CN112724391A - Application of chain extender in improving viscosity of polyester compound, modified polyester compound and preparation method thereof - Google Patents
Application of chain extender in improving viscosity of polyester compound, modified polyester compound and preparation method thereof Download PDFInfo
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- CN112724391A CN112724391A CN202011474258.7A CN202011474258A CN112724391A CN 112724391 A CN112724391 A CN 112724391A CN 202011474258 A CN202011474258 A CN 202011474258A CN 112724391 A CN112724391 A CN 112724391A
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- chain extender
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- type chain
- polyester compound
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- 239000004970 Chain extender Substances 0.000 title claims abstract description 161
- 229920000728 polyester Polymers 0.000 title claims abstract description 92
- 150000001875 compounds Chemical class 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 51
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 48
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 6
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 23
- -1 polybutylene terephthalate Polymers 0.000 claims description 21
- 239000003963 antioxidant agent Substances 0.000 claims description 20
- 230000003078 antioxidant effect Effects 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000002667 nucleating agent Substances 0.000 claims description 14
- 239000002270 dispersing agent Substances 0.000 claims description 13
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical group O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 12
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 11
- YPNZYYWORCABPU-UHFFFAOYSA-N oxiran-2-ylmethyl 2-methylprop-2-enoate;styrene Chemical group C=CC1=CC=CC=C1.CC(=C)C(=O)OCC1CO1 YPNZYYWORCABPU-UHFFFAOYSA-N 0.000 claims description 11
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 5
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 4
- 150000007519 polyprotic acids Polymers 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 10
- 239000000155 melt Substances 0.000 abstract description 10
- 230000007547 defect Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000007790 solid phase Substances 0.000 abstract description 3
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical group CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 16
- 238000001125 extrusion Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 9
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical class CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003562 lightweight material Substances 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—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
- C08G63/91—Polymers modified by chemical after-treatment
-
- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
- C08G81/027—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyester or polycarbonate sequences
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides an application of a chain extender in improving the viscosity of a polyester compound, a modified polyester compound and a preparation method thereof, belonging to the field of polyester processing. The invention provides an application of a chain extender in improving the viscosity of a polyester compound, wherein the chain extender is a hydroxyl addition type chain extender and/or a carboxyl addition type chain extender. The chain extender is a hydroxyl addition type chain extender and/or a carboxyl addition type chain extender, can perform chain extension reaction with terminal hydroxyl or carboxyl of PBT or TPEE, can prolong the molecular chain of a polyester compound, and obviously improves the molecular weight, so that the intrinsic viscosity of the polyester compound is increased, the melt index is lowered, the defects of high equipment requirement, high energy consumption and low economic benefit of the traditional method such as a solid-phase tackifying technology are overcome, and the chain extender has the advantages of short time consumption, high efficiency and good economic benefit.
Description
Technical Field
The invention relates to the technical field of polyester processing, in particular to application of a chain extender in improving the viscosity of a polyester compound, a modified polyester compound and a preparation method thereof.
Background
PBT (polybutylene terephthalate) belongs to one of five engineering plastics and is greatly applied in the global scope, but with the increasing number of domestic PBT manufacturers, the domestic PBT capacity faces a serious surplus situation. The traditional method for producing high-viscosity PBT, such as the solid-phase tackifying technology, has the defects of high equipment requirement, high energy consumption and low economic benefit.
TPEE (thermoplastic polyester elastomer, which is a block copolymer containing polyester hard blocks and polyether soft blocks) belongs to thermoplastic elastomers, is used as a polyether block of PBT, has similar but completely different performance from that of PBT, is changed into an elastomer due to the addition of polyether blocks, has wide application in automobile lightweight materials, is used as an extension of PBT materials, has great significance in modification, and has wide requirements in the fields of automobile lightweight materials, rail base plates and blown film injection molding. The market of domestic TPEE is still in a growth state at present, but the domestic TPEE with different melt indexes is greatly required at present, is realized only by a polymerization process and also faces the same condition as PBT, and has the defects of high energy consumption and low economic benefit.
