CN115286901B - High-strength high-impact PBT material and preparation method thereof - Google Patents
High-strength high-impact PBT material and preparation method thereof Download PDFInfo
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- CN115286901B CN115286901B CN202111604718.8A CN202111604718A CN115286901B CN 115286901 B CN115286901 B CN 115286901B CN 202111604718 A CN202111604718 A CN 202111604718A CN 115286901 B CN115286901 B CN 115286901B
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- 239000000463 material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- -1 acrylic ester Chemical class 0.000 claims abstract description 46
- 239000003607 modifier Substances 0.000 claims abstract description 36
- YPNZYYWORCABPU-UHFFFAOYSA-N oxiran-2-ylmethyl 2-methylprop-2-enoate;styrene Chemical compound C=CC1=CC=CC=C1.CC(=C)C(=O)OCC1CO1 YPNZYYWORCABPU-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011159 matrix material Substances 0.000 claims abstract description 18
- 239000003365 glass fiber Substances 0.000 claims abstract description 17
- 229920001577 copolymer Polymers 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 4
- 238000013467 fragmentation Methods 0.000 claims abstract description 4
- 238000006062 fragmentation reaction Methods 0.000 claims abstract description 4
- 230000002441 reversible effect Effects 0.000 claims abstract description 4
- 238000012546 transfer Methods 0.000 claims abstract description 4
- 229920001400 block copolymer Polymers 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 14
- 239000004816 latex Substances 0.000 claims description 14
- 229920000126 latex Polymers 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 239000012989 trithiocarbonate Substances 0.000 claims description 14
- 230000000379 polymerizing effect Effects 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000000835 fiber Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 239000007983 Tris buffer Substances 0.000 claims description 3
- 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 description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 claims description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 abstract description 37
- 238000001746 injection moulding Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 239000004793 Polystyrene Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 229920000058 polyacrylate Polymers 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 229920002223 polystyrene Polymers 0.000 abstract description 2
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract 1
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 abstract 1
- 239000000839 emulsion Substances 0.000 description 6
- 238000005452 bending Methods 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 229920005604 random copolymer Polymers 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920006124 polyolefin elastomer Polymers 0.000 description 2
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920006113 non-polar polymer Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012360 testing method 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
Abstract
The invention relates to the technical field of high polymer materials, and discloses a high-strength high-impact PBT material and a preparation method thereof. The invention adopts an emulsion polymerization system, adopts a reversible addition fragmentation chain transfer free radical polymerization technology to prepare the styrene-glycidyl methacrylate/acrylic ester segmented copolymer toughening modifier, and prepares the high-strength high-impact PBT material through blending and injection molding with a polybutylene terephthalate (PBT) matrix, glass fiber and the like. The toughening modifier adopted by the invention has the processability of polystyrene, the toughness of polyacrylate and the reaction compatibility between the polyglycidyl methacrylate and the PBT matrix, and the molecular structure is a block structure, so that the interface bonding strength between the toughening modifier and the PBT matrix can be improved, the remarkable toughening effect can be obtained by regulating and controlling the molecular chain structure, and meanwhile, the preparation process of the toughening modifier is environment-friendly and energy-saving, and the obtained PBT material has excellent mechanical property and wide application prospect.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high-strength high-impact PBT material and a preparation method of a base.
Background
Polybutylene terephthalate (PBT) is a linear crystalline saturated polyester, has excellent heat resistance, fatigue resistance, weather resistance, easy molding, low hygroscopicity and the like, and is widely used in the fields of electronic appliances, automobile industry and the like. Glass fiber is a common method for enhancing the mechanical property of PBT, and the PBT material after glass fiber reinforcement has remarkable improvement on tensile strength, bending strength and heat distortion temperature. However, the PBT material is very sensitive to gaps, has low impact strength at the gaps, and has the problem of warping due to the characteristic of glass fiber anisotropy, so that a toughening modifier is also required to be added in the preparation process to improve the toughness of the material.
The existing toughening modifier mostly adopts a nonpolar polymer elastomer grafted and modified by polar groups so as to enhance the compatibility between the toughening modifier and a PBT matrix, thereby obtaining good toughening effects, such as a maleic anhydride grafted and modified polyolefin elastomer, a glycidyl methacrylate grafted and modified polyolefin elastomer and the like. However, because the traditional free radical polymerization process is adopted, the service life of the free radicals is very short, and the precise control of the molecular chain structure of the polymer cannot be realized, the graft chains are randomly distributed on the molecular chain of the rubber phase polymer, and the molecular weight of the graft chains is different, so that the further improvement of the interfacial bonding strength between the rubber phase and the matrix is limited, and the performance of the material is also influenced. Therefore, developing more efficient tougheners to further enhance the overall properties of PBT materials is a difficulty of current research.
