CN116554653A - High-strength flame-retardant PBT/PET composite material and preparation method thereof - Google Patents
High-strength flame-retardant PBT/PET composite material and preparation method thereof Download PDFInfo
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- CN116554653A CN116554653A CN202310381025.XA CN202310381025A CN116554653A CN 116554653 A CN116554653 A CN 116554653A CN 202310381025 A CN202310381025 A CN 202310381025A CN 116554653 A CN116554653 A CN 116554653A
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- 239000002131 composite material Substances 0.000 title claims abstract description 95
- 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 53
- 239000003063 flame retardant Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003365 glass fiber Substances 0.000 claims abstract description 80
- 239000000463 material Substances 0.000 claims abstract description 58
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 46
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 46
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 46
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000003112 inhibitor Substances 0.000 claims abstract description 33
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 33
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 25
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 25
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 16
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims abstract description 14
- 235000019799 monosodium phosphate Nutrition 0.000 claims abstract description 14
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000004593 Epoxy Substances 0.000 claims abstract description 5
- CEUBMGAULVNXLX-UHFFFAOYSA-N ethane pyridine Chemical compound CC.C1=CC=NC=C1.C1=CC=NC=C1 CEUBMGAULVNXLX-UHFFFAOYSA-N 0.000 claims abstract 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 claims abstract description 4
- 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 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000000498 cooling water Substances 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 9
- 239000004615 ingredient Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 238000012216 screening Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 8
- 235000013877 carbamide Nutrition 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims 1
- 229920000728 polyester Polymers 0.000 abstract description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 80
- 239000005020 polyethylene terephthalate Substances 0.000 description 80
- 229920001707 polybutylene terephthalate Polymers 0.000 description 75
- 230000000052 comparative effect Effects 0.000 description 16
- 238000005452 bending Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- -1 Polybutylene terephthalate Polymers 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction 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
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- 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
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)
Abstract
The invention discloses a high-strength flame-retardant PBT/PET composite material and a preparation method thereof, and relates to the technical field of polyester modified materials. The high-strength flame-retardant PBT/PET composite material comprises a PBT slice, a PET slice, modified glass fibers, an antioxidant auxiliary agent and a composite transesterification inhibitor; wherein the modified glass fiber is prepared by mixing phosphorus pentachloride, 2-methyl-5-epoxy ethane-pyridine and acidified alkali-free chopped glass fiber; the antioxidant auxiliary agent is any one or two of antioxidant 168 and antioxidant 1010; the composite transesterification inhibitor is obtained by mixing sodium dihydrogen phosphate and composite magnesium aluminum hydrotalcite; the high-strength flame-retardant PBT/PET composite material prepared by the method disclosed by the invention has the advantages of high strength and good flame retardance.
Description
Technical Field
The invention relates to the technical field of polyester modified materials, in particular to a high-strength flame-retardant PBT/PET composite material and a preparation method thereof.
Background
Polybutylene terephthalate (PBT) and polyethylene terephthalate (PET) are all semi-crystalline polyester polymer materials, and are common engineering plastics. PET is a plentiful and inexpensive engineering plastic, but its low crystallization rate affects processability. The PBT/PET alloy composite material has very good chemical stability, mechanical strength, electrical insulation property and thermal stability, and can be applied to automobile parts and the like.
However, because PBT and PET are sensitive to temperature and are easy to hydrolyze at high temperature, even if antioxidant, heat stabilizer and other materials are added, the materials cannot be recycled well. One key factor in the hydrolytic performance of polyesters is their carboxyl end concentration, which is a good method to improve the hydrolytic performance of polyesters. Thus, the skilled man ameliorates this problem by adding a transesterification inhibitor to the PBT/PET composite material, however another problem arises that the mechanical properties and flame retardant properties of the resulting PBT/PET composite material are poor.
Therefore, the invention solves the problems by preparing a high-strength flame-retardant PBT/PET composite material.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a high-strength flame-retardant PBT/PET composite material, which comprises the following components in percentage by mass:
preferably or alternatively, the viscosity of the PBT slice is 0.8-1.0 dL/g, the melting point is 220-226 ℃, and the carboxyl end group content is less than or equal to 60ml/t.
