CN117285804B - Method for preparing polybutylene terephthalate and application thereof - Google Patents
Method for preparing polybutylene terephthalate and application thereof Download PDFInfo
- Publication number
- CN117285804B CN117285804B CN202311284998.8A CN202311284998A CN117285804B CN 117285804 B CN117285804 B CN 117285804B CN 202311284998 A CN202311284998 A CN 202311284998A CN 117285804 B CN117285804 B CN 117285804B
- Authority
- CN
- China
- Prior art keywords
- polybutylene terephthalate
- parts
- glycidyl methacrylate
- carbon nanotubes
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001707 polybutylene terephthalate Polymers 0.000 title claims abstract description 82
- -1 polybutylene terephthalate Polymers 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 93
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 64
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 64
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 49
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229920001577 copolymer Polymers 0.000 claims abstract description 38
- 238000010438 heat treatment Methods 0.000 claims abstract description 38
- IHEDBVUTTQXGSJ-UHFFFAOYSA-M 2-[bis(2-oxidoethyl)amino]ethanolate;titanium(4+);hydroxide Chemical class [OH-].[Ti+4].[O-]CCN(CC[O-])CC[O-] IHEDBVUTTQXGSJ-UHFFFAOYSA-M 0.000 claims abstract description 36
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003063 flame retardant Substances 0.000 claims abstract description 35
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000004970 Chain extender Substances 0.000 claims abstract description 20
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 20
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 72
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 25
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 20
- 238000009210 therapy by ultrasound Methods 0.000 claims description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 9
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 claims description 9
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical group [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000002738 chelating agent Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000002048 multi walled nanotube Substances 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 239000002109 single walled nanotube Substances 0.000 claims description 5
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 5
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 5
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 5
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical group CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 4
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 206010000369 Accident Diseases 0.000 description 1
- LQLQDKBJAIILIQ-UHFFFAOYSA-N Dibutyl terephthalate Chemical compound CCCCOC(=O)C1=CC=C(C(=O)OCCCC)C=C1 LQLQDKBJAIILIQ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010892 electric spark Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to the technical field of polybutylene terephthalate, in particular to a method for preparing polybutylene terephthalate and application thereof; the raw materials comprise terephthalic acid, 1, 4-butanediol, carboxylated carbon nano tubes, modified triethanolamine titanate, glycidyl methacrylate grafted butadiene styrene copolymer, flame retardant, antioxidant and chain extender; according to the invention, terephthalic acid and 1, 4-butanediol are used for preparing polybutylene terephthalate in one step under the conditions of modified triethanolamine titanate and heating, glycidyl methacrylate is added for grafting butadiene styrene copolymer, flame retardant and carboxylated carbon nano tube during the preparation, and chemical bonds are connected to the main chain of polybutylene terephthalate.
Description
Technical Field
The invention relates to the technical field of polybutylene terephthalate, in particular to a method for preparing polybutylene terephthalate and application thereof.
Background
Polybutylene terephthalate (PBT), polyoxymethylene (POM), polyamide (PA), polyphenylene oxide (PPO) and Polycarbonate (PC) are commonly called as five-large engineering plastics, and polybutylene terephthalate is the most recently developed and fastest-growing general engineering plastic. In the early stage, polybutylene terephthalate was produced by a DMI method, namely, dimethyl terephthalate and 1, 4-butanediol are subjected to esterification reaction firstly, the products produced by the reaction are esterified product monomers of dibutyl terephthalate (BHBT) and methanol, and the products produced by the reaction are polymerized by the monomer BHBT to produce PBT, and meanwhile, 1, 4-butanediol is separated and esterification byproducts are produced. The polybutylene terephthalate has better oil resistance, acid resistance, alkali resistance, thermal aging resistance and fatigue resistance, excellent mechanical property, high mechanical strength, good dimensional stability, easy molding processing and secondary processing, and is widely applied to various engineering processing. However, polybutylene terephthalate has obvious disadvantages of low impact strength, flammability, high insulation of PBT, easy generation of static electricity, even fire accident caused by electric spark, great threat to life and property safety of people, and the disadvantages limit the application and development of polybutylene terephthalate, especially in the fields of aerospace, electronics and the like with more strict safety requirements. This requires polybutylene terephthalate to optimize its properties and increase its toughness, flame retardant properties and antistatic properties.
Therefore, the production of polybutylene terephthalate enhances the toughness, improves the flame retardant property and the antistatic property, and has positive significance in further reducing the production cost.
Disclosure of Invention
The invention aims to provide a method for preparing polybutylene terephthalate and application thereof, wherein the preparation method is simple, the operation is simple, the raw material utilization rate is high, and the prepared polybutylene terephthalate has good flame retardance, strong antistatic property and high toughness, and can be applied to plastic products with high requirements on impact resistance and antistatic property.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the method for preparing the polybutylene terephthalate comprises the following raw materials in parts by weight: 40-60 parts of terephthalic acid, 55-85 parts of 1, 4-butanediol, 2-5 parts of carboxylated carbon nanotubes, 2-3 parts of modified triethanolamine titanate, 8-18 parts of glycidyl methacrylate grafted butadiene styrene copolymer, 4-6 parts of flame retardant, 0.5-1 part of antioxidant and 0.5-1 part of chain extender;
The preparation method of the polybutylene terephthalate comprises the following steps:
Step one: respectively placing modified triethanolamine titanate, glycidyl methacrylate grafted butadiene styrene copolymer, flame retardant and carboxylated carbon nanotubes in an oven at 80-90 ℃ and drying for 8-12 h;
step two: putting terephthalic acid and 1, 4-butanediol in parts by weight into a reaction kettle, introducing nitrogen, evacuating, rapidly adding dried modified triethanolamine titanate, glycidyl methacrylate grafted butadiene styrene copolymer, a flame retardant, carboxylated carbon nano tubes, an antioxidant and a chain extender, stirring at a speed of 80-120 r/min, reacting at 180-190 ℃ for 4-6 h to obtain a mixture;
Step three: and (3) vacuumizing the reaction kettle of the mixture obtained in the step two, heating to 240-250 ℃ under the vacuum degree of 1-50 Pa, continuously stirring at the speed of 80-120 r/min, reacting for 4-6 h, discharging after the reaction is finished, and performing hot press molding to obtain the polybutylene terephthalate.
