WO2022110672A1 - 一种减震阻尼无卤阻燃增强pbt材料及其制备方法 - Google Patents
一种减震阻尼无卤阻燃增强pbt材料及其制备方法 Download PDFInfo
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- WO2022110672A1 WO2022110672A1 PCT/CN2021/092845 CN2021092845W WO2022110672A1 WO 2022110672 A1 WO2022110672 A1 WO 2022110672A1 CN 2021092845 W CN2021092845 W CN 2021092845W WO 2022110672 A1 WO2022110672 A1 WO 2022110672A1
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- 239000000463 material Substances 0.000 title claims abstract description 61
- 239000003063 flame retardant Substances 0.000 title claims abstract description 45
- 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 42
- 238000013016 damping Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 239000000945 filler Substances 0.000 claims abstract description 21
- 239000003365 glass fiber Substances 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 12
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- 239000011574 phosphorus Substances 0.000 claims abstract description 12
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 11
- 230000035939 shock Effects 0.000 claims description 29
- 239000003963 antioxidant agent Substances 0.000 claims description 17
- 239000000314 lubricant Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- -1 aliphatic carboxylate Chemical class 0.000 claims description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical group C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- 238000009775 high-speed stirring Methods 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical group C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 229920000388 Polyphosphate Polymers 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical group NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 2
- 125000001741 organic sulfur group Chemical group 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 239000001205 polyphosphate Substances 0.000 claims description 2
- 235000011176 polyphosphates Nutrition 0.000 claims description 2
- 229920001897 terpolymer Polymers 0.000 claims description 2
- 238000005809 transesterification reaction Methods 0.000 claims description 2
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical group [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 17
- 229920000728 polyester Polymers 0.000 abstract description 6
- 229920006351 engineering plastic Polymers 0.000 abstract description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 39
- 238000010521 absorption reaction Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 4
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 4
- 239000000806 elastomer Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- REBHQKBZDKXDMN-UHFFFAOYSA-M [PH2]([O-])=O.C(C)[Al+]CC Chemical group [PH2]([O-])=O.C(C)[Al+]CC REBHQKBZDKXDMN-UHFFFAOYSA-M 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 1
- 239000005043 ethylene-methyl acrylate Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Definitions
- the invention relates to a shock-absorbing, damping, halogen-free, flame-retardant reinforced PBT material and a preparation method thereof, in particular to a shock-absorbing, damping, halogen-free, flame-retardant reinforced PBT used in the fields of cooling fan frames, motor casings, speaker shells and the like in the electrical and electronic industries.
- the material and the preparation method thereof belong to the technical field of engineering plastics.
- Polybutylene terephthalate has excellent electrical properties, mechanical strength and processability due to its crystallization and linear saturation.
- the modified polyester has been widely used in the fields of electronics and electricity.
- Flame-retardant glass fiber reinforced PBT materials are often used as cooling fan frames, motor casings and other components, and have received a lot of recognition in the industry. , the material requirements are more stringent.
- Traditional materials need to be given new functions, such as shock absorption and damping, so as to effectively absorb or moderate the energy produced by the workpiece during high-speed operation, reduce vibration to reduce noise and improve the stability of the workpiece function.
- CN01814142 and CN02830074 disclose that a thermoplastic elastomer obtained by dynamically crosslinking a crosslinkable polymer to obtain a multi-block copolymer has excellent shock absorption effect and is used as a shoe Sock bottom material; CN03809473 is made of polypropylene into foam material with cushioning and shock absorption effect through molding processing; CN200980107747 discloses that thermoplastic elasticity is mixed with flame retardant and foaming agent to make flame retardant composition foam for use Insulation, shock absorption and protection are used alone or in combination in the form of sheets, surface materials, pipes, profiles, gaskets, etc.; CN200710100042 obtains polyurethane-vinyl polymer IPN (blended, Copolymerization and interpenetrating polymer network) two-component damping material; CN201110025089 discloses adding calcium carbonate or carbon black and mixing calcium stearate into
- a high damping member containing rubber or the like as a base resin is used to moderate or absorb the transmission of vibration energy, that is, for vibration isolation, vibration damping, vibration damping, and vibration isolation.