Disclosure of Invention
In view of the above, the present invention aims to provide an application of a chain extender in increasing the viscosity of a polyester compound, a modified polyester compound and a preparation method thereof. The method utilizes the hydroxyl addition type chain extender and/or the carboxyl hydroxyl addition type chain extender for modification, and has the advantages of short time consumption, high efficiency and good economic benefit.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an application of a chain extender in improving the viscosity of a polyester compound, wherein the chain extender is a hydroxyl addition type chain extender and/or a carboxyl addition type chain extender, and the polyester compound is prepared by reacting polyalcohol and polybasic acid.
Preferably, the carboxyl addition type chain extender is an epoxy type chain extender, and the hydroxyl addition type chain extender is an isocyanate chain extender.
Preferably, the epoxy chain extender is a styrene glycidyl methacrylate polymer, and the number average molecular weight of the styrene glycidyl methacrylate polymer is 5000-10000.
Preferably, the isocyanate is Hexamethylene Diisocyanate (HDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Lysine Diisocyanate (LDI) or Toluene Diisocyanate (TDI).
Preferably, the polyester-based compound is polybutylene terephthalate or a thermoplastic polyester elastomer
The invention also provides a preparation method of the modified polyester compound, which comprises the following steps:
mixing a polyester compound, a chain extender, an antioxidant auxiliary agent, a nucleating agent, a slipping agent and a dispersant for chain extension reaction, wherein the chain extender is a hydroxyl addition type chain extender and/or a carboxyl addition type chain extender.
Preferably, the mass of the chain extender is 0.5 to 1.2% of the mass of the polyester compound.
Preferably, when the chain extender is a mixture of a hydroxyl addition type chain extender and a carboxyl addition type chain extender, the mass ratio of the hydroxyl addition type chain extender to the carboxyl addition type chain extender in the mixture is 1: 1-3: 7; the mixture is added for three times, part of the hydroxyl addition type chain extender is added for the first time, the part of the hydroxyl addition type chain extender accounts for 50-75% of the mass percentage of the hydroxyl addition type chain extender in the mixture, part of the carboxyl addition type chain extender is added for the second time, the part of the carboxyl addition type chain extender accounts for 75-90% of the mass percentage of the carboxyl addition type chain extender in the mixture, and the rest of the hydroxyl addition type chain extender and the carboxyl addition type chain extender are added for the third time.
Preferably, the mass of the antioxidant auxiliary agent is 0.5-1.0% of that of the polyester compound, and the antioxidant auxiliary agent is an antioxidant 1010.
The invention also provides the modified polyester compound obtained by the preparation method in the technical scheme.
The invention provides an application of a chain extender in improving the viscosity of a polyester compound, wherein the chain extender is a hydroxyl addition type chain extender and/or a carboxyl addition type chain extender, and the polyester compound is prepared by reacting polyalcohol and polybasic acid. The chain extender is a hydroxyl addition type chain extender and/or a carboxyl addition type chain extender, can perform chain extension reaction with the terminal hydroxyl or terminal carboxyl of the polyester compound, can prolong the molecular chain of the polyester compound and obviously improve the molecular weight, so that the intrinsic viscosity of the polyester compound is increased, the melt index is lowered, the defects of high equipment requirement, high energy consumption and low economic benefit of the traditional method such as a solid-phase tackifying technology are overcome, and the chain extender has the advantages of short time consumption, high efficiency and good economic benefit.
The invention also provides a preparation method of the modified polyester compound, which comprises the following steps: mixing a polyester compound, a chain extender, an antioxidant auxiliary agent, a nucleating agent, a slipping agent and a dispersant for chain extension reaction, wherein the chain extender is a hydroxyl addition type chain extender and/or a carboxyl addition type chain extender. The polyester compound is modified by the hydroxyl addition type chain extender and/or the carboxyl addition type chain extender, so that the viscosity of the polyester compound can be improved, and the melt index of the polyester compound can be reduced. The data of the embodiment show that PBT with the viscosity of 0.8dL/g and TPEE with the melt index of 30g/10min are used as raw materials, the PBT carboxyl is reduced to 3.3-5.2 mmol/kg from 10mmol/kg, the intrinsic viscosity is improved to 1.6-2.6 g/dL from 0.8g/dL, the tensile strength is improved to 48.5-50.3 MPa from the original 45MPa, the elongation at break is improved to 86% from 40%, the impact strength of the product is improved to 85-90 MPa from the original 80MPa, and the notch impact strength and the dielectric property of the PBT both reach the general standard of the optical cable and optical fiber outer sheath protective shell; the carboxyl of TPEE is reduced to 3.3-5.01 mmol/kg from 13mmol/kg, the melt index is reduced to 1.2-2.5 g/10min from 30g/10min, the tensile strength is improved to 39-42 MPa from 35MPa, the elongation at break is improved to 615-665% from 590%, and the HDT is improved to 74.5-78 ℃ from 73 ℃.