Further preferably, the modified triethanolamine titanate is prepared by taking 10g of granular activated carbon, drying at 110-120 ℃ for 8-10 h, transferring to a reaction kettle, adding 3-5 g of tetrabutyl titanate, vacuumizing to 1X 10 -4～3×10-4 Pa, maintaining pressure for 1-2 h, heating to 50-70 ℃, stirring for 0.5-1 h, opening the reaction kettle, rapidly adding 3-5 g of triethanolamine, adding 0.2g of potassium hydroxide, stirring while vacuumizing, vacuumizing to 1X 10 -3～3×10-3 Pa, heating to 80-100 ℃, stirring for 1-2 h, heating to 180-220 ℃, preserving heat and maintaining pressure for 0.5-1 h, cooling to room temperature at a speed of 5 ℃/min, taking out, grinding, and sieving with a 200-mesh sieve to obtain the modified triethanolamine titanate.
The granular activated carbon is of a porous structure, active sites in the granular activated carbon are re-exposed after vacuum drying, the adsorption capacity is enhanced, tetrabutyl titanate is added, negative pressure is applied, the tetrabutyl titanate is adsorbed into the granular activated carbon, the tetrabutyl titanate is firmly adsorbed by the active sites in the granular activated carbon through heating, triethanolamine is added again, and under the actions of low vacuum, heating and potassium hydroxide base catalysis, the triethanolamine and the tetrabutyl titanate undergo transesterification, so that the waterproof protection of the tetrabutyl titanate is realized, and the prepared carbon-loaded titanium catalyst has good waterproof performance.
The transesterification reaction of triethanolamine and tetrabutyl titanate is as follows:
Further preferably, the glycidyl methacrylate grafted butadiene styrene copolymer is prepared by adding 10g of butadiene and 8g of styrene into a reaction kettle, evacuating with nitrogen, heating to 30-50 ℃, reacting for 10-20 min, adding 8-10 g of glycidyl methacrylate, adding 1-2 g of chelating agent sodium pyrophosphate, heating to 60-100 ℃ and reacting for 30-60 min to obtain the glycidyl methacrylate grafted butadiene styrene copolymer. Butadiene and styrene are subjected to polymerization reaction under the condition of heating to form a chain polymer, then glycidyl methacrylate is added, and the chain polymer is polymerized again to a main chain through double bond polymerization under the auxiliary action of heating and chelating agents to form the glycidyl methacrylate grafted butadiene styrene copolymer with benzene rings, ester bonds and epoxy groups, and complex functional groups are introduced into the polybutylene terephthalate in the subsequent polymerization reaction process of the polybutylene terephthalate, so that the rigidity and toughness of the polybutylene terephthalate are improved.
Wherein the reactions involved in butadiene, styrene and glycidyl methacrylate are:
Further preferably, the flame retardant is aluminum borate whisker and diethyl aluminum hypophosphite with the mass ratio of 3: 2-3, and uniformly mixing to obtain a compound mixture.
Further preferably, the carboxylated carbon nanotubes are prepared by placing 10g of carbon nanotubes into a reaction vessel, wherein the carbon nanotubes are single-wall carbon nanotubes and multi-wall carbon nanotubes according to a mass ratio of 1: 4-6; mixing 60g of sulfuric acid and 20g of nitric acid to prepare a mixed acid solution; adding the prepared mixed acid solution into a reaction container, covering the reaction container, putting the reaction container into an ultrasonic water bath at 80 ℃, intermittently carrying out ultrasonic treatment for 4-6 hours at 400W power, carrying out ultrasonic treatment for 20 minutes each time, suspending ultrasonic treatment for 5 minutes, washing the carbon nano tube with deionized water until the pH value is 7 after ultrasonic treatment is finished, and drying to obtain the carboxylated carbon nano tube.
The mass ratio of sulfuric acid to nitric acid is 3:1, carrying out carboxylation modification on carbon nano-tubes, realizing corrosion on the surfaces of the carbon nano-tubes, introducing carboxylic acid functional groups in the corrosion process, so that the surfaces of the formed carboxylated carbon nano-tubes are rich in carboxylic acid structures, in-situ compatibilization between the carbon nano-tubes and glycidyl methacrylate grafted butadiene styrene copolymer and polybutylene terephthalate is facilitated, an integral structure connected by chemical bonds is formed, and finally, introducing the carbon nano-tubes into the polybutylene terephthalate, and improving the strength and antistatic performance of the polybutylene terephthalate.