- CN201511004497 By adding a cross-linked polymer containing polystyrene hard segment and ethylene branched polydiene soft segment into ABS resin and hollow glass microspheres to synergistically play a role in sound insulation and shock absorption, it is used as an automotive interior material;
- CN202010068682 discloses A polymer composite material containing polymer foam particles with a skin structure and at least one dynamic covalent bond on the polymer chain, which is obtained by direct foaming or 3D printing, is made into packaging materials, building materials, shock absorption Materials, automotive buffer parts, sports protective products, fitness equipment protective parts, etc.
- the purpose of the present invention is to overcome the deficiencies of the above-mentioned prior art and provide a shock-absorbing and damping halogen-free flame-retardant reinforced PBT material and a preparation method thereof.
- the PBT material has good mechanical properties and shock-absorbing and damping effects.
- the technical solution adopted in the present invention is: a shock absorption damping halogen-free flame retardant reinforced PBT material
- the PBT material comprises the following components by weight: 30-45 parts of PBT resin, 8-45 parts of sheet filler 15 parts, 6-12 parts of shock-absorbing polymer, 2-5 parts of compatibilizer, 20-30 parts of glass fiber, 10-20 parts of phosphorus-based flame retardant, 5-10 parts of nitrogen-containing flame retardant synergist and processing Auxiliary 0.1 to 2 parts.
- sheet fillers are added to the PBT material, a multi-block copolymerized elastomer is used as a shock-absorbing polymer, an acrylate compatibilizer, a phosphorus-containing halogen-free flame retardant and a nitrogen-containing flame retardant synergist are used.
- the compound flame retardant is reinforced by glass fiber to obtain a PBT material with high mechanical properties and shock absorption and damping effect.
- the shock absorbing polymer needs to be used in combination with the flake filler, and the amount of the shock absorbing polymer cannot be less than 6 parts, and the amount of the flake filler can not be less than 8 parts, in order to have the effect of reducing Vibration damping effect.
- the dosage of the PBT resin is 32-40 parts, the dosage of the compatibilizer is 2-3 parts, and the dosage of the phosphorus-based flame retardant is 10-15 parts
- the dosage of the nitrogen-containing flame retardant synergist is 5-6 parts, the dosage of the processing aid is 1-1.5 parts, the dosage of the shock-absorbing polymer is 7-10 parts, and the sheet-shaped
- the amount of filler is 9-12 parts.
- the intrinsic viscosity of the PBT resin is 0.7-1.0 dl/g
- the flake filler is 40-400 mesh mica powder.
- the shock absorption polymer is a hydrogenated styrene-butadiene block copolymer, and the purity of the hydrogenated styrene-butadiene block copolymer is greater than 98%, The cyclohexane content in the impurities is less than 0.5%, and the Shore hardness is 65 to 90;
- the compatibilizer is an acrylate compatibilizer, and the acrylate compatibilizer is ethylene-acrylate, ethylene-acrylate-methyl at least one of glycidyl acrylate terpolymers.
- the glass fiber is an alkali-free glass fiber, the diameter of the glass fiber is 10-13 ⁇ m, and the length is 3-5 mm; the phosphorus-based flame retardant is diethyl Aluminum phosphinate.
- high modulus fiberglass can be used.
- the nitrogen-containing flame retardant synergist is melamine cyanurate or melamine polyphosphate
- the processing aid is a lubricant, a transesterification inhibitor, and an antioxidant. , at least one of the pigments.
- the lubricant is at least one of an aliphatic carboxylate-based wax lubricant and a polyolefin-based wax lubricant;
- the antioxidant is a hindered phenolic antioxidant At least one of antioxidants, phosphite antioxidants, and organic sulfur antioxidants.