Disclosure of Invention
(one) solving the technical problems
Aiming at the defects of the prior art, the invention provides a high-strength high-impact PBT material and a preparation method thereof.
(II) technical scheme
In order to achieve the purpose of the invention, the following technical scheme is adopted:
the high-strength high-impact PBT material is characterized by comprising the following raw materials in parts by weight: 40-70 parts of PBT matrix, 1-10 parts of styrene-glycidyl methacrylate/acrylic ester block copolymer toughening modifier, 10-30 parts of glass fiber and 0.5-2 parts of antioxidant; the styrene-glycidyl methacrylate/acrylic ester block copolymer toughening modifier is prepared by reversible addition fragmentation chain transfer (RAFT) emulsion polymerization, and the structural formulas of the styrene-glycidyl methacrylate/acrylic ester block copolymer toughening modifier are shown as the formulas (I), (II) and (III):
wherein x is the average degree of polymerization of a, y is the average degree of polymerization of B, m is the average degree of polymerization of D, n is the average degree of polymerization of E, x=10-20, y=20-40, m=100-300, n=400-700.
Chain linkThe structures of the formula (IV) and (V) are shown as follows:
chain linkThe structure of (C) is shown as a formula (VI):
chain linkThe structure of (C) is shown as a formula (VII):
chain linkThe structure of (C) is shown as formulas (VIII), (IX):
the preparation method of the styrene-glycidyl methacrylate/acrylic ester block copolymer toughening modifier comprises the following steps:
stirring and dissolving 1.0-3.0 parts by weight of macromolecular trithiocarbonate compound in 100-300 parts by weight of water to form a water phase, adding 20-60 parts by weight of D monomer (comprising styrene and glycidyl methacrylate, wherein the glycidyl methacrylate is 5-10 parts by weight), and stirring for 15-30min to obtain an emulsified dispersion liquid. Heating the obtained emulsion dispersion to 60-80 ℃ in inert atmosphere, adding 0.04-0.08 part by weight of water-soluble initiator, polymerizing for 2-4 hours, adding 80-140 parts by weight of E monomer and 150-200 parts by weight of water, continuing polymerizing for 3-5 hours to obtain a styrene-glycidyl methacrylate/acrylic ester block copolymer, and stably dispersing the block copolymer in the water in a particle form to form latex; and demulsification, cleaning and drying are carried out on the latex to obtain the styrene-glycidyl methacrylate/acrylic ester block copolymer toughening modifier.
The structural formula of the macromolecular trithiocarbonate compound is shown as the formula (X), (XI) and (XII):
the water-soluble initiator is ammonium persulfate or potassium persulfate.
The intrinsic viscosity of the PBT matrix is between 0.7 and 1.0dl/g.
The glass fiber is a long fiber with the diameter of 6-25 mu m.
The antioxidant is one or more of pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tri (nonylphenyl) phosphite and tri (2, 4-di-tert-butyl) phosphite.
The preparation method of the high-strength high-impact PBT material is characterized by comprising the following steps of:
adding PBT, a styrene-glycidyl methacrylate/acrylic ester segmented copolymer toughening modifier and an antioxidant into a mixer for mixing, adding the mixed materials into a main feeding hopper of an extruder, adding glass fibers from a side feeding port, and extruding and granulating by a double-screw extruder to obtain the high-strength high-impact PBT material.
(III) beneficial effects
Compared with the prior art, the invention provides the high-strength high-impact PBT material and the preparation method thereof, and the PBT material has the following beneficial effects: the toughening modifier adopted by the invention is a styrene-glycidyl methacrylate/acrylic ester segmented copolymer toughening modifier, has the processability of polystyrene, the toughness of polyacrylate and the reaction compatibility between the glycidyl methacrylate and a PBT matrix, has a block structure, can improve the interfacial bonding strength between the toughening modifier and the PBT matrix, can obtain obvious toughening effect by regulating and controlling a molecular chain structure, is environment-friendly and energy-saving in the preparation process of the toughening modifier, and has excellent mechanical property and wide application prospect.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in further detail below.
Mixing the materials by adopting a daily water TMV150 mixer for 10min.
