CN117887053A - Functional polyester elastomer material and manufacturing method thereof - Google Patents
Functional polyester elastomer material and manufacturing method thereof Download PDFInfo
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- CN117887053A CN117887053A CN202410047982.3A CN202410047982A CN117887053A CN 117887053 A CN117887053 A CN 117887053A CN 202410047982 A CN202410047982 A CN 202410047982A CN 117887053 A CN117887053 A CN 117887053A
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- polyester elastomer
- polytetrahydrofuran
- elastomer material
- stirring
- branching agent
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- 229920000728 polyester Polymers 0.000 title claims abstract description 109
- 229920001971 elastomer Polymers 0.000 title claims abstract description 74
- 239000000806 elastomer Substances 0.000 title claims abstract description 74
- 239000000463 material Substances 0.000 title claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 title abstract description 10
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 66
- 239000006085 branching agent Substances 0.000 claims abstract description 35
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 11
- 150000002009 diols Chemical class 0.000 claims abstract description 8
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 40
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 238000002360 preparation method Methods 0.000 claims description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 238000007599 discharging Methods 0.000 claims description 13
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- QZHXKQKKEBXYRG-UHFFFAOYSA-N 4-n-(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC1=CC=C(N)C=C1 QZHXKQKKEBXYRG-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 8
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 7
- LKRUZYNPJUZODM-UHFFFAOYSA-N adamantane-1,3-dicarbonyl chloride Chemical compound C1C(C2)CC3CC1(C(=O)Cl)CC2(C(Cl)=O)C3 LKRUZYNPJUZODM-UHFFFAOYSA-N 0.000 claims description 7
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- 229940035437 1,3-propanediol Drugs 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 abstract description 7
- 229920001577 copolymer Polymers 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 230000003712 anti-aging effect Effects 0.000 abstract 1
- 238000007792 addition Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 150000001263 acyl chlorides Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Abstract
The invention relates to the technical field of materials and discloses a functional polyester elastomer material and a manufacturing method thereof, wherein the polyester elastomer material is prepared by taking a polyester oligomer as a hard segment, taking a polytetrahydrofuran branching agent and low molecular diol as soft segments and performing polycondensation reaction under the action of a catalyst, wherein the polyester oligomer containing a cage-type adamantane and rigid phenylsulfone segmented copolymer structure is taken as the hard segment of the polyester elastomer, so that the polyester elastomer can show excellent high and low temperature resistance and mechanical properties of the polyester elastomer, and the prepared polyester elastomer can show long-acting anti-aging performance and generate micro-crosslinking by taking the polytetrahydrofuran branching agent as the soft segment, so that the polyester elastomer has higher structural compactness and higher mechanical strength.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a functional polyester elastomer material and a manufacturing method thereof.
Background
At present, the technical requirements of the image module are higher and higher in the continuous development of the camera optical module industry, so that a plurality of links such as manufacturing, production and transportation of the camera module are all required to be carried out under the protection of the protection cover so as to prevent foreign matters from influencing the quality of the camera. At present, the camera module protective cover mainly solves the problem that the protective cover is difficult to tear through products such as silicone rubber, and as the protective cover product gradually tends to be ultrathin, the structural member made of the silicone rubber material is high in manufacturing cost, and the performances such as mechanical strength and hardness are poor, so that the special requirements of consumers on the product performances are gradually difficult to meet, and in order to solve the problem, other materials need to be developed to manufacture the protective cover product.
The comprehensive performance of the polyester elastomer is relatively excellent, but in order to meet the market demand of continuous development of the protective cover of the camera module, the modification of the polyester elastomer has become a research hot spot. For example, the mechanical properties, heat resistance, etc. of the polyester elastomer can be improved by adding nanofillers or functional additives. In addition, by a blending or copolymerization method, the polyester elastomer and other high polymer materials can be compounded, so that the material with multiple excellent performances is obtained.
For example, the patent of CN201811562711.2 discloses a thermoplastic polyester elastomer fiber, a preparation method and a textile product, and the thermoplastic polyester elastomer fiber can effectively improve the heat resistance and the mechanical property of the thermoplastic polyester elastomer by blending and modifying the polyester elastomer by using modified POSS and rare earth oxide heat-resistant additive, but the poor compatibility between inorganic materials and high polymer materials may negatively affect the comprehensive properties of the polyester elastomer, so that the POSS needs to be modified first.