- the present invention provides a method for preparing the above-mentioned PBT material, comprising the following steps:
- the PBT resin is pre-dried, and the pre-dried PBT resin, phosphorus-based flame retardant, nitrogen-containing flame retardant synergist, sheet filler, shock-absorbing polymer, compatibilizer, glass fiber, processed
- the additives are added to the high-speed stirring mixer according to the proportion, and the mixture is evenly mixed or separately fed into the pre-mixer through the metering feeder to obtain the mixed material;
- step (2) The mixed material of step (1) is fed into the twin-screw extruder, and under the conveying and shearing action of the twin-screw extruder, fully melt and plasticize, knead and knead, extrude through the die, and draw Strips, cooling, dicing, drying, and finally packaging to obtain shock-absorbing, damping, halogen-free, flame-retardant reinforced PBT materials.
- the pre-drying temperature is 120-140° C.
- the pre-drying time is 4-6 hours.
- the feeding speed of the twin-screw extruder is 450-800 kg/hour
- the temperature of the twin-screw extruder from the feeding port to the die head is respectively Feeding section 220 ⁇ 230°C, conveying section 230 ⁇ 240°C, melt mixing section I 203 ⁇ 240°C, melt mixing section II 240 ⁇ 250°C, natural exhaust section 250 ⁇ 260°C, kneading section I 240 ⁇ 250°C 240 ⁇ 250°C in the second stage of kneading, 230 ⁇ 240°C in the vacuum exhaust section, 230 ⁇ 240°C in the extrusion metering section, and the screw speed is 250 ⁇ 400rpm.
- the present invention firstly reports that the polyester containing glass fiber halogen-free flame retardant system in engineering plastics has shock absorption and damping effect;
- the shock-absorbing damping halogen-free flame-retardant reinforced polyester material obtained by the present invention has a tensile strength of more than 70 MPa and a notched impact strength of more than 6.2 kJ/m 2 (ISO standard);
- the shock-absorbing, damping, halogen-free, flame-retardant reinforced polyester material obtained by the present invention can obtain structural and functional components through molding processes such as injection molding, extrusion, and molding, and can be widely used in cooling fans and motor housings in the electrical and electronic industries. , audio components and automotive buffers and other fields.
- A. PBT resin respectively choose A1: Taiwan Changchun 1200-211M, the intrinsic viscosity is 0.8dl/g; A2: Taiwan Changchun 1100-211M, the intrinsic viscosity is 1.0dl/g;
- B. Glass fiber choose B1: ECS11-4.5-534A (glass fiber diameter 11 ⁇ m, length 4.5mm, Jushi Group); B2: HMG436S-10-4.0 (glass fiber diameter 10 ⁇ m, length 4.0mm, Taishan Glass Fiber Co., Ltd.) ;
- C. Mica powder select C1: AY-03N (Jingda Mica Materials Co., Ltd., 40 mesh); C2: mica powder 400 mesh (Dachao Chemical Co., Ltd.);
- E. Nitrogen-containing flame retardant synergist E1: MCA (Sichuan Fine Chemical); E2: MPP (Shouguang Weidong Chemical);
- F. Damping polymer SEBS, S.O.E.S1605, Asahi Kasei (purity greater than 98%, cyclohexane content in impurities less than 0.5%, Shore hardness 65-90);
- Processing aids including antioxidants (1010, 168, 412S, Lianlong), pigments (zinc sulfide, Huntsman; black mother PE2718, Cabot), lubricants (PED 521, Clariant; PETS) , hair base).
- the components and amounts of the PBT materials in Examples 1 to 7 are shown in Table 1.
- the processing aids are antioxidant 101025wt%, antioxidant 16825wt%, lubricant PETS 50wt%; in Examples 2, 3 and Comparative Example 2, the processing aids are antioxidants Agent 101020wt%, antioxidant 16820wt%, zinc sulfide 20wt%, lubricant PETS 40wt%; in Examples 4, 5 and Comparative Example 3, the processing aids are antioxidant 101020wt%, antioxidant 412S 20wt%, black masterbatch PE271810wt%, lubricant PED52150wt%; the performance test results of the PBT materials of Examples 1-7 are shown in Table 2.