The reaction involved in carboxylating the modified carbon nanotubes is:
Further preferably, the antioxidant is 2, 6-di-tert-butyl-p-cresol or 4,4' -methylenebis (2, 6-di-tert-butylphenol); the chain extender is one or more of methyl methacrylate, glycidyl methacrylate, ethyl acrylate and vinyl acetate.
Further preferably, the second step of the preparation method of the polybutylene terephthalate is to react under normal pressure and nitrogen atmosphere; and thirdly, carrying out the reaction under low air pressure, namely, nitrogen atmosphere, and in order to maintain the low air pressure and the nitrogen atmosphere in the third step, vacuumizing the reaction kettle so that the air pressure is lower than 3 multiplied by 10 -4 Pa, and then adjusting the flow of the nitrogen and the opening of a vacuumizing valve so that the vacuum degree is maintained at 1-50 Pa.
Further preferably, in the third step of the preparation method of the polybutylene terephthalate, after the reaction is finished, hot-press molding is performed, and the material is discharged while hot, directly transferred into a die or equipment for hot-press molding, and hot-press molded under a nitrogen atmosphere.
Further preferably, the material comprises the following raw materials in parts by weight: 50 parts of terephthalic acid, 65 parts of 1, 4-butanediol, 3 parts of carboxylated carbon nanotubes, 3 parts of modified triethanolamine titanate, 12 parts of glycidyl methacrylate grafted butadiene styrene copolymer, 5 parts of flame retardant, 0.8 part of antioxidant and 0.8 part of chain extender.
Further preferably, the polybutylene terephthalate can be applied to plastic products with high requirements on impact resistance and static resistance, such as automobile circuit plastic protective shells, outdoor energy-saving lamp protective covers and the like.
Under the action of catalyst modified triethanolamine titanate, terephthalic acid and 1, 4-butanediol mainly undergo esterification reaction at 180-190 ℃, and then undergo polycondensation reaction at 240-250 ℃ and low pressure, and finally form polybutylene terephthalate, which is the main reaction, and the involved reactions are:
in addition, in the process of preparing polybutylene terephthalate, the glycidyl methacrylate grafted butadiene styrene copolymer and the carboxylated carbon nanotubes participate in the reaction at the same time, and substances linked by chemical bonds are formed, wherein the reactions possibly involved are:
the invention has the beneficial effects that:
1. The basic raw materials of preparing polybutylene terephthalate from terephthalic acid and 1, 4-butanediol are subjected to esterification reaction and polycondensation reaction in one step under the action of a catalyst and heating, and the preparation method is simple, easy to operate and high in raw material utilization rate; in the process of preparing the polybutylene terephthalate, the glycidyl methacrylate grafted butadiene styrene copolymer, the flame retardant and the carboxylated carbon nano tube are added, so that the glycidyl methacrylate grafted butadiene styrene copolymer and the carboxylated carbon nano tube are connected to the main chain of the polybutylene terephthalate in a chemical bond mode, the toughness and antistatic performance of the polybutylene terephthalate are improved, the flame retardant is a mixture of aluminum borate whisker and diethyl aluminum hypophosphite, and the whisker-shaped structure and the carboxylated carbon nano tube enhance the strength of the polybutylene terephthalate together while the flame retardant performance of the polybutylene terephthalate is improved.
2. The modified triethanolamine titanate is used as a titanium catalyst, activated carbon is used as a carrier, the activated carbon has a larger specific surface area and rich pore channel structures, the contact area between the titanium catalyst and reaction materials can be increased after the modified triethanolamine titanate is loaded, the catalytic effect is increased, and the rapid and efficient reaction is facilitated; in addition, when the modified triethanolamine titanate is prepared, activated carbon is firstly used for adsorbing tetrabutyl titanate, triethylamine is used for carrying out transesterification with tetrabutyl titanate, and the tetrabutyl titanate is subjected to water resistance modification, so that the prepared carbon-loaded modified triethanolamine titanate has better water resistance than pure tetrabutyl titanate, does not hydrolyze or seldom hydrolyze when meeting water, is beneficial to protecting the catalytic activity of the carbon-loaded modified triethanolamine titanate and prolonging the recycling service life of the carbon-loaded modified triethanolamine titanate, and has fewer inactive titanium catalysts and fewer titanium elements in the polybutylene terephthalate, is beneficial to reducing the cost increase caused by the supplement of the catalyst, and ensures the purity of the polybutylene terephthalate.
3. The glycidyl methacrylate grafted butadiene styrene copolymer is polymerized into a complex side chain structure containing benzene rings and epoxy functional groups by using butadiene, styrene and glycidyl methacrylate, and can be grafted on a main chain of polybutylene terephthalate through ring opening reaction, so that the side chain structure is introduced into the benzene rings of the polybutylene terephthalate, the single linear chain structure of the polybutylene terephthalate can be improved into a complex structure with linear chain and branched chain to a certain extent, the toughness of the polybutylene terephthalate is improved, the number of benzene rings is increased, and the impact strength of the polybutylene terephthalate is increased; in addition, the glycidyl methacrylate grafted butadiene styrene copolymer can be grafted with carboxylated carbon nanotubes in the raw materials, so that the compatibility of the polybutylene terephthalate and the carboxylated carbon nanotubes is improved, and the toughness and the impact resistance of the prepared polybutylene terephthalate are further ensured.