Based on the structure, the structure of the polyester elastomer is designed, so that the polyester elastomer is improved, and the comprehensive performance of the polyester elastomer is improved, so that the development requirements of various industries are met.
Disclosure of Invention
The invention aims to provide a functional polyester elastomer material and a manufacturing scheme thereof, and the mechanical property, ageing resistance and high and low temperature resistance of a polyester elastomer are enhanced by designing a polyester elastomer molecular chain.
The aim of the invention can be achieved by the following technical scheme:
a functional polyester elastomer material is prepared from the following raw materials in parts by weight: 180-200 parts of polyester oligomer, 10-15 parts of polytetrahydrofuran branching agent, 40-55 parts of low molecular diol and 0.5-1.5 parts of catalyst;
the polyester oligomer contains cage adamantane and rigid phenylsulfone block structures;
The polytetrahydrofuran branching agent is a polytetrahydrofuran derivative containing an aniline antioxidant in the structure.
Further, the polyester oligomer is prepared by the following specific steps:
Sequentially adding 1, 3-adamantane dicarboxylic acid chloride and toluene into a polymerization kettle, introducing nitrogen, exhausting oxygen in the polymerization kettle, stirring until the oxygen is dissolved, placing the polymerization kettle in an ice bath condition, adding 4,4' -dihydroxydiphenyl sulfone into a polymer, removing the ice bath after the oxygen is added, adding an accelerator into the polymerization kettle under the stirring condition, adding the accelerator, raising the temperature, stirring for 1-2 hours at the temperature of 50-60 ℃, steaming to remove the solvent, cooling and discharging to obtain the product, namely the polyester oligomer.
In the technical scheme, 1, 3-adamantane dicarboxylic acid chloride and 4,4' -dihydroxydiphenyl sulfone are used as reaction monomers, and the principle that the active acyl chloride substituent and the active hydroxyl substituent in the two structures can undergo polycondensation reaction is utilized, and under the action of an accelerator, continuous polycondensation reaction can be carried out between the two components, so that the polyester oligomer with a cage-type adamantane and rigid phenyl sulfone segmented copolymer structure is obtained, and the prepared polyester oligomer is end capped by the acyl chloride by controlling the dosage of the two components.
Further, the molar ratio of the 1, 3-adamantane dicarboxylic acid chloride to the 4,4' -dihydroxydiphenyl sulfone is 1:0.8-0.9.
Further, the promoter is triethylamine or pyridine.
Further, the polytetrahydrofuran branching agent is prepared by the following specific steps:
step A, preparation of mono-epoxy end capped polytetrahydrofuran
Stirring and mixing polytetrahydrofuran ether glycol and tetrabutylammonium chloride to form a uniform solution, preheating the solution to 40-50 ℃, adding epichlorohydrin into the solution under the condition of continuous stirring, further raising the temperature to 55-60 ℃, adding sodium hydroxide into the solution after the addition is finished, stirring at constant temperature for 2-4h, cooling and discharging to obtain a product, namely monoepoxy end capped polytetrahydrofuran;
In the technical scheme, the hydroxyl substituent at the end part of the polytetrahydrofuran ether glycol can act on tetrabutylammonium chloride and sodium hydroxide in the front and back directions to generate a ring opening-closing process, and the monoepoxy end capped polytetrahydrofuran can be prepared by controlling the dosage of the polytetrahydrofuran ether glycol and the epoxy chloropropane.
Step B, preparation of polytetrahydrofuran branching agent
And (3) mixing the monoepoxy-terminated polytetrahydrofuran and the 4,4' -diaminodiphenylamine, mechanically stirring and uniformly mixing, starting heating, raising the temperature to 60-65 ℃, maintaining for 3-6 hours under the condition of continuous stirring, cooling and discharging, and purifying to obtain the product, namely the polytetrahydrofuran branching agent.
In the technical scheme, the epoxy group in the monoepoxy end-capped polytetrahydrofuran structure has higher reactivity, can carry out ring-opening addition with the primary amino group in the 4,4 '-diaminodiphenylamine structure, and can form the polytetrahydrofuran branching agent with the 4,4' -diaminodiphenylamine as a bridging agent by controlling the dosage of the epoxy group and the primary amino group.
Further, in the step A, the molar ratio of the polytetrahydrofuran ether glycol to the epichlorohydrin is 1:0.4-0.5.
Further, in the step A, the number average molecular weight of the polytetrahydrofuran ether glycol is 250-650.