- the loss tangent of PBT materials with good shock absorption effect is higher than that without shock absorption effect, and with the increase of frequency, the loss tangent increases significantly, while PBT materials without shock absorption effect, Instead, the loss tangent decreases slightly with increasing frequency.
- the PBT material prepared by the invention has shock absorption and damping effects while maintaining good mechanical properties.
- Comparative Example 1 does not contain shock-absorbing polymer, and its shock-absorbing damping is not as good as the present invention
- Comparative Example 2 does not contain flaky filler, and its shock-absorbing damping is not as good as the present invention
- Comparative Example 3 the amount of shock-absorbing polymer and flaky filler is used in parts Outside the scope of the present invention, its shock damping is not as good as the present invention.
- test groups 1-5 and control groups 1-4 were set up.
- test groups 1 to 5 and control groups 1 to 4 only the amount of shock absorbing polymer and flake filler is different, as shown in Table 3; the specific materials of each component are the same, and the amount of other components is the same.
- the performance tests were carried out on the PBT materials of the experimental groups 1 to 5 and the control group 1 to 4, and the test results are shown in Table 3.
- the PBT material has a good shock absorbing and damping effect.
- the amount of shock-absorbing polymer and flake filler is not all within the scope of the present invention, and its shock-absorbing and damping effect is not as good as that of test group 1; control group 1 does not contain shock-absorbing polymer, and control group 2 does not contain Flake filler, its shock absorption and damping effect is far less than that of test group 1. It is indicated that the compounding of the shock absorbing polymer and the flake filler in the present invention has a synergistic effect and can greatly improve the shock absorbing and damping performance.