4. The flame retardant is a compound mixture of aluminum borate whisker and diethyl aluminum hypophosphite, and the diethyl aluminum hypophosphite with good flame retardant effect and whisker-shaped aluminum borate are compounded, so that the whisker structure can form a crisscross structure in the finally prepared polybutylene terephthalate while ensuring good flame retardant effect, and the toughness and strength can be increased; the diethyl aluminum hypophosphite contains diethyl and has good compatibility with the polybutylene terephthalate, and the strength of the polybutylene terephthalate is not reduced due to the introduction of the flame retardant.
5. The carboxylated carbon nanotubes are carboxylated carbon nanotubes, under the action of ultrasound, strong acid is used for modifying the carbon nanotubes, and carboxylic acid functional groups are formed on the carbon nanotubes, so that the carbon nanotubes can be connected with polybutylene terephthalate or glycidyl methacrylate grafted butadiene styrene copolymer through chemical bonds, the compatibility of the carbon nanotubes in polybutylene terephthalate is enhanced, and meanwhile, the carbon nanotubes connected with the chemical bonds can better exert the antistatic performance of the carbon nanotubes in polybutylene terephthalate, and the toughness and strength of the polybutylene terephthalate are enhanced in an auxiliary manner. The antioxidant and the chain extender in other assistants can further ensure the oxidation resistance of the prepared polybutylene terephthalate, increase the length of a main chain or a branched chain and ensure the performance of the polybutylene terephthalate.
Detailed Description
The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are only some, but not all, of the embodiments of the present invention. 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
The method for preparing the polybutylene terephthalate comprises the following raw materials in parts by weight: 40 parts of terephthalic acid, 55 parts of 1, 4-butanediol, 2 parts of carboxylated carbon nanotubes, 2 parts of modified triethanolamine titanate, 8 parts of glycidyl methacrylate grafted butadiene styrene copolymer, 4 parts of flame retardant, 0.5 part of antioxidant and 0.5 part of chain extender;
The modified triethanolamine titanate is prepared by taking 10g of granular activated carbon, drying at 110 ℃ for 8 hours, transferring to a reaction kettle, adding 3g of tetrabutyl titanate, vacuumizing to 1X 10 -4 Pa, maintaining pressure for 1 hour, heating to 50 ℃, stirring for 0.5 hour, opening the reaction kettle, rapidly adding 3g of triethanolamine, adding 0.2g of potassium hydroxide, vacuumizing while stirring, vacuumizing to 1X 10 -3 Pa, heating to 80 ℃, stirring for 1 hour, heating to 180 ℃, preserving heat and maintaining pressure for 0.5 hour, cooling to room temperature at a speed of 5 ℃/min, taking out, grinding, and sieving with a 200-mesh sieve to obtain the modified triethanolamine titanate;
The glycidyl methacrylate grafted butadiene-styrene copolymer is prepared by adding 10g of butadiene and 8g of styrene into a reaction kettle, evacuating with nitrogen, heating to 30 ℃, reacting for 10min, adding 8g of glycidyl methacrylate, adding 1g of chelating agent sodium pyrophosphate, heating to 60 ℃, and reacting for 30min to obtain the glycidyl methacrylate grafted butadiene-styrene copolymer;
The carboxylated carbon nanotubes are prepared by putting 10g of carbon nanotubes into a reaction container, wherein the carbon nanotubes are single-wall carbon nanotubes and multi-wall carbon nanotubes according to the mass ratio of 1:4, mixing; mixing 60g of sulfuric acid and 20g of nitric acid to prepare a mixed acid solution; adding the prepared mixed acid solution into a reaction container, covering the reaction container, putting the reaction container into an ultrasonic water bath at 80 ℃, intermittently performing ultrasonic treatment for 4 hours at 400W power, performing ultrasonic treatment for 5 minutes every 20 minutes, washing the carbon nano tube with deionized water until the pH value is 7 after the ultrasonic treatment is finished, and drying to obtain carboxylated carbon nano tubes;
The flame retardant is aluminum borate whisker and diethyl aluminum hypophosphite according to the mass ratio of 3:2, uniformly mixing to obtain a compound mixture; the antioxidant is 2, 6-di-tert-butyl-p-cresol; the chain extender is methyl methacrylate;
The preparation method of the polybutylene terephthalate comprises the following steps:
Step one: respectively placing modified triethanolamine titanate, glycidyl methacrylate grafted butadiene-styrene copolymer, flame retardant and carboxylated carbon nanotubes in an oven at 80 ℃ in parts by weight, and drying for 8 hours;
Step two: putting terephthalic acid and 1, 4-butanediol in parts by weight into a reaction kettle, introducing nitrogen, emptying, rapidly adding dried modified triethanolamine titanate, glycidyl methacrylate grafted butadiene styrene copolymer, a flame retardant, carboxylated carbon nano tubes, an antioxidant and a chain extender under the normal pressure and nitrogen atmosphere, stirring at a speed of 80r/min, reacting for 4 hours at 180 ℃ to obtain a mixture;
Step three: and (3) vacuumizing the reaction kettle of the mixture obtained in the step two, carrying out reaction under low pressure, namely, nitrogen atmosphere, and in order to maintain the low pressure and the nitrogen atmosphere of the step three, vacuumizing the reaction kettle first, so that the air pressure is lower than 3X 10 - 4 Pa, then adjusting the flow of nitrogen and the opening size of a vacuumizing valve, so that the vacuum degree is 1Pa, heating to 240 ℃, continuously stirring at the speed of 80r/min, reacting for 4 hours, discharging after the reaction is finished, hot-press forming, discharging while the hot, directly transferring into a die or equipment for hot-press forming, and carrying out hot-press forming under the nitrogen atmosphere to obtain the polybutylene terephthalate.
