A C21 dicarboxylic acid modified polyester resin material and preparation method thereof

Abstract

The invention discloses a C21 dicarboxylic acid modified polyester resin material and a preparation method thereof, and relates to the technical field of polymer materials. When preparing C21 dicarboxylic acid modified polyester resin material, the present invention sequentially reacts benzophenone-4,4'-dicarboxylic acid with trimethylsilyl acetylene and 1-naphthol to obtain naphthopyran functional monomer; C21 dicarboxylic acid and 3-(dimethylamino)-1-propanethiol are reacted to obtain modified C21 dicarboxylic acid; naphthopyran functional monomer, modified C21 dicarboxylic acid and 1,3-propylene glycol are polymerized to obtain polyester; glass fiber is sequentially reacted with aminopropyl triethoxysilane, 2,4-pentanedione and 3-chloropropyl isocyanate to obtain modified glass fiber; polyester and modified glass fiber are melt-mixed, and injection molding is used to obtain C21 dicarboxylic acid modified polyester resin material. The C21 dicarboxylic acid modified polyester resin material prepared by the present invention has excellent anti-aging, antibacterial, self-repairing and mechanical properties.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, in particular to a C21 dicarboxylic acid modified polyester resin material and a preparation method thereof. Background Art

[0002] Polyester resin is a polymer compound formed by the polycondensation of diols and dibasic acids or polyols and polyacids. It is generally divided into saturated polyester resin and unsaturated polyester resin. Polyester resin can be used to make plastic products such as bottles, bags, plastic wrap, building materials such as tiles, insulation boards, wallboards, electrical insulation materials such as insulating paints and circuit boards, and packaging materials such as food packaging and medical packaging. Polyester resin is widely used in many fields such as chemical industry, construction, automobile, electronics, packaging, etc. due to its easy processing, light weight, corrosion resistance, and non-toxicity, playing a vital role. With the continuous expansion of application fields, the performance requirements for polyester resin are also getting higher and higher. Polyester resin is susceptible to mechanical damage such as scratches, scrapes, punctures, etc. during use. These damages are usually irreversible and will directly lead to the performance degradation of polyester resin.

[0003] The chemical name of C21 dicarboxylic acid is 2-cyclohexene-1-octanoic acid, 5(6)-carboxy-4-hexyl. It is a liquid 21-carbon monocyclic dicarboxylic acid prepared from vegetable oil fatty acids. The molecular structure of C21 dicarboxylic acid contains two carboxyl groups, which can participate in the polymerization reaction of polyester and is a potential raw material for preparing polyester resin. Using C21 dicarboxylic acid as raw material to prepare polyester resin can reduce the use of petrochemical raw materials, be green and environmentally friendly, and save resources.

[0004] The present application improves upon the existing polyester resin preparation technology, and uses green and environmentally friendly C21 dicarboxylic acid as a raw material to prepare a polyester resin material with self-healing properties, thereby further improving the comprehensive properties of the polyester resin, broadening the application areas of the polyester resin, and extending the service life of the polyester resin. Summary of the invention

[0005] The object of the present invention is to provide a C21 dicarboxylic acid modified polyester resin material and a preparation method thereof, so as to solve the problems existing in the prior art.

[0006] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0007] A C21 dicarboxylic acid modified polyester resin material, wherein the C21 dicarboxylic acid modified polyester resin material is prepared by reacting a propargyl alcohol functional monomer and 1-naphthol to obtain a naphthopyran functional monomer; polymerizing the naphthopyran functional monomer, modified C21 dicarboxylic acid, and 1,3-propylene glycol to obtain polyester; reacting pre-modified glass fiber and 3-chloropropyl isocyanate to obtain modified glass fiber; and melt-mixing the polyester and the modified glass fiber and performing injection molding to obtain the material;

[0008] The propargyl alcohol functional monomer is prepared by reacting benzophenone-4,4'-dicarboxylic acid and trimethylsilyl acetylene;

[0009] The modified C21 dicarboxylic acid is prepared by reacting C21 dicarboxylic acid and 3-(dimethylamino)-1-propanethiol;

[0010] The pre-modified glass fiber is prepared by reacting pre-treated glass fiber and 2,4-pentanedione;

[0011] The pretreated glass fiber is prepared by reacting glass fiber and aminopropyltriethoxysilane.

[0012] A method for preparing a C21 dicarboxylic acid modified polyester resin material, the method comprising the following preparation steps:

[0013] (1) Add propargyl alcohol functional monomer and 1-naphthol in a molar ratio of 1:1 to toluene with a mass of 10 to 12 times that of 1-naphthol, add dodecylbenzenesulfonic acid with a mass of 0.04 to 0.06 times that of 1-naphthol, stir at 48 to 52°C and 200 to 300 r / min for 3 to 4 hours, add deionized water with an equal volume of toluene and mix evenly, cool to 10 to 30°C and continue stirring for 10 to 14 minutes, extract with ethyl acetate with a volume of 2 to 3 times that of toluene, take the organic phase, and dry at 50 to 60°C under vacuum for 8 to 10 hours to obtain naphthopyran functional monomer;

[0014] (2) Naphthopyran functional monomer, modified C21 dicarboxylic acid and 1,3-propylene glycol are uniformly mixed in a molar ratio of 1:1:2.1-2.2, placed in a reactor, and triphenyl phosphate in an amount of 0.08-0.1 times the mass of 1,3-propylene glycol and antimony trioxide in an amount of 0.04-0.06 times the mass of 1,3-propylene glycol are added, and stirred at 220-240°C, a pressure of 0.3-0.4 MPa, and 100-200 r / min to react until the water output reaches 90% of the theoretical value, then the temperature is raised to 260-270°C, vacuum is drawn to maintain the pressure in the reactor below 65 Pa, the stirring reaction is continued for 2-3 hours, and nitrogen is filled to discharge the material to obtain polyester;

[0015] (3) Pretreated glass fiber, 2,4-pentanedione, and tetrahydrofuran were mixed evenly in a mass ratio of 1: (4-6): (28-32), stirred at 58-62°C and 200-300 r / min for 5-6 hours, filtered, washed with anhydrous ethanol for 3-5 times, and dried at 65-75°C for 8-10 hours under vacuum conditions to obtain pre-modified glass fiber; pre-modified glass fiber, 3-chloropropyl isocyanate, stannous isooctanoate, and toluene were mixed evenly in a mass ratio of 1: (4-6): (0.04-0.06): (24-28), stirred at 70-80°C and 200-300 r / min for 2-3 hours, filtered, washed with anhydrous ethanol for 3-5 times, and dried at 65-75°C for 8-10 hours under vacuum conditions to obtain modified glass fiber;

[0016] (4) The polyester and modified glass fiber are mixed evenly in a mass ratio of 1:(0.08-0.1), placed in a screw extruder for injection molding, and demolded after cooling to room temperature to obtain a C21 dicarboxylic acid modified polyester resin material.