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- 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
一种减震阻尼无卤阻燃增强PBT材料,所述PBT材料包含如下重量份的组分:PBT树脂30~45份、片状填料8~15份、减震聚合物6~12份、相容剂2~5份、玻璃纤维20~30份、磷系阻燃剂10~20份、含氮阻燃协效剂5~10份和加工助剂0.1~2份。首次公开报道在工程塑料中含玻纤无卤阻燃体系的聚酯具有减震阻尼效果;得到的减震阻尼无卤阻燃增强聚酯材料,拉伸强度在70MPa以上,缺口冲击强度在6.2kJ/m 2以上(ISO标准)。
Description
本发明涉及一种减震阻尼无卤阻燃增强PBT材料及其制备方法,尤其涉及电子电气行业的冷却风扇扇框、马达外壳、音箱壳体等领域使用的减震阻尼无卤阻燃增强PBT材料及其制备方法,属于工程塑料技术领域。
聚对苯二甲酸丁二醇酯(PBT)因结晶和线性饱和,其具有优良的电性能、机械强度和加工性,改性后的聚酯在电子电气等领域得到广泛的应用。阻燃玻纤增强的PBT材料常用作冷却风扇扇框、马达外壳等部件,在业界获得大量的认可,但随着功能要求的提高,如转速越来越高、阻燃厚度越来越小等,对材料的要求更为苛刻。传统的材料需赋予新的功能,如减震阻尼等,这样才能有效地吸收或缓和制件在高速运转过程中生产的能量,减震以降低噪音和提升制件功能的稳定性。
公开报道聚合物实现减震阻尼的方法众多,CN01814142和CN02830074公开了将可交联聚合物通过动态交联反应得到一种多嵌段共聚物的热塑性弹性体具有优异的减震效果,用作鞋袜底制材;CN03809473通过模塑加工,将聚丙烯做成发泡材料具有缓冲减震作用;CN200980107747公开了热塑性弹性中混入阻燃剂和发泡剂等做成阻燃性组合物泡沫用作绝缘、减震、保护以板材、面材、管材、型材、衬垫等形式单独或复合使用;CN200710100042通过将异氰酸酯与含乙烯基单体混合共聚反应得到聚氨酯-乙烯基聚合物IPN(共混、共聚和互穿聚合物网络)双组分阻尼材料;CN201110025089公开了在环氧化天然橡胶中加入碳酸钙或炭黑并混入硬脂酸钙,获得高阻尼组合物用作桥梁建筑、生产机械等缓和或吸收振动能量传递,即为了进行免震、减震、减振、防振等而使用将橡胶等作为基础树脂含有的高阻尼部件。CN201511004497通过在ABS树脂中加入含有聚苯乙烯硬段和乙烯支化聚二烯软段的交联聚合物与空心玻璃微珠协效起到隔音减震作用,用作汽车内饰材料;CN202010068682公开了一种含通过 直接发泡或3D打印制得,且具有表皮结构聚合物泡沫颗粒及聚合物链上含有至少一种动态共价键的聚合物复合材料制作成包装材料、建筑材料、减震材料、汽车缓冲件、运动防护制品、健身器材防护件等用途。
以上专利通常采用聚合物弹性体做基体,或在通用塑料中加入弹性体,通过发泡的方法;或复配含共价键的聚合物来实现减震阻尼的作用,未见空开报道加玻纤且阻燃的减震阻尼工程材料及其实现方法。
发明内容
本发明的目的在于克服上述现有技术的不足之处而提供一种减震阻尼无卤阻燃增强PBT材料及其制备方法,该PBT材料具有良好的机械性能和减震阻尼效果。
为实现上述目的,本发明采取的技术方案为:一种减震阻尼无卤阻燃增强PBT材料,所述PBT材料包含如下重量份的组分:PBT树脂30~45份、片状填料8~15份、减震聚合物6~12份、相容剂2~5份、玻璃纤维20~30份、磷系阻燃剂10~20份、含氮阻燃协效剂5~10份和加工助剂0.1~2份。
本发明在PBT材料中加入片状填料,采用多嵌段共聚的弹性体作为减震聚合物,采用丙烯酸酯类相容剂,含磷的无卤阻燃剂与含氮的阻燃协效剂复配阻燃,通过玻璃纤维增强,来获得高机械性能且具有减震阻尼效果的PBT材料。