Example 2
The method for preparing the polybutylene terephthalate comprises the following raw materials in parts by weight: 60 parts of terephthalic acid, 85 parts of 1, 4-butanediol, 5 parts of carboxylated carbon nanotubes, 3 parts of modified triethanolamine titanate, 18 parts of glycidyl methacrylate grafted butadiene styrene copolymer, 6 parts of flame retardant, 1 part of antioxidant and 1 part of chain extender;
The modified triethanolamine titanate is prepared by taking 10g of granular activated carbon, drying at 120 ℃ for 10 hours, transferring to a reaction kettle, adding 5g of tetrabutyl titanate, vacuumizing to 3X 10 -4 Pa, maintaining pressure for 2 hours, heating to 70 ℃, stirring for 1 hour, opening the reaction kettle, rapidly adding 5g of triethanolamine, adding 0.2g of potassium hydroxide, vacuumizing while stirring to 3X 10 -3 Pa, heating to 100 ℃, stirring for 2 hours, heating to 220 ℃, preserving heat and maintaining pressure for 1 hour, cooling to room temperature at a speed of 5 ℃/min, taking out, grinding, and sieving with a 200-mesh sieve to obtain the modified triethanolamine titanate;
The glycidyl methacrylate grafted butadiene-styrene copolymer is prepared by adding 10g of butadiene and 8g of styrene into a reaction kettle, evacuating with nitrogen, heating to 50 ℃, reacting for 20min, adding 10g of glycidyl methacrylate, adding 2g of chelating agent sodium pyrophosphate, heating to 100 ℃, and reacting for 60min to obtain the glycidyl methacrylate grafted butadiene-styrene copolymer;
the carboxylated carbon nanotubes are prepared by putting 10g of carbon nanotubes into a reaction container, wherein the carbon nanotubes are single-wall carbon nanotubes and multi-wall carbon nanotubes according to the mass ratio of 1:6, mixing; mixing 60g of sulfuric acid and 20g of nitric acid to prepare a mixed acid solution; adding the prepared mixed acid solution into a reaction container, covering the reaction container, putting the reaction container into an ultrasonic water bath at 80 ℃, intermittently performing ultrasonic treatment for 6 hours at 400W power, performing ultrasonic treatment for 20 minutes each time, suspending ultrasonic treatment for 5 minutes, washing the carbon nano tube with deionized water until the pH value is 7 after the ultrasonic treatment is finished, and drying to obtain carboxylated carbon nano tubes;
The flame retardant is aluminum borate whisker and diethyl aluminum hypophosphite according to the mass ratio of 3:3, uniformly mixing to obtain a compound mixture; the antioxidant is 4,4' -methylenebis (2, 6-di-tert-butylphenol); the chain extender is glycidyl methacrylate;
The preparation method of the polybutylene terephthalate comprises the following steps:
Step one: respectively placing modified triethanolamine titanate, glycidyl methacrylate grafted butadiene-styrene copolymer, flame retardant and carboxylated carbon nanotubes in a baking oven at 90 ℃ and drying for 12 hours;
Step two: putting terephthalic acid and 1, 4-butanediol in parts by weight into a reaction kettle, introducing nitrogen, emptying, rapidly adding dried modified triethanolamine titanate, glycidyl methacrylate grafted butadiene styrene copolymer, a flame retardant, carboxylated carbon nano tubes, an antioxidant and a chain extender under the normal pressure and nitrogen atmosphere, stirring at the speed of 120r/min, reacting at the nitrogen flow rate of 40ml/min for 6 hours at the temperature of 190 ℃ to obtain a mixture;
step three: and (3) vacuumizing the reaction kettle of the mixture obtained in the step two, carrying out reaction under low pressure, namely, nitrogen atmosphere, and in order to maintain the low pressure and the nitrogen atmosphere of the step three, vacuumizing the reaction kettle so that the air pressure is lower than 3X 10 - 4 Pa, adjusting the flow of nitrogen and the opening size of a vacuumizing valve so that the vacuum degree is 50Pa, heating to 250 ℃, continuously stirring at the speed of 120r/min, reacting for 6 hours, discharging after the reaction is finished, carrying out hot press forming, discharging while the material is hot, directly transferring into a die or equipment for the hot press forming, and carrying out hot press forming under the nitrogen atmosphere to obtain the polybutylene terephthalate.