Preferably or alternatively, the viscosity of the PET slice is 0.6-0.8 dL/g, the melting point is 255-260 ℃, and the carboxyl end group content is less than or equal to 40ml/t.
Preferably or alternatively, the modified glass fiber is prepared by mixing phosphorus pentachloride, (2-methyl-5-epoxy ethane-pyridine) and acidified alkali-free chopped glass fiber, wherein the diameter of the alkali-free chopped glass fiber is 10-13 mm, and the chopping length is 3-4.5 mm.
Preferably or alternatively, the antioxidant auxiliary is any one or two of an antioxidant 168 and an antioxidant 1010.
Preferably or alternatively, the compound transesterification inhibitor is obtained by mixing sodium dihydrogen phosphate and compound magnesium aluminum hydrotalcite.
Preferably or alternatively, a preparation method of the high-strength flame-retardant PBT/PET composite material comprises the following preparation steps:
(1) Batching; the composition and the proportion are calculated according to mass fraction, and the composition comprises 20-40% of PBT slice; 29.6 to 49.6 percent of PET slice; 30-50% of modified glass fiber; 0.1 to 0.2 percent of antioxidant auxiliary agent; 0.1 to 0.2 percent of compound transesterification inhibitor;
(2) PBT slice, PET slice and modified glass fiber in the ingredients are put into a double-screw extruder, and simultaneously, an antioxidant auxiliary agent and a composite transesterification inhibitor are added into the double-screw extruder. The twin screw extruder temperature was set to one zone: 230-250 ℃, 230-250 ℃ in the second region, 230-250 ℃ in the third region, 230-260 ℃ in the fourth region, 230-260 ℃ in the fifth region, 230-260 ℃ in the sixth region, 230-260 ℃ in the seventh region, 240-270 ℃ in the eighth region and 240-270 ℃ in the ninth region. Discharging by a twin-screw extruder, feeding the discharged materials into a granulator with the rotating speed of 800-1200 r/min through a cooling water tank at 20-30 ℃, screening the materials by a vibrating screen, and feeding the materials into a homogenizing bin to obtain modified glass fiber reinforced PET/PBT material particles;
(3) The modified glass fiber reinforced PET/PBT material particles obtained in the step 2 are put into a solid polymerization tower, the modified material is heated for 16 to 24 hours by using nitrogen with the temperature of 150 to 155 ℃, and the flow rate of the nitrogen is 1000 to 2000m 3 And/h, preparing the high-strength flame-retardant PBT/PET composite material.
Preferably or alternatively, the preparation method of the modified glass fiber comprises the following steps: the method comprises the steps of dispersing acidified alkali-free chopped glass fibers with the diameter of 10-13 mm and the chopping length of 3-4.5 mm in (2-methyl-5-epoxy ethane-pyridine) with the mass of 0.6-0.8 times, carrying out ultrasonic treatment for 20-40 min at 30-40 kHz, adding phosphorus pentachloride with the mass of 0.06-0.08 times of the acidified alkali-free chopped glass fibers, and stirring for 2-3 h at 200-400 r/min to prepare the modified glass fibers.
Preferably or alternatively, the mass ratio of the composite magnesium aluminum hydrotalcite and the sodium dihydrogen phosphate in the composite transesterification inhibitor is 1:0.8-1:1.2.
Preferably or alternatively, the preparation method of the composite magnesium aluminum hydrotalcite comprises the following steps: dispersing magnesium aluminum hydrotalcite in decarbonated deionized water with the mass of 20-40 times, adding carbamide with the mass of 0.4-0.8 times, heating to 70-90 ℃, stirring for 2-3 hours at 200-400 r/min, filtering, standing, naturally cooling to room temperature, washing 2-4 times with decarbonated deionized water, and drying in an oven at 50-70 ℃ for 11-13 hours to obtain the composite magnesium aluminum hydrotalcite.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a high-strength flame-retardant PBT/PET composite material and a preparation method thereof, wherein the high-strength flame-retardant PBT/PET composite material comprises a PBT slice, a PET slice, modified glass fibers, an antioxidant auxiliary agent and a composite transesterification inhibitor; wherein the modified glass fiber is prepared by mixing phosphorus pentachloride, 2-methyl-5-epoxy ethane-pyridine and acidified alkali-free chopped glass fiber; the antioxidant auxiliary agent is any one or two of antioxidant 168 and antioxidant 1010; the composite transesterification inhibitor is obtained by mixing sodium dihydrogen phosphate and composite magnesium aluminum hydrotalcite.