Further, in the step B, the molar ratio of the monoepoxy-terminated polytetrahydrofuran to the 4,4' -diaminodiphenylamine is 1:2.
Further, the low molecular diol is at least one of ethylene glycol, 1, 3-propylene glycol or 1, 4-butanediol; the catalyst is tetrabutyl titanate.
A method for manufacturing a functional polyester elastomer material, comprising the following specific steps:
first step, preparation of prepolymer
Sequentially adding the polyester oligomer, the low molecular diol, the catalyst and the dehydrating agent into a polymerization kettle, introducing nitrogen to discharge air in the kettle, controlling the temperature in the kettle to be 100-120 ℃, controlling the stirring speed to be 800-1000r/min, and stirring for reacting for 1-2h to form a prepolymer;
Second step, preparation of polyester elastomer Material
And adding a polytetrahydrofuran branching agent into the prepolymer, after the polytetrahydrofuran branching agent is added, further raising the temperature in the kettle to 150-160 ℃, carrying out polycondensation reaction for 1-2h, and cooling and discharging after the reaction is finished, thus obtaining the polyester elastomer material.
In the technical scheme, firstly, the polyester oligomer and the low molecular diol are prepolymerized to form a prepolymer, then the prepolymer is further polycondensed by using the polytetrahydrofuran branching agent as a soft segment, and the polytetrahydrofuran branching agent contains four equivalent substituted hydroxyl groups because the polyester oligomer contains a terminal acyl chloride group, so that the prepolymer can be further polycondensed to generate branching, and finally the branched polyester elastomer material with the structure containing both the cage adamantane, the rigid phenylsulfone block structure and the flexible polytetrahydrofuran is prepared.
The invention has the beneficial effects that:
(1) The invention adopts the polyester oligomer containing the cage adamantane and rigid phenylsulfone segmented copolymer structure as the hard segment of the polyester elastomer, the cage structure can show good stability under high and low temperature conditions, and the phenylsulfone structure can also show excellent stability under high and low temperature conditions, and the polyester elastomer can show excellent high and low temperature resistance by utilizing the synergistic effect of the cage adamantane and the rigid phenylsulfone. Furthermore, the presence of these stabilizing structures also enhances the mechanical properties of the polyester elastomer to some extent.
(2) According to the invention, the polytetrahydrofuran derivative containing the aniline antioxidant in the structure is prepared as a soft segment, and the aniline antioxidant is introduced into the polyester elastomer structure in a chemical bond connection mode, so that the prepared polyester elastomer can show long-acting ageing resistance.
(3) The polyester oligomer prepared by the invention contains a large number of rigid and cage-shaped structures, so that larger steric hindrance is generated in the subsequent polycondensation process, and micro-crosslinking is generated with the branching agent containing four equivalent substituted hydroxyl polytetrahydrofuran, so that the whole polyester elastomer forms a micro-crosslinking structure, on one hand, the micro-crosslinking structure can enable the structural density of the polyester elastomer to be higher, and further has higher mechanical strength, and on the other hand, the micro-crosslinking structure can also avoid the toughness of the polyester elastomer from being reduced due to excessive crosslinking. In addition, by using the polyester oligomer and the polytetrahydrofuran branching agent as precursors, the rigidity and the flexibility of the molecular chain of the polyester elastomer can be relatively balanced, the effect of hardness and softness can be achieved, and the defect that the elasticity of the polyester elastomer is reduced due to the fact that the rigidity of the polyester oligomer is too high can be effectively avoided.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A functional polyester elastomer material is prepared from the following raw materials in parts by weight: 180 parts of polyester oligomer, 10 parts of polytetrahydrofuran branching agent, 40 parts of ethylene glycol and 0.5 part of tetrabutyl titanate;
the preparation method of the polyester elastomer material is as follows:
first step, preparation of prepolymer
Sequentially adding polyester oligomer, ethylene glycol and tetrabutyl titanate into a polymerization kettle, introducing nitrogen to discharge air in the kettle, controlling the temperature in the kettle to be 100 ℃, controlling the stirring speed to be 1000r/min, and stirring and reacting for 1h to form a prepolymer;
Second step, preparation of polyester elastomer Material
Adding the polytetrahydrofuran branching agent into the prepolymer, after the addition, further raising the temperature in the kettle to 150 ℃, carrying out polycondensation reaction for 2 hours, and after the reaction is finished, cooling and discharging to obtain the polyester elastomer material.