The materials were co-extruded using a Keplong CTE65 twin screw extruder with a screw speed of 500r/min and an extrusion temperature of 240 ℃.
And (3) adopting an Abog 470H injection molding machine to perform injection molding on the material, wherein the injection molding temperature is 285 ℃, the injection molding pressure is 1500bar, and the pressure is 800bar.
The tensile properties of the materials were measured according to GB/T1040.2-2006 using a Zwick/Roell Z020 universal material tester, with a tensile rate of 10mm/min.
The bending performance of the material is measured by a Zwick/Roell Z020 universal material tester according to GB/T9341-2008, and the bending rate is 2mm/min.
The notched impact strength of the material was measured according to GB/T1043.1-2008 using a CE ΛST pendulum impact machine.
Embodiment one:
the high-strength high-impact PBT material comprises the following raw materials in parts by weight: 40 parts of PBT matrix, 1 part of styrene-glycidyl methacrylate/acrylic ester block copolymer toughening modifier, 30 parts of glass fiber and 0.5 part of antioxidant; the styrene-glycidyl methacrylate/acrylate segmented copolymer toughening modifier is prepared by reversible addition fragmentation chain transfer (RAFT) emulsion polymerization, and has a structural formula shown in a formula (I), wherein x is the average polymerization degree of A, y is the average polymerization degree of B, m is the average polymerization degree of D, n is the average polymerization degree of E, and x=10, y=20, m=100 and n=700.
Chain linkThe structure of (C) is shown as a formula (IV).
Chain linkThe structure of (C) is shown as a formula (VI).
Chain linkThe structure of (C) is shown as a formula (VII).
Chain linkThe structure of (C) is shown as a formula (VIII).
The preparation method of the styrene-glycidyl methacrylate/acrylic ester block copolymer toughening modifier comprises the following steps:
1.0 part by weight of a macromolecular trithiocarbonate compound was stirred and dissolved in 100 parts by weight of water to form a water phase, 20 parts by weight of D monomer (comprising styrene and glycidyl methacrylate, wherein glycidyl methacrylate is 5 parts by weight) was added and stirred for 15 minutes to obtain an emulsified dispersion. Heating the obtained emulsion dispersion to 60 ℃ under inert atmosphere, adding 0.04 part by weight of water-soluble initiator, polymerizing for 2 hours, adding 140 parts by weight of E monomer and 200 parts by weight of water, continuing polymerizing for 5 hours to obtain a styrene-glycidyl methacrylate/acrylic ester block copolymer, and stably dispersing the block copolymer in the water in a particle form to form latex; and demulsification, cleaning and drying are carried out on the latex to obtain the styrene-glycidyl methacrylate/acrylic ester block copolymer toughening modifier.
The structural formula of the macromolecular trithiocarbonate compound is shown as a formula (X).
The water-soluble initiator is ammonium persulfate.
The intrinsic viscosity of the PBT matrix was 0.7dl/g.
The glass fiber is a long fiber with the diameter of 6 mu m.
The antioxidant is pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate).
Adding PBT, a styrene-glycidyl methacrylate/acrylic ester segmented copolymer toughening modifier and an antioxidant into a mixer for mixing, adding the mixed materials into a main feeding hopper of an extruder, adding glass fibers from a side feeding port, and extruding and granulating by a double-screw extruder to obtain the high-strength high-impact PBT material.
Embodiment two:
the high-strength high-impact PBT material comprises the following raw materials in parts by weight: 70 parts of PBT matrix, 10 parts of styrene-glycidyl methacrylate/acrylic ester block copolymer toughening modifier, 10 parts of glass fiber and 2 parts of antioxidant; the styrene-glycidyl methacrylate/acrylate segmented copolymer toughening modifier is prepared by reversible addition fragmentation chain transfer (RAFT) emulsion polymerization, and has a structural formula shown in a formula (II), wherein x is the average polymerization degree of A, y is the average polymerization degree of B, m is the average polymerization degree of D, n is the average polymerization degree of E, and x=20, y=40, m=300 and n=400.
Chain linkThe structure of (C) is shown as a formula (V).
Chain linkThe structure of (C) is shown as a formula (VI).
Chain linkThe structure of (C) is shown as a formula (VII).
Chain linkThe structure of (C) is shown as a formula (IX).