Modified glass fibers are added into the PBT slice and the PET slice, so that the PBT/PET composite material can be toughened, and the bending strength of the PBT/PET composite material is enhanced; on the one hand, hydrotalcite in the composite hydrotalcite releases molecular crystal water in the thermal decomposition process, the process absorbs heat to cause the temperature of PET to drop below the ignition point, and meanwhile, ester bonds in the PET degrade when meeting water, so that the melt viscosity of the PET is reduced, molten drops are formed, flame is taken away, and the hydrotalcite is heated and decomposed to generate magnesium oxide and calcium oxide which are covered on the surface of the PET, thereby playing a role in flame retardance and heat insulation; the hydrotalcite is decomposed to generate gaseous carbon dioxide, so that the surrounding oxygen concentration is diluted, the flame retardant property of the high-strength flame retardant PBT/PET composite material is enhanced, but the hydrotalcite severely reduces the tensile property of a polyester system; on the other hand, urea in the composite hydrotalcite is heated and decomposed to form ammonia, the ammonia is chlorinated to form ammonium chloride under the action of part of phosphorus pentachloride in the modified glass fiber, the ammonium chloride continuously reacts with the phosphorus pentachloride under the action of pyridine in the modified glass fiber to form hexachlorocyclophosphazene, the hexachlorophosphazene reacts with hydroxyl on a branched chain of the PBT/PET composite material to graft, so that the high-strength flame-retardant PBT/PET composite material with a hyperbranched structure is formed, and the tensile property of the high-strength flame-retardant PBT/PET composite material is enhanced.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to more clearly illustrate the method provided by the invention, the following examples are used for describing the detailed description, and the test method of each index of the high-strength flame-retardant PBT/PET composite material prepared in the following examples is as follows:
flexural strength: the high strength flame retardant PBT/PET composites prepared in the same quality examples and comparative examples were tested for flexural strength according to GB 9341.
Tensile strength: the high-strength flame-retardant PBT/PET composite materials prepared in the same quality examples and comparative examples were taken and tested for bending strength according to GB 1040.
Flame retardancy: the high strength flame retardant PBT/PET composites prepared in the same quality examples and comparative examples were tested for vertical burn rating according to GB 2408.
Example 1
(1) Dispersing an acidified alkali-free chopped glass fiber with the diameter of 10mm and the chopping length of 3mm in (2-methyl-5-ethylene oxide-pyridine) with the mass of 0.6 times of that of the chopped glass fiber, carrying out ultrasonic treatment for 20min at 30kHz, then adding phosphorus pentachloride with the mass of 0.06 times of that of the acidified alkali-free chopped glass fiber, and stirring for 2h at 200r/min to prepare a modified glass fiber;
(2) Dispersing magnesium aluminum hydrotalcite in de-carbon dioxide deionized water with the mass being 20 times of that of the magnesium aluminum hydrotalcite, then adding carbamide with the mass being 0.4 times of that of the magnesium aluminum hydrotalcite, heating to 70 ℃, stirring for 2 hours at 200r/min, filtering, standing, naturally cooling to room temperature, washing for 2 times with the de-carbon dioxide deionized water, and drying for 11 hours in a 50 ℃ oven to prepare composite magnesium aluminum hydrotalcite; mixing composite magnesium aluminum hydrotalcite and sodium dihydrogen phosphate according to the mass ratio of 1:0.8 to prepare a composite transesterification inhibitor;
(3) Batching; the composition and the proportion are calculated according to mass fraction, and the composition comprises 20% of PBT slice; 29.6% of PET slices; 30% of modified glass fibers; 0.1% of antioxidant auxiliary; 0.1% of a complex transesterification inhibitor;
(4) PBT slice, PET slice and modified glass fiber in the ingredients are put into a double-screw extruder, and simultaneously, an antioxidant auxiliary agent and a composite transesterification inhibitor are added into the double-screw extruder. The twin screw extruder temperature was set to one zone: 230 ℃, 230 ℃ in the second area, 230 ℃ in the third area, 230 ℃ in the fourth area, 230 ℃ in the fifth area, 230 ℃ in the sixth area, 230 ℃ in the seventh area, 230 ℃ in the eighth area, 240 ℃ in the ninth area and 240 ℃. Discharging by a twin-screw extruder, feeding the discharged materials into a granulator with the rotating speed of 800r/min through a cooling water tank at 20 ℃, screening the materials by a vibrating screen, and feeding the materials into a homogenizing bin to obtain modified glass fiber reinforced PET/PBT material particles;
(5) The modified glass fiber reinforced PET/PBT material particles obtained in the step 4 are placed into a solid polymerization tower, the modified material is heated for 16h by using nitrogen with the temperature of 150 ℃, and the nitrogen flow is 1000m 3 And/h, preparing the high-strength flame-retardant PBT/PET composite material.
