CN113185639A - High-strength low-relaxation polyisoprene rubber and preparation method thereof - Google Patents

High-strength low-relaxation polyisoprene rubber and preparation method thereof Download PDF

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CN113185639A
CN113185639A CN202110470963.8A CN202110470963A CN113185639A CN 113185639 A CN113185639 A CN 113185639A CN 202110470963 A CN202110470963 A CN 202110470963A CN 113185639 A CN113185639 A CN 113185639A
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polyisoprene rubber
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CN113185639B (en
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徐云祥
杨英
李世其
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Sichuan University
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
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Abstract

The invention belongs to the technical field of rubber, and particularly relates to high-strength low-relaxation polyisoprene rubber and a preparation method thereof. The invention provides a modified polyisoprene rubber, which is prepared by vulcanizing polyisoprene containing unsaturated terminal groups. The invention utilizes the fact that the end group can generate in-situ crosslinking when the polyisoprene rubber containing the unsaturated end group is vulcanized, and can form soft and hard in-situ crosslinking nano particles or micro phases with adjustable size by utilizing the high density and high crosslinking degree of the local functional group. The formation of the in-situ crosslinking nano particles increases the crosslinking density and the entanglement density on one hand, and further strengthens the toughened rubber through a strain amplification effect, nano particle deformation and the like on the other hand. In addition, the in-situ crosslinked nanoparticles are connected with the main chain through covalent bonds, so that the defect of increased stress relaxation caused by introduction of weak bonds into the inorganic nano filler reinforced rubber is overcome.

Description

High-strength low-relaxation polyisoprene rubber and preparation method thereof
Technical Field
The invention belongs to the technical field of rubber, and particularly relates to high-strength low-relaxation polyisoprene rubber and a preparation method thereof.
Background
Functional filling rubber materials, damping gaskets, rubber structural components and the like in strategic weaponry systems all require rubber materials to have the characteristics of high strength, high toughness and low relaxation, but there is a significant contradiction between high strength and low relaxation in rubber materials. Natural rubber materials have high strength, but their internal non-rubber components cause large stress relaxation. Although the isoprene rubber based on the polyisoprene main chain overcomes the adverse effect of non-rubber components in the natural rubber on the stress relaxation performance, the strength of the isoprene rubber is different from that of the natural rubber. The general method for reinforcing rubber is to reinforce with nano filler, but the common filler reinforcing system can simultaneously introduce larger stress relaxation factors while reinforcing rubber. Therefore, the development of rubber materials with high strength and low relaxation property has become one of the key material bottleneck problems to be broken through in the development plans of related equipment at home and abroad and related industry fields.
Disclosure of Invention
In order to solve the problems, the invention provides a high-strength low-relaxation polyisoprene rubber and a preparation method thereof, the polyisoprene rubber is provided with unsaturated end groups (including end groups at two ends of a main chain and also including block-type end groups), the end groups can be subjected to in-situ crosslinking during vulcanization (unsaturated bonds positioned at the end groups have higher reactivity and can be partially separated due to more rigid structure or polarity difference to cause partial end groups and end groups to be crosslinked to form nano particles or micro phases), and the soft and hard in-situ crosslinked nano particles or micro phases with adjustable sizes can be formed by utilizing the high density and high crosslinking degree of local functional groups. The formation of the in-situ crosslinking nano particles increases the crosslinking density and the entanglement density on one hand, and further strengthens the toughened rubber through a strain amplification effect, nano particle deformation and the like on the other hand. In addition, the in-situ crosslinked nanoparticles are connected with the main chain through covalent bonds, so that the defect of stress relaxation increase caused by introducing weak bonds into the inorganic nano filler reinforced rubber (the inorganic nano filler is combined with the rubber molecular chain through Van der Waals force or weak bonds) is overcome.
The technical scheme of the invention is as follows:
the first technical problem to be solved by the invention is to provide a modified polyisoprene rubber, wherein the modified polyisoprene rubber is prepared by vulcanizing polyisoprene containing unsaturated terminal groups; the unsaturated end groups include both terminal ends of the polyisoprene backbone, and also include block-type end groups. In addition, the in-situ crosslinked nano particles are connected with the main chain through covalent bonds, so that the defect of increased stress relaxation caused by introduction of weak bonds in the inorganic nano filler reinforced rubber is overcome, namely the effects of toughening and reinforcing and reducing the stress relaxation are achieved.
Further, the polyisoprene containing the unsaturated terminal group is prepared by the following method I:
the method comprises the following steps: aging and reacting the functional precursor for 30-100 min at 40-60 ℃ under the action of a catalyst; adding isoprene, and continuously reacting for 8-15 h at 40-60 ℃; washing and drying the obtained product to obtain polyisoprene containing unsaturated end groups;
wherein the functional precursor is selected from at least one of the following substances:
Figure BDA0003045310030000021
Figure BDA0003045310030000031
wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12And R13Is an alkyl chain or a cyclic structure having 0 to 20 carbon atoms.
Further, the molar ratio of the functional precursor to the catalyst is: 20-50: 1, the molar ratio of functional precursor to isoprene is: 1: 50-500, preferably 1: 100 to 300.
Further, the catalyst is a mixture of F, G and H, and the molar ratio of F, G to H is: f: g: h is 0.8-1.2: 15-25: 1-3; wherein, the substance F is neodymium neodecanoate or neodymium isopropanol or neodymium phosphate, the substance G is triisobutylaluminum or diisobutylaluminum hydride, and the substance H is diisobutylaluminum chloride or dichlorodimethylsilyl; preferably, F: g: h1: 10: 1.
further, in the first method, acidified ethanol is added dropwise after the reaction is finished to quench the reaction, the obtained product is washed by acidified water and ethanol for multiple times, and vacuum drying is carried out at 30-50 ℃.
Further, the polyisoprene containing the unsaturated terminal group is prepared by the following method II:
the second method comprises the following steps: dissolving polar polyisoprene rubber in a reaction solvent, adding an unsaturated monomer and a condensing agent, and carrying out condensation reaction for 8-18 h at normal temperature to obtain polyisoprene with unsaturated terminal groups; the unsaturated monomer is selected from at least one of the following substances:
Figure BDA0003045310030000051
wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12And R13Is an alkyl chain or a cyclic structure having 0 to 20 carbon atoms.