Example 3
The method for preparing the polybutylene terephthalate comprises the following raw materials in parts by weight: 50 parts of terephthalic acid, 65 parts of 1, 4-butanediol, 3 parts of carboxylated carbon nanotubes, 2 parts of modified triethanolamine titanate, 12 parts of glycidyl methacrylate grafted butadiene styrene copolymer, 5 parts of flame retardant, 0.7 part of antioxidant and 0.8 part of chain extender;
the modified triethanolamine titanate is prepared by taking 10g of granular activated carbon, drying at 115 ℃ for 9 hours, transferring to a reaction kettle, adding 4g of tetrabutyl titanate, vacuumizing to 2X 10 -4 Pa, maintaining pressure for 2 hours, heating to 60 ℃, stirring for 0.7 hours, opening the reaction kettle, rapidly adding 4g of triethanolamine, adding 0.2g of potassium hydroxide, vacuumizing while stirring, vacuumizing to 2X 10 -3 Pa, heating to 90 ℃, stirring for 2 hours, heating to 200 ℃, preserving heat and maintaining pressure for 0.7 hours, cooling to room temperature at a speed of 5 ℃/min, taking out, grinding, and sieving with a 200-mesh sieve to obtain the modified triethanolamine titanate;
The glycidyl methacrylate grafted butadiene-styrene copolymer is prepared by adding 10g of butadiene and 8g of styrene into a reaction kettle, evacuating with nitrogen, heating to 40 ℃, reacting for 15min, adding 9g of glycidyl methacrylate, adding 2g of sodium pyrophosphate serving as a chelating agent, heating to 80 ℃, and reacting for 40min to obtain the glycidyl methacrylate grafted butadiene-styrene copolymer;
The carboxylated carbon nanotubes are prepared by putting 10g of carbon nanotubes into a reaction container, wherein the carbon nanotubes are single-wall carbon nanotubes and multi-wall carbon nanotubes according to the mass ratio of 1:5, mixing; mixing 60g of sulfuric acid and 20g of nitric acid to prepare a mixed acid solution; adding the prepared mixed acid solution into a reaction container, covering the reaction container, putting the reaction container into an ultrasonic water bath at 80 ℃, intermittently performing ultrasonic treatment for 5 hours at 400W power, performing ultrasonic treatment for 20 minutes each time, suspending ultrasonic treatment for 5 minutes, washing the carbon nano tube with deionized water until the pH value is 7 after the ultrasonic treatment is finished, and drying to obtain carboxylated carbon nano tubes;
The flame retardant is aluminum borate whisker and diethyl aluminum hypophosphite according to the mass ratio of 3:3, uniformly mixing to obtain a compound mixture; the antioxidant is 2, 6-di-tert-butyl-p-cresol; the chain extender is ethyl acrylate;
The preparation method of the polybutylene terephthalate comprises the following steps:
Step one: respectively placing modified triethanolamine titanate, glycidyl methacrylate grafted butadiene styrene copolymer, flame retardant and carboxylated carbon nanotubes in an oven at 85 ℃ and drying for 10 hours;
Step two: putting terephthalic acid and 1, 4-butanediol in parts by weight into a reaction kettle, introducing nitrogen, emptying, rapidly adding dried modified triethanolamine titanate, glycidyl methacrylate grafted butadiene styrene copolymer, a flame retardant, carboxylated carbon nano tubes, an antioxidant and a chain extender under the normal pressure and nitrogen atmosphere, stirring at the speed of 100r/min, reacting for 5 hours at 185 ℃ to obtain a mixture;
Step three: and (3) vacuumizing the reaction kettle of the mixture obtained in the step two, carrying out reaction under low pressure, namely, nitrogen atmosphere, and in order to maintain the low pressure and the nitrogen atmosphere of the step three, vacuumizing the reaction kettle so that the air pressure is lower than 3X 10 - 4 Pa, adjusting the flow of nitrogen and opening the vacuumizing valve so that the vacuum degree is 25Pa, heating to 245 ℃, continuously stirring at the speed of 100r/min, reacting for 5 hours, discharging after the reaction is finished, carrying out hot press forming, discharging while the material is hot, directly transferring into a die or equipment for the hot press forming, and carrying out hot press forming under the nitrogen atmosphere to obtain the polybutylene terephthalate.
Comparative example: polybutylene terephthalate was prepared using terephthalic acid, 1, 4-butanediol, and modified triethanolamine titanate, and the other conditions were the same as in example 1 except that glycidyl methacrylate was not used to graft butadiene styrene copolymer, flame retardant, carboxylated carbon nanotubes, antioxidant, and chain extender.
And (3) testing: the polybutylene terephthalate prepared in examples 1 to 3 and comparative example was subjected to performance test. Wherein the thermal properties are: the melting point is obtained by a differential scanning thermal analyzer (DSC), the scanning temperature range is 30-300 ℃, the heating rate is 10 ℃/min, the thermal weight loss temperature is obtained by a thermal gravimetric analyzer (TG), the scanning temperature range is 30-700 ℃, and the heating rate is 10 ℃/min; mechanical property test: the tensile property is tested by adopting a universal testing machine and referring to GB/T1040-2018, the notch impact strength is tested by adopting a cantilever beam impact testing machine and referring to GB/T1043.1-2008, and the higher the notch impact strength is, the stronger the toughness is; the antistatic performance is characterized by surface resistivity, and is tested by referring to standard GB/T1410-2006, and the smaller the surface resistivity is, the stronger the antistatic performance is.