Wherein the polyester oligomer is prepared by the following specific steps:
Adding 1.3g of 1, 3-adamantane dicarboxylic acid chloride and toluene into a polymerization kettle in sequence, introducing nitrogen, exhausting oxygen in the polymerization kettle, stirring until the oxygen is dissolved, placing the polymerization kettle in an ice bath condition, adding 1g of 4,4' -dihydroxydiphenyl sulfone into the polymer, removing the ice bath after the oxygen is added, adding 0.2g of pyridine into the polymerization kettle under the stirring condition, adding the pyridine, raising the temperature, stirring for 2 hours at the temperature of 55 ℃, steaming to remove the solvent, cooling and discharging to obtain the product, namely the polyester oligomer.
The content of ester groups in the polyester oligomer structure was tested using soap back titration, and the test result showed that the content of ester groups in the polyester oligomer structure was 3.819mmo l/g, which confirmed that 1, 3-adamantane dicarboxylic acid chloride and 4,4' -dihydroxydiphenyl sulfone were block copolymers linked by ester groups.
Wherein the polytetrahydrofuran branching agent is prepared by the following specific steps:
step A, preparation of mono-epoxy end capped polytetrahydrofuran
Stirring and mixing 1.5g of polytetrahydrofuran ether glycol with the number average molecular weight of 650 and 0.03g of tetrabutylammonium chloride to form a uniform solution, preheating the solution to 45 ℃, adding 0.1g of epichlorohydrin into the solution under the condition of continuous stirring, further increasing the temperature to 60 ℃ after the addition, adding 0.4g of sodium hydroxide into the solution, stirring at constant temperature for 3 hours, cooling and discharging to obtain a product, namely the monoepoxy-terminated polytetrahydrofuran;
step B, preparation of polytetrahydrofuran branching agent
Mixing 1.2g of mono-epoxy end-capped polytetrahydrofuran and 0.68g of 4,4' -diaminodiphenylamine, mechanically stirring and uniformly mixing, starting heating, raising the temperature to 60 ℃, keeping for 4 hours under the condition of continuous stirring, cooling and discharging, and purifying to obtain the product, namely the polytetrahydrofuran branching agent.
The element analysis is carried out on the polytetrahydrofuran branching agent by using an EMA 502 type organic element analyzer, the carbon element content in the polytetrahydrofuran branching agent is 57.17 percent, the nitrogen element content is 4.69 percent, and according to the analysis, the mono-epoxy end-capped polytetrahydrofuran structure does not contain nitrogen element, so the nitrogen element is from aniline antioxidant 4,4' -diaminodiphenylamine.
Example 2
A functional polyester elastomer material is prepared from the following raw materials in parts by weight: 190 parts of the polyester oligomer prepared in the embodiment 1 of the invention, 12 parts of the polytetrahydrofuran branching agent prepared in the embodiment 1 of the invention, 70 parts of 1, 4-butanediol and 1.2 parts of tetrabutyl titanate;
the preparation method of the polyester elastomer material is as follows:
first step, preparation of prepolymer
Sequentially adding the polyester oligomer, 1, 4-butanediol and tetrabutyl titanate prepared in the embodiment 1 of the invention into a polymerization kettle, introducing nitrogen to discharge air in the kettle, controlling the temperature in the kettle to 120 ℃, controlling the stirring speed to 1000r/min, and stirring for reacting for 1h to form a prepolymer;
Second step, preparation of polyester elastomer Material
The polytetrahydrofuran branching agent prepared in the embodiment 1 of the invention is added into a prepolymer, after the addition, the temperature in a kettle is further increased to 160 ℃, the polycondensation reaction is carried out for 1h, after the reaction is finished, the temperature is reduced, and the material is discharged, thus obtaining the polyester elastomer material.
Example 3
A functional polyester elastomer material is prepared from the following raw materials in parts by weight: 200 parts of the polyester oligomer prepared in the embodiment 1 of the invention, 15 parts of the polytetrahydrofuran branching agent prepared in the embodiment 1 of the invention, 75 parts of 1, 3-propanediol and 1.5 parts of tetrabutyl titanate;
the preparation method of the polyester elastomer material is as follows:
first step, preparation of prepolymer
Sequentially adding the polyester oligomer, 1, 3-propylene glycol and tetrabutyl titanate prepared in the embodiment 1 of the invention into a polymerization kettle, introducing nitrogen to discharge air in the kettle, controlling the temperature in the kettle to 120 ℃, controlling the stirring speed to 1000r/min, and stirring for reacting for 1h to form a prepolymer;
Second step, preparation of polyester elastomer Material
The polytetrahydrofuran branching agent prepared in the embodiment 1 of the invention is added into a prepolymer, after the addition, the temperature in a kettle is further increased to 160 ℃, the polycondensation reaction is carried out for 1h, after the reaction is finished, the temperature is reduced, and the material is discharged, thus obtaining the polyester elastomer material.