[0017] As an optimization, the preparation method of the propargyl alcohol functional monomer in step (1) is as follows: benzophenone-4,4'-dicarboxylic acid and tetrahydrofuran are mixed uniformly at a mass ratio of 1:(8-10) to prepare a benzophenone solution; under argon protection, trimethylsilyl acetylene and tetrahydrofuran are mixed uniformly at a mass ratio of 1:(20-24), stirred at -70--60°C, 100-200 r / min for 20-30 min, and stirred at 100-200 r / min for 10 min. Add trimethylsilyl acetylene and an equal molar amount of n-butyl lithium dropwise at a uniform speed, continue stirring for 55-65 min after the addition is completed, add benzophenone solution dropwise at a molar ratio of benzophenone-4,4'-dicarboxylic acid to trimethylsilyl acetylene of 1:2 within 15 min, stir at 10-30°C, 100-200 r / min for 4-5 h, and dry at 40-50°C under vacuum conditions for 10-12 h to obtain propargyl alcohol functional monomer.

[0018] As an optimization, the preparation method of the modified C21 dicarboxylic acid in step (2) is: C21 dicarboxylic acid and 3-(dimethylamino)-1-propanethiol are added in a molar ratio of 1:1 to toluene with a mass of 10 to 12 times that of the C21 dicarboxylic acid, and azobisisobutyronitrile with a mass of 0.03 to 0.05 times that of the C21 dicarboxylic acid is added, and the mixture is stirred at 50 to 60° C. and 200 to 300 r / min for 4 to 5 hours, and dried at 50 to 60° C. under vacuum conditions for 8 to 10 hours to obtain the modified C21 dicarboxylic acid.

[0019] As an optimization, the structural formula of the C21 dicarboxylic acid is as follows:

[0020] .

[0021] As an optimization, the preparation method of the pretreated glass fiber in step (3) is as follows: glass fiber and anhydrous ethanol are uniformly mixed in a mass ratio of 1:(40~50), stirred at 20~30°C and 200~300r / min for 26~30min, silane hydrolyzate of 20~24 times the mass of the glass fiber is added, stirred at 55~65°C and 200~300r / min for reaction for 2~3h, filtered, washed with anhydrous ethanol for 3~5 times, and dried at 65~75°C under vacuum conditions for 8~10h to obtain the pretreated glass fiber.

[0022] As an optimization, the preparation method of the silane hydrolyzate is: aminopropyltriethoxysilane and deionized water are mixed evenly in a mass ratio of 1:(19~21), stirred at 200~300r / min for 8~10min at 20~30°C, adjusted the pH to 5.6~6.0 with an oxalic acid aqueous solution, and continued stirring for 20~22min to prepare a silane hydrolyzate.

[0023] As an optimization, the monofilament diameter of the glass fiber is 5-10 μm and the length is 1-3 mm.

[0024] As an optimization, the concentration of the oxalic acid aqueous solution is 2 mol / L.

[0025] As an optimization, the process parameters of the injection molding in step (4) are as follows: setting the extruder barrel temperature to 250-260°C, the screw speed to 100-110 r / min, the injection temperature to 236-240°C, the injection pressure to 57-63 MPa, the holding time to 16-18 s, and the mold temperature to 79-81°C.

[0026] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0027] When preparing the C21 dicarboxylic acid modified polyester resin material, the present invention comprises the following steps: reacting benzophenone-4,4'-dicarboxylic acid and trimethylsilyl acetylene to obtain a propargyl alcohol functional monomer; reacting the propargyl alcohol functional monomer and 1-naphthol to obtain a naphthopyran functional monomer; reacting the C21 dicarboxylic acid and 3-(dimethylamino)-1-propanethiol to obtain a modified C21 dicarboxylic acid; polymerizing the naphthopyran functional monomer, the modified C21 dicarboxylic acid and 1,3-propylene glycol to obtain a polyester; reacting glass fiber and aminopropyltriethoxysilane to obtain a pretreated glass fiber; reacting the pretreated glass fiber and 2,4-pentanedione to obtain a premodified glass fiber; reacting the premodified glass fiber and 3-chloropropyl isocyanate to obtain a modified glass fiber; and melt-mixing the polyester and the modified glass fiber, and performing injection molding to obtain the C21 dicarboxylic acid modified polyester resin material.

[0028] First, benzophenone-4,4'-dicarboxylic acid and trimethylsilyl acetylene are reacted to obtain propargyl alcohol functional monomers; propargyl alcohol functional monomers and 1-naphthol are reacted to obtain naphthopyran functional monomers; the carboxyl group on the naphthopyran functional monomer can participate in the polymerization reaction of polyester, and the naphthopyran structure is introduced into the polyester molecular chain. Naphthopyran can absorb ultraviolet light and meet the requirements of traditional ultraviolet absorbers. Under the continuous irradiation of ultraviolet light, the CO bond on the pyran ring breaks to cause a ring-opening reaction, and when the ultraviolet light is removed, a reversible ring-closing reaction occurs. This reversible ring-opening reaction can absorb ultraviolet light and release the ultraviolet light in a harmless form, thereby giving the C21 dicarboxylic acid modified polyester resin material excellent anti-aging properties. The mechanism of action is as follows:

[0029] .

