CN114874520A - Preparation method of anti-aging chloroprene rubber - Google Patents
Preparation method of anti-aging chloroprene rubber Download PDFInfo
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Abstract
The invention discloses an anti-aging chloroprene rubber and a preparation method thereof. The aging-resistant chloroprene rubber takes chloroprene rubber, shellac resin, polymethyl methacrylate, styrene-butadiene-styrene block copolymer, trioctyl trimellitate, functional auxiliaries, fillers, coupling agents and triallyl isocyanurate as raw materials, and the interaction among the raw materials improves the heat resistance, aging resistance, mechanical performance and flame retardance of the chloroprene rubber.
Description
Technical Field
The invention relates to the technical field of plastic products, in particular to a preparation method of anti-aging chloroprene rubber.
Background
Chloroprene rubber is a synthetic rubber produced by alpha-polymerization of chloroprene, and has the characteristics of high elasticity, solvent resistance and the like, and also has excellent performances such as weather resistance and ozone resistance. Chloroprene rubber is widely used in the fields of manufacturing automobile parts, adhesives, coatings, adhesive soles and the like, and in recent years, the demand for chloroprene rubber in the fields of industrial products, automobile parts and the like is increasing.
However, the unsaturated rubber using diene as a molecular main chain has the defects of poor aging resistance and heat resistance, and in order to further improve the application and performance of the chloroprene rubber, numerous researchers search for the chloroprene rubber, such as: filling modification, blending modification, grafting modification and chemical modification.
CN105419029A discloses an example of a heat-resistant and aging-resistant chloroprene rubber pipe material, which comprises the following raw materials: chloroprene rubber, chlorinated butyl rubber, polyoctene rubber, polyisoprene rubber, polyether urethane, zinc oxide, bis (2, 4-dichlorobenzoyl) peroxide, 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide, stearic acid, nano calcium carbonate, hollow glass beads, nano montmorillonite, basic sodium aluminum carbonate, a silane coupling agent, an anti-aging agent DFC-34, an anti-aging agent A, dipentaerythritol diphosphite, hexaphenoxycyclotriphosphazene, vinyl silicone oil, an accelerator, zinc ricinoleate, aluminum dihydrogen phosphate and 1, 3-bis (citraconimidomethyl) benzene. The heat-resistant and aging-resistant chloroprene rubber pipe provided by the invention has the advantages of high strength, good heat resistance and aging resistance, excellent storage stability, capability of meeting the use requirements of various fields and long service life. But chloroprene rubber has poor aging resistance, mechanical resistance and flame retardant property.
Therefore, the invention discloses an anti-aging chloroprene rubber and a preparation method thereof.
Disclosure of Invention
In view of the above-mentioned defects of the prior art, the present invention provides an aging-resistant chloroprene rubber and a preparation method thereof.
An aging-resistant chloroprene rubber comprises the following raw materials: neoprene, shellac resin, polymethyl methacrylate, styrene-butadiene-styrene block copolymer, trioctyl trimellitate, triallyl isocyanurate.
Further, the anti-aging chloroprene rubber comprises the following raw materials in parts by weight: 35-50 parts of chloroprene rubber, 5-15 parts of lac resin, 20-35 parts of polymethyl methacrylate, 6-12 parts of styrene-butadiene-styrene block copolymer, 3-8 parts of trioctyl trimellitate and 1-5 parts of triallyl isocyanurate.
Unsaturated chloroprene rubbers having dienes as the molecular backbone have the problem of poor aging resistance and heat resistance.
In order to improve the heat resistance and aging resistance of chloroprene rubber, the invention takes 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, melamine cyanurate, 2,4, 6-tri [ (p-carboxyphenyl) amino ] -1,3, 5-triazine, POSS containing carboxyl and isopropanol as raw materials to prepare triazine through high-temperature reaction, ZrSP-Na, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester and 1,1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane are further added to the intermediate substance with the three-dimensional network structure to process the intermediate substance, so that the functional auxiliary agent is prepared, and has good heat resistance, aging resistance, flame retardant property and mechanical property.
Further preferably, the aging-resistant chloroprene rubber is prepared from the following raw materials in parts by weight: 35-50 parts of chloroprene rubber, 5-15 parts of shellac resin, 20-35 parts of polymethyl methacrylate, 6-12 parts of styrene-butadiene-styrene block copolymer, 3-8 parts of trioctyl trimellitate, 5-15 parts of functional additive, 3-10 parts of filler, 4-8 parts of coupling agent and 1-5 parts of triallyl isocyanurate.
The filler is one or a mixture of more than two of montmorillonite and precipitated silica; preferably, the filler is prepared from montmorillonite and precipitated silica according to the mass ratio of (1-3): (1-3) mixing.
The coupling agent is one or a mixture of two of silane coupling agent, titanate coupling agent and borate coupling agent.
The coupling agent is one or a mixture of more than two of 3- (methacryloyloxy) propyl trimethoxy silane, vinyl triethoxy silane, vinyl tri-tert-butyl peroxy silane, vinyl trimethoxy silane, gamma-aminopropyl triethoxy silane, gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, gamma-mercaptopropyl trimethoxy silane and 3-isocyanatopropyl triethoxy silane.