Comparative example 1
A functional polyester elastomer material is prepared from the following raw materials in parts by weight: 190 parts of polyester oligomer prepared in example 1 of the invention, 12 parts of polytetrahydrofuran ether glycol, 70 parts of 1, 4-butanediol and 1.2 parts of tetrabutyl titanate;
the preparation method of the polyester elastomer material is as follows:
first step, preparation of prepolymer
Sequentially adding the polyester oligomer, 1, 4-butanediol and tetrabutyl titanate prepared in the embodiment 1 of the invention into a polymerization kettle, introducing nitrogen to discharge air in the kettle, controlling the temperature in the kettle to be 200 ℃, controlling the stirring speed to be 1000r/min, and stirring for reacting for 1h to form a prepolymer;
Second step, preparation of polyester elastomer Material
And adding polytetrahydrofuran ether glycol into the prepolymer, after the addition, further raising the temperature in the kettle to 240 ℃, carrying out polycondensation reaction for 1h, and after the reaction is finished, cooling and discharging to obtain the polyester elastomer material.
Comparative example 2
A functional polyester elastomer material is prepared from the following raw materials in parts by weight: 190 parts of polyester oligomer prepared in example 1 of the invention, 70 parts of 1, 4-butanediol and 1.2 parts of tetrabutyl titanate;
the preparation method of the polyester elastomer material is as follows:
Sequentially adding the polyester oligomer, 1, 4-butanediol and tetrabutyl titanate prepared in the embodiment 1 of the invention into a polymerization kettle, introducing nitrogen to discharge air in the kettle, controlling the temperature in the kettle to 160 ℃, controlling the stirring speed to 1000r/min, and stirring for 2 hours to form a prepolymer;
Comparative example 3
A functional polyester elastomer material is prepared from the following raw materials in parts by weight: 12 parts of polytetrahydrofuran branching agent prepared in the embodiment 1 of the invention, 190 parts of terephthalic acid, 70 parts of 1, 4-butanediol and 1.2 parts of tetrabutyl titanate;
the preparation method of the polyester elastomer material is as follows:
first step, preparation of prepolymer
Sequentially adding terephthalic acid, 1, 4-butanediol and tetrabutyl titanate into a polymerization kettle, introducing nitrogen to discharge air in the kettle, controlling the temperature in the kettle to be 180 ℃, controlling the stirring speed to be 1000r/min, and stirring and reacting for 1h to form a prepolymer;
Second step, preparation of polyester elastomer Material
The polytetrahydrofuran branching agent prepared in the embodiment 1 of the invention is added into a prepolymer, after the addition, the temperature in a kettle is further increased to 200 ℃, the polycondensation reaction is carried out for 1h, after the reaction is finished, the temperature is reduced, and the material is discharged, thus obtaining the polyester elastomer material.
The following performance tests were performed on the polyester elastomer materials prepared in examples 1 to 3 and comparative examples 1 to 3 according to the present invention:
According to the standard GB/T1040-2006, carrying out tensile property test; after the test is finished, aging the sample for 24 hours at the temperature of 150 ℃, testing the tensile property again, and evaluating the ageing resistance;
Carrying out a Vicat softening temperature test according to the standard GB/T1633-2000;
According to the standard GB/T5470-2008, carrying out embrittlement temperature test;
Hardness testing is carried out according to the standard GB/T1033-2008;
The results are recorded in the following table:
Analysis of the test data in the table shows that the polyester elastomer prepared by using the polyester oligomer and the polytetrahydrofuran branching agent prepared in the embodiment 1 of the invention as raw materials has good mechanical properties, ageing resistance, mechanical properties and high and low temperature resistance.
In comparative example 1, polytetrahydrofuran ether glycol is directly used as a soft segment, so that the molecular chain of the polyester elastomer does not contain an antioxidant, the ageing resistance is obviously reduced, a micro-crosslinking structure cannot be generated, and the mechanical property, the high temperature resistance and the mechanical property are negatively influenced.