本发明的无卤阻燃体系中,减震聚合物需与片状填料复配使用,且减震聚合物的用量不能低于6份,片状填料的用量不能低于8份,才能具有减震阻尼效果。
作为本发明所述PBT材料的优选实施方式,所述PBT树脂的用量为32~40份,所述相容剂的用量为2~3份,所述磷系阻燃剂的用量为10~15份,所述含氮阻燃协效剂的用量为5~6份,所述加工助剂的用量为1~1.5份,所述减震聚合物的用量为7~10份,所述片状填料的用量为9-12份。
作为本发明所述PBT材料的优选实施方式,所述PBT树脂的特性粘度为0.7~1.0dl/g,所述片状填料为40~400目的云母粉。
作为本发明所述PBT材料的优选实施方式,所述减震聚合物为氢化苯乙烯-丁二烯嵌段共聚物,所述氢化苯乙烯-丁二烯嵌段共聚物的纯度大于98%,杂质中环己烷含量小于0.5%,邵氏硬度为65~90;所述相容剂为丙烯酸酯类相容剂,所述丙烯酸酯类相容剂为乙烯-丙烯酸酯、乙烯-丙烯酸酯-甲基丙烯酸缩水甘油酯三元共聚物中的至少一种。
作为本发明所述PBT材料的优选实施方式,所述玻璃纤维为无碱玻璃纤维,所述玻璃纤维的直径为10~13μm,长度为3~5mm;所述磷系阻燃剂为二乙基次膦酸铝。如果要获得更高强度性能减震阻尼材料,可采用高模量玻璃纤维。
作为本发明所述PBT材料的优选实施方式,所述含氮阻燃协效剂为三聚氰胺氰尿酸盐或三聚氰胺聚磷酸盐,所述加工助剂为润滑剂、酯交换抑制剂、抗氧剂、颜料中的至少一种。
作为本发明所述PBT材料的优选实施方式,所述润滑剂为脂肪族羧酸酯类蜡润滑剂、聚烯烃类蜡润滑剂中的至少一种;所述抗氧剂为受阻酚类抗氧剂、亚磷酸酯抗氧剂、有机硫抗氧剂中的至少一种。
第二方面,本发明提供了上述PBT材料的制备方法,包括以下步骤:
(1)将PBT树脂进行预干燥处理,将预干燥后的PBT树脂、磷系阻燃剂、含氮阻燃协效剂、片状填料、减震聚合物、相容剂、玻璃纤维、加工助剂按照比例加入高速搅拌混料机,混合均匀或单独通过计量喂料器进入预混机,得混合物料;
(2)将步骤(1)的混合物料送入双螺杆挤出机中,在双螺杆挤出机的输送和剪切作用下,充分熔融塑化、捏合混炼、经机头挤出、拉条、冷却、切粒、干燥,最后包装,即得减震阻尼无卤阻燃增强PBT材料。
作为本发明所述制备方法的优选实施方式,所述步骤(1)中,预干燥温度为120~140℃,预干燥时间为4~6小时。
作为本发明所述制备方法的优选实施方式,所述步骤(2)中,双螺杆挤出机的喂料速度为450~800kg/小时,双螺杆挤出机从加料口到机头的温度分别为加料段220~230℃、输送段230~240℃、熔融混合I段203~240℃、熔融混合II 段240~250℃、自然排气段250~260℃、混炼I段240~250℃、混炼II段240~250℃、真空排气段230~240℃、挤出计量段230~240℃,螺杆转速为250~400rpm。
与现有技术相比,本发明的有益效果为:
(1)本发明首次公开报道在工程塑料中含玻纤无卤阻燃体系的聚酯具有减震阻尼效果;
(2)本发明得到的减震阻尼无卤阻燃增强聚酯材料,拉伸强度在70MPa以上,缺口冲击强度在6.2kJ/m
2以上(ISO标准);
(3)本发明得到的减震阻尼无卤阻燃增强聚酯材料,可通过注塑、挤出、模压等成型工艺获得结构功能部件,可广泛应用于与电子电气行业的散热风扇、马达壳体、音响部件和汽车缓冲件等领域。
为更好地说明本发明的目的、技术方案和优点,下面将结合具体实施例对本发明作进一步说明。
本发明实施例及对比例中PBT材料的制备方法为:
(1)将PBT树脂在130℃下干燥4小时以上,控制水分小于0.03%;
(2)按配比准备好各种原料;
(3)将经干燥处理后的PBT树脂、磷系阻燃剂、含氮阻燃协效剂、片状填料、减震聚合物、相容剂、玻璃纤维、加工助剂按比例加入高速搅拌混料机,混合均匀或单独通过计量喂料器进入预混机得到混合物料;
(4)将上述混合物料送入双螺杆挤出机中,调节喂料量为450~800kg/小时,在双螺杆挤出机中侧喂,双螺杆挤出机的各段螺杆温度从加料口到机头的温度分别为加料段230℃、输送段240℃、熔融混合I段240℃、熔融混合II段250℃、自然排气段260℃、混炼I段250℃、混炼II段240℃、真空排气段230℃、挤出计量段230℃,螺杆转速为400rpm,在双螺杆挤出机的输送和剪切作用下,充分熔融塑化、捏合混炼、经机头挤出、拉条、冷却、切粒、干燥,最后包装,即得减震阻尼无卤阻燃增强PBT材料。