| Example 1 | Example 2 | Example 3 | Comparative example | |
| Melting point (. Degree. C.) | 228.7 | 234.1 | 231.4 | 221.3 |
| Thermal weight loss temperature (. Degree. C.) | 478 | 492 | 485 | 425 |
| Tensile Strength (MPa) | 72.5 | 83.7 | 76.8 | 51.2 |
| Notched impact strength (KJ/m 2) | 45.8 | 51.2 | 46.7 | 8.4 |
| Surface resistivity (Ω) | 2×107 | 5×106 | 8×106 | 5×1014 |
As shown in the table, the polybutylene terephthalate prepared by the method has better thermal performance, the melting point and the thermal weight loss temperature are improved, the flame retardant performance is improved, the tensile strength and the notch impact strength are increased, the mechanical performance is improved, the strength and the toughness are enhanced, the surface resistivity is reduced, and the antistatic performance is enhanced.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (7)
1. The method for preparing the polybutylene terephthalate is characterized by comprising the following raw materials in parts by mass: 40-60 parts of terephthalic acid, 55-85 parts of 1, 4-butanediol, 2-5 parts of carboxylated carbon nanotubes, 2-3 parts of modified triethanolamine titanate, 8-18 parts of glycidyl methacrylate grafted butadiene styrene copolymer, 4-6 parts of flame retardant, 0.5-1 part of antioxidant and 0.5-1 part of chain extender;
The preparation method of the polybutylene terephthalate comprises the following steps:
Step one: respectively placing modified triethanolamine titanate, glycidyl methacrylate grafted butadiene styrene copolymer, flame retardant and carboxylated carbon nanotubes in an oven at 80-90 ℃ and drying for 8-12 h;
step two: putting terephthalic acid and 1, 4-butanediol in parts by weight into a reaction kettle, introducing nitrogen, evacuating, rapidly adding dried modified triethanolamine titanate, glycidyl methacrylate grafted butadiene styrene copolymer, a flame retardant, carboxylated carbon nano tubes, an antioxidant and a chain extender, stirring at a speed of 80-120 r/min, reacting at 180-190 ℃ for 4-6 h to obtain a mixture;
Step three: vacuumizing the reaction kettle of the mixture obtained in the step two to ensure that the vacuum degree is 1-50 Pa, heating to 240-250 ℃, continuously stirring at the speed of 80-120 r/min, reacting for 4-6 h, discharging after the reaction is finished, and performing hot press molding to obtain polybutylene terephthalate;
The modified triethanolamine titanate is prepared by taking 10g of granular activated carbon, drying at 110-120 ℃ for 8-10 h, transferring to a reaction kettle, adding 3-5 g of tetrabutyl titanate, vacuumizing to 1X 10 -4～3×10-4 Pa, maintaining pressure for 1-2 h, heating to 50-70 ℃, stirring for 0.5-1 h, opening the reaction kettle, rapidly adding 3-5 g of triethanolamine, adding 0.2g of potassium hydroxide, vacuumizing to 1X 10 -3～3×10-3 Pa while stirring, heating to 80-100 ℃ and stirring for 1-2 h, heating to 180-220 ℃, preserving heat and maintaining pressure for 0.5-1 h, cooling to room temperature at a speed of 5 ℃/min, taking out, grinding, and sieving with a 200-mesh sieve to obtain the modified triethanolamine;
The glycidyl methacrylate grafted butadiene-styrene copolymer is prepared by adding 10g of butadiene and 8g of styrene into a reaction kettle, evacuating with nitrogen, heating to 30-50 ℃, reacting for 10-20 min, adding 8-10 g of glycidyl methacrylate, adding 1-2 g of chelating agent sodium pyrophosphate, heating to 60-100 ℃ and reacting for 30-60 min to obtain the glycidyl methacrylate grafted butadiene-styrene copolymer;
The carboxylated carbon nanotubes are prepared by putting 10g of carbon nanotubes into a reaction container, wherein the carbon nanotubes are single-wall carbon nanotubes and multi-wall carbon nanotubes according to the mass ratio of 1: 4-6; mixing 60g of sulfuric acid and 20g of nitric acid to prepare a mixed acid solution; adding the prepared mixed acid solution into a reaction container, covering the reaction container, putting the reaction container into an ultrasonic water bath at 80 ℃, intermittently carrying out ultrasonic treatment for 4-6 hours at 400W power, carrying out ultrasonic treatment for 20 minutes each time, suspending ultrasonic treatment for 5 minutes, washing the carbon nano tube with deionized water until the pH value is 7 after ultrasonic treatment is finished, and drying to obtain the carboxylated carbon nano tube.
2. The method of polybutylene terephthalate according to claim 1, characterized in that: the flame retardant is aluminum borate whisker and diethyl aluminum hypophosphite according to the mass ratio of 3: 2-3, and uniformly mixing to obtain a compound mixture.
3. The method of polybutylene terephthalate according to claim 1, characterized in that: the antioxidant is 2, 6-di-tert-butyl-p-cresol or 4,4' -methylenebis (2, 6-di-tert-butylphenol); the chain extender is one or more of methyl methacrylate, glycidyl methacrylate, ethyl acrylate and vinyl acetate.
4. The method of polybutylene terephthalate according to claim 1, characterized in that: the second step of the preparation method of the polybutylene terephthalate is to react under normal pressure and nitrogen atmosphere; and thirdly, carrying out the reaction under low air pressure, namely, nitrogen atmosphere, and in order to maintain the low air pressure and the nitrogen atmosphere in the third step, vacuumizing the reaction kettle so that the air pressure is lower than 3 multiplied by 10 -4 Pa, and then adjusting the flow of the nitrogen and the opening of a vacuumizing valve so that the vacuum degree is maintained at 1-50 Pa.
5. The method of polybutylene terephthalate according to claim 1, characterized in that: in the third step of the preparation method of the polybutylene terephthalate, after the reaction is finished, hot-press molding is carried out, the material is discharged while the material is hot, and the material is directly transferred into a die or equipment for hot-press molding and hot-press molding is carried out in a nitrogen atmosphere.
