing agent.

21. A vulcanized rubber comprising comprising the rubber compound of claim 20 vulcanized by a vulcanized agent.

22. The rubber compound of claim 20 further comprising one or more rubber compounding agent, wherein said rubber compounding agent is selected from the group consisting of a co-sulfurizing agent, stearic acid, magnesium oxide, accelerator and antioxidant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0156] The invention is further illustrated below by some embodiments, but the invention is not thereby limited to the following described embodiments. Experimental methods for which no specific conditions are indicated in the following embodiments follow the conventional methods and conditions or are selected according to the trade description.

[0157] Zhan catalysts used in the following embodiment were the compounds 4aa and/or 4v of general formula I, as documented in our granted patent CN200910175790.6, with the following structures:

##STR00015##

[0158] The raw material NBR and LHNBR product raw rubber, and the relevant characteristic parameters of the rubber material involved in the following embodiments, are expressed by testing according to the following methods: [0159] (1) Acrylonitrile content: Tested in accordance with the method specified in the standard SH/T 1157.2-2015 “Determination of bound acrylonitrile content in raw rubber acrylonitrile-butadiene rubber (NBR) Part 2: Kjeldahl method for nitrogen determination”, with NMR hydrogen spectrometry analysis evaluation as an auxiliary verification method. [0160] (2) Hydrogenation degree: tested according to the method specified in the standard SH/T 1763 “Determination of residual unsaturation in hydrogenated nitrile butadiene rubber (HNBR) of nitrile rubber (NBR) by the iodine titration method”. [0161] (3) Glass transition temperature (Tg): tested by DSC8500 differential scanning calorimeter in accordance with the method specified in the standard GB/T 29611-2013 “Determination of glass transition temperature of raw rubber by differential scanning calorimetry (DSC)”. [0162] (4) Molecular weight and molecular weight polydispersity index (PDI): tested by ECS000113 type room temperature gel permeation chromatograph (Z-1601) in accordance with the method specified in the standard GB/T21863-2008 “Gel Gel permeation chromatography (GPC) with tetrahydrofuran as eluent”.

Example 1

[0163] Under nitrogen displacement conditions, 100 g of NBR [ACN 33%, ML(1+4) 35, 100° C.] was added into 500 mL of anhydrous chlorobenzene to a 1 L stainless steel reactor, completely dissolved at 60° C. under nitrogen seal conditions, then added “Zhan catalyst” (4v) at a dosage of 0.03% of NBR, the degradation reaction of NBR was carried out at 80° C. for 1.5 hours to obtain a LNBR degradate; hydrogen was then introduced until the pressure reached 8 MPa and the temperature was increased to 150° C. The reaction was carried out for 4 hours to obtain a LHNBR solution. The solution of the hydrogenation reaction product was removed from the chlorobenzene solvent at 130° C. under negative pressure to obtain a LHNBR raw rubber with a product yield of >98%.

[0164] The characteristic parameters of the resulting raw LHNBR were: molecular weight (Mw) of 37,950, molecular weight polydispersity index of 2.1, ACN of 33%, Hydrogenation degree of 92% (iodine value: 24), and glass transition temperature (Tg) of −31.2° C. (Tig: −31.7° C.; Teg: −26.9° C.).

Example 2

[0165] Under nitrogen displacement conditions, 100 g of NBR [ACN 33%, ML(1+4) 35 at 100° C. ] was added into 500 mL of anhydrous chlorobenzene to a 1 L stainless steel reactor, after completed dissolution at 60° C. under nitrogen sealing, then added “Zhan catalyst” (4v) at a dosage of 0.04% of the NBR, degradation of the NBR at 80° C. for 1 hour to obtain LNBR, hydrogen was then introduced until the pressure reached 8 MPa and the temperature was increased to 150° C. The reaction was carried out for 5 hours to obtain a LHNBR solution. The solution of the hydrogenation reaction product was removed from the chlorobenzene solvent at 130° C. under negative pressure to obtain a raw LHNBR with a product yield of >98%.

[0166] The characteristic parameters of the resulting raw LHNBR were: molecular weight (Mw) of 44960, molecular weight polydispersity index: 2.2, ACN: 33%, Hydrogenation degree: 96% (iodine value: 14), and glass transition temperature (Tg): −32.5° C. (Tig: −36.1° C.; Teg: −28.8° C.).