The preparation method of the styrene-glycidyl methacrylate/acrylic ester block copolymer toughening modifier comprises the following steps:
3.0 parts by weight of a macromolecular trithiocarbonate compound was stirred and dissolved in 300 parts by weight of water to form a water phase, 60 parts by weight of D monomer (comprising styrene and glycidyl methacrylate, wherein glycidyl methacrylate is 10 parts by weight) was added and stirred for 30 minutes to obtain an emulsified dispersion. Heating the obtained emulsion dispersion to 80 ℃ under inert atmosphere, adding 0.08 weight part of water-soluble initiator, polymerizing for 4 hours, adding 80 weight parts of E monomer and 150 weight parts of water, continuing polymerizing for 3 hours to obtain a styrene-glycidyl methacrylate/acrylic ester block copolymer, and stably dispersing the block copolymer in the water in a particle form to form latex; and demulsification, cleaning and drying are carried out on the latex to obtain the styrene-glycidyl methacrylate/acrylic ester block copolymer toughening modifier.
The structural formula of the macromolecular trithiocarbonate compound is shown as a formula (XI).
The water-soluble initiator is potassium persulfate.
The intrinsic viscosity of the PBT matrix was 1.0dl/g.
The glass fiber is a long fiber with the diameter of 25 mu m.
The antioxidant is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) stearyl propionate.
Adding PBT, a styrene-glycidyl methacrylate/acrylic ester segmented copolymer toughening modifier and an antioxidant into a mixer for mixing, adding the mixed materials into a main feeding hopper of an extruder, adding glass fibers from a side feeding port, and extruding and granulating by a double-screw extruder to obtain the high-strength high-impact PBT material.
Embodiment III:
the high-strength high-impact PBT material comprises the following raw materials in parts by weight: 50 parts of PBT matrix, 5 parts of styrene-glycidyl methacrylate/acrylic ester block copolymer toughening modifier, 10 parts of glass fiber and 1 part of antioxidant; the styrene-glycidyl methacrylate/acrylate segmented copolymer toughening modifier is prepared by reversible addition fragmentation chain transfer (RAFT) emulsion polymerization, and has a structural formula shown in a formula (III), wherein x is the average polymerization degree of a, y is the average polymerization degree of B, m is the average polymerization degree of D, n is the average polymerization degree of E, and x=10, y=30, m=300, and n=700.
Chain linkThe structure of (C) is shown as a formula (IV).
Chain linkThe structure of (C) is shown as a formula (VI).
Chain linkThe structure of (C) is shown as a formula (VII).
Chain linkThe structure of (C) is shown as a formula (IX).
The preparation method of the styrene-glycidyl methacrylate/acrylic ester block copolymer toughening modifier comprises the following steps:
3.0 parts by weight of a macromolecular trithiocarbonate compound was stirred and dissolved in 300 parts by weight of water to form a water phase, 60 parts by weight of D monomer (comprising styrene and glycidyl methacrylate, wherein glycidyl methacrylate is 7 parts by weight) was added and stirred for 20 minutes to obtain an emulsified dispersion. Heating the obtained emulsion dispersion to 70 ℃ under inert atmosphere, adding 0.06 weight part of water-soluble initiator, polymerizing for 4 hours, adding 140 weight parts of E monomer and 200 weight parts of water, continuing polymerizing for 5 hours to obtain a styrene-glycidyl methacrylate/acrylic ester block copolymer, and stably dispersing the block copolymer in the water in a particle form to form latex; and demulsification, cleaning and drying are carried out on the latex to obtain the styrene-glycidyl methacrylate/acrylic ester block copolymer toughening modifier.
The structural formula of the macromolecular trithiocarbonate compound is shown as a formula (XII).
The water-soluble initiator is potassium persulfate.
The intrinsic viscosity of the PBT matrix was 0.9dl/g.
The glass fiber is a long fiber with the diameter of 8 mu m.
The antioxidant is tris (nonylphenyl) phosphite.
Adding PBT, a styrene-glycidyl methacrylate/acrylic ester segmented copolymer toughening modifier and an antioxidant into a mixer for mixing, adding the mixed materials into a main feeding hopper of an extruder, adding glass fibers from a side feeding port, and extruding and granulating by a double-screw extruder to obtain the high-strength high-impact PBT material.