Further, the polar polyisoprene rubber comprises at least one of the following substances:
Figure BDA0003045310030000061
wherein D is-OH, -COOH or-NH2E is an alkyl chain or a cyclic structure with 0-20 carbon atoms; x is more than or equal to 10 and less than or equal to 10000, y is more than or equal to 5 and less than or equal to 20, andm is not less than 20, n is not less than 100 and not more than 10000, l is not less than 5 and not more than 20. Preferably, 100. ltoreq. x.ltoreq.1000, 10. ltoreq. y.ltoreq.15, 10. ltoreq. m.ltoreq.15, 100. ltoreq. n.ltoreq.1000.
Further, in the second method, the reaction solvent is tetrahydrofuran, chloroform, dichloromethane, n-hexane or toluene; wherein the proportion of the polar polyisoprene rubber to the reaction solvent is as follows: 0.5-2 g/100 mL.
Further, in the second method, the condensing agent is selected according to the following principle:
when a condensation reaction of a carboxyl group with a hydroxyl group or an amino group occurs, the condensing agent is selected from: dicyclohexylcarbodiimide (DCC), N, N ' -Diisopropylcarbodiimide (DIC), N- (3-dimethylaminopropyl) -N ' -ethylcarbodiimide hydrochloride (EDC. HCl), 4, 5-Dicyanoimidazole (DCI), N, N ' -Carbonyldiimidazole (CDI), N-hydroxysuccinimide (NHS) (HOSu), N-hydroxythiosuccinimide sodium salt (sulfoo-NHS), 1-hydroxy-7-azobenzotriazol (HOAT), 1-hydroxybenzotriazole (HOBt), 6-chloro-1-hydroxybenzotriazole (Cl-HOBt), O- (7-azobenzotriazol) -N, N, N ', N ' -tetramethylurea Hexafluorophosphate (HATU), benzotriazol-N, one of N, N ', N' -tetramethyluronium Hexafluorophosphate (HBTU), O-benzotriazol-N, N, N ', N' -tetramethyluronium tetrafluoroborate (TBTU), 6-chlorobenzotriazol-1, 1,3, 3-tetramethyluronium Hexafluorophosphate (HCTU), O- (1, 2-dihydro-2-oxo-pyridinyl) -1,1,3, 3-tetramethyluronium tetrafluoroborate (TPTU), N-ethoxycarbonyl-2-ethoxy-1, 2-Dihydroquinoline (DQ), bis (2-oxo-3-oxazolidinyl) hypophosphoryl chloride (BOP-Cl);
when the self-condensation and mutual condensation reactions of hydroxyl groups and amino groups occur, the condensing agent is selected from: diisopropyl azodicarboxylate (DIAD), diethyl azodicarboxylate (DEAD), benzotriazol-1-yl-oxytripyrrolidinylphosphine hexafluorophosphate (PyBOP), benzotriazol-1-tris (trimethylamino) -hexafluorophosphate (BOP), and tripyrrolidinylphosphonium bromide hexafluorophosphate (PyBrOP);
when condensation of the acid chloride with an amino, hydroxyl or carboxyl group occurs, the condensing agent is an organic base, such as one of triethylamine, triethylenediamine (DABCO), 1, 8-diazabicycloundecen-7-ene (DBU), 1, 5-diazabicyclo [4.3.0] non-5-ene (DBN), 4-Dimethylaminopyridine (DMAP), pyridine, N-methylmorpholine, tetramethylethylenediamine, Tetramethylguanidine (TMG), potassium/sodium tert-butoxide, N-Diisopropylethylamine (DIPEA), Diisopropylamine (DIPA).
Further, in the second method, the molar ratio of the polar polyisoprene rubber, the unsaturated monomer and the condensing agent is: polar polyisoprene rubber: unsaturated monomer: condensing agent 1: 5-15: 5-15, preferably 1: 8-12: 8 to 12.
Further, the vulcanization means: the polyisoprene with the unsaturated end group is mixed with the vulcanizing agent and the auxiliary agent by two-roll milling or solution blending, and then vulcanized and formed at high temperature.
Further, the vulcanization temperature is 120-190 ℃, and the vulcanization time is 15-120 min; preferably 140-150 ℃ for 20-40 min.
Further, the vulcanizing agent is sulfur, tetramethylthiuram disulfide (TMTD), dipentamethylenethiuram tetrasulfide (DPTT) (TRA), 4- (2-benzothiazyldithio) Morpholine (MDB), tetraethylthiuram disulfide (TETD), tetrabutylthiuram disulfide (TBTD), tetramethylthiuram tetrasulfide (TMTT), 4 '-dimorpholine disulfide (DTDM), N-polysulfido-bis (dimethylamine), N' -polysulfido-bis (diethylamine), cyclopentylidenethioimine, dicumyl peroxide (DCP), di-tert-butyl peroxide (DTBP), 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane (DBPMH), Benzoyl Peroxide (BPO), 2, 4-dichlorobenzoyl peroxide (DCPB), tert-butyl perbenzoate (TBPB), At least one of bis (tert-butylperoxyisopropyl) benzene (BIPB), 3,5,7, 7-pentamethyl-1, 2, 4-trioxane (PMTO), Cumyl Hydroperoxide (CHP).
Furthermore, an auxiliary agent can be added in the vulcanization process according to needs, wherein the auxiliary agent comprises zinc oxide, stearic acid, an antioxidant, an anti-aging agent or a vulcanization accelerator.
Further, the vulcanization formula in the vulcanization process is as follows: 0.5-5 parts of vulcanizing agent, preferably 1-3 parts, 0.5-3 parts of vulcanization accelerator, 3-8 parts of zinc oxide, 1-4 parts of stearic acid, 1-3 parts of antioxidant and 1-3 parts of anti-aging agent.
Further, the time of the two-roller open mixing is 5-30 min, preferably 12-18 min; the solvent used for blending the solution comprises tetrahydrofuran, chloroform, dichloromethane, normal hexane or toluene; the stirring time for blending the solution is 1-24 h, preferably 2-8 h.
The second technical problem to be solved by the present invention is to provide a preparation method of the modified polyisoprene rubber, wherein the preparation method comprises: selecting polyisoprene with unsaturated terminal groups as a raw material, and vulcanizing the polyisoprene with the unsaturated terminal groups to obtain the modified polyisoprene rubber.