Example 3

[0167] Under nitrogen displacement conditions, 100 g of NBR [ACN of 33%, ML(1+4) 35 at 100° C.] was added 500 mL of anhydrous chlorobenzene to a 1 L stainless steel reactor, dissolved completely at 60° C. under nitrogen seal, then added Zhan catalyst (4v) at a dosage of 0.05% of NBR; the degradation reaction of the NBR was carried out at 80° C. and the reaction was carried out for 1 hour to obtain LNBR; hydrogen was then introduced until the pressure reached 8 MPa and the temperature was increased to 150° C. The reaction was carried out for 6 hours to obtain a highly hydrogenated LHNBR solution. The solution of the hydrogenation reaction product is removed from the chlorobenzene solvent at 130° C. under negative pressure to obtain a raw LHNBR with a product yield of >98%.

[0168] The properties of the resulting raw LHNBR were: molecular weight (Mw) of 45140, molecular weight polydispersity index: 2.2, combined ACN: 33%, hydrogenation degree: 99% (iodine value: 8), and glass transition temperature (Tg): −29.8° C. (Tig: −33.5° C.; Teg: −26.2° C.).

Example 4

[0169] Under nitrogen displacement conditions, 100 g of NBR [ACN 33%, ML(1+4) 35 at 100° C.] was added 500 mL of anhydrous chlorobenzene to a 1 L stainless steel reactor, after completed dissolution at 60° C. under nitrogen sealing conditions, then added Zhan catalyst (4v) at a dosage 0.06% of the NBR. The NBR was subjected to a degradation reaction at 80° C. for 2 hours to obtain LNBR; hydrogen is then introduced to a pressure of 8 MPa and the reaction was carried out at 150° C. for 6 hours to obtain a highly hydrogenated LHNBR solution. The solution of the hydrogenation product was removed from the chlorobenzene solvent at 130° C. under negative pressure, resulting in a raw LHNBR with a yield of >98%.

[0170] The characteristic parameters of the resulting raw LHNBR were: molecular weight (Mw) of 243.5 million, molecular weight polydispersity index: 2.4, ACN: 33%, hydrogenation: 99% (iodine value: 8), and glass transition temperature (Tg): −30.9° C. (Tig: −31.5° C.; Teg: −27.2° C.).

Example 5

[0171] Under nitrogen displacement conditions, 100 g of nitrile rubber [33% acrylonitrile by weight, Moonny viscosity ML(1+4) 35 at 100° C.] was added 500 mL of anhydrous chlorobenzene to a 1 L stainless steel reactor, completely dissolved at 60° C. under nitrogen seal conditions, then added Zhan catalyst (4v) at a dosage of 0.06% of the NBR, NBR was subjected to a degradation reaction at 80° C. for 2.5 hours to obtain LNBR; hydrogen was then introduced until the pressure reached 8 MPa and the temperature was increased to 150° C. The reaction was carried out for 6 hours to obtain a highly hydrogenated LHNBR solution. The solution of the hydrogenation reaction product was removed from the chlorobenzene solvent at 130° C. under negative pressure to obtain a raw LHNBR with a product yield of >98%.

[0172] The characteristic parameters of the resulting raw LHNBR were: molecular weight (Mw): 8210, molecular weight polydispersity index: 2.7, ACN: 33%, hydrogenation: 99% (iodine value: 8) and glass transition temperature (Tg): −42.8° C. (Tig: −49.8° C.; Teg: −36.2° C.).

Example 6

[0173] Under nitrogen displacement, 100 g of liquid nitrile rubber [33% acrylonitrile by weight, molecular weight (Mw) 15780, molecular weight polydispersity index 3.2] and 500 mL of anhydrous chlorobenzene were added to a 1 L stainless steel reactor, under nitrogen seal, added Zhan catalyst (4aa) at 60° C. at a dosage 0.03% of NBR, hydrogen was then introduced until the pressure reached 8 MPa and then the temperature was increased to 150° C. The reaction was carried out for 4 hours to obtain a highly hydrogenated LHNBR solution. The solution of the hydrogenation reaction product was removed from the chlorobenzene solvent at 130° C. under negative pressure to obtain a raw LHNBR with a product yield of >98%.

[0174] The characteristic parameters of the resulting LHNBR raw rubber were: molecular weight (Mw) of 16250, molecular weight polydispersity index: 3.3, ACN: 33%, hydrogenation: 99% (iodine value: 7) and glass transition temperature (Tg): −38.8° C. (Tig: −44.5° C.; Teg: −33.9° C.).