Example 4
The high-strength high-impact PBT material is characterized by comprising the following raw materials in parts by weight: 70 parts of PBT matrix, 10 parts of styrene-glycidyl methacrylate/acrylic ester block copolymer toughening modifier, 10 parts of glass fiber and 1 part of antioxidant; the styrene-glycidyl methacrylate/acrylate segmented copolymer toughening modifier is prepared by reversible addition fragmentation chain transfer (RAFT) emulsion polymerization, and has a structural formula shown in a formula (I), wherein x is the average polymerization degree of A, y is the average polymerization degree of B, m and p are the average polymerization degrees of D, n is the average polymerization degree of E, and x=20, y=30, m=200 and n=400.
Chain linkThe structure of (C) is shown as a formula (V).
Chain linkThe structure of (C) is shown as a formula (VI).
Chain linkThe structure of (C) is shown as a formula (VII).
Chain linkThe structure of (C) is shown as a formula (VIII).
The preparation method of the styrene-glycidyl methacrylate/acrylic ester block copolymer toughening modifier comprises the following steps:
2.0 parts by weight of a macromolecular trithiocarbonate compound was stirred and dissolved in 200 parts by weight of water to form a water phase, 40 parts by weight of D monomer (comprising styrene and glycidyl methacrylate, wherein glycidyl methacrylate is 5 parts by weight) was added and stirred for 30 minutes to obtain an emulsified dispersion. Heating the obtained emulsion dispersion to 70 ℃ under inert atmosphere, adding 0.04 part by weight of water-soluble initiator, polymerizing for 3 hours, adding 80 parts by weight of E monomer and 200 parts by weight of water, continuing polymerizing for 4 hours to obtain a styrene-glycidyl methacrylate/acrylic ester block copolymer, and stably dispersing the block copolymer in the water in a particle form to form latex; and demulsification, cleaning and drying are carried out on the latex to obtain the styrene-glycidyl methacrylate/acrylic ester block copolymer toughening modifier.
The structural formula of the macromolecular trithiocarbonate compound is shown as a formula (X).
The water-soluble initiator is ammonium persulfate.
The intrinsic viscosity of the PBT matrix was 0.8dl/g.
The glass fiber is a long fiber with the diameter of 14 mu m.
The antioxidant is tris (2, 4-di-tert-butyl) phosphite.
Adding PBT, a styrene-glycidyl methacrylate/acrylic ester segmented copolymer toughening modifier and an antioxidant into a mixer for mixing, adding the mixed materials into a main feeding hopper of an extruder, adding glass fibers from a side feeding port, and extruding and granulating by a double-screw extruder to obtain the high-strength high-impact PBT material.
Comparative example 1
The high-strength high-impact PBT material is characterized by comprising the following raw materials in parts by weight: 70 parts of PBT matrix, 10 parts of styrene-glycidyl methacrylate/acrylic ester random copolymer toughening modifier, 10 parts of glass fiber and 1 part of antioxidant.
The preparation method of the styrene-glycidyl methacrylate/acrylic ester random copolymer toughening modifier comprises the following steps:
2.0 parts by weight of a macromolecular trithiocarbonate compound was stirred and dissolved in 400 parts by weight of water to form a water phase, 40 parts by weight of D monomer (comprising styrene and glycidyl methacrylate, wherein glycidyl methacrylate is 5 parts by weight) and 80 parts by weight of E monomer were added and stirred for 30 minutes to obtain an emulsified dispersion. Heating the obtained emulsion dispersion to 70 ℃ under inert atmosphere, adding 0.04 part by weight of water-soluble initiator, and polymerizing for 5 hours to obtain a styrene-glycidyl methacrylate/acrylic ester random copolymer, wherein the random copolymer is stably dispersed in water in a particle form to form latex; and demulsification, cleaning and drying are carried out on the latex to obtain the styrene-glycidyl methacrylate/acrylic ester random copolymer toughening modifier.
The structural formula of the macromolecular trithiocarbonate compound is shown as a formula (X), wherein X is the average polymerization degree of A, y is the average polymerization degree of B, x=20 and y=30.
Chain linkThe structure of (C) is shown as a formula (V).
Chain linkThe structure of (C) is shown as a formula (VI). .
The water-soluble initiator is ammonium persulfate.
The intrinsic viscosity of the PBT matrix was 0.8dl/g.
The glass fiber is a long fiber with the diameter of 14 mu m.
The antioxidant is tris (2, 4-di-tert-butyl) phosphite.
Adding PBT, a styrene-glycidyl methacrylate/acrylic ester segmented copolymer toughening modifier and an antioxidant into a mixer for mixing, adding the mixed materials into a main feeding hopper of an extruder, adding glass fibers from a side feeding port, and extruding and granulating by a double-screw extruder to obtain the high-strength high-impact PBT material.