Example 2
(1) Dispersing an acidified alkali-free chopped glass fiber with a diameter of 12mm and a chopped length of 4.2mm in (2-methyl-5-ethylene oxide-pyridine) with a mass which is 0.7 times that of the chopped glass fiber, carrying out ultrasonic treatment at 35kHz for 30min, then adding phosphorus pentachloride with a mass which is 0.07 times that of the acidified alkali-free chopped glass fiber, and stirring at 300r/min for 2.5h to prepare a modified glass fiber;
(2) Dispersing magnesium aluminum hydrotalcite in decarbonated deionized water with the mass of 30 times of that of the magnesium aluminum hydrotalcite, then adding carbamide with the mass of 0.6 times of that of the magnesium aluminum hydrotalcite, heating to 80 ℃, stirring for 2.5 hours at 300r/min, filtering, standing, naturally cooling to room temperature, washing with the decarbonated deionized water for 3 times, and drying in a baking oven at 60 ℃ for 12 hours to prepare the composite magnesium aluminum hydrotalcite; mixing composite magnesium aluminum hydrotalcite and sodium dihydrogen phosphate according to the mass ratio of 1:1 to prepare a composite transesterification inhibitor;
(3) Batching; the composition and the proportion are calculated according to mass fraction, and comprise 30% of PBT slice; 29.7% of PET slices; 40% of modified glass fibers; 0.15% of antioxidant auxiliary; 0.15% of a complex transesterification inhibitor;
(4) PBT slice, PET slice and modified glass fiber in the ingredients are put into a double-screw extruder, and simultaneously, an antioxidant auxiliary agent and a composite transesterification inhibitor are added into the double-screw extruder. The twin screw extruder temperature was set to one zone: 240 ℃, 240 ℃ in the second area, 240 ℃ in the third area, 245 ℃ in the fourth area, 245 ℃ in the fifth area, 245 ℃ in the sixth area, 245 ℃ in the seventh area, 245 ℃ in the eighth area, 255 ℃ in the ninth area, and 255 ℃. Discharging by a twin-screw extruder, feeding the discharged materials into a granulator with the rotating speed of 1000r/min through a cooling water tank at 25 ℃, screening the materials by a vibrating screen, and feeding the materials into a homogenizing bin to obtain modified glass fiber reinforced PET/PBT material particles;
(5) The modified glass fiber reinforced PET/PBT material particles obtained in the step 4 are placed into a solid polymerization tower, the modified material is heated for 20h by using 153 ℃ nitrogen, and the nitrogen flow is 1500m 3 And/h, preparing the high-strength flame-retardant PBT/PET composite material.