Example 7

[0175] Under nitrogen displacement conditions, 100 g of LNBR [ACN 43%, molecular weight (Mw) 32660, molecular weight polydispersity index 4.3] and 500 mL of anhydrous chlorobenzene were added to a 1 L stainless steel reactor, under nitrogen sealing conditions, added Zhan catalyst (4aa) at 60° C. at a dosage of 0.02% of NBR, then hydrogen was introduced until the pressure reached 8 MPa and the temperature was increased to 150° C. The reaction was carried out for 3 hours to obtain a highly hydrogenated LHNBR solution. The solution of the hydrogenation reaction product was removed from the chlorobenzene solvent at 130° C. under negative pressure to obtain a raw LHNBR with a product yield of >98%.

[0176] The characteristic parameters of the resulting raw LHNBR were: molecular weight (Mw) of 33420, molecular weight polydispersity index: 4.3, ACN: 43%, hydrogenation: 91% (iodine value: 25) and glass transition temperature (Tg): −30.2° C. (Tig: −34.7° C.; Teg: −26.9° C.).

Example 8

[0177] Under nitrogen displacement conditions, 100 g of LNBR [25% acrylonitrile by weight, molecular weight (Mw) 32770, molecular weight polydispersity index 5.5] and 500 mL of anhydrous chlorobenzene were added to a 1 L stainless steel reactor, under nitrogen sealing conditions, add Zhan catalyst (4aa) at 60° C. at a dosage of 0.03% of the NBR, then hydrogen was introduced until the pressure reached 8 MPa and then the temperature was increased to 150° C. The reaction was carried out for 4 hours to obtain a highly hydrogenated LHNBR solution. The solution of the hydrogenation reaction product was removed from the chlorobenzene solvent at 130° C. under negative pressure to obtain a raw LHNBR with a product yield of >98%.

[0178] The characteristics of the resulting raw LHNBR are: molecular weight (Mw) of 33,950, molecular weight polydispersity index: 5.6, ACN: 25%, hydrogenation degree: 95% (iodine value: 13) and glass transition temperature (Tg): −32.9° C. (Tig: −36.6° C.; Teg: −29.4° C.).

Example 9

[0179] 1. Preparation of Vulcanized Rubber

[0180] In parts by weight, the rubber material comprised: 100 parts of LHNBR (raw rubber obtained from Example 3), 14 parts of F-40, 0.5 parts of PDM, 0.5 parts of stearic acid, 6 parts of magnesium oxide, 50 parts of carbon black N-330, 10 parts of silica AS-70, 0.5 parts of MBZ and 1.0 parts of antioxidant 445.

Preparation of rubber and vulcanized rubber according to the following process steps: [0181] (1) Mixing: first, the components of the the rubber material were put into the kneader machine and mixed at 30-60° C. for 8-10 min and then forced to discharge the rubber; then, a section of the rubber material obtained from mixing is thinly passed or ground 3-5 times on an open refiner or a three-roller mill, discharged and parked for 12 hours to obtain the required rubber material. [0182] (2) Vulcanisation: using an electric plate vulcaniser, a section of the above rubber was vulcanized at 180° C.×8 minutes; then a section of the vulcanized specimen is vulcanized at 150° C.×4 hours and then cooled to room temperature to obtain a vulcanized rubber.

2. Vulcanized Rubber Performance Test

[0183] Test Shore A hardness according to GB/T 531.1-2008 with GSD-719K type rubber hardness tester; test standard according to GB/T 528-2009, GB/T 529-2008 and GB/T 532-2008 respectively, in AI-7000-LU type. The tensile and fracture properties were tested on an electronic tensile tester. The performance test results are shown in Table 1.

TABLE-US-00001 TABLE 1 Vulcanized rubber properties Shore hardness 82 Breaking strength, MPa 7.6 Elongation at break, % 199 100% set tensile strength, MPa 3.1

Example 10

[0184] The raw LHNBR obtained from Example 4 was used, and other preparation steps and conditions were the same as in Example 9 to produce the vulcanized rubber, the performance test results of which are shown in Table 2.

TABLE-US-00002 TABLE 2 Vulcanized rubber properties Shore hardness 67 Breaking strength, MPa 4.8 Elongation at break, % 163 100% set tensile strength, MPa 3.5