The third technical problem to be solved by the invention is to provide polyisoprene with unsaturated end groups, wherein the polyisoprene with unsaturated end groups is prepared by adopting the following method I or method II:
the method comprises the following steps: aging and reacting the functional precursor for 30-100 min at 40-60 ℃ under the action of a catalyst; adding isoprene, and continuously reacting for 8-15 h at 40-60 ℃; washing and drying the obtained product to obtain polyisoprene containing unsaturated end groups;
wherein the functional precursor is selected from at least one of the following substances:
Figure BDA0003045310030000081
Figure BDA0003045310030000091
wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12And R13Is an alkyl chain or a cyclic structure with 0 to 20 carbon atoms;
the second method comprises the following steps: dissolving polar polyisoprene rubber in a reaction solvent, adding an unsaturated monomer and a condensing agent, and carrying out condensation reaction for 8-18 h at normal temperature to obtain polyisoprene with unsaturated terminal groups; the unsaturated monomer is selected from at least one of the following substances:
Figure BDA0003045310030000101
wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12And R13Is an alkyl chain or a cyclic structure having 0 to 20 carbon atoms.
Further, in the first method, the molar ratio of the functional precursor to the catalyst is: 20-50: 1, the molar ratio of functional precursor to isoprene is: 1: 50-500, preferably 1: 100 to 300.
Further, in the first method, the catalyst is a mixture of F, G and H, and the molar ratio of F, G to H is: f: g: h is 0.8-1.2: 15-25: 1-3; wherein, the substance F is neodymium neodecanoate or neodymium isopropanol or neodymium phosphate, the substance G is triisobutylaluminum or diisobutylaluminum hydride, and the substance H is diisobutylaluminum chloride or dichlorodimethylsilyl; preferably, F: g: h1: 10: 1.
further, in the second method, the polar polyisoprene rubber comprises at least one of the following substances:
Figure BDA0003045310030000111
wherein D is-OH, -COOH or-NH2E is an alkyl chain or a cyclic structure with 0-20 carbon atoms; x is more than or equal to 10 and less than or equal to 10000, y is more than or equal to 5 and less than or equal to 20, m is more than or equal to 5 and less than or equal to 20, n is more than or equal to 100 and less than or equal to 10000, and l is more than or equal to 5 and less than or equal to 20. Preferably, 100. ltoreq. x.ltoreq.1000, 10. ltoreq. y.ltoreq.15, 10. ltoreq. m.ltoreq.15, 100. ltoreq. n.ltoreq.1000.
Further, in the second method, the reaction solvent is tetrahydrofuran, chloroform, dichloromethane, n-hexane or toluene; wherein the proportion of the polar polyisoprene rubber to the reaction solvent is as follows: 0.5-2 g/100 mL.
Further, in the second method, the condensing agent is selected according to the following principle:
when a condensation reaction of a carboxyl group with a hydroxyl group or an amino group occurs, the condensing agent is selected from: dicyclohexylcarbodiimide (DCC), N, N ' -Diisopropylcarbodiimide (DIC), N- (3-dimethylaminopropyl) -N ' -ethylcarbodiimide hydrochloride (EDC. HCl), 4, 5-Dicyanoimidazole (DCI), N, N ' -Carbonyldiimidazole (CDI), N-hydroxysuccinimide (NHS) (HOSu), N-hydroxythiosuccinimide sodium salt (sulfoo-NHS), 1-hydroxy-7-azobenzotriazol (HOAT), 1-hydroxybenzotriazole (HOBt), 6-chloro-1-hydroxybenzotriazole (Cl-HOBt), O- (7-azobenzotriazol) -N, N, N ', N ' -tetramethylurea Hexafluorophosphate (HATU), benzotriazol-N, one of N, N ', N' -tetramethyluronium Hexafluorophosphate (HBTU), O-benzotriazol-N, N, N ', N' -tetramethyluronium tetrafluoroborate (TBTU), 6-chlorobenzotriazol-1, 1,3, 3-tetramethyluronium Hexafluorophosphate (HCTU), O- (1, 2-dihydro-2-oxo-pyridinyl) -1,1,3, 3-tetramethyluronium tetrafluoroborate (TPTU), N-ethoxycarbonyl-2-ethoxy-1, 2-Dihydroquinoline (DQ), bis (2-oxo-3-oxazolidinyl) hypophosphoryl chloride (BOP-Cl);
when the self-condensation and mutual condensation reactions of hydroxyl groups and amino groups occur, the condensing agent is selected from: diisopropyl azodicarboxylate (DIAD), diethyl azodicarboxylate (DEAD), benzotriazol-1-yl-oxytripyrrolidinylphosphine hexafluorophosphate (PyBOP), benzotriazol-1-tris (trimethylamino) -hexafluorophosphate (BOP), and tripyrrolidinylphosphonium bromide hexafluorophosphate (PyBrOP);
when condensation of the acid chloride with an amino, hydroxyl or carboxyl group occurs, the condensing agent is an organic base, such as one of triethylamine, triethylenediamine (DABCO), 1, 8-diazabicycloundecen-7-ene (DBU), 1, 5-diazabicyclo [4.3.0] non-5-ene (DBN), 4-Dimethylaminopyridine (DMAP), pyridine, N-methylmorpholine, tetramethylethylenediamine, Tetramethylguanidine (TMG), potassium/sodium tert-butoxide, N-Diisopropylethylamine (DIPEA), Diisopropylamine (DIPA).
Further, in the second method, the molar ratio of the polar polyisoprene rubber, the unsaturated monomer and the condensing agent is: polar polyisoprene rubber: unsaturated monomer: condensing agent 1: 5-15: 5-15, preferably 1: 8-12: 8 to 12.
The fourth technical problem to be solved by the invention is to provide a method for improving the strength of polyisoprene rubber and simultaneously reducing the stress relaxation, wherein the method comprises the following steps: firstly, modifying polyisoprene to obtain polyisoprene with unsaturated end groups, and then vulcanizing.