Example 3
(1) Dispersing an acidified alkali-free chopped glass fiber with a diameter of 13mm and a chopped length of 4.5mm in (2-methyl-5-ethylene oxide-pyridine) with a mass which is 0.8 times that of the chopped glass fiber, carrying out ultrasonic treatment at 40kHz for 40min, then adding phosphorus pentachloride with a mass which is 0.08 times that of the acidified alkali-free chopped glass fiber, and stirring at 400r/min for 3h to prepare a modified glass fiber;
(2) Dispersing magnesium aluminum hydrotalcite in decarbonated deionized water with the mass being 40 times of that of the magnesium aluminum hydrotalcite, then adding carbamide with the mass being 0.8 times of that of the magnesium aluminum hydrotalcite, heating to 90 ℃, stirring for 3 hours at 400r/min, filtering, standing, naturally cooling to room temperature, washing for 4 times with the decarbonated deionized water, and drying for 13 hours in a baking oven with the temperature being 70 ℃ to obtain composite magnesium aluminum hydrotalcite; mixing composite magnesium aluminum hydrotalcite and sodium dihydrogen phosphate according to the mass ratio of 1:1.2 to prepare a composite transesterification inhibitor;
(3) Batching; the composition and the proportion are calculated according to mass fraction, and the composition comprises 40% of PBT slice; 29.6% of PET slices; 30.4% of modified glass fiber; 0.1% of antioxidant auxiliary; 0.1% of a complex transesterification inhibitor;
(4) PBT slice, PET slice and modified glass fiber in the ingredients are put into a double-screw extruder, and simultaneously, an antioxidant auxiliary agent and a composite transesterification inhibitor are added into the double-screw extruder. The twin screw extruder temperature was set to one zone: 250 ℃, 250 ℃ in the second region, 250 ℃ in the third region, 260 ℃ in the fourth region, 260 ℃ in the fifth region, 260 ℃ in the sixth region, 260 ℃ in the seventh region, 260 ℃ in the eighth region, 270 ℃ in the ninth region, and 270 ℃. Discharging by a twin-screw extruder, feeding the discharged materials into a granulator with the rotating speed of 1200r/min through a cooling water tank at 30 ℃, screening the materials by a vibrating screen, and feeding the materials into a homogenizing bin to obtain modified glass fiber reinforced PET/PBT material particles;
(5) The modified glass fiber reinforced PET/PBT material particles obtained in the step 4 are placed into a solid polymerization tower, the modified material is heated for 24 hours by using nitrogen with the temperature of 155 ℃, and the nitrogen flow is 2000m 3 And/h, preparing the high-strength flame-retardant PBT/PET composite material.
Comparative example 1
(1) Dispersing magnesium aluminum hydrotalcite in decarbonated deionized water with the mass of 30 times of that of the magnesium aluminum hydrotalcite, then adding carbamide with the mass of 0.6 times of that of the magnesium aluminum hydrotalcite, heating to 80 ℃, stirring for 2.5 hours at 300r/min, filtering, standing, naturally cooling to room temperature, washing with the decarbonated deionized water for 3 times, and drying in a baking oven at 60 ℃ for 12 hours to prepare the composite magnesium aluminum hydrotalcite; mixing composite magnesium aluminum hydrotalcite and sodium dihydrogen phosphate according to the mass ratio of 1:1 to prepare a composite transesterification inhibitor;
(2) Batching; the composition and the proportion are calculated according to mass fraction, and comprise 30% of PBT slice; 29.7% of PET slices; 40% of modified glass fibers; 0.15% of antioxidant auxiliary; 0.15% of a complex transesterification inhibitor;
(3) PBT slice, PET slice and alkali-free chopped glass fiber with the diameter of 12mm and the chopped length of 4.2mm in the ingredients are put into a double-screw extruder, and simultaneously, an antioxidant auxiliary agent and a composite transesterification inhibitor are added into the double-screw extruder. The twin screw extruder temperature was set to one zone: 240 ℃, 240 ℃ in the second area, 240 ℃ in the third area, 245 ℃ in the fourth area, 245 ℃ in the fifth area, 245 ℃ in the sixth area, 245 ℃ in the seventh area, 245 ℃ in the eighth area, 255 ℃ in the ninth area, and 255 ℃. Discharging by a twin-screw extruder, feeding the discharged materials into a granulator with the rotating speed of 1000r/min through a cooling water tank at 25 ℃, screening the materials by a vibrating screen, and feeding the materials into a homogenizing bin to obtain modified glass fiber reinforced PET/PBT material particles;
(4) And (3) placing the modified glass fiber reinforced PET/PBT material particles obtained in the step (3) into a solid polymerization tower, and heating the modified material for 20 hours by using 153 ℃ nitrogen with the nitrogen flow rate of 1500m < 3 >/h to prepare the high-strength flame-retardant PBT/PET composite material.
Comparative example 2
(1) Dispersing magnesium aluminum hydrotalcite in decarbonated deionized water with the mass of 30 times of that of the magnesium aluminum hydrotalcite, then adding carbamide with the mass of 0.6 times of that of the magnesium aluminum hydrotalcite, heating to 80 ℃, stirring for 2.5 hours at 300r/min, filtering, standing, naturally cooling to room temperature, washing with the decarbonated deionized water for 3 times, and drying in a baking oven at 60 ℃ for 12 hours to prepare the composite magnesium aluminum hydrotalcite; mixing composite magnesium aluminum hydrotalcite and sodium dihydrogen phosphate according to the mass ratio of 1:1 to prepare a composite transesterification inhibitor;
(2) Batching; the composition and the proportion are calculated according to mass fraction, and comprise 30% of PBT slice; 29.7% of PET slices; 40% of modified glass fibers; 0.15% of antioxidant auxiliary; 0.15% of a complex transesterification inhibitor;
(3) And (3) putting the PBT slice and the PET slice in the ingredients into a double-screw extruder, and simultaneously adding the antioxidant auxiliary agent and the composite transesterification inhibitor into the double-screw extruder. The twin screw extruder temperature was set to one zone: 240 ℃, 240 ℃ in the second area, 240 ℃ in the third area, 245 ℃ in the fourth area, 245 ℃ in the fifth area, 245 ℃ in the sixth area, 245 ℃ in the seventh area, 245 ℃ in the eighth area, 255 ℃ in the ninth area, and 255 ℃. Discharging by a twin-screw extruder, feeding the discharged materials into a granulator with the rotating speed of 1000r/min through a cooling water tank at 25 ℃, screening the materials by a vibrating screen, and feeding the materials into a homogenizing bin to obtain modified glass fiber reinforced PET/PBT material particles;
(4) The modified glass fiber reinforced PET/PBT material particles obtained in the step 3 are placed into a solid polymerization tower, the modified material is heated for 20h by using 153 ℃ nitrogen, and the nitrogen flow is 1500m 3 And/h, preparing the high-strength flame-retardant PBT/PET composite material.
Comparative example 3
(1) Dispersing an acidified alkali-free chopped glass fiber with a diameter of 12mm and a chopped length of 4.2mm in (2-methyl-5-ethylene oxide-pyridine) with a mass which is 0.7 times that of the chopped glass fiber, carrying out ultrasonic treatment at 35kHz for 30min, then adding phosphorus pentachloride with a mass which is 0.07 times that of the acidified alkali-free chopped glass fiber, and stirring at 300r/min for 2.5h to prepare a modified glass fiber;
(2) Mixing magnesium aluminum hydrotalcite and sodium dihydrogen phosphate according to the mass ratio of 1:1 to prepare a composite transesterification inhibitor;
(3) Batching; the composition and the proportion are calculated according to mass fraction, and comprise 30% of PBT slice; 29.7% of PET slices; 40% of modified glass fibers; 0.15% of antioxidant auxiliary; 0.15% of a complex transesterification inhibitor;
(4) PBT slice, PET slice and modified glass fiber in the ingredients are put into a double-screw extruder, and simultaneously, an antioxidant auxiliary agent and a composite transesterification inhibitor are added into the double-screw extruder. The twin screw extruder temperature was set to one zone: 240 ℃, 240 ℃ in the second area, 240 ℃ in the third area, 245 ℃ in the fourth area, 245 ℃ in the fifth area, 245 ℃ in the sixth area, 245 ℃ in the seventh area, 245 ℃ in the eighth area, 255 ℃ in the ninth area, and 255 ℃. Discharging by a twin-screw extruder, feeding the discharged materials into a granulator with the rotating speed of 1000r/min through a cooling water tank at 25 ℃, screening the materials by a vibrating screen, and feeding the materials into a homogenizing bin to obtain modified glass fiber reinforced PET/PBT material particles;
(5) The modified glass fiber reinforced PET/PBT material particles obtained in the step 4 are placed into a solid polymerization tower, the modified material is heated for 20h by using 153 ℃ nitrogen, and the nitrogen flow is 1500m 3 And/h, preparing the high-strength flame-retardant PBT/PET composite material.