6. The method of polybutylene terephthalate according to claim 1, characterized in that: the material comprises the following raw materials in parts by weight: 50 parts of terephthalic acid, 65 parts of 1, 4-butanediol, 3 parts of carboxylated carbon nanotubes, 3 parts of modified triethanolamine titanate, 12 parts of glycidyl methacrylate grafted butadiene styrene copolymer, 5 parts of flame retardant, 0.8 part of antioxidant and 0.8 part of chain extender.
7. Use of polybutylene terephthalate obtainable by the process according to any of claims 1 to 6 in plastic articles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311284998.8A CN117285804B (en) | 2023-10-07 | 2023-10-07 | Method for preparing polybutylene terephthalate and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311284998.8A CN117285804B (en) | 2023-10-07 | 2023-10-07 | Method for preparing polybutylene terephthalate and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117285804A CN117285804A (en) | 2023-12-26 |
| CN117285804B true CN117285804B (en) | 2024-04-30 |
Family
ID=89244183
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311284998.8A Active CN117285804B (en) | 2023-10-07 | 2023-10-07 | Method for preparing polybutylene terephthalate and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117285804B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110483957A (en) * | 2019-07-29 | 2019-11-22 | 江阴爱科森博顿聚合体有限公司 | A kind of preparation method of the dedicated PBT material of high rigidity optical cable |
| CN114672139A (en) * | 2022-05-07 | 2022-06-28 | 林淑红 | Biodegradable film blowing resin film and preparation method thereof |
| CN116003971A (en) * | 2022-10-19 | 2023-04-25 | 张余 | High-strength high-toughness biodegradable plastic and preparation method thereof |
| CN116102720A (en) * | 2023-02-09 | 2023-05-12 | 江苏金之虹新材料有限公司 | Poly (terephthalic acid) -carbonic acid-butanediol copolyester and preparation method thereof |
| CN116554490A (en) * | 2023-04-19 | 2023-08-08 | 沈阳化工大学 | Preparation method of nano silicon nitride particle grafted modified enhanced PBAT |
-
2023
- 2023-10-07 CN CN202311284998.8A patent/CN117285804B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110483957A (en) * | 2019-07-29 | 2019-11-22 | 江阴爱科森博顿聚合体有限公司 | A kind of preparation method of the dedicated PBT material of high rigidity optical cable |
| CN114672139A (en) * | 2022-05-07 | 2022-06-28 | 林淑红 | Biodegradable film blowing resin film and preparation method thereof |
| CN116003971A (en) * | 2022-10-19 | 2023-04-25 | 张余 | High-strength high-toughness biodegradable plastic and preparation method thereof |
| CN116102720A (en) * | 2023-02-09 | 2023-05-12 | 江苏金之虹新材料有限公司 | Poly (terephthalic acid) -carbonic acid-butanediol copolyester and preparation method thereof |
| CN116554490A (en) * | 2023-04-19 | 2023-08-08 | 沈阳化工大学 | Preparation method of nano silicon nitride particle grafted modified enhanced PBAT |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117285804A (en) | 2023-12-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108166095A (en) | A kind of hydrophilic antistatic graphene Modified polyester chips and preparation method thereof | |
| CN108598196B (en) | High-weather-resistance solar cell back plate and preparation method thereof | |
| CN117285804B (en) | Method for preparing polybutylene terephthalate and application thereof | |
| CN108329640A (en) | A kind of flame-proof environmental protection CABLE MATERIALS and preparation method thereof | |
| CN114395213B (en) | High-strength copper sheet commutator material and preparation method thereof | |
| CN109054307A (en) | A kind of weather-proof PET/PC alloy material of shock resistance and preparation method thereof | |
| CN115160562A (en) | Phosphorus-containing flame-retardant high-temperature-resistant copolymerized nylon and preparation method thereof | |
| CN113549307A (en) | Modified full-bio-based PBAT biodegradable plastic and preparation method thereof | |
| CN113278290A (en) | High-temperature-resistant silicon rubber and preparation method thereof | |
| CN113652018A (en) | High-strength polyethylene gas pipeline and preparation method thereof | |
| CN105754186A (en) | Novel blending-compatibilizing method for high-performance LDPE/PET | |
| CN114106251A (en) | Toughening agent for PBT (polybutylene terephthalate), and preparation method and application thereof | |
| CN1392169A (en) | Thermal synthesis process for preparing grafted polyvinyl-maleic anhydride copolymer in solvent | |
| CN112646164A (en) | Graphene composite bio-based polyether polyol and preparation method thereof | |
| CN113930070B (en) | Preparation method and application of low-dielectric-constant bio-based high-temperature nylon | |
| CN111763347B (en) | High-heat-resistance degradable modified polystyrene foam packaging material and preparation method thereof | |
| CN109096691A (en) | A kind of wear-resistant cable sheath material | |
| CN110629551B (en) | Method for preparing GN @ cellulose based solid-solid phase change fiber through heterogeneous phase and application | |
| CN114854180B (en) | Thermoplastic cellulose/PBAT composite film and preparation method thereof | |
| CN114031897B (en) | Epoxy resin composite material applied to high-temperature-resistant cable core | |
| CN110591082B (en) | Copolymerized nylon resin and preparation method and application thereof | |
| CN109096497A (en) | A kind of waste and old polyester textile depth degradation graphene copolymerization modification method | |
| CN114773621B (en) | Preparation method of lignin flame retardant and preparation method of full biomass flame retardant plastic | |
| CN115340754B (en) | Biodegradable starch film blowing material and preparation process thereof | |
| CN110437394B (en) | Multilayer modified bio-based core-shell particle and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |