CN115558084A - Cardanol-terminated high-molecular-weight brominated epoxy resin and method thereof, flame-retardant polyester filament and method thereof, and flame-retardant high-molecular material - Google Patents
Cardanol-terminated high-molecular-weight brominated epoxy resin and method thereof, flame-retardant polyester filament and method thereof, and flame-retardant high-molecular material Download PDFInfo
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- CN115558084A CN115558084A CN202211398131.0A CN202211398131A CN115558084A CN 115558084 A CN115558084 A CN 115558084A CN 202211398131 A CN202211398131 A CN 202211398131A CN 115558084 A CN115558084 A CN 115558084A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 92
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 92
- 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 title claims abstract description 39
- 239000003063 flame retardant Substances 0.000 title claims abstract description 39
- 229920000728 polyester Polymers 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims description 21
- 238000000034 method Methods 0.000 title description 9
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims abstract description 64
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims abstract description 61
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims abstract description 61
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims abstract description 61
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000002861 polymer material Substances 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 13
- 229920005669 high impact polystyrene Polymers 0.000 claims description 12
- 239000004797 high-impact polystyrene Substances 0.000 claims description 12
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- 229920002292 Nylon 6 Polymers 0.000 claims description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000009987 spinning Methods 0.000 abstract description 16
- 238000004132 cross linking Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 10
- 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 compound 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 description 9
- 239000005020 polyethylene terephthalate Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000009863 impact test Methods 0.000 description 5
- -1 polyethylene terephthalate Polymers 0.000 description 5
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000009864 tensile test Methods 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000013100 final test Methods 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- RGDDVTHQUAQTIE-UHFFFAOYSA-N 2-pentadecylphenol Chemical compound CCCCCCCCCCCCCCCC1=CC=CC=C1O RGDDVTHQUAQTIE-UHFFFAOYSA-N 0.000 description 1
- 244000226021 Anacardium occidentale Species 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000020226 cashew nut Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/04—Melting filament-forming substances
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
Abstract
The invention provides cardanol-terminated brominated epoxy resin with a medium and high molecular weight and a preparation method thereof, flame-retardant polyester filament and a preparation method thereof, and a flame-retardant high polymer material, and solves the technical problems that excessive crosslinking of the existing polyester and EP type brominated epoxy resin with a medium and high molecular weight can generate gel, and a spinneret plate hole can be blocked in a continuous spinning process to cause interruption of the spinning process. Cardanol end-capped high molecular weight brominatingThe structural formula of the epoxy resin is as follows:
wherein n is a positive integer, and n is more than or equal to 6 and less than or equal to 99; r 1 And R 2 Is the carbon pentadecyl side chain of cardanol. The invention also provides a preparation method of the cardanol-terminated brominated epoxy resin with high molecular weight, a flame-retardant polyester filament yarn and a preparation method thereof, and a flame-retardant high polymer material, and the preparation method can be widely applied to the technical field of high polymer materials.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to cardanol-terminated high-molecular-weight brominated epoxy resin and a preparation method thereof, flame-retardant polyester filament and a preparation method thereof, and a flame-retardant high polymer material.
Background
Brominated epoxy resin is an epoxy resin material containing bromine in a molecular structure, is widely applied to electronic circuits and flame retardance of various engineering plastics, and belongs to a high-molecular flame retardant. The brominated epoxy resin can be generally divided into low, medium and high molecular weight according to molecular weight, wherein the molecular weight is 4000-60000.
It is known that EP type high molecular weight brominated epoxy resin (formula shown below) with molecular weight of 4000-60000, especially 8000-30000, is widely used for flame retarding of polyester plastics such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and the like.
Wherein n is a positive integer, and n is more than or equal to 12 and less than or equal to 49.
The synthesis method of the EP type medium and high molecular weight brominated epoxy resin adopts a two-step method: firstly synthesizing high-purity tetrabromobisphenol A glycidyl ether, and then further polymerizing the high-purity tetrabromobisphenol A glycidyl ether with tetrabromobisphenol A (TBBA) under the action of a catalyst to generate the tetrabromobisphenol A glycidyl ether. Wherein the catalyst uses quaternary ammonium salts such as tetraethylammonium bromide, tetramethylammonium chloride; research shows that tetramethylammonium chloride is used as an etherification catalyst, the epoxy value and the mass fraction of a polymerization intermediate product in a cyclization product are the highest, and the catalytic effect is the best.