The titanate coupling agent is one or a mixture of more than two of titanate coupling agent TMC-201, titanate coupling agent TMC-102 and titanate coupling agent TMC-101;
the borate coupling agent is one or a mixture of more than two of tris (trimethylsilane) borate TMSB, distearoyl isopropyl borate, a borate coupling agent PRA-20 and an alkyl borate coupling agent FRT 90.
The preparation method of the functional auxiliary agent comprises the following steps:
(1) adding 5-10 parts by weight of aminopropylheptyl-polyhedral oligomeric silsesquioxane into 80-100 parts by weight of N, N-dimethylformamide, stirring for 5-15min at the speed of 100-300r/min, then adding 8-10 parts by weight of maleic anhydride, heating to 55-75 ℃, stirring for 6-10h at the speed of 100-300r/min, after finishing, removing N, N-dimethylformamide by reduced pressure distillation, and drying to obtain POSS containing carboxyl;
(2) uniformly mixing 4-7 parts by weight of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, 3-7 parts by weight of melamine cyanurate, 5-8 parts by weight of 2,4, 6-tris [ (p-carboxyphenyl) amino ] -1,3, 5-triazine, 1-5 parts by weight of POSS containing carboxyl prepared in the step (1) and 30-50 parts by weight of isopropanol, heating to 200-225 ℃ in a nitrogen atmosphere for reaction for 2h, then heating to 250-270 ℃ for reaction for 2-4h, cooling to room temperature after the reaction is finished, centrifuging, taking precipitate, washing and drying to obtain an intermediate product;
(3) adding 5-10 parts by weight of the intermediate product prepared in the step (2) into 30-80 parts by weight of dimethylacetamide, stirring for 10-30min at the speed of 100-300r/min, heating to 70-90 ℃ for reaction for 1-5h, adding 4-6 parts by weight of ZrSP-Na and 2-4 parts by weight of modifier, heating to 120-160 ℃ for reaction for 6-12h, cooling to room temperature after the reaction is finished, centrifuging, taking precipitate, washing and drying to obtain the functional additive.
The modifier is one or a mixture of two of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester and 1,1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane. Preferably, the modifier is prepared by mixing beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester and 1,1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane according to the mass ratio of (1-3) to (1-3).
According to the invention, the amino propyl heptyl-cage polysilsesquioxane is treated by maleic anhydride to prepare POSS containing carboxyl, and the POSS containing carboxyl is further introduced into 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, melamine cyanurate and 2,4, 6-tri [ (p-carboxyphenyl) amino ] -1,3, 5-triazine to participate in the reaction, so that on one hand, the dispersity of POSS is improved, and the heat resistance is improved; on the other hand, POSS containing carboxyl and 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, melamine cyanurate, 2,4, 6-tri [ (p-carboxyphenyl) amino ] -1,3, 5-triazine react with each other to generate a triazine-containing network structure, so that under the high-temperature condition, the char forming rate is improved, and under the high-temperature combustion condition of POSS, a silicon oxide continuous oxide framework and a heat-resistant graphite structure are formed, so that the flame retardant and smoke suppression performances are obviously improved, and meanwhile, the substances are nontoxic and easy to prepare and do not harm human health; finally, ZrSP-Na, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester and 1,1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane are adopted for crosslinking and modifying treatment, so that the aging resistance, the heat resistance and the mechanical property of the chloroprene rubber are improved; meanwhile, the method avoids the migration of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester and 1,1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane from the chloroprene rubber, so that the aging resistance is reduced, and the environmental pollution is reduced. The beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester and 1,1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane have synergistic effects, and the aging resistance and the mechanical properties are remarkably improved.
The invention also discloses a preparation method of the aging-resistant chloroprene rubber, which comprises the following steps: according to the formula, chloroprene rubber, shellac resin, polymethyl methacrylate, styrene-butadiene-styrene block copolymer, trioctyl trimellitate, functional auxiliary agents, fillers, coupling agents and triallyl isocyanurate are put into an internal mixer to be internally mixed for 5-10min, and then the mixture is sent into a double-screw extruder to be granulated and cooled to prepare the anti-aging chloroprene rubber.
The chloroprene rubber is prepared from chloroprene rubber, shellac resin, polymethyl methacrylate, styrene-butadiene-styrene block copolymer, trioctyl trimellitate, functional auxiliary agents, fillers, coupling agents and triallyl isocyanurate which are used as raw materials, and the heat resistance, aging resistance, mechanical performance and flame retardant performance of the chloroprene rubber are improved through the interaction among the raw materials; the lac resin, polymethyl methacrylate, styrene-butadiene-styrene block copolymer and triallyl isocyanurate are introduced into the chloroprene rubber, so that the distribution of the chloroprene rubber is obviously promoted, and the mechanical and processing properties of the chloroprene rubber are improved. The chloroprene rubber is further added with a filler, so that the chloroprene rubber has the mechanical property and the heat resistance, and simultaneously, a coupling agent is added to improve the dispersion property of the filler, enhance the binding capacity with a machine body and improve the mechanical property of the chloroprene rubber; and finally, adding a functional aid, wherein the functional aid improves the dispersibility of the functional aid under the interaction of the coupling agent and triallyl isocyanurate, further increases the interaction force between the functional aid and the chloroprene rubber, further improves the flame retardance, heat resistance, aging resistance and mechanical properties of the chloroprene rubber, prolongs the service life of the chloroprene rubber, can adapt to specific use environment conditions, and has a wide market application prospect.
The invention has the beneficial effects that: 1. the chloroprene rubber is prepared from chloroprene rubber, shellac resin, polymethyl methacrylate, styrene-butadiene-styrene block copolymer, trioctyl trimellitate, functional auxiliary agents, fillers, coupling agents and triallyl isocyanurate which are used as raw materials, and the heat resistance, aging resistance, mechanical performance and flame retardant performance of the chloroprene rubber are improved through the interaction among the raw materials.
2. The invention adds functional auxiliary agent, the invention takes 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, melamine cyanurate, 2,4, 6-tri [ (p-carboxyphenyl) amino ] -1,3, 5-triazine, POSS containing carboxyl and isopropanol as raw materials to prepare triazine through high temperature reaction, ZrSP-Na, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester and 1,1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane are further added to the intermediate substance with the three-dimensional network structure to process the intermediate substance, so that the functional additive is prepared, and has good heat resistance, aging resistance, flame retardant property and mechanical property.
Detailed Description
The above summary of the present invention is described in further detail below with reference to specific embodiments, but it should not be understood that the scope of the above subject matter of the present invention is limited to the following examples.
Neoprene, type: M130H, electro chemistry in Japan, was purchased from Dingxin plastics materials, Inc. of Dongguan.
Shellac resin, molecular weight: 964-1100, melting point: 115 ℃ and 120 ℃, density: 1.035-1.140, purchased from reh commercial ltd, of south china.
Polymethyl methacrylate, trade name: 8803, available from Enxiang plastics materials Co., Ltd, Dongguan.
Styrene-butadiene-styrene block copolymer, trade name: CH1302-1HE, available from Yucheng plastication, Inc., of Dongguan.
Montmorillonite, particle size: 325 mesh, purchased from the chemical industry ltd.
Precipitation method silica, type: E-200A, purchased from overseas Shanghai electric International trade, Inc.
Titanate coupling agent TMC-201, type: KR-38S, Kenreqi, USA.
Distearoyl isopropyl borate, type: PEA, purchased from MAGNILODI Biochemical technology, Inc., Guangzhou.
Aminopropylheptyl-caged polysilsesquioxane, cat no: 9502028, available from Fosmann technologies (Beijing) Inc.
Melamine cyanurate, cat No.: r054415, purchased from shanghai yan chemical technology ltd.
The preparation method of ZrSP-Na in the embodiment comprises the following steps: s1, adding 10g of 1, 3-propane sultone into 30mL of toluene, stirring for 10min at a speed of 180r/min, then adding 15mL of 0.0087mol/L toluene solution of triethyl phosphite and 30mL of toluene, heating to 111 ℃, reacting for 24h, then adding 10mL of petroleum ether, repeatedly extracting for 3 times, taking a lower-layer substance, and drying to obtain a substance a; s2, adding 12g of the substance a into 150mL of concentrated hydrochloric acid, uniformly mixing, heating to 120 ℃ for reaction for 72 hours, then carrying out reduced pressure distillation to remove the concentrated hydrochloric acid, adding 100mL of ethyl acetate for extraction treatment, repeatedly extracting for 3 times, taking the lower-layer substance, and drying to obtain a substance b; adding 4g of the substance b into 20mL of water, stirring for 10min at a speed of 180r/min, then adding 30mL of mixed solution of zirconium oxychloride octahydrate, continuing stirring for 12h, centrifuging to obtain precipitate after the reaction is finished, washing the precipitate to be neutral, and drying to obtain ZrSP, wherein the preparation method of the mixed solution of zirconium oxychloride octahydrate comprises the following steps: adding 3.2g of zirconium oxychloride octahydrate into 50mL of 0.1mol/L hydrochloric acid, and uniformly mixing to obtain a mixed solution of the zirconium oxychloride octahydrate; s3, adding 1.6g of NaOH into 160mL of water, uniformly mixing, then adding 10g of ZrSP, stirring at 180r/min for 6h at room temperature, evaporating water after the reaction is finished, and drying to obtain ZrSP-Na.
Example 1
The anti-aging chloroprene rubber comprises the following raw materials in parts by weight: 50 parts by weight of chloroprene rubber, 15 parts by weight of shellac resin, 35 parts by weight of polymethyl methacrylate, 12 parts by weight of styrene-butadiene-styrene block copolymer, 6 parts by weight of trioctyl trimellitate, 5 parts by weight of triallyl isocyanurate.
The preparation method of the aging-resistant chloroprene rubber comprises the following steps: according to the formula, chloroprene rubber, shellac resin, polymethyl methacrylate, styrene-butadiene-styrene block copolymer, trioctyl trimellitate and triallyl isocyanurate are put into an internal mixer to be internally mixed for 10min, and then the mixture is sent into a double-screw extruder to be granulated and cooled to prepare the anti-aging chloroprene rubber.
Example 2
The anti-aging chloroprene rubber is prepared from the following raw materials in parts by weight: 50 parts by weight of chloroprene rubber, 15 parts by weight of shellac resin, 35 parts by weight of polymethyl methacrylate, 12 parts by weight of styrene-butadiene-styrene block copolymer, 6 parts by weight of trioctyl trimellitate, 5 parts by weight of filler, 6 parts by weight of coupling agent, 5 parts by weight of triallyl isocyanurate.
The filler is prepared from montmorillonite and precipitated silica according to a mass ratio of 2:1 are mixed.
The coupling agent is prepared by mixing 3-isocyanatopropyl triethoxysilane, titanate coupling agent TMC-201 and distearoyl oxyisopropyl borate according to the mass ratio of 2:1: 1.
The preparation method of the aging-resistant chloroprene rubber comprises the following steps: according to the formula, chloroprene rubber, shellac resin, polymethyl methacrylate, styrene-butadiene-styrene block copolymer, trioctyl trimellitate, filler, coupling agent and triallyl isocyanurate are put into an internal mixer for internal mixing for 10min, and then the mixture is sent into a double-screw extruder for granulation and cooling to prepare the aging-resistant chloroprene rubber.
Example 3
The anti-aging chloroprene rubber is prepared from the following raw materials in parts by weight: 50 parts by weight of chloroprene rubber, 15 parts by weight of shellac resin, 35 parts by weight of polymethyl methacrylate, 12 parts by weight of styrene-butadiene-styrene block copolymer, 6 parts by weight of trioctyl trimellitate, 10 parts by weight of functional assistant, 5 parts by weight of filler, 6 parts by weight of coupling agent, and 5 parts by weight of triallyl isocyanurate.
The filler is prepared from montmorillonite and precipitated silica according to a mass ratio of 2:1 are mixed.
The coupling agent is prepared by mixing 3-isocyanatopropyl triethoxysilane, titanate coupling agent TMC-201 and distearoyl oxyisopropyl borate according to the mass ratio of 2:1: 1.
The preparation method of the functional auxiliary agent comprises the following steps:
(1) adding 5 parts by weight of aminopropylheptyl-polyhedral oligomeric silsesquioxane into 100 parts by weight of N, N-dimethylformamide, stirring for 10min at a speed of 180r/min, then adding 10 parts by weight of maleic anhydride, heating to 60 ℃, stirring for 10h at a speed of 180r/min, removing N, N-dimethylformamide through reduced pressure distillation after the reaction is finished, and drying to obtain POSS containing carboxyl;
(2) uniformly mixing 7 parts by weight of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, 7 parts by weight of melamine cyanurate, 8 parts by weight of 2,4, 6-tris [ (p-carboxyphenyl) amino ] -1,3, 5-triazine, 5 parts by weight of POSS containing carboxyl prepared in the step (1) and 50 parts by weight of isopropanol, heating to 225 ℃ in a nitrogen atmosphere for reaction for 2 hours, then heating to 270 ℃ for reaction for 3 hours, cooling to room temperature after the reaction is finished, centrifuging, taking precipitate, washing and drying to obtain an intermediate product;
(3) adding 8 parts by weight of the intermediate product prepared in the step (2) into 30 parts by weight of dimethylacetamide, stirring for 10min at a speed of 180r/min, heating to 80 ℃ for reaction for 3h, adding 4 parts by weight of ZrSP-Na and 2 parts by weight of modifier, heating to 160 ℃ for reaction for 6h, cooling to room temperature after the reaction is finished, centrifuging to obtain precipitate, washing and drying to obtain the functional additive.
The modifier is prepared by mixing beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester and 1,1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane according to the mass ratio of 2: 1.
The preparation method of the aging-resistant chloroprene rubber comprises the following steps: according to the formula, chloroprene rubber, shellac resin, polymethyl methacrylate, styrene-butadiene-styrene block copolymer, trioctyl trimellitate, filler, coupling agent, functional assistant and triallyl isocyanurate are put into an internal mixer for internal mixing for 10min, and then the mixture is fed into a double-screw extruder for granulation and cooling to prepare the aging-resistant chloroprene rubber.
Example 4
The anti-aging chloroprene rubber is prepared from the following raw materials in parts by weight: 50 parts by weight of chloroprene rubber, 15 parts by weight of shellac resin, 35 parts by weight of polymethyl methacrylate, 12 parts by weight of styrene-butadiene-styrene block copolymer, 6 parts by weight of trioctyl trimellitate, 10 parts by weight of functional assistant, 5 parts by weight of filler, 6 parts by weight of coupling agent, and 5 parts by weight of triallyl isocyanurate.
The filler is prepared from montmorillonite and precipitated silica according to a mass ratio of 2:1 are mixed.
The coupling agent is prepared by mixing 3-isocyanatopropyl triethoxysilane, titanate coupling agent TMC-201 and distearoyl oxyisopropyl borate according to the mass ratio of 2:1: 1.
The preparation method of the functional auxiliary agent comprises the following steps:
(1) adding 5 parts by weight of aminopropylheptyl-polyhedral oligomeric silsesquioxane into 100 parts by weight of N, N-dimethylformamide, stirring for 10min at a speed of 180r/min, then adding 10 parts by weight of maleic anhydride, heating to 60 ℃, stirring for 10h at a speed of 180r/min, removing N, N-dimethylformamide through reduced pressure distillation after the reaction is finished, and drying to obtain POSS containing carboxyl;
(2) uniformly mixing 7 parts by weight of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, 7 parts by weight of melamine cyanurate, 8 parts by weight of 2,4, 6-tris [ (p-carboxyphenyl) amino ] -1,3, 5-triazine, 5 parts by weight of POSS containing carboxyl prepared in the step (1) and 50 parts by weight of isopropanol, heating to 225 ℃ in a nitrogen atmosphere for reaction for 2 hours, then heating to 270 ℃ for reaction for 3 hours, cooling to room temperature after the reaction is finished, centrifuging, taking precipitate, washing and drying to obtain an intermediate product;
(3) adding 8 parts by weight of the intermediate product prepared in the step (2) into 30 parts by weight of dimethylacetamide, stirring for 10min at a speed of 180r/min, heating to 80 ℃ for reaction for 3h, adding 4 parts by weight of ZrSP-Na and 2 parts by weight of modifier, heating to 160 ℃ for reaction for 6h, cooling to room temperature after the reaction is finished, centrifuging to obtain precipitate, washing and drying to obtain the functional additive.
The modifier is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester.
The preparation method of the aging-resistant chloroprene rubber comprises the following steps: according to the formula, chloroprene rubber, shellac resin, polymethyl methacrylate, styrene-butadiene-styrene block copolymer, trioctyl trimellitate, filler, coupling agent, functional assistant and triallyl isocyanurate are put into an internal mixer for internal mixing for 10min, and then the mixture is sent into a double-screw extruder for granulation and cooling to prepare the aging-resistant chloroprene rubber.
Example 5
The anti-aging chloroprene rubber is prepared from the following raw materials in parts by weight: 50 parts by weight of chloroprene rubber, 15 parts by weight of shellac resin, 35 parts by weight of polymethyl methacrylate, 12 parts by weight of styrene-butadiene-styrene block copolymer, 6 parts by weight of trioctyl trimellitate, 10 parts by weight of functional assistant, 5 parts by weight of filler, 6 parts by weight of coupling agent, and 5 parts by weight of triallyl isocyanurate.
The filler is prepared from montmorillonite and precipitated silica according to a mass ratio of 2:1 are mixed.
The coupling agent is prepared by mixing 3-isocyanatopropyl triethoxysilane, titanate coupling agent TMC-201 and distearoyl oxyisopropyl borate according to the mass ratio of 2:1: 1.
The preparation method of the functional auxiliary agent comprises the following steps:
(1) adding 5 parts by weight of aminopropylheptyl-polyhedral oligomeric silsesquioxane into 100 parts by weight of N, N-dimethylformamide, stirring for 10min at a speed of 180r/min, then adding 10 parts by weight of maleic anhydride, heating to 60 ℃, stirring for 10h at a speed of 180r/min, removing N, N-dimethylformamide through reduced pressure distillation after the reaction is finished, and drying to obtain POSS containing carboxyl;
(2) uniformly mixing 7 parts by weight of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, 7 parts by weight of melamine cyanurate, 8 parts by weight of 2,4, 6-tris [ (p-carboxyphenyl) amino ] -1,3, 5-triazine, 5 parts by weight of POSS containing carboxyl prepared in the step (1) and 50 parts by weight of isopropanol, heating to 225 ℃ in a nitrogen atmosphere for reaction for 2 hours, then heating to 270 ℃ for reaction for 3 hours, cooling to room temperature after the reaction is finished, centrifuging, taking precipitate, washing and drying to obtain an intermediate product;
(3) adding 8 parts by weight of the intermediate product prepared in the step (2) into 30 parts by weight of dimethylacetamide, stirring for 10min at a speed of 180r/min, heating to 80 ℃ for reaction for 3h, adding 4 parts by weight of ZrSP-Na and 2 parts by weight of modifier, heating to 160 ℃ for reaction for 6h, cooling to room temperature after the reaction is finished, centrifuging to obtain precipitate, washing and drying to obtain the functional additive. The modifier is 1,1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane.
The preparation method of the aging-resistant chloroprene rubber comprises the following steps: according to the formula, chloroprene rubber, shellac resin, polymethyl methacrylate, styrene-butadiene-styrene block copolymer, trioctyl trimellitate, filler, coupling agent, functional assistant and triallyl isocyanurate are put into an internal mixer for internal mixing for 10min, and then the mixture is sent into a double-screw extruder for granulation and cooling to prepare the aging-resistant chloroprene rubber.
Example 6
Essentially the same as example 5, except that: the preparation method of the functional auxiliary agent comprises the following steps:
(1) uniformly mixing 7 parts by weight of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, 7 parts by weight of melamine cyanurate, 8 parts by weight of 2,4, 6-tris [ (p-carboxyphenyl) amino ] -1,3, 5-triazine and 50 parts by weight of isopropanol, heating to 225 ℃ in a nitrogen atmosphere for reaction for 2 hours, then heating to 270 ℃ for reaction for 3 hours, cooling to room temperature after the reaction is finished, washing, centrifuging, taking precipitate, and drying to obtain an intermediate product;
(2) adding 8 parts by weight of the intermediate product prepared in the step (1) into 30 parts by weight of dimethylacetamide, stirring for 10min at a speed of 180r/min, heating to 80 ℃ for reaction for 3h, adding 4 parts by weight of ZrSP-Na and 2 parts by weight of modifier, heating to 160 ℃ for reaction for 6h, cooling to room temperature after the reaction is finished, centrifuging to obtain precipitate, washing and drying to obtain the functional additive. The modifier is 1,1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane.
Example 7
Essentially the same as example 5, except that: the preparation method of the functional auxiliary agent comprises the following steps:
(1) adding 5 parts by weight of aminopropylheptyl-polyhedral oligomeric silsesquioxane into 100 parts by weight of N, N-dimethylformamide, stirring for 10min at a speed of 180r/min, then adding 10 parts by weight of maleic anhydride, heating to 60 ℃, reacting for 10h at a speed of 180r/min, after the reaction is finished, removing the N, N-dimethylformamide by reduced pressure distillation, and drying to obtain POSS containing carboxyl;
(2) and (2) adding 8 parts by weight of POSS (polyhedral oligomeric silsesquioxane) containing carboxyl prepared in the step (1) into 30 parts by weight of dimethylacetamide, stirring for 10min at a speed of 180r/min, heating to 80 ℃ for reaction for 3h, adding 4 parts by weight of ZrSP-Na and 2 parts by weight of modifier, heating to 160 ℃ for reaction for 6h, cooling to room temperature after the reaction is finished, centrifuging, taking precipitate, washing and drying to obtain the functional additive. The modifier is 1,1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane.
Example 8
Essentially the same as example 5, except that: the preparation method of the functional auxiliary agent comprises the following steps:
(1) adding 5 parts by weight of aminopropylheptyl-polyhedral oligomeric silsesquioxane into 100 parts by weight of N, N-dimethylformamide, stirring for 10min at a speed of 180r/min, then adding 10 parts by weight of maleic anhydride, heating to 60 ℃, reacting for 10h at a speed of 180r/min, after the reaction is finished, removing the N, N-dimethylformamide by reduced pressure distillation, and drying to obtain POSS containing carboxyl;
(2) uniformly mixing 7 parts by weight of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, 7 parts by weight of melamine cyanurate, 8 parts by weight of 2,4, 6-tris [ (p-carboxyphenyl) amino ] -1,3, 5-triazine, 5 parts by weight of POSS containing carboxyl and 50 parts by weight of isopropanol, heating to 225 ℃ in a nitrogen atmosphere for reaction for 2 hours, then heating to 270 ℃ for reaction for 3 hours, cooling to room temperature after the reaction is finished, washing, centrifuging, taking out precipitate, and drying to obtain the functional assistant.
Example 9
Essentially the same as example 5, except that: the preparation method of the functional auxiliary agent comprises the following steps: adding 5 parts by weight of aminopropylheptyl-polyhedral oligomeric silsesquioxane into 100 parts by weight of N, N-dimethylformamide, stirring for 10min at the speed of 180r/min, then adding 10 parts by weight of maleic anhydride, heating to 60 ℃, reacting for 10h at the speed of 180r/min, after the reaction is finished, removing the N, N-dimethylformamide by reduced pressure distillation, and drying to obtain the functional additive.
Example 10
Essentially the same as example 5, except that: the preparation method of the functional auxiliary agent comprises the following steps:
uniformly mixing 7 parts by weight of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, 7 parts by weight of melamine cyanurate, 8 parts by weight of 2,4, 6-tris [ (p-carboxyphenyl) amino ] -1,3, 5-triazine and 50 parts by weight of isopropanol, heating to 225 ℃ in a nitrogen atmosphere for reaction for 2 hours, then heating to 270 ℃ for reaction for 3 hours, cooling to room temperature after the reaction is finished, washing, centrifuging to take out precipitate, and drying to obtain the functional assistant.
Test example 1
And (3) testing mechanical properties:
the aging-resistant chloroprene rubbers prepared in examples 1 to 10 were used to prepare standard test specimens from a 25t press (Shanghai Qicould hydro mechanical Co., Ltd.) under the following vulcanization conditions: keeping the temperature at 160 ℃ for 10min and pressing the plate for molding. And (3) carrying out tensile strength test on the test sample by referring to GB/T528-2009 determination of tensile stress strain performance of vulcanized rubber or thermoplastic rubber.
TABLE 1 mechanical Property test results for Neoprene
| Tensile strength/MPa | |
| Example 1 | 6.1 |
| Example 2 | 8.4 |
| Example 3 | 27.6 |
| Example 4 | 25.2 |
| Example 5 | 23.5 |
| Example 6 | 20.7 |
| Example 7 | 16.3 |
| Example 8 | 18.1 |
| Example 9 | 10.8 |
| Example 10 | 13.5 |
As can be seen from table 1, the neoprene prepared in example 3 has good mechanical properties, which may be attributed to: chloroprene rubber, lac resin, polymethyl methacrylate, styrene-butadiene-styrene block copolymer, trioctyl trimellitate, functional additives, fillers, coupling agents and triallyl isocyanurate are used as raw materials, and the interaction among the raw materials improves the mechanical property of the chloroprene rubber; the lac resin, polymethyl methacrylate, styrene-butadiene-styrene block copolymer and triallyl isocyanurate are introduced into the chloroprene rubber, so that the distribution of the chloroprene rubber is obviously promoted, and the mechanical and processing properties of the chloroprene rubber are improved. The chloroprene rubber is further added with a filler, so that the chloroprene rubber has the mechanical property and the heat resistance, and simultaneously, a coupling agent is added to improve the dispersion property of the filler, enhance the binding capacity with a machine body and improve the mechanical property of the chloroprene rubber; and finally, adding a functional aid, wherein the functional aid improves the dispersibility of the functional aid under the interaction of the coupling agent and triallyl isocyanurate, further increases the interaction force between the functional aid and the chloroprene rubber, further improves the flame retardance, heat resistance, aging resistance and mechanical properties of the chloroprene rubber, prolongs the service life of the chloroprene rubber, can adapt to specific use environment conditions, and has a wide market application prospect.
Test example 2
The chloroprene rubbers prepared in examples 1 to 10 were tested with reference to GB/T2408-2008 "horizontal and vertical methods for measuring Plastic burning Properties".
TABLE 2 flame retardancy test results for Neoprene
| L-94 | |
| Example 1 | V-2 |
| Example 2 | V-2 |
| Example 3 | V-0 |
| Example 4 | V-0 |
| Example 5 | V-0 |
| Example 6 | V-0 |
| Example 7 | V-1 |
| Example 8 | V-0 |
| Example 9 | V-1 |
| Example 10 | V-1 |
As can be seen from table 2, the neoprene prepared in example 3 has good flame retardant properties, and the properties are significantly due to examples 6-8, which may be due to: the preparation method comprises the steps of treating aminopropylheptyl-polyhedral oligomeric silsesquioxane by maleic anhydride to prepare POSS containing carboxyl, and further introducing the POSS containing the carboxyl into 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, melamine cyanurate and 2,4, 6-tri [ (p-carboxyphenyl) amino ] -1,3, 5-triazine for participating in reaction, so that on one hand, the dispersity of POSS is improved, and the heat resistance is improved; on the other hand, the POSS containing carboxyl and 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, melamine cyanurate and 2,4, 6-tri [ (p-carboxyphenyl) amino ] -1,3, 5-triazine react with each other to generate a triazine-containing network structure, so that the char yield is improved under the high-temperature condition, and a silicon oxide continuous oxide framework and a heat-resistant graphite structure are formed under the high-temperature combustion condition of the POSS, so that the flame retardance and the smoke suppression performance of the POSS are obviously improved, and meanwhile, the substances are nontoxic and easy to prepare and do not harm human health; and finally, ZrSP-Na, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate and 1,1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane are adopted for crosslinking and modifying, so that the aging resistance, heat resistance, flame retardance and mechanical properties of the chloroprene rubber are improved.
Test example 3
And (3) aging resistance test:
the test piece of test example 1 was left at 120 ℃ for 150 hours and then taken out to test the tensile strength retention rate.
TABLE 3 ageing resistance test results for Neoprene
| Retention ratio of tensile strength/%) | |
| Example 1 | 56.8 |
| Example 2 | 60.3 |
| Example 3 | 86.2 |
| Example 4 | 83.6 |
| Example 5 | 82.3 |
| Example 6 | 79.5 |
| Example 7 | 74.1 |
| Example 8 | 76.3 |
| Example 9 | 66.7 |
| Example 10 | 71.4 |
As can be seen from table 3, the aging resistance of the neoprene prepared in example 3 is significantly better than that of examples 4-5, which may be due to: the preparation method comprises the steps of treating aminopropylheptyl-polyhedral oligomeric silsesquioxane by maleic anhydride to prepare POSS containing carboxyl, and further introducing the POSS containing the carboxyl into 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, melamine cyanurate and 2,4, 6-tri [ (p-carboxyphenyl) amino ] -1,3, 5-triazine for participating in reaction, so that on one hand, the dispersity of POSS is improved, and the heat resistance is improved; on the other hand, POSS containing carboxyl and 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, melamine cyanurate, 2,4, 6-tri [ (p-carboxyphenyl) amino ] -1,3, 5-triazine react with each other to generate a triazine-containing network structure, so that under the high-temperature condition, the char forming rate is improved, and under the high-temperature combustion condition of POSS, a silicon oxide continuous oxide framework and a heat-resistant graphite structure are formed, so that the flame retardant and smoke suppression performances are obviously improved, and meanwhile, the substances are nontoxic and easy to prepare and do not harm human health; finally, ZrSP-Na, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester and 1,1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane are adopted for crosslinking and modifying treatment, so that the aging resistance, the heat resistance and the mechanical property of the chloroprene rubber are improved; meanwhile, the method avoids the migration of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester and 1,1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane from the chloroprene rubber, so that the aging resistance is reduced, and the environmental pollution is reduced. The beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester and 1,1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane have synergistic effects, and the aging resistance and the mechanical properties are remarkably improved.
The aging resistance of example 3 is significantly better than that of examples 6 to 8, which is probably due to: the preparation method comprises the steps of treating aminopropylheptyl-polyhedral oligomeric silsesquioxane with maleic anhydride to prepare POSS containing carboxyl, and further introducing the POSS containing the carboxyl into 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, melamine cyanurate and 2,4, 6-tri [ (p-carboxyphenyl) amino ] -1,3, 5-triazine for participating in a reaction, so that on one hand, the dispersity of POSS is improved, and the heat resistance is improved; on the other hand, POSS containing carboxyl and 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, melamine cyanurate, 2,4, 6-tri [ (p-carboxyphenyl) amino ] -1,3, 5-triazine react with each other to generate a triazine-containing network structure, so that under the high-temperature condition, the char forming rate is improved, and under the high-temperature combustion condition of POSS, a silicon oxide continuous oxide framework and a heat-resistant graphite structure are formed, so that the flame retardant and smoke suppression performances are obviously improved, and meanwhile, the substances are nontoxic and easy to prepare and do not harm human health.
Claims (8)
1. An aging-resistant chloroprene rubber is characterized in that: the method comprises the following raw materials: neoprene, lac resin, polymethyl methacrylate, styrene-butadiene-styrene block copolymer, trioctyl trimellitate, filler, coupling agent and triallyl isocyanurate.
2. The weatherable neoprene rubber of claim 1 wherein: the feed comprises the following raw materials in parts by weight: 35-50 parts of chloroprene rubber, 5-15 parts of shellac resin, 20-35 parts of polymethyl methacrylate, 6-12 parts of styrene-butadiene-styrene block copolymer, 3-8 parts of trioctyl trimellitate, 3-10 parts of filler, 4-8 parts of coupling agent and 1-5 parts of triallyl isocyanurate.
3. The weatherable neoprene rubber of claim 2 wherein: also comprises 5 to 15 weight portions of functional auxiliary agent.
4. The weatherable neoprene rubber of claim 3 wherein: the preparation method of the functional auxiliary agent comprises the following steps:
(1) adding 5-10 parts by weight of aminopropylheptyl-polyhedral oligomeric silsesquioxane into 80-100 parts by weight of N, N-dimethylformamide, stirring for 5-15min, then adding 8-10 parts by weight of maleic anhydride, heating to 55-75 ℃, stirring for 6-10h, removing N, N-dimethylformamide through reduced pressure distillation after the reaction is finished, and drying to obtain POSS containing carboxyl;
(2) uniformly mixing 4-7 parts by weight of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, 3-7 parts by weight of melamine cyanurate, 5-8 parts by weight of 2,4, 6-tris [ (p-carboxyphenyl) amino ] -1,3, 5-triazine, 1-5 parts by weight of POSS containing carboxyl and 30-50 parts by weight of isopropanol, heating to 225 ℃ in a nitrogen atmosphere for reaction for 2h, then heating to 250 ℃ and 270 ℃ for reaction for 2-4h, cooling to room temperature after the reaction is finished, washing, centrifuging, taking precipitate, and drying to obtain an intermediate product;
(3) adding 5-10 parts by weight of the intermediate product prepared in the step (2) into 30-80 parts by weight of dimethylacetamide, stirring for 10-30min, heating to 70-90 ℃ for reaction for 1-5h, adding 4-6 parts by weight of ZrSP-Na and 2-4 parts by weight of modifier, heating to 120-160 ℃ for reaction for 6-12h, cooling to room temperature after the reaction is finished, centrifuging, taking precipitate, washing and drying to obtain the functional additive.
5. The weatherable neoprene rubber of claim 2 wherein: the filler is one or a mixture of more than two of montmorillonite and precipitated silica.
6. The weatherable neoprene rubber of claim 2 wherein: the coupling agent is one or a mixture of two of silane coupling agent, titanate coupling agent and borate coupling agent.
7. The weatherable neoprene rubber of claim 4 wherein: the modifier is one or a mixture of two of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester and 1,1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane.
8. A process for the preparation of an aging-resistant chloroprene rubber as claimed in any of claims 1 to 7, comprising the following steps: according to the formula, chloroprene rubber, shellac resin, polymethyl methacrylate, styrene-butadiene-styrene block copolymer, trioctyl trimellitate, functional auxiliary agents, fillers, coupling agents and triallyl isocyanurate are put into an internal mixer for internal mixing, and then the mixture is sent into a double-screw extruder for granulation and cooling to prepare the aging-resistant chloroprene rubber.
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| JP2003082238A (en) * | 2001-09-11 | 2003-03-19 | Asahi Kasei Corp | Excellent flame-retardant polymer composition |
| CN105315527A (en) * | 2015-11-23 | 2016-02-10 | 苏州盖德精细材料有限公司 | Neoprene-based UL yellow adhesive and preparation method thereof |
| CN110655652A (en) * | 2019-09-02 | 2020-01-07 | 厦门大学 | Metal hybrid POSS flame retardant, preparation method and application |
| US20210087437A1 (en) * | 2018-01-11 | 2021-03-25 | Arlanxeo Deutschland Gmbh | Polychloroprene-based contact adhesives containing ethylene-vinyl acetate copolymer |
| EP3885401A1 (en) * | 2020-03-25 | 2021-09-29 | Avanzare Innovacion Tencologica S.L. | Self-sensing flame resistant polymeric materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003082238A (en) * | 2001-09-11 | 2003-03-19 | Asahi Kasei Corp | Excellent flame-retardant polymer composition |
| CN105315527A (en) * | 2015-11-23 | 2016-02-10 | 苏州盖德精细材料有限公司 | Neoprene-based UL yellow adhesive and preparation method thereof |
| US20210087437A1 (en) * | 2018-01-11 | 2021-03-25 | Arlanxeo Deutschland Gmbh | Polychloroprene-based contact adhesives containing ethylene-vinyl acetate copolymer |
| CN110655652A (en) * | 2019-09-02 | 2020-01-07 | 厦门大学 | Metal hybrid POSS flame retardant, preparation method and application |
| EP3885401A1 (en) * | 2020-03-25 | 2021-09-29 | Avanzare Innovacion Tencologica S.L. | Self-sensing flame resistant polymeric materials |
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