Further, the method for modifying polyisoprene to obtain polyisoprene with unsaturated terminal groups is one of the following two methods:
the method comprises the following steps: aging and reacting the functional precursor for 30-100 min at 40-60 ℃ under the action of a catalyst; adding isoprene, and continuously reacting for 8-15 h at 40-60 ℃; washing and drying the obtained product to obtain polyisoprene containing unsaturated end groups;
wherein the functional precursor is selected from at least one of the following substances:
Figure BDA0003045310030000131
Figure BDA0003045310030000141
wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12And R13Is an alkyl chain or a cyclic structure with 0 to 20 carbon atoms;
the second method comprises the following steps: dissolving polar polyisoprene rubber in a reaction solvent, adding an unsaturated monomer and a condensing agent, and carrying out condensation reaction for 8-18 h at normal temperature to obtain polyisoprene with unsaturated terminal groups; the unsaturated monomer is selected from at least one of the following substances:
Figure BDA0003045310030000151
wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12And R13Is an alkyl chain or a cyclic structure having 0 to 20 carbon atoms.
Further, in the first method, the molar ratio of the functional precursor to the catalyst is: 20-50: 1, the molar ratio of functional precursor to isoprene is: 1: 50-500, preferably 1: 100 to 300.
Further, in the first method, the catalyst is a mixture of F, G and H, and the molar ratio of F, G to H is: f: g: h is 0.8-1.2: 15-25: 1-3; wherein, the substance F is neodymium neodecanoate or neodymium isopropanol or neodymium phosphate, the substance G is triisobutylaluminum or diisobutylaluminum hydride, and the substance H is diisobutylaluminum chloride or dichlorodimethylsilyl; preferably, F: g: h1: 10: 1.
further, in the second method, the polar polyisoprene rubber comprises at least one of the following substances:
Figure BDA0003045310030000161
wherein D is-OH, -COOH or-NH2E is an alkyl chain or a cyclic structure with 0-20 carbon atoms; x is more than or equal to 10 and less than or equal to 10000, y is more than or equal to 5 and less than or equal to 20, m is more than or equal to 5 and less than or equal to 20, n is more than or equal to 100 and less than or equal to 10000, and l is more than or equal to 5 and less than or equal to 20. Preferably, 100. ltoreq. x.ltoreq.1000, 10. ltoreq. y.ltoreq.15, 10. ltoreq. m.ltoreq.15, 100. ltoreq. n.ltoreq.1000.
Further, in the second method, the reaction solvent is tetrahydrofuran, chloroform, dichloromethane, n-hexane or toluene; wherein the proportion of the polar polyisoprene rubber to the reaction solvent is as follows: 0.5-2 g/100 mL.
Further, in the second method, the condensing agent is selected according to the following principle:
when a condensation reaction of a carboxyl group with a hydroxyl group or an amino group occurs, the condensing agent is selected from: dicyclohexylcarbodiimide (DCC), N, N ' -Diisopropylcarbodiimide (DIC), N- (3-dimethylaminopropyl) -N ' -ethylcarbodiimide hydrochloride (EDC. HCl), 4, 5-Dicyanoimidazole (DCI), N, N ' -Carbonyldiimidazole (CDI), N-hydroxysuccinimide (NHS) (HOSu), N-hydroxythiosuccinimide sodium salt (sulfoo-NHS), 1-hydroxy-7-azobenzotriazol (HOAT), 1-hydroxybenzotriazole (HOBt), 6-chloro-1-hydroxybenzotriazole (Cl-HOBt), O- (7-azobenzotriazol) -N, N, N ', N ' -tetramethylurea Hexafluorophosphate (HATU), benzotriazol-N, one of N, N ', N' -tetramethyluronium Hexafluorophosphate (HBTU), O-benzotriazol-N, N, N ', N' -tetramethyluronium tetrafluoroborate (TBTU), 6-chlorobenzotriazol-1, 1,3, 3-tetramethyluronium Hexafluorophosphate (HCTU), O- (1, 2-dihydro-2-oxo-pyridinyl) -1,1,3, 3-tetramethyluronium tetrafluoroborate (TPTU), N-ethoxycarbonyl-2-ethoxy-1, 2-Dihydroquinoline (DQ), bis (2-oxo-3-oxazolidinyl) hypophosphoryl chloride (BOP-Cl);
when the self-condensation and mutual condensation reactions of hydroxyl groups and amino groups occur, the condensing agent is selected from: diisopropyl azodicarboxylate (DIAD), diethyl azodicarboxylate (DEAD), benzotriazol-1-yl-oxytripyrrolidinylphosphine hexafluorophosphate (PyBOP), benzotriazol-1-tris (trimethylamino) -hexafluorophosphate (BOP), and tripyrrolidinylphosphonium bromide hexafluorophosphate (PyBrOP);
when condensation of the acid chloride with an amino, hydroxyl or carboxyl group occurs, the condensing agent is an organic base, such as one of triethylamine, triethylenediamine (DABCO), 1, 8-diazabicycloundecen-7-ene (DBU), 1, 5-diazabicyclo [4.3.0] non-5-ene (DBN), 4-Dimethylaminopyridine (DMAP), pyridine, N-methylmorpholine, tetramethylethylenediamine, Tetramethylguanidine (TMG), potassium/sodium tert-butoxide, N-Diisopropylethylamine (DIPEA), Diisopropylamine (DIPA).
The invention has the beneficial effects that:
the invention utilizes the fact that the end group can generate in-situ crosslinking when the polyisoprene rubber containing the unsaturated end group is vulcanized, and can form soft and hard in-situ crosslinking nano particles or micro phases with adjustable size by utilizing the high density and high crosslinking degree of the local functional group. The formation of the in-situ crosslinking nano particles increases the crosslinking density and the entanglement density on one hand, and further strengthens the toughened rubber through a strain amplification effect, nano particle deformation and the like on the other hand. In addition, the in-situ crosslinked nanoparticles are connected with the main chain through covalent bonds, so that the defect that stress relaxation is increased due to introduction of weak bonds into the inorganic nano filler reinforced rubber is overcome (the inorganic nano filler and the rubber molecular chain are weakly combined through Van der Waals force or weak bonds).