In the high-temperature double-screw processing process of the polyester, the end groups of the polyester high-molecular structure are hydroxyl and carboxyl, and can react with a chain extender, such as EP type high-molecular-weight brominated epoxy resin with an epoxy functional group at the end group, so as to further crosslink, increase the melt viscosity and molecular weight of the polyester, and further improve the mechanical property of the polyester, which is beneficial in the conventional application processes of polyester injection molding, film blowing, sheet making and the like. However, in polyester spinning applications, particularly in filament spinning processes, polyester and high molecular weight brominated epoxy resins of EP type can cause clogging of spinneret holes during continuous spinning, causing spinning process interruptions. The analysis shows that the technical problem is caused because the polyester and the brominated epoxy resin are gathered in the handpiece for a long time at high temperature, and the end group of the polyester and the epoxy group of the brominated epoxy resin are continuously crosslinked to generate gel, thereby causing the blockage of a spinneret plate hole. The processing technology problem is puzzled in the industry for a long time and cannot be solved.
Disclosure of Invention
The invention aims to solve the technical defects, and provides a cardanol end-capped high-molecular-weight brominated epoxy resin and a preparation method thereof, a flame-retardant polyester filament and a preparation method thereof, and a flame-retardant high-molecular material, which are involved in polyester continuous spinning and have no spinneret orifice blockage phenomenon.
Therefore, the invention provides a cardanol-terminated high-molecular-weight brominated epoxy resin which has a structure shown in the following formula (I):
wherein n is a positive integer, and n is more than or equal to 6 and less than or equal to 99; r 1 And R 2 Is the side chain of the carbon pentadecyl of cardanol.
Preferably, n is a positive integer, and 12. Ltoreq. N.ltoreq.49.
Preferably, R 1 、R 2 Has a bond structure represented by any one of the following formulas (II), (III), (IV) and (V):
or
Or
Or
Cardanol is an agricultural byproduct, is extracted from natural cashew nut shell oil, and has the advantages of rich source, low cost and reproducibility. The cardanol has a chemical structure with a benzene ring structure, a phenolic hydroxyl group and a C15 unsaturated straight chain, wherein the benzene ring has rigidity, and the C fifteen straight chain has good toughness and has the structural characteristics of rigid-flexible coordination. Generally cardanol is a mixture of four alkylphenols with different degrees of saturation, 3% saturated hydrocarbyl cardanol, 42% monoalkenyl cardanol, 17% dialkenyl cardanol, and 38% triakenyl cardanol, respectively. The structure schematic diagram is as follows:
unsaturated double bonds on the cardanol side chain hydrocarbon groups can be hydrogenated to obtain saturated hydrocarbon groups, and the stability of the cardanol and the synthesized product thereof in terms of oxidation resistance and the like can be further improved after hydrogenation.
The preparation method of the cardanol end-capped high-molecular-weight brominated epoxy resin comprises the following steps of: under the protection of nitrogen or inert gas, reacting cardanol with brominated epoxy resin under a heating condition to finish the end capping of epoxy end groups of the brominated epoxy resin by the cardanol, so as to obtain the cardanol end capped brominated epoxy resin with high molecular weight; wherein the brominated epoxy resin has a structure represented by the following formula (VI):
wherein n is a positive integer, and n is more than or equal to 6 and less than or equal to 99.
The chemical equation for the above reaction is as follows:
wherein n is a positive integer, and n is more than or equal to 6 and less than or equal to 99; r, R 1 And R 2 Is C15 long-chain group of cardanol.
Preferably, the brominated epoxy resin is added into a reaction kettle, heated to 200-220 ℃ under the protection of nitrogen or inert gas, and stirred to be dissolved; then adding cardanol into a reaction kettle, wherein the molar ratio of the added cardanol to the brominated epoxy resin is 2:1; and (4) continuously stirring, taking the materials out of the reaction kettle after the reaction is finished, cooling and crushing to obtain the cardanol end-capped brominated epoxy resin with the high molecular weight.