Detailed Description
The invention provides an application of a chain extender in improving the viscosity of a polyester compound, wherein the chain extender is a hydroxyl addition type chain extender and/or a carboxyl addition type chain extender, and the polyester compound is prepared by reacting polyalcohol and polybasic acid.
In the present invention, unless otherwise specified, all the raw materials used are commercially available in the art.
In the present invention, the carboxyl addition type chain extender is preferably an epoxy type chain extender, and the hydroxyl addition type chain extender is preferably an isocyanate chain extender.
In the invention, the epoxy chain extender is preferably a styrene glycidyl methacrylate polymer, and the number average molecular weight of the styrene glycidyl methacrylate polymer is preferably 5000-10000.
In the present invention, the isocyanate chain extender is preferably Hexamethylene Diisocyanate (HDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Lysine Diisocyanate (LDI), or Toluene Diisocyanate (TDI).
In the invention, the chain extender is preferably a mixture of a hydroxyl addition type chain extender and a carboxyl addition type chain extender, and the mass ratio of the hydroxyl addition type chain extender to the carboxyl addition type chain extender in the mixture is preferably 1: 1-3: 7.
In the present invention, the polyester-based compound is preferably polybutylene terephthalate (PBT) or thermoplastic polyester elastomer (TPEE).
The invention also provides a preparation method of the modified polyester compound, which comprises the following steps:
mixing a polyester compound, a chain extender, an antioxidant auxiliary agent, a nucleating agent, a slipping agent and a dispersant for chain extension reaction, wherein the chain extender is a hydroxyl addition type chain extender and/or a carboxyl addition type chain extender.
In the present invention, the mass of the chain extender is preferably 0.5 to 1.2%, more preferably 0.8 to 1.0% of the mass of the polyester compound. In the present invention, the kind of the chain extender is preferably consistent with the above scheme, and is not described herein again.
In the invention, when the chain extender is preferably a mixture of a hydroxyl addition type chain extender and a carboxyl addition type chain extender, the mass ratio of the hydroxyl addition type chain extender to the carboxyl addition type chain extender in the mixture is preferably 1: 1-3: 7; the mixture is preferably added for three times, part of the hydroxyl addition type chain extender is preferably added for the first time, the mass percentage of the part of the hydroxyl addition type chain extender in the mixture is preferably 50-75%, more preferably 60-70%, part of the carboxyl addition type chain extender is preferably added for the second time, the mass percentage of the part of the carboxyl addition type chain extender in the mixture in the carboxyl addition type chain extender is preferably 75-90%, more preferably 80-85%, and the rest of the hydroxyl addition type chain extender and the carboxyl hydroxyl addition type chain extender are preferably added for the third time. In the invention, the two chain extenders are added in batches after being compounded, so that the branched chain reaction of the final product is more complete, and the chain extension effect is optimal. In the invention, PBT is used as dibasic acid polymerization polyester, the polymerization molecular chain of the PBT is quite regular, uniform and symmetrical, and is ABAB type polyester, and the terminal carboxyl group generally reacts completely, so that the PBT is more suitable for reacting mainly with a hydroxyl addition type chain extender (isocyanate chain extender) and assisting with a carboxyl addition type chain extender; the polyether segment PTMEG is embedded into the PBT chain segment of the TPEE, the TPEE belongs to a ternary irregular polymerization compound, the PTMEG end is provided with-OH, the butanediol also carries hydroxyl, so that the polymerization reaction alcohol is excessive, the hydroxyl end is higher, the TPEE is more suitable for carboxyl end addition molding, and the hydroxyl addition molding is auxiliary, namely the carboxyl addition molding chain extender is taken as the main part and the hydroxyl addition molding chain extender is taken as the auxiliary part.
In the invention, the mass of the antioxidant aid is preferably 0.5-1.0%, more preferably 0.6-0.8% of that of the polyester compound, the antioxidant aid is preferably antioxidant 1010(2, 6-di-tert-butyl phenol high-molecular derivative), and the antioxidant aid has the functions of improving the antioxidant performance and the stability of a system during high-temperature extrusion. The antioxidant does not participate in chain extension reaction and belongs to one of high-temperature stabilizers.
In the invention, the mass of the slipping agent is preferably 0.3-0.8%, more preferably 0.4-0.6% of that of the polyester compound, the slipping agent is preferably an amide compound, more preferably erucamide or oleamide, and the slipping agent has the effects of reducing friction of system components and ensuring smoother and smoother extrusion.
In the invention, the mass of the nucleating agent is preferably 0.2-1.0% of that of the polyester compound, more preferably 0.5-0.8%, the nucleating agent is preferably a substituted aromatic amide organic compound or acetic anhydride modified cellulose nanocrystal, and the nucleating agent has the effects of changing the original homogeneous nucleation of the polymer into the original anisotropic nucleation, accelerating the crystallization speed, changing the crystal nucleus size and improving the mechanical properties of the product.
In the present invention, the mass of the dispersant is preferably 0.2 to 1.0%, more preferably 0.4 to 0.8% of the mass of the polyester compound, and the dispersant is preferably tributyl citrate.
In the present invention, the mixing is preferably such that the polyester-based compound, the chain extender, the nucleating agent, the antioxidant aid, the slipping agent and the dispersant are added to the screw extruder in this order.
In the present invention, it is preferable that white oil is further added during the mixing, the mass of the white oil is preferably 0.2 to 1.0%, more preferably 0.4 to 0.8% of the mass of the polyester-based compound, and the mass content of tributyl citrate in the white oil is preferably 0.4 to 0.8%, more preferably 0.55 to 0.65% of the mass of the polyester-based compound. In the invention, the white oil has the function of enabling the surface layer of the polyester compound to contain an oil film and helping to uniformly adsorb the coating auxiliary agent on the surface of the particles. In the present invention, the white oil is preferably added to the screw extruder after the addition of the polyester-based compound and before the addition of the chain extender.
In the invention, when the polyester compound is preferably polybutylene terephthalate, the temperature of the chain extension reaction is preferably 230-260 ℃, more preferably 240-250 ℃, the screw rotation speed of the screw extruder is preferably 150-200 r/min, more preferably 160-180 r/min, and the extrusion speed of the screw extruder is preferably 100-120 kg/h, more preferably 105-115 kg/h. In the present invention, the chain extension reaction is carried out during extrusion. In the extrusion process, under the condition of twin-screw high-temperature reaction, the-OH and free H-containing bonds contained in the PBT polyester chain are easy to react with the isocyanic acid radical to perform addition reaction.
In the invention, when the polyester compound is preferably a thermoplastic polyester elastomer, the temperature of the chain extension reaction is preferably 200-240 ℃, more preferably 210-230 ℃, the screw rotation speed of the screw extruder is preferably 120-150 r/min, more preferably 130-140 r/min, and the extrusion rate of the screw extruder is preferably 80-100 kg/h, more preferably 85-95 kg/h.
And extruding and granulating in a water cutting mode, drying and dewatering the granules in an oven after granulation, wherein the drying temperature is 80 ℃, and the drying time is 4 hours, so that the moisture of the product is below 300ppm, and the redundant residual smell can be removed.
The invention also provides the polyester compound obtained by the preparation method in the technical scheme. The melt strength of the product obtained by chain extension, tackification and modification is higher. PBT has wide application in optical fiber cable jackets, the viscosity of the product is required to reach more than 1.4, and the high-viscosity PBT is better than the low-viscosity PBT in the aspect of insulating dielectric property. According to the advocated national lightweight materials, the TPEE has application in the aspects of automobile exhaust pipes, dust cover interior trims and the like due to excellent ageing resistance and temperature resistance, but needs excellent mechanical property and strength, and the low-melting-index TPEE can achieve the performances in the aspects.
To further illustrate the present invention, the following will describe in detail the application of the chain extender provided by the present invention in increasing the viscosity of the polyester-based compound, the modified polyester-based compound and the preparation method thereof with reference to the examples, 9 but 0 should not be construed as limiting the scope of the present invention.
Example 1
Raw materials: the chain extender is a mixture of styrene glycidyl methacrylate polymer (with the number average molecular weight of 10000) and hexamethylene diisocyanate, the mass percentages of the styrene glycidyl methacrylate polymer and the hexamethylene diisocyanate in the mixture are respectively 50% and 50%, and the using amount of the chain extender is 0.8% of the weight of the PBT; a polyester compound PBT; the antioxidant is 0.5 percent of the antioxidant 1010 accounting for the mass of the polyester compound; the dosage of the slipping agent (erucamide) is 0.3 percent of the mass of the polyester compound; nucleating agent (substituted aromatic amide organic compound), the amount of which is 0.2 percent of the mass of the polyester compound; the dispersant of tributyl citrate, the amount of which is 0.5 percent of the mass of the polyester compound; the amount of white oil was 0.2% by mass of the polyester-based compound, and the amount of tributyl citrate in the white oil was 0.70% by mass of the polyester-based compound.
Adding a polyester compound, white oil, a chain extender, a nucleating agent, an antioxidant assistant, a slipping agent and a dispersing agent into a screw extruder in sequence for chain extension reaction, wherein the temperature of the chain extension reaction is 230 ℃, the screw rotating speed of the screw extruder is 150r/min, and the extrusion speed of the screw extruder is 100kg/h, so as to obtain the modified PBT, wherein the chain extender is added for three times, part of the hydroxyl addition type chain extender added for the first time accounts for 50% of the mass percentage of the hydroxyl addition type chain extender in the chain extender 9, part of the carboxyl hydroxyl addition type chain extender added for the second time accounts for 75% of the mass percentage of the carboxyl hydroxyl addition type chain extender in the chain extender, and the rest of the hydroxyl addition type chain extender and the carboxyl hydroxyl addition type chain extender are preferably added for the third time.
The experimental results are as follows: the PBT carboxyl is reduced from 10mmol/kg to 4.51mmol/kg, the intrinsic viscosity is increased from 0.8g/dl to 1.6g/dl, the tensile strength is increased from the original 45MPa to 49.5MPa, the elongation at break is increased from 40% to 86%, and the impact strength of the product is increased from the original 80MPa to 85 MPa.
Example 2
The same as example 1, except that the polyester-based compound was TPEE, the temperature of the chain extension reaction was 200 ℃, the screw rotation speed of the screw extruder was 120r/min, and the extrusion rate of the screw extruder was 80 kg/h.
The experimental results are as follows: the carboxyl of TPEE is reduced to 5.01mmol/kg from 13mmol/kg, the melt index is reduced to 2.5g/10min from 30g/10min, the tensile strength is improved to 40MPa from 35MPa, the elongation at break is improved to 630 percent from 590 percent, and the HDT is improved to 78 percent from 73 ℃. After chain extension, the tensile strength of the product is improved and the elasticity is increased due to chain growth. The elasticity is increased, so that the screw extrusion is smoother, and the extrusion speed per unit time is higher and is 80 m/min.
Example 3
Raw materials: the chain extender is a mixture of styrene glycidyl methacrylate polymer (with the number average molecular weight of 5000) and hexamethylene diisocyanate, the mass percentage of the styrene glycidyl methacrylate polymer and the mass percentage of the hexamethylene diisocyanate in the mixture are respectively 40% and 60%, and the using amount of the chain extender is 0.5% of the weight of the PBT; a polyester compound PBT; the antioxidant assistant 1010, the amount of which is 1.0 percent of the mass of the polyester compound; the using amount of the slipping agent (erucamide) is 0.8 percent of the mass of the polyester compound; the nucleating agent (substituted aromatic amide organic compound) accounts for 1.0 percent of the mass of the polyester compound; the dispersant of tributyl citrate, the amount of which is 0.5 percent of the mass of the polyester compound; the amount of white oil was 0.8% by mass of the polyester-based compound, and the amount of tributyl citrate in the white oil was 0.62% by mass of the polyester-based compound.
Adding a polyester compound, white oil, a chain extender, a nucleating agent, an antioxidant assistant, a slipping agent and a dispersing agent into a screw extruder in sequence for chain extension reaction, wherein the temperature of the chain extension reaction is 260 ℃, the screw rotating speed of the screw extruder is 200r/min, and the extrusion speed of the screw extruder is 120kg/h, so as to obtain the modified PBT, wherein the chain extender is added for three times, part of the hydroxyl addition type chain extender added for the first time accounts for 75% of the mass percentage of the hydroxyl addition type chain extender in the chain extender, part of the carboxyl hydroxyl addition type chain extender added for the second time accounts for 90% of the mass percentage of the carboxyl hydroxyl addition type chain extender in the chain extender, and the rest of the hydroxyl addition type chain extender and the carboxyl hydroxyl addition type chain extender are preferably added for the third time.
The experimental results are as follows: the PBT carboxyl is reduced from 10mmol/kg to 5.2mmol/kg, the intrinsic viscosity is increased from 0.8g/dl to 1.7g/dl, the tensile strength is increased from the original 45MPa to 48.3MPa, the elongation at break is increased from 40% to 72%, and the impact strength of the product is increased from the original 80MPa to 86.2 MPa.
Example 4
The same as example 3, except that the polyester-based compound was TPEE, the temperature of the chain extension reaction was 240 ℃, the screw rotation speed of the screw extruder was 150r/min, and the extrusion rate of the screw extruder was 100 kg/h.
The experimental results are as follows: the carboxyl of TPEE is reduced to 4.5mmol/kg from 13mmol/kg, the melt index is reduced to 2.0g/10min from 30g/10min, the tensile strength is improved to 39MPa from 35MPa, the elongation at break is improved to 665% from 590%, and the HDT is improved to 74.5 ℃ from 73 ℃.
Example 5
Raw materials: the chain extender is a mixture of styrene glycidyl methacrylate polymer (with the number average molecular weight of 5000) and hexamethylene diisocyanate, the mass percentages of the styrene glycidyl methacrylate polymer and the hexamethylene diisocyanate in the mixture are respectively 45% and 55%, and the using amount of the chain extender is 1.0% of the weight of the PBT; a polyester compound PBT; the antioxidant auxiliary agent 1010, the dosage of which is 0.8 percent of the mass of the polyester compound; the using amount of the slipping agent (erucamide) is 0.4 percent of the mass of the polyester compound; nucleating agent (substituted aromatic amide organic compound), the amount of which is 0.8 percent of the mass of the polyester compound; dispersant tributyl citrate, the amount is 0.7% of the mass of the polyester compound; the amount of white oil was 0.8% by mass of the polyester-based compound, and the amount of tributyl citrate in the white oil was 0.53% by mass of the polyester-based compound.
Adding a polyester compound, white oil, a chain extender, a nucleating agent, an antioxidant assistant, a slipping agent and a dispersing agent into a screw extruder in sequence for chain extension reaction, wherein the temperature of the chain extension reaction is 240 ℃, the screw rotating speed of the screw extruder is 160r/min, and the extrusion speed of the screw extruder is 115kg/h, so as to obtain the modified PBT, wherein the chain extender is added for three times, part of the hydroxyl addition type chain extender added for the first time accounts for 65% of the mass percentage of the hydroxyl addition type chain extender in the chain extender, part of the carboxyl hydroxyl addition type chain extender added for the second time accounts for 80% of the mass percentage of the carboxyl hydroxyl addition type chain extender in the chain extender, and the rest of the hydroxyl addition type chain extender and the carboxyl hydroxyl addition type chain extender are preferably added for the third time.