Comparative example 4
(1) Dispersing an acidified alkali-free chopped glass fiber with a diameter of 12mm and a chopped length of 4.2mm in (2-methyl-5-ethylene oxide-pyridine) with a mass which is 0.7 times that of the chopped glass fiber, carrying out ultrasonic treatment at 35kHz for 30min, then adding phosphorus pentachloride with a mass which is 0.07 times that of the acidified alkali-free chopped glass fiber, and stirring at 300r/min for 2.5h to prepare a modified glass fiber;
(2) Batching; the composition and the proportion are calculated according to mass fraction, and comprise 30% of PBT slice; 29.7% of PET slices; 40% of modified glass fibers; 0.15% of antioxidant auxiliary; 0.15% of sodium dihydrogen phosphate serving as a transesterification inhibitor;
(3) PBT slice, PET slice and modified glass fiber in the ingredients are put into a double-screw extruder, and simultaneously, an antioxidant auxiliary agent and sodium dihydrogen phosphate serving as a transesterification inhibitor are added into the double-screw extruder. The twin screw extruder temperature was set to one zone: 240 ℃, 240 ℃ in the second area, 240 ℃ in the third area, 245 ℃ in the fourth area, 245 ℃ in the fifth area, 245 ℃ in the sixth area, 245 ℃ in the seventh area, 245 ℃ in the eighth area, 255 ℃ in the ninth area, and 255 ℃. Discharging by a twin-screw extruder, feeding the discharged materials into a granulator with the rotating speed of 1000r/min through a cooling water tank at 25 ℃, screening the materials by a vibrating screen, and feeding the materials into a homogenizing bin to obtain modified glass fiber reinforced PET/PBT material particles;
(4) The modified glass fiber reinforced PET/PBT material particles obtained in the step 3 are placed into a solid polymerization tower, the modified material is heated for 20h by using 153 ℃ nitrogen, and the nitrogen flow is 1500m 3 And/h, preparing the high-strength flame-retardant PBT/PET composite material.
Effect example
The following Table 1 shows the results of analysis of flexural strength, tensile strength, flame retardant properties of the high strength flame retardant PBT/PET composites prepared using examples 1 to 3 of the present invention and comparative examples 1 to 4.
TABLE 1
| Flexural Strength (MPa) | Tensile Strength (MPa) | Vertical combustion rating | |
| Example 1 | 269 | 149 | V-0 |
| Example 2 | 286 | 152 | V-0 |
| Example 3 | 275 | 151 | V-0 |
| Comparative example 1 | 236 | 152 | V-1 |
| Comparative example 2 | 239 | 150 | V-1 |
| Comparative example 3 | 250 | 125 | V-4 |
| Comparative example 4 | 278 | 136 | V-2 |
From Table 1, it can be found that the high-strength flame-retardant PBT/PET composite materials prepared in examples 1, 2 and 3 have higher bending strength, higher tensile strength and better flame retardant property; from comparison of experimental data of examples 1, 2 and 3 and comparative example 1, it can be found that the modified glass fiber is used for preparing the high-strength flame-retardant PBT/PET composite material, and the prepared high-strength flame-retardant PBT/PET composite material has higher bending strength and better flame retardant property; from the experimental data of examples 1, 2, 3 and comparative example 2, it can be found that the glass fiber is used to prepare the high-strength flame-retardant PBT/PET composite material, and the prepared high-strength flame-retardant PBT/PET composite material has higher bending strength; from the experimental data of examples 1, 2 and 3 and comparative example 3, it can be found that the high-strength flame-retardant PBT/PET composite material is prepared by using the composite magnesia-alumina hydrotalcite, and the prepared high-strength flame-retardant PBT/PET composite material has higher bending strength, higher tensile strength and better flame retardant property; from the experimental data of examples 1, 2, 3 and comparative example 4, it can be found that the high-strength flame-retardant PBT/PET composite material prepared by using the magnesium aluminum hydrotalcite has higher tensile strength and better flame retardant property.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (10)
1. A high-strength flame-retardant PBT/PET composite material is characterized in that, according to mass fraction,
comprising the following steps:
2. the high-strength flame-retardant PBT/PET composite material according to claim 1, wherein the viscosity of the PBT slice is 0.8-1.0 dL/g, the melting point is 220-226 ℃, and the carboxyl end group content is less than or equal to 60ml/t.