Preferably, the brominated epoxy resin is added into a reaction kettle, heated to 200-220 ℃ under the protection of nitrogen or inert gas, and stirred to be dissolved; and then adding excessive cardanol into a reaction kettle, wherein the molar ratio of the added cardanol to the brominated epoxy resin is more than 2:1; continuously stirring, and after the reaction is finished, vacuumizing to extract unreacted cardanol; and (3) taking the materials from the reaction kettle, cooling and crushing to obtain the cardanol end-capped brominated epoxy resin with high molecular weight.
Wherein, the continuous stirring time is determined according to the actual production; taking out the materials from the reaction kettle, and discharging the materials from the bottom of the kettle in actual operation; the material is taken out and cooled, preferably naturally cooled to room temperature.
The flame-retardant polyester filament comprises polyester and the cardanol-terminated high-molecular-weight brominated epoxy resin.
Preferably, the polyester is one or two of PBT and PET.
The flame-retardant polyester filament is prepared by uniformly mixing the raw materials, and extruding and spinning the mixture from a spinneret orifice through a screw extruder at the temperature of between 250 and 260 ℃.
The flame-retardant high polymer material comprises a high polymer and the cardanol end-capped medium-high molecular weight brominated epoxy resin, wherein the high polymer comprises one or more of PBT, PET, ABS, HIPS and PA 6.
The invention has the beneficial effects that: the invention provides a cardanol-terminated brominated epoxy resin with a high molecular weight and a preparation method thereof, a flame-retardant polyester filament yarn and a flame-retardant high polymer material, wherein the environment-friendly end capping is performed by the reaction of phenolic hydroxyl groups of bio-based cardanol and epoxy groups at two ends of the brominated epoxy resin, so that the high molecular weight brominated epoxy resin is subjected to de-epoxidation and can not react with the chain extension of hydroxyl groups and carboxyl groups of polyester, and the technical problem that the spinning process is interrupted due to the blockage of spinneret plate holes in the continuous spinning process is fundamentally solved. Meanwhile, after cardanol with a C15 long straight chain group is introduced, the flexibility of the brominated epoxy resin is improved, the melt viscosity is reduced, the processability is more excellent, and the phenomenon of spinneret orifice blockage does not occur when the brominated epoxy resin participates in polyester continuous spinning. In addition, compared with brominated epoxy resin without end capping, the invention greatly improves the toughness of the flame-retardant high polymer material, and increases the impact strength and the elongation at break.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only preferred embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise.
Fig. 1 is an infrared spectrum of cardanol, the cardanol end-capped high molecular weight brominated epoxy resin prepared in example 2.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application clearer, the present application is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
The method used in the invention is a conventional method if not specially specified; the raw materials and the apparatus used were, unless otherwise specified, conventional commercially available products. Wherein the cardanol is purchased from Wuhan Laina white pharmaceutical chemical Co Ltd, and the purity is more than 99%; the high molecular weight brominated epoxy resin is EP-20000 which is purchased from Shandongtiantian chemical Co., ltd, has a bromine content of 52-53%, a molecular weight (Mw) of 20000-30000 and a softening point of 140-145 ℃.
Example 1:
385 kg (17.5 mol) of brominated epoxy resin EP20000 (with the molecular weight of 22000) is weighed and put in a reaction kettle, heated under the protection of nitrogen, the temperature is controlled between 200 and 220 ℃, and stirred to be dissolved; then adding 10.58 kg (35 mol) of cardanol into the reaction kettle, continuously stirring for 1 hour, discharging materials from the bottom of the kettle after the reaction is finished, naturally cooling to room temperature, and crushing into powder to obtain the cardanol end-capped high molecular weight brominated epoxy resin.
The bromine content of the cardanol-terminated high molecular weight brominated epoxy resin was tested to be 50.8%,1% by weight, of the thermal weight loss temperature 337.9 ℃ (under nitrogen atmosphere, temperature ramp rate 20 ℃/min).
In addition, the cardanol-terminated high molecular weight brominated epoxy resin obtained in example 1 was subjected to GPC (gel permeation chromatography) tests, and the results of the GPC tests are shown in table 1 below:
table 1: example 1GPC measurement results
As can be seen from table 1 above: the product of example 1 was 1 component, a cardanol-terminated high molecular weight brominated epoxy resin. The cardanol-terminated high molecular weight brominated epoxy resin has a number average molecular weight (Mn) of 6434, a weight average molecular weight (Mw) of 24807, a peak molecular weight (Mp) of 18535, and a z average molecular weight (Mz) of 52431.
Example 2:
385 kg (17.5 mol) of brominated epoxy resin EP20000 (with the molecular weight of 22000) is weighed and put in a reaction kettle, heated under the protection of nitrogen, the temperature is controlled between 200 and 220 ℃, and stirred to be dissolved; then adding 11.64 kg (38.5 mol) of cardanol into the reaction kettle, continuously stirring for 1 hour, after the reaction is finished, vacuumizing and maintaining the vacuum degree to be more than-0.1MPa for 15 minutes, extracting unreacted cardanol, discharging materials from the kettle bottom, naturally cooling to room temperature, and crushing into powder to obtain the cardanol end-capped high molecular weight brominated epoxy resin.
In order to verify the successful synthesis of the cardanol-terminated high molecular weight brominated epoxy resin, cardanol and the cardanol-terminated high molecular weight brominated epoxy resin obtained in example 2 were subjected to infrared characterization, and the formed infrared spectrum is shown in fig. 1.
As can be seen from FIG. 1, 3318cm was found in comparison with the cardanol-terminated high molecular weight brominated epoxy resin obtained in example 2 (i.e., the terminated brominated epoxy resin in FIG. 1) -1 The absorption peak of the phenolic hydroxyl group of cardanol is basically disappeared, and a new 3527cm is appeared -1 An absorption peak corresponding to a new hydroxyl-OH absorption peak generated by ring-opening reaction of cardanol with brominated epoxy resin EP 20000. 846cm -1 And 910cm -1 Corresponding to the absorption peak of an epoxy group, and 846cm after end-capping modification -1 The peak corresponding to the absorption of epoxy group disappeared (this peak is evident in the cardanol-terminated high molecular weight brominated epoxy resin) 910cm -1 The absorption peak is generated by stretching vibration of the benzene ring in cardanol (which does not completely disappear). Thus, it can be confirmed that cardanol-terminated high molecular weight brominated epoxy resin obtained in example 2 was obtained.
Example 3
As a flame-retardant polyester filament, the polyester PET spun filament is prepared from the following raw materials in percentage by weight:
wherein the antioxidant 1010/168 (2): the mass ratio of the antioxidant 1010 to the antioxidant 168 is 2: 1.
The raw materials are uniformly mixed, and are extruded and spun from spinneret orifices through a screw extruder at the temperature of 250-260 ℃, and the spinneret orifices are not blocked after continuous spinning for 8 hours. Therefore, the problem of blockage of spinning spinneret holes of polyester PET and brominated epoxy resin flame-retardant systems (EP type high molecular weight brominated epoxy resins) is effectively solved.
Comparative example 4
As a flame-retardant polyester filament, the polyester PET spun filament is prepared from the following raw materials in percentage by weight:
wherein the antioxidant 1010/168 (2): the mass ratio of the antioxidant 1010 to the antioxidant 168 is 2: 1.
The raw materials are uniformly mixed, and are extruded and spun from spinneret orifices through a screw extruder at the temperature of 250-260 ℃, the phenomenon of filament breakage due to blockage of the spinneret orifices occurs when continuous spinning is carried out for 3 hours, and the spinning process is forced to be interrupted.
Example 5
As a flame-retardant high polymer material, the high impact polystyrene HIPS flame-retardant material is prepared from the following raw materials in parts by weight:
HIPS 80 parts
Cardanol end-capped high molecular weight brominated epoxy resin prepared in example 2 (20 parts)
The raw materials are uniformly mixed, extruded and granulated by a screw extruder at the temperature of 250-260 ℃, and injection molded to form an impact sample strip and a tensile sample.
Comparative example 6
As a flame-retardant high polymer material, the high impact polystyrene HIPS flame-retardant material is prepared from the following raw materials in parts by weight:
HIPS 80 parts
Brominated epoxy resin EP20000 20 parts
The raw materials are uniformly mixed, extruded and granulated by a screw extruder at 250-260 ℃, and injection molded to form an impact sample strip and a tensile sample.
The impact test was performed on each of the impact specimens injection-molded in example 5 and comparative example 6, and the tensile test was performed on each of the tensile specimens injection-molded in example 5 and comparative example 6, specifically as follows:
1. impact test
Test standards for impact testing: GB/T1043.1-2008 'determination of impact property of plastic simply supported beam'.
Sample specification: the length (80 plus or minus 2) mm, the width (10 plus or minus 0.2) mm, the thickness (4 plus or minus 0.2) mm and the span length (60 mm).
The test method comprises the following steps: the test is symmetrically and vertically clung to the support, the impact speed of the pendulum bob is 2.9m/s, the pendulum bob is stably released, and the energy absorbed by the impact section test is read. Not less than 5 specimens per group. The average of all test data is the final test result.
The impact test results are shown in table 2 below:
table 2: example 5 and comparative example 6 impact test results
As can be seen from the test results in Table 2, the HIPS material compounded by the brominated epoxy resin after the cardanol modification end capping is adopted is improved by 22% in unnotched impact strength and 37% in notched impact strength compared with the HIPS compounded by the traditional brominated epoxy resin, and the toughness of the material is greatly improved.
2. Tensile test
Test standards: determination of the tensile Properties of plastics (GB/T1040).
Sample size: samples were prepared according to GB/T1040.
The test method comprises the following steps: and clamping the sample, enabling the long axis of the sample to be consistent with the tension direction of the central lines of the upper clamp and the lower clamp, continuously loading the sample to be damaged at a certain speed, and reading a damaged loading value. The loading speed was 2mm/min and there were less than 5 specimens per group, which were rejected if the specimen breaking point was not in the middle parallel section. The average of all test data is the final test result.
The tensile test results are shown in table 3 below:
table 3: example 5 and comparative example 6 tensile test results
| Application examples | Tensile strength/MPa | Elongation at break/% |
| Example 5 | 21.9 | 16.1 |
| Comparative example 6 | 21.2 | 5.3 |
As shown in the test results in Table 3, the HIPS material compounded by the brominated epoxy resin after the cardanol modification end capping has the elongation at break greatly increased from 5.3% to 16.1% on the premise that the tensile strength is slightly increased compared with that of the HIPS material compounded by the traditional brominated epoxy resin, and the toughness of the material is greatly improved.
The invention provides a cardanol-terminated brominated epoxy resin with a high molecular weight and a preparation method thereof, a flame-retardant polyester filament yarn and a flame-retardant high polymer material. Meanwhile, after cardanol with a C15 long straight chain group is introduced, the flexibility of the brominated epoxy resin is improved, the melt viscosity is reduced, the processability is more excellent, and the phenomenon of spinneret orifice blockage does not occur when the brominated epoxy resin participates in the continuous polyester spinning. In addition, the existing EP-type brominated epoxy resin mainly has a rigid benzene ring structure, and has another disadvantage of being hard and brittle, and usually sacrifices the flexibility of the flame-retardant polymer material when the flame-retardant polymer material is flame-retardant, and exhibits lower impact strength and smaller elongation at break. Compared with brominated epoxy resin without an end cap, such as EP type brominated epoxy resin, the invention provides the cardanol end-capped high-molecular-weight brominated epoxy resin, and the pentadecyl phenol (cardanol) structure with introduced rigid-flexible phase greatly improves the toughness of a flame-retardant high polymer material, and increases the impact strength and the elongation at break.
It should be noted that:
(1) In examples 1 and 2, inert gases such as helium, neon, argon, xenon, and the like may be used in addition to the nitrogen gas shield.
(2) The brominated epoxy resin EP-20000 used in the examples 1 and 2 is a preferred raw material, and other high molecular weight brominated epoxy resins in EP type can be used instead; a small amount of quaternary ammonium salt catalyst contained in the EP type medium-high molecular weight brominated epoxy resin plays a role in accelerating the reaction speed in the process of end capping the epoxy end group of the brominated epoxy resin by cardanol.
(3) The cardanol end-capped high molecular weight brominated epoxy resin has a structural formula, wherein the polymerization degree n is a positive integer and is more than or equal to 6 and less than or equal to 99. Considering that the cardanol end-capped high-molecular-weight brominated epoxy resin is melt-mixed with high-molecular polymers such as polyester PBT (polybutylene terephthalate), PET (polyethylene terephthalate) and the like, the smaller n is, the better the dispersion of the cardanol end-capped high-molecular-weight brominated epoxy resin in the high-molecular polymers is, but the poorer the mechanical property of the generated flame-retardant high-molecular material is; the larger n is, the better the mechanical properties of the resulting flame-retardant polymer material are, but the poorer the dispersibility is, and therefore, n is preferably 12. Ltoreq. N.ltoreq.49, more preferably 32. Ltoreq. N.ltoreq.49.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Finally, it is noted that the above-mentioned embodiments illustrate rather than limit the invention, and that, while the invention has been described with reference to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. For example, by adjusting the ratio of the end-capping agent cardanol to the brominated epoxy resin, brominated epoxy resins with different molecular weights are selected, and cardanol derivatives (such as hydrogenated cardanol) are replaced by cardanol.
Claims (10)
1. A cardanol-terminated high molecular weight brominated epoxy resin is characterized by having a structure shown as the following formula (I):
wherein n is a positive integer, n is more than or equal to 6 and less than or equal to 99 1 And R 2 Is the side chain of the carbon pentadecyl of cardanol.
2. The cardanol-terminated high molecular weight brominated epoxy resin according to claim 1, wherein n is a positive integer, and 12. Ltoreq. N.ltoreq.49.
3. The cardanol-terminated high molecular weight brominated epoxy resin according to claim 1, wherein R is 1 、R 2 Has a bond line structure represented by any one of the following formulas (II), (III), (IV) and (V):
4. a process for preparing a cardanol-terminated high molecular weight brominated epoxy resin according to any one of claims 1 to 3, comprising: under the protection of nitrogen or inert gas, reacting the cardanol with brominated epoxy resin under the heating condition to finish the end capping of the cardanol on the epoxy end group of the brominated epoxy resin, so as to obtain the cardanol end capped brominated epoxy resin with high molecular weight; wherein the brominated epoxy resin has a structure represented by the following formula (VI):
wherein n is a positive integer, and n is more than or equal to 6 and less than or equal to 99.
5. The preparation method of the cardanol-terminated high-molecular-weight brominated epoxy resin as claimed in claim 4, wherein the brominated epoxy resin is added into a reaction kettle, heated to 200-220 ℃ under the protection of nitrogen or inert gas, and stirred to be molten; then adding the cardanol into the reaction kettle, wherein the molar ratio of the added cardanol to the brominated epoxy resin is equal to 2:1; and continuously stirring, taking out the materials from the reaction kettle after the reaction is finished, cooling and crushing to obtain the cardanol end-capped medium-high molecular weight brominated epoxy resin.
6. The preparation method of the cardanol-terminated high-molecular-weight brominated epoxy resin as claimed in claim 4, wherein the brominated epoxy resin is added into a reaction kettle, heated to 200-220 ℃ under the protection of nitrogen or inert gas, and stirred to be dissolved; then adding excessive cardanol into the reaction kettle, wherein the molar ratio of the added cardanol to the brominated epoxy resin is more than 2:1; continuously stirring, and after the reaction is finished, vacuumizing to extract unreacted cardanol; and taking out the material from the reaction kettle, cooling and crushing to obtain the cardanol-terminated high molecular weight brominated epoxy resin.
7. A flame retardant polyester filament yarn prepared from a polyester, the cardanol-terminated moderately high molecular weight brominated epoxy resin according to any one of claims 1 to 3.
8. A flame retardant polyester filament according to claim 7, wherein said polyester is one or both of PBT and PET.
9. The preparation of a flame retardant polyester filament according to claim 7 or 8, wherein the raw materials are mixed uniformly and extruded from the spinneret orifice through a screw extruder at 250-260 ℃.
10. A flame-retardant high polymer material is characterized in that raw materials of the flame-retardant high polymer material comprise a high polymer and the cardanol end-capped medium-high molecular weight brominated epoxy resin as described in any one of claims 1 to 3, wherein the high polymer comprises one or more of PBT, PET, ABS, HIPS and PA 6.
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