The results of the performance tests for the high strength, high impact PBT materials described in examples 1-4 and comparative example 1 are shown in Table 1.
TABLE 1
As can be seen from Table 1, the high strength and high impact PBT material can be obtained by blending the styrene-glycidyl methacrylate/acrylic ester block copolymer toughening modifier, glass fiber and a PBT matrix. The test results of the example 4 and the comparative example 1 with the same composition of the raw materials show that the tensile strength and the bending strength of the two materials are not much different, but the notch impact strength of the example 4 is obviously better than that of the comparative example 1, which shows that the elastomer network constructed by the molecular structure design of the copolymer is favorable for dissipating the impact energy, so that the high-strength high-impact PBT material prepared by the invention has wide application prospect.
The above examples are provided for the purpose of clearly illustrating the invention and are not to be construed as limiting the invention in any way. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (8)
1. The high-strength high-impact PBT material is characterized by comprising the following raw materials in parts by weight: 40-70 parts of PBT matrix, 1-10 parts of styrene-glycidyl methacrylate/acrylic ester block copolymer toughening modifier, 10-30 parts of glass fiber and 0.5-2 parts of antioxidant; the styrene-glycidyl methacrylate/acrylate segmented copolymer toughening modifier is prepared by reversible addition fragmentation chain transfer (RAFT) emulsion polymerization, and the structural formula of the styrene-glycidyl methacrylate/acrylate segmented copolymer toughening modifier is shown as formula (I) or (II) or (III):
wherein x is the average degree of polymerization of a, y is the average degree of polymerization of B, m is the average degree of polymerization of D, n is the average degree of polymerization of E, x=10-20, y=20-40, m=100-300, n=400-700;
chain linkThe structure of (C) is shown as a formula (IV) or (V):
chain linkThe structure of (C) is shown as a formula (VI):
chain linkThe structure of (C) is shown as a formula (VII):
chain linkThe structure of (A) is shown as formula (VII)I) Or (IX):
2. the high-strength high-impact PBT material according to claim 1, wherein the preparation method of the styrene-glycidyl methacrylate/acrylate block copolymer toughening modifier is as follows:
stirring and dissolving 1.0-3.0 parts by weight of macromolecular trithiocarbonate compound in 100-300 parts by weight of water to form a water phase, adding 20-60 parts by weight of D monomer comprising styrene and glycidyl methacrylate, wherein the glycidyl methacrylate is 5-10 parts by weight, stirring for 15-30min to obtain an emulsified dispersion liquid, heating the obtained emulsified dispersion liquid to 60-80 ℃ under inert atmosphere, adding 0.04-0.08 part by weight of water-soluble initiator, polymerizing for 2-4 hours, adding 80-140 parts by weight of E monomer and 150-200 parts by weight of water, continuing polymerizing for 3-5 hours to obtain a styrene-glycidyl methacrylate/acrylate block copolymer, and stably dispersing the block copolymer in the water in the form of particles to form latex; and demulsification, cleaning and drying are carried out on the latex to obtain the styrene-glycidyl methacrylate/acrylic ester block copolymer toughening modifier.
3. The high strength and high impact PBT material according to claim 2, wherein the macromolecular trithiocarbonate compound has a structural formula shown in formula (X) or (XI) or (XII):
4. the high strength, high impact PBT material of claim 2, wherein the water soluble initiator is ammonium persulfate or potassium persulfate.
5. The high strength, high impact PBT material of claim 1, wherein the PBT matrix has an intrinsic viscosity of 0.7 to 1.0dl/g.
6. The high strength and high impact PBT material of claim 1, wherein the glass fibers are long fibers with a diameter of 6-25 μm.
7. The high-strength high-impact PBT material according to claim 1, wherein the antioxidant is one or more of pentaerythritol tetrakis (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tris (nonylphenyl) phosphite and tris (2, 4-di-tert-butyl) phosphite.
8. The method for preparing the high-strength high-impact PBT material according to any one of claims 1 to 2 and 5 to 7, comprising the following steps:
adding PBT, a styrene-glycidyl methacrylate/acrylic ester segmented copolymer toughening modifier and an antioxidant into a mixer for mixing, adding the mixed materials into a main feeding hopper of an extruder, adding glass fibers from a side feeding port, and extruding and granulating by a double-screw extruder to obtain the high-strength high-impact PBT material.
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