3. The high-strength flame-retardant PBT/PET composite material according to claim 1, wherein the viscosity of the PET chips is 0.6-0.8 dL/g, the melting point is 255-260 ℃, and the carboxyl end group content is less than or equal to 40ml/t.
4. The high strength flame retardant PBT/PET composite of claim 1, wherein the modified glass fiber is made from a blend of phosphorus pentachloride, 2-methyl-5-ethylene oxide-pyridine, and acidified alkali free chopped glass fiber; the diameter of the alkali-free chopped glass fiber is 10-13 mm, and the chopping length is 3-4.5 mm.
5. The high-strength flame-retardant PBT/PET composite material according to claim 1, wherein the antioxidant auxiliary agent is any one or two of an antioxidant 168 and an antioxidant 1010.
6. The high-strength flame-retardant PBT/PET composite material according to claim 1, wherein the composite transesterification inhibitor is obtained by mixing sodium dihydrogen phosphate and composite magnesium aluminum hydrotalcite.
7. The preparation method of the high-strength flame-retardant PBT/PET composite material is characterized by comprising the following preparation steps:
(1) Batching; the composition and the proportion are calculated according to mass fraction, and the composition comprises 20-40% of PBT slice; 29.6 to 49.6 percent of PET slice; 30-50% of modified glass fiber; 0.1 to 0.2 percent of antioxidant auxiliary agent; 0.1 to 0.2 percent of compound transesterification inhibitor;
(2) PBT slice, PET slice and modified glass fiber in the ingredients are put into a double-screw extruder, and simultaneously, an antioxidant auxiliary agent and a composite transesterification inhibitor are added into the double-screw extruder. The twin screw extruder temperature was set to one zone: 230-250 ℃, 230-250 ℃ in the second region, 230-250 ℃ in the third region, 230-260 ℃ in the fourth region, 230-260 ℃ in the fifth region, 230-260 ℃ in the sixth region, 230-260 ℃ in the seventh region, 240-270 ℃ in the eighth region and 240-270 ℃ in the ninth region. Discharging by a twin-screw extruder, feeding the discharged materials into a granulator with the rotating speed of 800-1200 r/min through a cooling water tank at 20-30 ℃, screening the materials by a vibrating screen, and feeding the materials into a homogenizing bin to obtain modified glass fiber reinforced PET/PBT material particles;
(3) The modified glass fiber reinforced PET/PBT material particles obtained in the step 2 are put into a solid polymerization tower, the modified material is heated for 16 to 24 hours by using nitrogen with the temperature of 150 to 155 ℃, and the flow rate of the nitrogen is 1000 to 2000m 3 And/h, preparing the high-strength flame-retardant PBT/PET composite material.
8. The high-strength flame-retardant PBT/PET composite material according to claim 7, wherein the preparation method of the modified glass fiber is as follows: the method comprises the steps of dispersing acidified alkali-free chopped glass fibers with the diameter of 10-13 mm and the chopping length of 3-4.5 mm in 2-methyl-5-epoxy ethane-pyridine with the mass of 0.6-0.8 times, carrying out ultrasonic treatment for 20-40 min at 30-40 kHz, adding phosphorus pentachloride with the mass of 0.06-0.08 times of the acidified alkali-free chopped glass fibers, and stirring for 2-3 h at 200-400 r/min to prepare the modified glass fibers.
9. The high-strength flame-retardant PBT/PET composite material according to claim 7, wherein the mass ratio of the composite magnesium aluminum hydrotalcite to the sodium dihydrogen phosphate in the composite transesterification inhibitor is 1:0.8-1:1.2.
10. The high-strength flame-retardant PBT/PET composite material according to claim 9, wherein the preparation method of the composite magnesium aluminum hydrotalcite is as follows: dispersing magnesium aluminum hydrotalcite in decarbonated deionized water with the mass of 20-40 times, adding carbamide with the mass of 0.4-0.8 times, heating to 70-90 ℃, stirring for 2-3 hours at 200-400 r/min, filtering, standing, naturally cooling to room temperature, washing 2-4 times with decarbonated deionized water, and drying in an oven at 50-70 ℃ for 11-13 hours to obtain the composite magnesium aluminum hydrotalcite.
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