The experimental results are as follows: the PBT carboxyl is reduced from 10mmol/kg to 3.3mmol/kg, the intrinsic viscosity is improved from 0.8g/dl to 2.6g/dl, the tensile strength is improved from original 45MPa to 50.3MPa, the elongation at break is reduced from 40% to 36%, the impact strength of the product is improved from original 80MPa to 90MPa, and the elongation at break is reduced because the PBT has high tensile strength and low elongation at break, the viscosity is improved to more than 2.0g/dl, and the melt viscosity is improved to improve the hardness and brittleness and reduce the elongation at break.
Example 6
The same as example 5, except that the polyester-based compound was TPEE, the temperature of the chain extension reaction was 230 ℃, the screw rotation speed of the screw extruder was 130r/min, and the extrusion rate of the screw extruder was 85 kg/h.
The experimental results are as follows: the carboxyl of TPEE is reduced to 3.5mmol/kg from 13mmol/kg, the melt index is reduced to 1.2g/10min from 30g/10min, the tensile strength is improved to 42MPa from 35MPa, the elongation at break is improved to 615% from 590%, and the HDT is improved to 75.5 ℃ from 73 ℃.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (10)
1. The application of the chain extender in improving the viscosity of the polyester compound is characterized in that the chain extender is a hydroxyl addition type chain extender and/or a carboxyl addition type chain extender, and the polyester compound is prepared by reacting polyalcohol with polybasic acid.
2. The use of claim 1, wherein said carboxyl addition type chain extender is an epoxy type chain extender and said hydroxyl addition type chain extender is an isocyanate chain extender.
3. The use according to claim 2, wherein the epoxy chain extender is a styrene glycidyl methacrylate polymer having a number average molecular weight of 5000 to 10000.
4. Use according to claim 2, characterized in that the isocyanate is hexamethylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, lysine diisocyanate or toluene diisocyanate.
5. The use according to claim 1, wherein the polyester-based compound is polybutylene terephthalate or a thermoplastic polyester elastomer.
6. A method for preparing a modified polyester compound, which is characterized by comprising the following steps:
mixing a polyester compound, a chain extender, an antioxidant auxiliary agent, a nucleating agent, a slipping agent and a dispersant for chain extension reaction, wherein the chain extender is a hydroxyl addition type chain extender and/or a carboxyl addition type chain extender.
7. The method according to claim 6, wherein the mass of the chain extender is 0.5 to 1.2% of the mass of the polyester compound.
8. The preparation method according to claim 6 or 7, wherein when the chain extender is a mixture of a hydroxyl addition type chain extender and a carboxyl addition type chain extender, the mass ratio of the hydroxyl addition type chain extender to the carboxyl addition type chain extender in the mixture is 1: 1-3: 7; the mixture is added for three times, part of the hydroxyl addition type chain extender is added for the first time, the part of the hydroxyl addition type chain extender accounts for 50-75% of the mass percentage of the hydroxyl addition type chain extender in the mixture, part of the carboxyl addition type chain extender is added for the second time, the part of the carboxyl addition type chain extender accounts for 75-90% of the mass percentage of the carboxyl addition type chain extender in the mixture, and the rest of the hydroxyl addition type chain extender and the carboxyl addition type chain extender are added for the third time.
9. The preparation method of claim 6, wherein the antioxidant additive accounts for 0.5-1.0% of the polyester compound in mass, and the antioxidant additive is antioxidant 1010.
10. A modified polyester compound obtained by the production process according to any one of claims 6 to 9.
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| CN115109395A (en) * | 2022-07-15 | 2022-09-27 | 华润化学材料科技股份有限公司 | Polyester engineering plastic and preparation method and application thereof |
| CN115044006A (en) * | 2022-07-18 | 2022-09-13 | 会通新材料(上海)有限公司 | High-hardness low-pressure thermoplastic polyester elastomer and preparation method and application thereof |
| CN115044006B (en) * | 2022-07-18 | 2024-02-09 | 会通新材料(上海)有限公司 | High-hardness low-pressure thermal plastic polyester elastomer and preparation method and application thereof |
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