[0030] Secondly, C21 dicarboxylic acid and 3-(dimethylamino)-1-propanethiol are reacted to obtain modified C21 dicarboxylic acid; C21 dicarboxylic acid is a liquid 21-carbon monocyclic dicarboxylic acid prepared from vegetable oil fatty acids, and the carbon-carbon double bond on the C21 dicarboxylic acid is reacted with the thiol group on the 3-(dimethylamino)-1-propanethiol to introduce a tertiary amine structure on the modified C21 dicarboxylic acid; two carboxyl groups on the modified C21 dicarboxylic acid can participate in the polymerization reaction of polyester, and a tertiary amine structure is introduced on the side chain of the polyester molecule. The tertiary amine structure introduced on the side chain of the polyester molecule can react with the chlorine atom introduced on the modified glass fiber to generate a quaternary ammonium salt, so that a cross-linking site is formed between the polyester molecular chain and the modified glass fiber, forming a cross-linking network, inhibiting relative slip between molecular chains, and improving the mechanical properties of the C21 dicarboxylic acid modified polyester resin material. At the same time, the generated quaternary ammonium salt structure belongs to a cationic antibacterial agent, which gives the C21 dicarboxylic acid modified polyester resin material excellent antibacterial properties.

[0031] Finally, the glass fiber and aminopropyltriethoxysilane are reacted to obtain pretreated glass fiber, and amino groups are introduced into the pretreated glass fiber; the amino groups on the pretreated glass fiber are reacted with 2,4-pentanedione to obtain premodified glass fiber, and enamine ketone bonds are generated on the modified glass fiber; the enamine ketone bonds on the premodified glass fiber are reacted with the isocyanate groups on 3-chloropropyl isocyanate to obtain modified glass fiber, and amide-enamine ketone bonds are generated on the modified glass fiber, and chlorine atoms are introduced; the chlorine atoms introduced into the modified glass fiber can react with the tertiary amine structures introduced into the side chains of the polyester molecules to generate quaternary ammonium salt structures. , and at the same time form a cross-linked network structure, inhibit the relative slip between molecular chains, and improve the mechanical properties of C21 dicarboxylic acid modified polyester resin materials. At the same time, amide-enamine ketone bonds are introduced into C21 dicarboxylic acid modified polyester resin materials. The amide-enamine ketone bond is a thermally reversible dynamic bond. At high temperatures, the amide-enamine ketone bond will break, and when the temperature drops, it will recombine to form an amide-enamine ketone bond. This thermally reversible dynamic bond can repair the material by regulating the temperature after the material is damaged, giving the C21 dicarboxylic acid modified polyester resin material the ability to self-repair. The mechanism of action is as follows:

[0032] . DETAILED DESCRIPTION

[0033] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0034] Embodiment 1:

[0035] A method for preparing a C21 dicarboxylic acid modified polyester resin material, the method comprising the following preparation steps:

[0036] (1) Benzophenone-4,4'-dicarboxylic acid and tetrahydrofuran were mixed at a mass ratio of 1:8 to prepare a benzophenone solution; under argon protection, trimethylsilyl acetylene and tetrahydrofuran were mixed at a mass ratio of 1:20, stirred at -70°C, 100 r / min for 30 min, and an equal molar amount of n-butyl lithium of trimethylsilyl acetylene was uniformly added dropwise within 10 min. After the addition was completed, stirring was continued for 65 min. Benzophenone solution was uniformly added dropwise within 15 min in a molar ratio of benzophenone-4,4'-dicarboxylic acid to trimethylsilyl acetylene of 1:2. The mixture was stirred at 10°C, 1 00r / min stirring reaction for 5h, under vacuum conditions, dried at 40°C for 12h to obtain a propargyl alcohol functional monomer; the propargyl alcohol functional monomer and 1-naphthol were added in a molar ratio of 1:1 to toluene with a mass 10 times that of 1-naphthol, and dodecylbenzenesulfonic acid with a mass 0.04 times that of 1-naphthol was added, and stirred at 48°C and 200r / min for 4h, and deionized water with an equal volume of toluene was added to mix evenly, cooled to 10°C and continued to stir for 14min, extracted with ethyl acetate with a volume 2 times that of toluene, and took the organic phase, and dried at 50°C for 10h under vacuum conditions to obtain a naphthopyran functional monomer;

[0037] (2) C21 dicarboxylic acid and 3-(dimethylamino)-1-propanethiol were added in a molar ratio of 1:1 to toluene with a mass of 10 times that of C21 dicarboxylic acid, and azobisisobutyronitrile with a mass of 0.03 times that of C21 dicarboxylic acid was added, and the mixture was stirred at 50°C and 200 r / min for 5 h, and dried at 50°C for 10 h under vacuum conditions to obtain modified C21 dicarboxylic acid; naphthopyran functional monomer, modified C21 dicarboxylic acid, and 1,3-propylene glycol were added in a molar ratio of 1:1:2.1, mix evenly, put in a reactor, add triphenyl phosphate in an amount of 0.08 times the mass of 1,3-propylene glycol, add antimony trioxide in an amount of 0.04 times the mass of 1,3-propylene glycol, react at 220°C, pressure 0.3MPa, 100r / min, stir until the water output reaches 90% of the theoretical value, heat to 260°C, evacuate to maintain the pressure in the reactor below 65Pa, continue stirring for 3h, fill with nitrogen and discharge to obtain polyester;

[0038] (3) Mix aminopropyltriethoxysilane and deionized water in a mass ratio of 1:19, stir at 20°C and 200 r / min for 10 min, adjust the pH to 5.6 with a 2 mol / L oxalic acid aqueous solution, continue stirring for 22 min, and prepare a silane hydrolyzate; mix glass fiber and anhydrous ethanol in a mass ratio of 1:40, stir at 20°C and 200 r / min for 30 min, add silane hydrolyzate 20 times the mass of glass fiber, stir at 55°C and 200 r / min for 3 h, filter, wash with anhydrous ethanol 3 times, and dry at 65°C under vacuum for 10 h. , to obtain pretreated glass fiber; the pretreated glass fiber, 2,4-pentanedione, and tetrahydrofuran were mixed uniformly in a mass ratio of 1:4:28, stirred at 58°C and 200r / min for 6h, filtered, washed with anhydrous ethanol 3 times, and dried at 65°C for 10h under vacuum conditions to obtain pre-modified glass fiber; the pre-modified glass fiber, 3-chloropropyl isocyanate, stannous isooctanoate, and toluene were mixed uniformly in a mass ratio of 1:4:0.04:24, stirred at 70°C and 200r / min for 3h, filtered, washed with anhydrous ethanol 3 times, and dried at 65°C for 10h under vacuum conditions to obtain modified glass fiber;

[0039] (4) Polyester and modified glass fiber were mixed evenly in a mass ratio of 1:0.08, placed in a screw extruder for injection molding, and the extruder barrel temperature was set to 250°C, the screw speed was 100 r / min, the injection temperature was 236°C, the injection pressure was 57 MPa, the holding time was 18 s, the mold temperature was 79°C, and the mold was demolded after cooling to room temperature to obtain a C21 dicarboxylic acid modified polyester resin material.

[0040] Embodiment 2:

[0041] A method for preparing a C21 dicarboxylic acid modified polyester resin material, the method comprising the following preparation steps:

[0042] (1) Benzophenone-4,4'-dicarboxylic acid and tetrahydrofuran were mixed at a mass ratio of 1:9 to prepare a benzophenone solution; under argon protection, trimethylsilyl acetylene and tetrahydrofuran were mixed at a mass ratio of 1:22, stirred at -65°C and 150 r / min for 25 min, and an equal molar amount of n-butyl lithium of trimethylsilyl acetylene was uniformly added dropwise within 10 min. After the addition was completed, stirring was continued for 60 min. Benzophenone solution was uniformly added dropwise within 15 min in a molar ratio of benzophenone-4,4'-dicarboxylic acid to trimethylsilyl acetylene of 1:2. The mixture was stirred at 20°C and 150 r / min for 25 min. / min stirring reaction for 4.5h, under vacuum conditions, dried at 45°C for 11h to obtain a propargyl alcohol functional monomer; the propargyl alcohol functional monomer and 1-naphthol were added in a molar ratio of 1:1 to toluene with a mass 11 times that of 1-naphthol, and dodecylbenzenesulfonic acid with a mass 0.05 times that of 1-naphthol was added, and stirred at 50°C and 250r / min for 3.5h, and an equal volume of deionized water was added to toluene to mix evenly, and the temperature was lowered to 20°C and continued to stir for 12min, and extracted with ethyl acetate with a volume 2.5 times that of toluene, and the organic phase was taken and dried at 55°C for 9h under vacuum conditions to obtain a naphthopyran functional monomer;

[0043] (2) C21 dicarboxylic acid and 3-(dimethylamino)-1-propanethiol were added in a molar ratio of 1:1 to toluene with a mass of 11 times that of C21 dicarboxylic acid, and azobisisobutyronitrile with a mass of 0.04 times that of C21 dicarboxylic acid was added, and the mixture was stirred at 55°C and 250 r / min for 4.5 h, and dried at 55°C under vacuum for 9 h to obtain modified C21 dicarboxylic acid; naphthopyran functional monomer, modified C21 dicarboxylic acid, and 1,3-propylene glycol were added in a molar ratio of 1:1 to obtain a modified C21 dicarboxylic acid; :1:2.15 are mixed evenly, placed in a reactor, and triphenyl phosphate with a mass of 0.09 times that of 1,3-propylene glycol and antimony trioxide with a mass of 0.05 times that of 1,3-propylene glycol are added, and the mixture is stirred at 230°C, a pressure of 0.35 MPa, and 150 r / min to react. When the water output reaches 90% of the theoretical value, the temperature is raised to 265°C, and vacuum is drawn to maintain the pressure in the reactor below 65 Pa. The reaction is continued by stirring for 2.5 hours, and the material is discharged by nitrogen gas to obtain polyester.

[0044] (3) Mix aminopropyltriethoxysilane and deionized water in a mass ratio of 1:20, stir at 25°C, 250 r / min for 9 minutes, adjust the pH to 5.8 with a 2 mol / L oxalic acid aqueous solution, continue stirring for 21 minutes, and prepare a silane hydrolyzate; mix glass fiber and anhydrous ethanol in a mass ratio of 1:45, stir at 25°C, 250 r / min for 28 minutes, add silane hydrolyzate 22 times the mass of glass fiber, stir at 60°C, 250 r / min for 2.5 hours, filter, wash with anhydrous ethanol 4 times, and dry at 70°C under vacuum for 9 hours to prepare Pretreated glass fiber was obtained; the pretreated glass fiber, 2,4-pentanedione and tetrahydrofuran were mixed evenly in a mass ratio of 1:4.5:30, stirred at 60°C and 250r / min for 5.5h, filtered, washed with anhydrous ethanol 4 times, and dried at 70°C for 9h under vacuum conditions to obtain pre-modified glass fiber; the pre-modified glass fiber, 3-chloropropyl isocyanate, stannous isooctanoate and toluene were mixed evenly in a mass ratio of 1:5:0.05:26, stirred at 75°C and 250r / min for 2.5h, filtered, washed with anhydrous ethanol 4 times, and dried at 70°C for 9h under vacuum conditions to obtain modified glass fiber;

[0045] (4) Polyester and modified glass fiber were mixed evenly in a mass ratio of 1:0.09, placed in a screw extruder for injection molding, and the extruder barrel temperature was set to 255°C, the screw speed was 105r / min, the injection temperature was 238°C, the injection pressure was 60MPa, the holding time was 17s, the mold temperature was 80°C, and the mold was demolded after cooling to room temperature to obtain a C21 dicarboxylic acid modified polyester resin material.

[0046] Embodiment 3:

[0047] A method for preparing a C21 dicarboxylic acid modified polyester resin material, the method comprising the following preparation steps:

[0048] (1) Benzophenone-4,4'-dicarboxylic acid and tetrahydrofuran were mixed at a mass ratio of 1:10 to prepare a benzophenone solution; under argon protection, trimethylsilyl acetylene and tetrahydrofuran were mixed at a mass ratio of 1:24, stirred at -60°C and 200 r / min for 20 minutes, and an equal molar amount of n-butyl lithium of trimethylsilyl acetylene was uniformly added dropwise within 10 minutes. After the addition was completed, stirring was continued for 55 minutes. Benzophenone solution was uniformly added dropwise within 15 minutes in a molar ratio of benzophenone-4,4'-dicarboxylic acid to trimethylsilyl acetylene of 1:2. The mixture was heated at 30°C. The mixture was stirred at 200 r / min for 4 hours, and dried at 50°C for 10 hours under vacuum conditions to obtain a propargyl alcohol functional monomer; the propargyl alcohol functional monomer and 1-naphthol were added to toluene with a molar ratio of 1:1, and dodecylbenzenesulfonic acid with a mass of 0.06 times that of 1-naphthol was added, and the mixture was stirred at 52°C and 300 r / min for 3 hours, and an equal volume of deionized water was added to toluene to mix evenly, and the mixture was cooled to 30°C and stirred for 10 minutes, and extracted with ethyl acetate with a volume of 3 times that of toluene, and the organic phase was taken and dried at 60°C for 8 hours under vacuum conditions to obtain a naphthopyran functional monomer;

[0049] (2) C21 dicarboxylic acid and 3-(dimethylamino)-1-propanethiol were added in a molar ratio of 1:1 to toluene with a mass of 12 times that of C21 dicarboxylic acid, and azobisisobutyronitrile with a mass of 0.05 times that of C21 dicarboxylic acid was added, and the mixture was stirred at 60°C and 300 r / min for 4 h, and dried at 60°C under vacuum for 8 h to obtain modified C21 dicarboxylic acid; naphthopyran functional monomer, modified C21 dicarboxylic acid, and 1,3-propylene glycol were added in a molar ratio of 1:1:2.2 are mixed evenly, placed in a reactor, and triphenyl phosphate with a mass of 0.1 times that of 1,3-propylene glycol and antimony trioxide with a mass of 0.06 times that of 1,3-propylene glycol are added, and the mixture is stirred at 240°C, a pressure of 0.4MPa, and 200r / min to react. When the water output reaches 90% of the theoretical value, the temperature is raised to 270°C, and vacuum is drawn to maintain the pressure in the reactor below 65Pa. The reaction is continued by stirring for 2h, and the material is discharged by nitrogen gas to obtain polyester.

[0050] (3) Mix aminopropyltriethoxysilane and deionized water in a mass ratio of 1:21, stir at 20°C and 200 r / min for 10 min, adjust the pH to 6.0 with a 2 mol / L oxalic acid aqueous solution, continue stirring for 20 min, and prepare a silane hydrolyzate; mix glass fiber and anhydrous ethanol in a mass ratio of 1:50, stir at 30°C and 300 r / min for 26 min, add silane hydrolyzate 24 times the mass of glass fiber, stir at 65°C and 300 r / min for 2 h, filter, wash with anhydrous ethanol 5 times, and dry at 75°C under vacuum for 8 h , to obtain pretreated glass fiber; the pretreated glass fiber, 2,4-pentanedione, and tetrahydrofuran were mixed uniformly in a mass ratio of 1:6:32, stirred at 62°C and 300r / min for 5h, filtered, washed with anhydrous ethanol 5 times, and dried at 75°C for 8h under vacuum conditions to obtain pre-modified glass fiber; the pre-modified glass fiber, 3-chloropropyl isocyanate, stannous isooctanoate, and toluene were mixed uniformly in a mass ratio of 1:6:0.06:28, stirred at 80°C and 300r / min for 2h, filtered, washed with anhydrous ethanol 5 times, and dried at 75°C for 8h under vacuum conditions to obtain modified glass fiber;

[0051] (4) Polyester and modified glass fiber were mixed evenly in a mass ratio of 1:0.1, placed in a screw extruder for injection molding, and the extruder barrel temperature was set to 260°C, the screw speed was 110 r / min, the injection temperature was 240°C, the injection pressure was 63 MPa, the holding time was 16 s, the mold temperature was 81°C, and the mold was demolded after cooling to room temperature to obtain a C21 dicarboxylic acid modified polyester resin material.

[0052] Comparative Example 1:

[0053] The preparation method of the C21 dicarboxylic acid modified polyester resin material of Comparative Example 1 is different from that of Example 2 in that step (1) is not performed, and step (2) is modified as follows: C21 dicarboxylic acid and 3-(dimethylamino)-1-propanethiol are added in a molar ratio of 1:1 to toluene with a mass of 11 times that of C21 dicarboxylic acid, and azobisisobutyronitrile with a mass of 0.04 times that of C21 dicarboxylic acid is added, and the mixture is stirred at 55°C and 250 r / min for 4.5 h, and dried at 55°C under vacuum for 9 h to obtain a modified C21 dicarboxylic acid; benzophenone-4,4'-dicarboxylic acid is added to the mixture, and the mixture is stirred at ... the mixture is dried at 55°C under vacuum for 9 h, and the modified C21 dicarboxylic acid is obtained; benzophenone-4,4'-dicarboxylic acid is added to the mixture, and the mixture is stirred at 250 r / min for 4.5 h, and the modified C21 dicarboxylic acid is obtained. -dicarboxylic acid, modified C21 dicarboxylic acid, and 1,3-propylene glycol were mixed uniformly in a molar ratio of 1:1:2.15, placed in a reactor, and triphenyl phosphate was added at a mass of 0.09 times that of 1,3-propylene glycol, and antimony trioxide was added at a mass of 0.05 times that of 1,3-propylene glycol, and stirred at 230°C, a pressure of 0.35MPa, and 150r / min to react, and stirred until the water output reached 90% of the theoretical value, then heated to 265°C, evacuated, and the pressure in the reactor was maintained below 65Pa, and the stirring reaction was continued for 2.5h, and the material was discharged by nitrogen filling to obtain polyester. The remaining steps were the same as those in Example 2.

[0054] Comparative Example 2:

[0055] The preparation method of the C21 dicarboxylic acid modified polyester resin material of Comparative Example 2 is different from that of Example 2 in step (2). Step (2) is modified as follows: naphthopyran functional monomer, C21 dicarboxylic acid, and 1,3-propylene glycol are uniformly mixed in a molar ratio of 1:1:2.15, placed in a reactor, triphenyl phosphate in an amount of 0.09 times the mass of 1,3-propylene glycol, and antimony trioxide in an amount of 0.05 times the mass of 1,3-propylene glycol are added, and the mixture is stirred at 230° C., a pressure of 0.35 MPa, and 150 r / min for reaction, and the mixture is stirred until the water output reaches 90% of the theoretical value, the mixture is heated to 265° C., vacuumized, the pressure in the reactor is maintained below 65 Pa, the reaction is continued with stirring for 2.5 hours, and the mixture is discharged by nitrogen gas to obtain polyester. The remaining steps are the same as those of Example 2.

[0056] Comparative Example 3:

[0057] The preparation method of the C21 dicarboxylic acid modified polyester resin material of Comparative Example 3 is different from that of Example 2 in that step (3) is different. Step (3) is modified as follows: 3-chloropropyltriethoxysilane and deionized water are mixed uniformly at a mass ratio of 1:20, stirred at 25°C and 250 r / min for 9 min, adjusted to pH 5.8 with an oxalic acid aqueous solution with a concentration of 2 mol / L, and stirred for 21 min to prepare a silane hydrolyzate; glass fiber and anhydrous ethanol are mixed uniformly at a mass ratio of 1:45, stirred at 25°C and 250 r / min for 28 min, silane hydrolyzate with a mass of 22 times that of the glass fiber is added, stirred at 60°C and 250 r / min for 2.5 h, filtered, washed with anhydrous ethanol 4 times, and dried at 70°C under vacuum for 9 h to prepare modified glass fiber. The remaining steps are the same as those of Example 2.

[0058] Comparative Example 4:

[0059] The preparation method of the C21 dicarboxylic acid modified polyester resin material of Comparative Example 4 is different from that of Example 2 in that step (3) is not performed, and step (4) is modified as follows: polyester and glass fiber are uniformly mixed in a mass ratio of 1:0.08, placed in a screw extruder for injection molding, and the extruder barrel temperature is set to 250° C., the screw speed is set to 100 r / min, the injection temperature is set to 236° C., the injection pressure is set to 57 MPa, the holding time is set to 18 s, the mold temperature is set to 79° C., and the mold is demolded after cooling to room temperature to obtain a C21 dicarboxylic acid modified polyester resin material.

[0060] Test Example 1

[0061] Antimicrobial performance testing

[0062] Test method: The examples and comparative examples were cut into 25 mm × 25 mm samples and sterilized by ultraviolet irradiation for 2 h; the Escherichia coli strains were activated and prepared to a concentration of 3 × 10 4 cfu / ml bacterial suspension; put the sample into the bacterial suspension, shake at 300r / min for 12min at room temperature, take 1ml of the bacterial suspension and dilute it to 100 times, take 1ml of the diluted bacterial suspension and inoculate it into agar medium, culture it at 37℃ for 16h, count the colonies according to the method in GB / T15979, and calculate the antibacterial rate. The results are shown in Table 1.

[0063] Table 1

[0064] ;

[0065] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 4 in Table 1, it can be found that the C21 dicarboxylic acid modified polyester resin material prepared in the present invention has good antibacterial properties.

[0066] By comparison, the antibacterial rates of Examples 1 to 3 are greater than that of Comparative Example 2, indicating that the modified C21 dicarboxylic acid is prepared by reacting C21 dicarboxylic acid and 3-(dimethylamino)-1-propanethiol; C21 dicarboxylic acid is a liquid twenty-one-carbon monocyclic dicarboxylic acid prepared from vegetable oil fatty acids, and the carbon-carbon double bond on the C21 dicarboxylic acid reacts with the sulfhydryl group on 3-(dimethylamino)-1-propanethiol to introduce a tertiary amine structure on the modified C21 dicarboxylic acid; the two carboxyl groups on the modified C21 dicarboxylic acid can participate in the polymerization reaction of the polyester, and a tertiary amine structure is introduced on the side chain of the polyester molecule. The tertiary amine structure introduced on the side chain of the polyester molecule can react with the chlorine atom introduced on the modified glass fiber to generate a quaternary ammonium salt, and the generated quaternary ammonium salt structure belongs to a cationic antibacterial agent, which gives the C21 dicarboxylic acid modified polyester resin material excellent antibacterial properties.

[0067] By comparison, the antibacterial rates of Examples 1 to 3 are greater than that of Comparative Example 4, indicating that the glass fiber is reacted with aminopropyltriethoxysilane, 2,4-pentanedione, and 3-chloropropyl isocyanate in sequence to obtain modified glass fiber, and chlorine atoms are introduced into the modified glass fiber; the chlorine atoms introduced into the modified glass fiber can react with the tertiary amine structure introduced into the side chain of the polyester molecule to generate a quaternary ammonium salt structure, and the generated quaternary ammonium salt structure belongs to a cationic antibacterial agent, which gives the C21 dicarboxylic acid modified polyester resin material excellent antibacterial properties.

[0068] Test Example 2

[0069] Testing of mechanical properties and anti-aging properties

[0070] Test method: According to GB / T1040, the examples and comparative examples were prepared into standard specimens, and their tensile strength F 1 The standard sample was irradiated with a xenon arc lamp for 15 days and its tensile strength F was tested. 2 , calculate the change rate of tensile strength of the embodiment and the comparative example before and after UV aging treatment, tensile strength change rate = (F 1 -F 2 ) / F 1 ×100%. The results are shown in Table 2.

[0071] Table 2

[0072] ;

[0073] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 4 in Table 2, it can be found that the C21 dicarboxylic acid modified polyester resin material prepared in the present invention has good mechanical properties and anti-aging properties.

[0074] By comparison, the tensile strengths of Examples 1 to 3 are greater than that of Comparative Example 2, indicating that the modified C21 dicarboxylic acid is prepared by reacting C21 dicarboxylic acid and 3-(dimethylamino)-1-propanethiol; C21 dicarboxylic acid is a liquid twenty-one-carbon monocyclic dicarboxylic acid prepared from vegetable oil fatty acids, and the carbon-carbon double bond on the C21 dicarboxylic acid reacts with the sulfhydryl group on 3-(dimethylamino)-1-propanethiol to introduce a tertiary amine structure on the modified C21 dicarboxylic acid; the two carboxyl groups on the modified C21 dicarboxylic acid can participate in the polymerization reaction of the polyester, and a tertiary amine structure is introduced on the side chain of the polyester molecule. The tertiary amine structure introduced on the side chain of the polyester molecule can react with the chlorine atom introduced on the modified glass fiber to generate a quaternary ammonium salt, so that a cross-linking site is formed between the polyester molecular chain and the modified glass fiber, forming a cross-linking network, inhibiting the relative slip between the molecular chains, and improving the mechanical properties of the C21 dicarboxylic acid modified polyester resin material.

[0075] By comparison, the tensile strength of Examples 1 to 3 is greater than that of Comparative Example 4, indicating that the glass fiber is reacted with aminopropyltriethoxysilane and 2,4-pentanedione 3-chloropropyl isocyanate in sequence to obtain modified glass fiber, and chlorine atoms are introduced into the modified glass fiber; the chlorine atoms introduced into the modified glass fiber can react with the tertiary amine structure introduced into the side chain of the polyester molecule to form a cross-linked network structure, inhibit the relative slip between the molecular chains, and improve the mechanical properties of the C21 dicarboxylic acid modified polyester resin material.

[0076] By comparison, the change rate of tensile strength of Examples 1 to 3 is less than that of Comparative Example 1, indicating that benzophenone-4,4'-dicarboxylic acid and trimethylsilyl acetylene are reacted to obtain propargyl alcohol functional monomers; propargyl alcohol functional monomers and 1-naphthol are reacted to obtain naphthopyran functional monomers; the carboxyl group on the naphthopyran functional monomer can participate in the polymerization reaction of polyester, and a naphthopyran structure is introduced into the polyester molecular chain. Naphthopyran can absorb ultraviolet light and meet the requirements of traditional ultraviolet absorbers. Under continuous irradiation of ultraviolet light, the CO bond on the pyran ring breaks to cause a ring-opening reaction, and when the ultraviolet light is removed, a reversible ring-closing reaction occurs. This reversible ring-opening reaction can absorb ultraviolet light and release the ultraviolet light in a harmless form, thereby giving the C21 dicarboxylic acid modified polyester resin material excellent anti-aging properties.

[0077] Test Example 3

[0078] Self-healing performance test

[0079] Test method: According to GB / T1040, the examples and comparative examples were prepared into standard specimens and their tensile strength M was tested. 1A 2mm deep and 15mm long crack was made in the middle of the standard specimen, and the specimen was kept at 160℃ for 1h and allowed to stand at room temperature for 10h to obtain the repaired specimen. The tensile strength M of the repaired specimen was tested by a tensile machine. 2 ; Calculate the self-repair rate of the standard spline, self-repair rate = (M 2 / M 1 ) × 100%. The results are shown in Table 3.

[0080] Table 3

[0081] ;

[0082] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 4 in Table 3, it can be found that the C21 dicarboxylic acid modified polyester resin material prepared in the present invention has good self-repairing performance.

[0083] By comparison, the self-repairing rates of Examples 1 to 3 are greater than those of Comparative Examples 3 to 4, indicating that the glass fiber and aminopropyltriethoxysilane are reacted to obtain a pretreated glass fiber, and an amino group is introduced into the pretreated glass fiber; the amino group on the pretreated glass fiber is reacted with 2,4-pentanedione to obtain a pre-modified glass fiber, and an enamine ketone bond is generated on the modified glass fiber; the enamine ketone bond on the pre-modified glass fiber is reacted with the isocyanate group on 3-chloropropyl isocyanate to obtain a modified glass fiber, an amide-enamine ketone bond is generated on the modified glass fiber, and a chlorine atom is introduced; The chlorine atoms introduced on the modified glass fiber can react with the tertiary amine structure introduced on the side chain of the polyester molecule to form a cross-linked network structure. An amide-enamine ketone bond is also introduced into the C21 dicarboxylic acid modified polyester resin material. The amide-enamine ketone bond is a thermally reversible dynamic bond. The amide-enamine ketone bond will break at high temperatures and recombine to form an amide-enamine ketone bond when the temperature drops. This thermally reversible dynamic bond can repair the material by regulating the temperature after the material is damaged, thus giving the C21 dicarboxylic acid modified polyester resin material self-healing properties.

[0084] By comparison, the self-repair rates of Examples 1 to 3 are greater than that of Comparative Example 2, indicating that although Comparative Example 2 contains amide-enamine ketone bonds, the amide-enamine ketone bonds in Comparative Example 2 do not form a cross-linked network structure with the polyester molecular chains, and therefore cannot exert self-repairing properties.

[0085] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A C21 dicarboxylic acid modified polyester resin material, characterized in that: The C21 dicarboxylic acid modified polyester resin material is prepared by reacting propargyl alcohol functional monomer and 1-naphthol to obtain naphthopyran functional monomer; polymerizing naphthopyran functional monomer, modified C21 dicarboxylic acid and 1,3-propylene glycol to obtain polyester; reacting pre-modified glass fiber and 3-chloropropyl isocyanate to obtain modified glass fiber; and melt-mixing the polyester and the modified glass fiber and performing injection molding to obtain the material. The propargyl alcohol functional monomer is prepared by reacting benzophenone-4,4'-dicarboxylic acid and trimethylsilyl acetylene; The modified C21 dicarboxylic acid is prepared by reacting C21 dicarboxylic acid and 3-(dimethylamino)-1-propanethiol; The pre-modified glass fiber is prepared by reacting pre-treated glass fiber and 2,4-pentanedione; The pretreated glass fiber is prepared by reacting glass fiber and aminopropyltriethoxysilane; The structural formula of the C21 dicarboxylic acid is as follows: 。 2. A method for preparing a C21 dicarboxylic acid modified polyester resin material, characterized in that: The preparation method of the C21 dicarboxylic acid modified polyester resin material comprises the following preparation steps: (1) Add propargyl alcohol functional monomer and 1-naphthol in a molar ratio of 1:1 to toluene with a mass of 10 to 12 times that of 1-naphthol, add dodecylbenzenesulfonic acid with a mass of 0.04 to 0.06 times that of 1-naphthol, stir at 48 to 52°C and 200 to 300 r / min for 3 to 4 hours, add deionized water with an equal volume of toluene and mix evenly, cool to 10 to 30°C and continue stirring for 10 to 14 minutes, extract with ethyl acetate with a volume of 2 to 3 times that of toluene, take the organic phase, and dry at 50 to 60°C under vacuum for 8 to 10 hours to obtain naphthopyran functional monomer; (2) Naphthopyran functional monomer, modified C21 dicarboxylic acid and 1,3-propylene glycol are uniformly mixed in a molar ratio of 1:1:2.1-2.2, placed in a reactor, and triphenyl phosphate in an amount of 0.08-0.1 times the mass of 1,3-propylene glycol and antimony trioxide in an amount of 0.04-0.06 times the mass of 1,3-propylene glycol are added, and stirred at 220-240°C, a pressure of 0.3-0.4 MPa, and 100-200 r / min to react until the water output reaches 90% of the theoretical value, then the temperature is raised to 260-270°C, vacuum is drawn to maintain the pressure in the reactor below 65 Pa, the stirring reaction is continued for 2-3 hours, and nitrogen is filled to discharge the material to obtain polyester; (3) Pretreated glass fiber, 2,4-pentanedione, and tetrahydrofuran were mixed evenly in a mass ratio of 1: (4-6): (28-32), stirred at 58-62°C and 200-300 r / min for 5-6 hours, filtered, washed with anhydrous ethanol for 3-5 times, and dried at 65-75°C for 8-10 hours under vacuum conditions to obtain pre-modified glass fiber; pre-modified glass fiber, 3-chloropropyl isocyanate, stannous isooctanoate, and toluene were mixed evenly in a mass ratio of 1: (4-6): (0.04-0.06): (24-28), stirred at 70-80°C and 200-300 r / min for 2-3 hours, filtered, washed with anhydrous ethanol for 3-5 times, and dried at 65-75°C for 8-10 hours under vacuum conditions to obtain modified glass fiber; (4) The polyester and modified glass fiber are mixed uniformly in a mass ratio of 1:(0.08-0.1), placed in a screw extruder for injection molding, and demolded after cooling to room temperature to obtain a C21 dicarboxylic acid modified polyester resin material; The preparation method of the modified C21 dicarboxylic acid in step (2) is as follows: C21 dicarboxylic acid and 3-(dimethylamino)-1-propanethiol are added in a molar ratio of 1:1 to toluene with a mass of 10 to 12 times that of the C21 dicarboxylic acid, and azobisisobutyronitrile with a mass of 0.03 to 0.05 times that of the C21 dicarboxylic acid is added, and the mixture is stirred at 50 to 60° C. and 200 to 300 r / min for 4 to 5 hours, and dried at 50 to 60° C. under vacuum conditions for 8 to 10 hours to obtain the modified C21 dicarboxylic acid. The structural formula of the C21 dicarboxylic acid is as follows: 。 3. The method for preparing a C21 dicarboxylic acid modified polyester resin material according to claim 2, characterized in that: The preparation method of the propargyl alcohol functional monomer in step (1) is as follows: benzophenone-4,4'-dicarboxylic acid and tetrahydrofuran are mixed in a mass ratio of 1:(8-10) to prepare a benzophenone solution; under argon protection, trimethylsilyl acetylene and tetrahydrofuran are mixed in a mass ratio of 1:(20-24), stirred at -70--60°C, 100-200 r / min for 20-30 min, and stirred at a constant speed within 10 min. Trimethylsilyl acetylene and n-butyl lithium in an equal molar amount are added dropwise. After the addition is completed, stirring is continued for 55-65 minutes. Benzophenone solution is added dropwise at a uniform rate within 15 minutes according to a molar ratio of benzophenone-4,4'-dicarboxylic acid to trimethylsilyl acetylene of 1:

2. The mixture is stirred at 10-30°C and 100-200 r / min for 4-5 hours. Dry at 40-50°C under vacuum conditions for 10-12 hours to obtain propargyl alcohol functional monomer.

4. The method for preparing a C21 dicarboxylic acid modified polyester resin material according to claim 2, characterized in that: The preparation method of the pretreated glass fiber in step (3) is as follows: glass fiber and anhydrous ethanol are uniformly mixed in a mass ratio of 1:(40-50), stirred at 20-30°C and 200-300 r / min for 26-30 min, silane hydrolyzate of 20-24 times the mass of the glass fiber is added, stirred at 55-65°C and 200-300 r / min for reaction for 2-3 h, filtered, washed with anhydrous ethanol for 3-5 times, and dried at 65-75°C under vacuum conditions for 8-10 h to obtain the pretreated glass fiber.

5. The method for preparing a C21 dicarboxylic acid modified polyester resin material according to claim 4, characterized in that: The preparation method of the silane hydrolyzate is as follows: aminopropyltriethoxysilane and deionized water are uniformly mixed in a mass ratio of 1:(19-21), stirred at 200-300 r / min for 8-10 min at 20-30° C., adjusted the pH to 5.6-6.0 with an oxalic acid aqueous solution, and continued stirring for 20-22 min to prepare a silane hydrolyzate.

6. The method for preparing a C21 dicarboxylic acid modified polyester resin material according to claim 4, characterized in that: The monofilament diameter of the glass fiber is 5-10 μm and the length is 1-3 mm.

7. The method for preparing a C21 dicarboxylic acid modified polyester resin material according to claim 5, characterized in that: The concentration of the oxalic acid aqueous solution is 2 mol / L.

8. The method for preparing a C21 dicarboxylic acid modified polyester resin material according to claim 2, characterized in that: The process parameters of the injection molding in step (4) are as follows: setting the extruder barrel temperature to 250-260°C, the screw speed to 100-110 r / min, the injection temperature to 236-240°C, the injection pressure to 57-63 MPa, the holding time to 16-18 s, and the mold temperature to 79-81°C.

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