The invention prepares the modified polyisoprene rubber with unsaturated bonds at two ends of a rubber molecular chain or at the end group of a branched chain, and the end group of the obtained polyisoprene containing the unsaturated groups can form local highly crosslinked nano particles or micro-phase after being vulcanized, thereby enhancing the obdurability of the rubber and endowing the rubber material with low relaxation performance. The strength of vulcanized rubber reaches 25MPa, and the elongation at break is 840%, which is equivalent to Hainan natural rubber. Tensile strain 40%, 3.5% relaxation at 3 hours, much lower than the relaxation rate of natural rubber, and even lower than vulcanized isoprene rubber. Therefore, the invention provides a new idea for synthesizing the polyisoprene rubber with high strength and low relaxation.
Description of the drawings:
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of OAIR obtained in example 1.
FIG. 2 is a NMR spectrum of HIR obtained in example 2.
FIG. 3 is the NMR spectrum of AIR obtained in example 3.
FIGS. 4a and 4b are transmission electron micrographs of OAIR-V and IR-V, respectively.
FIG. 5 is a stress-strain curve for OAIR-V, HIR-V, AIR-V, NR-V and IR-V obtained for examples and comparative examples.
FIG. 6 is a curve fitted to the stress relaxation of OAIR-V, HIR-V, AIR-V, NR-V and IR-V.
FIG. 7 is a diagram showing the mechanism of producing a modified polyisoprene rubber by vulcanizing polyisoprene having an unsaturated terminal group according to the present invention.
Detailed Description
The modified polyisoprene rubber main chain end group or the block end group prepared by the invention contains unsaturated bonds, so that local highly crosslinked nano particles or micro phases with softness and adjustable size (the longer the length of a side chain, the higher the degree of freedom of the unsaturated bonds on the chain, the softer the formed nano particles, and the longer the length of the block end group, the larger the nano particles formed by in-situ crosslinking) can be formed during vulcanization, and the entanglement density of the tail end is increased. In addition, the unique nano particles enhance and toughen the effect, so that the strength and the elongation at break of the vulcanized rubber are equivalent to those of Hainan natural rubber, and the stress relaxation rate is far lower than that of vulcanized natural rubber.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
The raw materials used in the embodiment of the invention are as follows:
1, 2-undecadiene (Moreau JL, Gaudemar M.journal of organic chemistry.1976, 108: 159-164) and 3-methyleneene-1, 8-diene (Lijiang Utility, Wangzyu, Zhoushijun, et al. methods for preparing neophytadiene-like compounds from fatty acids: 2017.) were synthesized according to literature reports. Neodymium neodecanoate [ Nd (VA) from Meryer3]The solid content is 0.69g/mL, and the solvent is n-hexane; triisobutylaluminum [ Al (i-Bu) from Acros Chemical Co., Ltd.)3]And diisobutylaluminum chloride [ Al (i-Bu)2Cl]The concentrations thereof were 1.1M and 0.8M, respectively; isoprene from Alfa, which was refluxed for 2 hours with calcium hydride and then distilled for future use. Both the n-hexane and tetrahydrofuran solvents require sodium/benzophenone to remove water and then are distilled for later use. Natural rubber is provided by the tropical agricultural academy of sciences of China. Commercial isoprene rubber is provided by the oil-monster petrochemical division of china. Vulcanizing agents available from Adamas Chemical company, including sulfur, vulcanization accelerator CZ, antioxidant RD, antioxidant 4020, zinc oxide (ZnO), and stearic acid. Other pharmaceutical agents, unless otherwise specified, are provided by Shanghai Tantake technology, Inc.
Example 1
Nd(VA)31, 2-undecadiene, Al (i-Bu)3And Al (i-Bu)2Sequentially and slowly injecting Cl into a sealed glass bottle, and carrying out aging reaction at 50 ℃ for 60 min; then adding an isoprene monomer, and continuing to react for 12h at 50 ℃; finally, a small amount of acidified ethanol is dripped to quench the reaction; washing the polymerization product for many times by acidified water and ethanol, and drying in vacuum at 40 ℃ to obtain the n-Octyl Allene Isoprene Rubber (OAIR). The reaction formula is shown as formula I, and the reaction proportion and the reaction formula are shown as formula IThe physical properties of the resulting rubber are shown in Table 1.
Figure BDA0003045310030000181
Mixing 100 parts of n-octyl allene isoprene rubber, 5 parts of zinc oxide, 2 parts of stearic acid, 1 part of antioxidant 4020, 1 part of antioxidant RD, 1 part of vulcanization accelerator CZ and 2 parts of sulfur in a milling machine, and vulcanizing to obtain OAIR-V.
Example 2
The 1, 2-undecadiene in example 1 was changed to 3-methyleneene-1, 8-diene, and the Hexenyl Isoprene Rubber (HIR) and HIR-V were synthesized according to the procedure of example 1, except that the conditions were changed. The reaction equation is shown in formula III, and the reaction ratio and the physical properties of the synthetic rubber are shown in Table 1.
Figure BDA0003045310030000191
Example 3
Hydroxylated isoprene rubber (B-PIP-OH) was dissolved in THF, acryloyl chloride, triethylamine and DMAP were added. Wherein the polar isoprene rubber: acryloyl chloride: triethylamine and DMAP ═ 1: 10: 10. the reaction was carried out at room temperature for 12 hours. After the reaction is finished, washing the reaction product in methanol for three times, and finally drying the reaction product in a vacuum oven at 40 ℃ to obtain the acrylate-based isoprene rubber (AIR). The reaction equation is shown in formula IV.
Figure BDA0003045310030000192
100 parts of AIR, 5 parts of zinc oxide, 2 parts of stearic acid, 1 part of antioxidant 4020, 1 part of antioxidant RD, 1 part of vulcanization accelerator CZ and 2 parts of sulfur are mixed and vulcanized in a milling machine to obtain AIR-V.
Comparative example 1
100 parts of commercial polyisoprene rubber, 5 parts of zinc oxide, 2 parts of stearic acid are mixed, 1 part of antioxidant 4020, 1 part of antioxidant RD, 1 part of vulcanization accelerator CZ and 2 parts of sulfur are mixed and vulcanized in a milling machine to obtain IR-V.
Comparative example 2
100 parts of natural rubber, 5 parts of zinc oxide, 2 parts of stearic acid, 1 part of antioxidant 4020, 1 part of antioxidant RD, 1 part of vulcanization accelerator CZ and 2 parts of sulfur are mixed and vulcanized in a milling machine to obtain NR-V.