Comparative example 2, without the addition of the polytetrahydrofuran ether glycol soft segment, leads to a further decrease in mechanical properties. The comparative example 3 adopts conventional terephthalic acid as a hard segment, and can obviously show that the high and low temperature resistance has larger influence and the mechanical property has larger amplitude reduction.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (10)
1. The functional polyester elastomer material is characterized by being prepared from the following raw materials in parts by weight: 180-200 parts of polyester oligomer, 10-15 parts of polytetrahydrofuran branching agent, 40-55 parts of low molecular diol and 0.5-1.5 parts of catalyst;
the polyester oligomer contains cage adamantane and rigid phenylsulfone block structures;
The polytetrahydrofuran branching agent is a polytetrahydrofuran derivative containing an aniline antioxidant in the structure.
2. A functional polyester elastomer material according to claim 1, wherein the polyester oligomer is prepared by the following specific steps:
Sequentially adding 1, 3-adamantane dicarboxylic acid chloride and toluene into a polymerization kettle, introducing nitrogen, exhausting oxygen in the polymerization kettle, stirring until the oxygen is dissolved, placing the polymerization kettle in an ice bath condition, adding 4,4' -dihydroxydiphenyl sulfone into a polymer, removing the ice bath after the oxygen is added, adding an accelerator into the polymerization kettle under the stirring condition, adding the accelerator, raising the temperature, stirring for 1-2 hours at the temperature of 50-60 ℃, steaming to remove the solvent, cooling and discharging to obtain the product, namely the polyester oligomer.
3. A functional polyester elastomer material according to claim 2, characterized in that the molar ratio of 1, 3-adamantane dicarboxylic acid dichloride and 4,4' -dihydroxydiphenyl sulfone is 1:0.8-0.9.
4. A functional polyester elastomer material according to claim 2, wherein the accelerator is triethylamine or pyridine.
5. A functional polyester elastomer material according to claim 1, characterized in that the polytetrahydrofuran branching agent is prepared by the following specific steps:
step A, preparation of mono-epoxy end capped polytetrahydrofuran
Stirring and mixing polytetrahydrofuran ether glycol and tetrabutylammonium chloride to form a uniform solution, preheating the solution to 40-50 ℃, adding epichlorohydrin into the solution under the condition of continuous stirring, further raising the temperature to 55-60 ℃, adding sodium hydroxide into the solution after the addition is finished, stirring at constant temperature for 2-4h, cooling and discharging to obtain a product, namely monoepoxy end capped polytetrahydrofuran;
step B, preparation of polytetrahydrofuran branching agent
And (3) mixing the monoepoxy-terminated polytetrahydrofuran and the 4,4' -diaminodiphenylamine, mechanically stirring and uniformly mixing, starting heating, raising the temperature to 60-65 ℃, maintaining for 3-6 hours under the condition of continuous stirring, cooling and discharging, and purifying to obtain the product, namely the polytetrahydrofuran branching agent.
6. A functional polyester elastomer material according to claim 5, wherein in step a, the molar ratio of polytetrahydrofuran ether glycol to epichlorohydrin is 1:0.4-0.5.
7. A functional polyester elastomer material according to claim 5, wherein in step a the polytetrahydrofuran ether glycol has a number average molecular weight of 250 to 650.
8. A functional polyester elastomer material according to claim 5, wherein in step B the molar ratio of mono-epoxy-terminated polytetrahydrofuran to 4,4' -diaminodiphenylamine is 1:2.
9. The functional polyester elastomer material of claim 1, wherein the low molecular diol is at least one of ethylene glycol, 1, 3-propanediol, or 1, 4-butanediol; the catalyst is tetrabutyl titanate.
10. A method of producing a functional polyester elastomer material as claimed in claim 1, comprising the specific steps of:
first step, preparation of prepolymer
Sequentially adding the polyester oligomer, the low molecular diol and the catalyst into a polymerization kettle, introducing nitrogen to discharge air in the kettle, controlling the temperature in the kettle to be 100-120 ℃, controlling the stirring speed to be 800-1000r/min, and stirring for reacting for 1-2h to form a prepolymer;
Second step, preparation of polyester elastomer Material
And adding a polytetrahydrofuran branching agent into the prepolymer, after the polytetrahydrofuran branching agent is added, further raising the temperature in the kettle to 150-160 ℃, carrying out polycondensation reaction for 1-2h, and cooling and discharging after the reaction is finished, thus obtaining the polyester elastomer material.
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