Table 1 shows the reaction recipes and rubber synthesis information for OAIR, HIR and AIR.
TABLE 1
Figure BDA0003045310030000201
And (3) performance testing:
the model of a Pop tester used for the nuclear magnetic resonance hydrogen spectrum test is Bruker AV 400, the test frequency is 400MHz, and the test solvent is deuterated chloroform.
Mechanical Property testing the instrument model Instron 5966 was used, the test specimen being dumbbell-shaped and measuring 35X 2X 1mm3The testing speed is 12mm/min, 60mm/min and 100mm/min, and the testing temperature is room temperature; each sample was tested in triplicate and the average was taken as the final data point.
Dynamic mechanical testing the Instrument model used was a TA Instrument Q800, and the dimensions of the samples tested were 12mm by 3mm by 0.5 mm. The relaxation test is room temperature test, constant temperature 5min, and relaxation time 180 min.
The apparatus used for TEM test is JEOL JEM-1011, and the sample is prepared by freezing section on leicaemuc6/FC6 ultra-thin microtome. The specimen size was 10mm by 3mm by 0.5 mm.
Nuclear magnetic maps of OAIR, HIR and AIR obtained in the examples are shown in fig. 1 to 3.
Table 2 shows the mechanical property data of OAIR-V, HIR-V, AIR-V, NR-V and IR-V.
TABLE 2
Figure BDA0003045310030000202
The morphology characteristics of the vulcanized n-octyl allene rubber and vulcanized commercial isoprene rubber aggregates are observed through a TEM test, and the result is shown in figure 4. OAIR-V (FIG. 4a) has a denser population and more large size aggregates than IR-V (FIG. 4b), which are highly crosslinked nanoparticles or microphases formed by crosslinking the unsaturated end groups of the n-octyldiene rubber.
The present invention performed mechanical property tests and stress relaxation tests on vulcanized rubber samples as shown in fig. 5 and 6. The strength and the elongation at break of the vulcanized rubber synthesized by the method are equivalent to those of natural rubber, and the stress relaxation rate is far lower than that of vulcanized natural rubber, even lower than that of commercial isoprene rubber.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A modified polyisoprene rubber, which is characterized in that the modified polyisoprene rubber is prepared by vulcanizing polyisoprene containing unsaturated terminal groups.
2. The modified polyisoprene rubber as claimed in claim 1, wherein the polyisoprene rubber containing unsaturated terminal groups is prepared by the following method one:
the method comprises the following steps: aging and reacting the functional precursor for 30-100 min at 40-60 ℃ under the action of a catalyst; adding isoprene, and continuously reacting for 8-15 h at 40-60 ℃; washing and drying the obtained product to obtain polyisoprene with unsaturated end groups;
wherein the functional precursor is selected from at least one of the following substances:
Figure FDA0003045310020000021
Figure FDA0003045310020000031
wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12And R13Is an alkyl chain or a cyclic structure with 0 to 20 carbon atoms;
further, the molar ratio of the functional precursor to the catalyst is: 20-50: 1, the molar ratio of functional precursor to isoprene is: 1: 50-500, preferably 1: 100-300 parts;
further, the catalyst is a mixture of F, G and H, and the molar ratio of F, G to H is: f: g: h is 0.8-1.2: 15-25: 1-3; wherein, the substance F is neodymium neodecanoate or neodymium isopropanol or neodymium phosphate, the substance G is triisobutylaluminum or diisobutylaluminum hydride, and the substance H is diisobutylaluminum chloride or dichlorodimethylsilyl.
3. The modified polyisoprene rubber as claimed in claim 1, wherein the polyisoprene with unsaturated terminal group is prepared by the following method II:
the second method comprises the following steps: dissolving polar polyisoprene rubber in a reaction solvent, adding an unsaturated monomer and a condensing agent, and carrying out condensation reaction for 8-18 h at normal temperature to obtain polyisoprene with unsaturated terminal groups; the unsaturated monomer is selected from at least one of the following substances:
Figure FDA0003045310020000041
wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12And R13Is an alkyl chain or a cyclic structure with 0 to 20 carbon atoms;
further, the polar polyisoprene rubber comprises at least one of the following substances:
Figure FDA0003045310020000051
wherein D is-OH, -COOH or-NH2E is an alkyl chain or a cyclic structure with 0-20 carbon atoms; x is more than or equal to 10 and less than or equal to 10000, y is more than or equal to 5 and less than or equal to 20, m is more than or equal to 5 and less than or equal to 20, n is more than or equal to 100 and less than or equal to 10000, and l is more than or equal to 5 and less than or equal to 20;
further, the reaction solvent is tetrahydrofuran, chloroform, dichloromethane, n-hexane or toluene; wherein the proportion of the polar polyisoprene rubber to the reaction solvent is as follows: 0.5-2 g/100 mL;
further, the condensing agent is selected according to the following principle:
when a condensation reaction of a carboxyl group with a hydroxyl group or an amino group occurs, the condensing agent is selected from: dicyclohexylcarbodiimide, N, N '-diisopropylcarbodiimide, N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride, 4, 5-dicyanoimidazole, N, N '-carbonyldiimidazole, N-hydroxysuccinimide, N-hydroxythiosuccinimide sodium salt, 1-hydroxy-7-azobenzotriazol, 1-hydroxybenzotriazole, 6-chloro-1-hydroxybenzotriazole, O- (7-azobenzotriazol) -N, N, N', N '-tetramethylurea hexafluorophosphate, benzotriazol-N, N, N', N '-tetramethylurea hexafluorophosphate, O-benzotriazol-N, N, N', N '-tetramethylurea tetrafluoroborate, N, N' -dimethylurea, One of 6-chlorobenzotriazole-1, 1,3, 3-tetramethylurea hexafluorophosphate, O- (1, 2-dihydro-2-oxo-pyridyl) -1,1,3, 3-tetramethylurea tetrafluoroborate, N-ethoxycarbonyl-2-ethoxy-1, 2-dihydroquinoline and bis (2-oxo-3-oxazolidinyl) phosphoryl chloride;
when the self-condensation and mutual condensation reactions of hydroxyl groups and amino groups occur, the condensing agent is selected from: one of diisopropyl azodicarboxylate, diethyl azodicarboxylate, benzotriazole-1-yl-oxytripyrrolidinylphosphine hexafluorophosphate, benzotriazole-1-tris (trimethylamino) -hexafluorophosphate, and tripyrrolidinylphosphonium bromide hexafluorophosphate;
when condensation reaction of acyl chloride and amino, hydroxyl or carboxyl occurs, the condensing agent is an organic base, preferably one of triethylamine, triethylene diamine, 1, 8-diazabicycloundec-7-ene, 1, 5-diazabicyclo [4.3.0] non-5-ene, 4-dimethylaminopyridine, pyridine, N-methylmorpholine, tetramethylethylenediamine, tetramethylguanidine, potassium/sodium tert-butoxide, N-diisopropylethylamine and diisopropylamine;
further, the molar ratio of the polar polyisoprene rubber, the unsaturated monomer and the condensing agent is as follows: polar polyisoprene rubber: unsaturated monomer: condensing agent 1: 5-15: 5-15, preferably 1: 8-12: 8 to 12.
4. The modified polyisoprene rubber as claimed in any one of claims 1 to 3, wherein the vulcanization is: mixing polyisoprene containing unsaturated end groups with a vulcanizing agent and an auxiliary agent through double-roller open milling or solution blending, and then vulcanizing and molding at high temperature;
further, the vulcanization temperature is 120-190 ℃, and the vulcanization time is 15-120 min; preferably 140-150 ℃ for 20-40 min;
further, the vulcanizing agent is sulfur, tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulfide, 4- (2-benzothiazyldithio) morpholine, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetramethylthiuram tetrasulfide, 4 '-dimorpholine disulfide, N-polysulfidic bis (dimethylamine), N' -polysulfidic bis (diethylamine), cycloheptathioimine, dicumyl peroxide, di-tert-butyl peroxide, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, benzoyl peroxide, 2, 4-dichlorobenzoyl peroxide, tert-butyl perbenzoate, di-tert-butylperoxyisopropyl benzene, 3,5,7, 7-pentamethyl-1, 2, 4-trioxohexane, At least one of cumyl hydroperoxide.
5. A method for preparing the modified polyisoprene rubber as described in any one of claims 1 to 4, wherein the method comprises the following steps: selecting polyisoprene with unsaturated terminal groups as a raw material, and vulcanizing the polyisoprene with the unsaturated terminal groups to obtain the modified polyisoprene rubber.
6. The polyisoprene with the unsaturated terminal group is characterized in that the polyisoprene with the unsaturated terminal group is prepared by the following method one or method two:
the method comprises the following steps: aging and reacting the functional precursor for 30-100 min at 40-60 ℃ under the action of a catalyst; adding isoprene, and continuously reacting for 8-15 h at 40-60 ℃; washing and drying the obtained product to obtain polyisoprene with unsaturated end groups;
wherein the functional precursor is selected from at least one of the following substances:
Figure FDA0003045310020000071
Figure FDA0003045310020000081
wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12And R13Is an alkyl chain or a cyclic structure with 0 to 20 carbon atoms;
the second method comprises the following steps: dissolving polar polyisoprene rubber in a reaction solvent, adding an unsaturated monomer and a condensing agent, and carrying out condensation reaction for 8-18 h at normal temperature to obtain polyisoprene with unsaturated terminal groups; the unsaturated monomer is selected from at least one of the following substances:
Figure FDA0003045310020000091
wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12And R13Is an alkyl chain or a cyclic structure having 0 to 20 carbon atoms.
7. The polyisoprene with unsaturated end groups as claimed in claim 6, wherein in the first method, the molar ratio of the functional precursor to the catalyst is: 20-50: 1, the molar ratio of functional precursor to isoprene is: 1: 50-500;
further, in the first method, the catalyst is a mixture of F, G and H, and the molar ratio of F, G to H is: f: g: h is 0.8-1.2: 15-25: 1-3; wherein, the substance F is neodymium neodecanoate or neodymium isopropanol or neodymium phosphate, the substance G is triisobutylaluminum or diisobutylaluminum hydride, and the substance H is diisobutylaluminum chloride or dichlorodimethylsilyl;
further, in the second method, the polar polyisoprene rubber comprises at least one of the following substances:
Figure FDA0003045310020000101
wherein D is-OH, -COOH or-NH2E is an alkyl chain or a cyclic structure with 0-20 carbon atoms; x is more than or equal to 10 and less than or equal to 10000, y is more than or equal to 5 and less than or equal to 20, m is more than or equal to 5 and less than or equal to 20, n is more than or equal to 100 and less than or equal to 10000, and l is more than or equal to 5 and less than or equal to 20;
further, in the second method, the reaction solvent is tetrahydrofuran, chloroform, dichloromethane, n-hexane or toluene; wherein the proportion of the polar polyisoprene rubber to the reaction solvent is as follows: 0.5-2 g/100 mL;
further, in the second method, the condensing agent is selected according to the following principle:
when a condensation reaction of a carboxyl group with a hydroxyl group or an amino group occurs, the condensing agent is selected from: dicyclohexylcarbodiimide, N, N '-diisopropylcarbodiimide, N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride, 4, 5-dicyanoimidazole, N, N '-carbonyldiimidazole, N-hydroxysuccinimide, N-hydroxythiosuccinimide sodium salt, 1-hydroxy-7-azobenzotriazol, 1-hydroxybenzotriazole, 6-chloro-1-hydroxybenzotriazole, O- (7-azobenzotriazol) -N, N, N', N '-tetramethylurea hexafluorophosphate, benzotriazol-N, N, N', N '-tetramethylurea hexafluorophosphate, O-benzotriazol-N, N, N', N '-tetramethylurea tetrafluoroborate, N, N' -dimethylurea, One of 6-chlorobenzotriazole-1, 1,3, 3-tetramethylurea hexafluorophosphate, O- (1, 2-dihydro-2-oxo-pyridyl) -1,1,3, 3-tetramethylurea tetrafluoroborate, N-ethoxycarbonyl-2-ethoxy-1, 2-dihydroquinoline and bis (2-oxo-3-oxazolidinyl) phosphoryl chloride;
when the self-condensation and mutual condensation reactions of hydroxyl groups and amino groups occur, the condensing agent is selected from: one of diisopropyl azodicarboxylate, diethyl azodicarboxylate, benzotriazole-1-yl-oxytripyrrolidinylphosphine hexafluorophosphate, benzotriazole-1-tris (trimethylamino) -hexafluorophosphate, and tripyrrolidinylphosphonium bromide hexafluorophosphate;
when condensation reaction of acyl chloride and amino, hydroxyl or carboxyl occurs, the condensing agent is an organic base, preferably one of triethylamine, triethylene diamine, 1, 8-diazabicycloundec-7-ene, 1, 5-diazabicyclo [4.3.0] non-5-ene, 4-dimethylaminopyridine, pyridine, N-methylmorpholine, tetramethylethylenediamine, tetramethylguanidine, potassium/sodium tert-butoxide, N-diisopropylethylamine and diisopropylamine;
further, the molar ratio of the polar polyisoprene rubber, the unsaturated monomer and the condensing agent is as follows: polar polyisoprene rubber: unsaturated monomer: condensing agent 1: 5-15: 5-15, preferably 1: 8-12: 8 to 12.
8. A method for improving strength of polyisoprene rubber and simultaneously reducing stress relaxation of the polyisoprene rubber is characterized by comprising the following steps: firstly, modifying polyisoprene to obtain polyisoprene with unsaturated end groups, and then vulcanizing.
9. The method for improving the strength of polyisoprene rubber while reducing the stress relaxation thereof as claimed in claim 8, wherein the method for modifying polyisoprene to obtain polyisoprene with unsaturated end group is one of the following two methods:
the method comprises the following steps: aging and reacting the functional precursor for 30-100 min at 40-60 ℃ under the action of a catalyst; adding isoprene, and continuously reacting for 8-15 h at 40-60 ℃; washing and drying the obtained product to obtain polyisoprene with unsaturated end groups;
wherein the functional precursor is selected from at least one of the following substances:
Figure FDA0003045310020000121
Figure FDA0003045310020000131
wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12And R13Is an alkyl chain or a cyclic structure with 0 to 20 carbon atoms;
the second method comprises the following steps: dissolving polar polyisoprene rubber in a reaction solvent, adding an unsaturated monomer and a condensing agent, and carrying out condensation reaction for 8-18 h at normal temperature to obtain polyisoprene with unsaturated terminal groups; the unsaturated monomer is selected from at least one of the following substances:
Figure FDA0003045310020000141
wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12And R13Is an alkyl chain or a cyclic structure having 0 to 20 carbon atoms.
10. The method of improving strength of polyisoprene rubber while reducing stress relaxation thereof as claimed in claim 9, wherein,
in the first method, the molar ratio of the functional precursor to the catalyst is as follows: 20-50: 1, the molar ratio of functional precursor to isoprene is: 1: 50-500;
further, in the first method, the catalyst is a mixture of F, G and H, and the molar ratio of F, G to H is: f: g: h is 0.8-1.2: 15-25: 1-3; wherein, the substance F is neodymium neodecanoate or neodymium isopropanol or neodymium phosphate, the substance G is triisobutylaluminum or diisobutylaluminum hydride, and the substance H is diisobutylaluminum chloride or dichlorodimethylsilyl;
further, in the second method, the polar polyisoprene rubber comprises at least one of the following substances:
Figure FDA0003045310020000151
wherein D is-OH, -COOH or-NH2E is an alkyl chain or a cyclic structure with 0-20 carbon atoms; x is more than or equal to 10 and less than or equal to 10000, y is more than or equal to 5 and less than or equal to 20, m is more than or equal to 5 and less than or equal to 20, n is more than or equal to 100 and less than or equal to 10000, and l is more than or equal to 5 and less than or equal to 20;
further, in the second method, the reaction solvent is tetrahydrofuran, chloroform, dichloromethane, n-hexane or toluene; wherein the proportion of the polar polyisoprene rubber to the reaction solvent is as follows: 0.5-2 g/100 mL;
further, in the second method, the condensing agent is selected according to the following principle:
when a condensation reaction of a carboxyl group with a hydroxyl group or an amino group occurs, the condensing agent is selected from: dicyclohexylcarbodiimide, N, N '-diisopropylcarbodiimide, N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride, 4, 5-dicyanoimidazole, N, N '-carbonyldiimidazole, N-hydroxysuccinimide, N-hydroxythiosuccinimide sodium salt, 1-hydroxy-7-azobenzotriazol, 1-hydroxybenzotriazole, 6-chloro-1-hydroxybenzotriazole, O- (7-azobenzotriazol) -N, N, N', N '-tetramethylurea hexafluorophosphate, benzotriazol-N, N, N', N '-tetramethylurea hexafluorophosphate, O-benzotriazol-N, N, N', N '-tetramethylurea tetrafluoroborate, N, N' -dimethylurea, One of 6-chlorobenzotriazole-1, 1,3, 3-tetramethylurea hexafluorophosphate, O- (1, 2-dihydro-2-oxo-pyridyl) -1,1,3, 3-tetramethylurea tetrafluoroborate, N-ethoxycarbonyl-2-ethoxy-1, 2-dihydroquinoline and bis (2-oxo-3-oxazolidinyl) phosphoryl chloride;
when the self-condensation and mutual condensation reactions of hydroxyl groups and amino groups occur, the condensing agent is selected from: one of diisopropyl azodicarboxylate, diethyl azodicarboxylate, benzotriazole-1-yl-oxytripyrrolidinylphosphine hexafluorophosphate, benzotriazole-1-tris (trimethylamino) -hexafluorophosphate, and tripyrrolidinylphosphonium bromide hexafluorophosphate;
when condensation reaction of acyl chloride and amino, hydroxyl or carboxyl occurs, the condensing agent is an organic base, preferably one of triethylamine, triethylene diamine, 1, 8-diazabicycloundec-7-ene, 1, 5-diazabicyclo [4.3.0] non-5-ene, 4-dimethylaminopyridine, pyridine, N-methylmorpholine, tetramethylethylenediamine, tetramethylguanidine, potassium/sodium tert-butoxide, N-diisopropylethylamine and diisopropylamine;
further, the molar ratio of the polar polyisoprene rubber, the unsaturated monomer and the condensing agent is as follows: polar polyisoprene rubber: unsaturated monomer: condensing agent 1: 5-15: 5-15, preferably 1: 8-12: 8 to 12.
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