本发明实施例及对比例的测试方法如下:
(1)将挤出切粒得到的产品在120~130℃下烘干,时间3~4小时;
(2)按照相应的标准注塑制备测试样片;
(3)拉伸强度按照ISO 527-2012标准测试,悬臂梁缺口冲击强度按照ISO180-2000标准测试,阻燃性能按照UL 94-2013标准测试,损耗角正切:阻尼减震性能通过动态粘弹性测试仪在不同温度下扫描频率测试。
本发明实施例及对比例中使用的原料信息如下:
A.PBT树脂,分别选用A1:台湾长春1200-211M,特性粘度为0.8dl/g;A2:台湾长春1100-211M,特性粘度为1.0dl/g;
B.玻璃纤维,选用B1:ECS11-4.5-534A(玻纤直径11μm,长度4.5mm,巨石集团);B2:HMG436S-10-4.0(玻纤直径10μm,长度4.0mm,泰山玻璃纤维有限公司);
C.云母粉,选用C1:AY-03N(精达云母材料有限公司,40目);C2:云母粉400目(大潮化工有限公司);
D.磷系阻燃剂,选用科莱恩EXOLIT OP 1230;
E.含氮阻燃协效剂:选用E1:MCA(四川精细化工);E2:MPP(寿光卫东化工);
F.减震聚合物:SEBS,选用S.O.E.S1605,旭化成(纯度大于98%,杂质中环己烷含量小于0.5%,邵氏硬度为65~90);
G.相容剂,分别选用G1:乙烯-丙烯酸酯-甲基丙烯酸缩水甘油酯三元共聚物,牌号PTW(杜邦);G2:乙烯-丙烯酸甲酯二元共聚物,牌号ELVALOYAC1125(杜邦);
H.加工助剂,分别选用抗氧剂(1010,168,412S,利安隆),颜料(硫化锌,亨斯迈;黑色母PE2718,卡博特),润滑剂(PED 521,科莱恩;PETS,发基)。
实施例1~7
实施例1~7PBT材料的各组分及用量如表1所示。实施例1,6,7和对比例1中加工助剂为抗氧剂101025wt%,抗氧剂16825wt%,润滑剂PETS 50wt%;实施例2,3和对比例2中加工助剂为抗氧剂101020wt%,抗氧剂16820wt%, 硫化锌20wt%,润滑剂PETS 40wt%;实施例4,5和对比例3中加工助剂为抗氧剂101020wt%,抗氧剂412S 20wt%,黑色母PE271810wt%,润滑剂PED52150wt%;实施例1~7PBT材料的性能测试结果如表2所示。
对比例1~3
对比例1~3PBT材料的各组分及用量如表1所示。对比例1~3PBT材料的性能测试结果如表2所示。
表1
表2
由表2可知,减震效果好的PBT材料,其损耗角正切都要比无减震效果的要高,且随着频率的提高,损耗角正切增加明显,而无减震效果的PBT材料,损耗角正切反而随频率增加略有降低。本发明制备得到的PBT材料,在保持良好的力学性能的同时,具有减震阻尼效果。对比例1不含有减震聚合物,其减震阻尼不如本发明;对比例2不含有片状填料,其减震阻尼不如本发明;对比例3中减震聚合物和片状填料的用量份不在本发明的范围内,其减震阻尼不如本发明。
效果例1
为了考察减震聚合物、片状填料的用量对PBT材料减震阻尼效果的影响, 设置了试验组1~5和对照组1~4。试验组1~5和对照组1~4中,仅减震聚合物、片状填料的用量不同,如表3所示;各组分的具体选用物质相同,其余组分的用量相同。同时,对试验组1~5和对照组1~4的PBT材料进行性能测试,测试结果如表3所示。
表3
由表3可知,减震聚合物、片状填料的用量在本发明的范围内时,PBT材料具有良好的减震阻尼效果。对照组3~4中,减震聚合物、片状填料的用量不全在本发明的范围内,其减震阻尼效果不如试验组1;对照组1不含减震聚合物,对照组2不含片状填料,其减震阻尼效果远远不如试验组1。说明,本发明中减震聚合物和片状填料复配,具有协同增效的作用,能大大提高减震阻尼性能。
最后所应当说明的是,以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。
Claims (10)
- 一种减震阻尼无卤阻燃增强PBT材料,其特征在于,所述PBT材料包含如下重量份的组分:PBT树脂30~45份、片状填料8~15份、减震聚合物6~12份、相容剂2~5份、玻璃纤维20~30份、磷系阻燃剂10~20份、含氮阻燃协效剂5~10份和加工助剂0.1~2份。
- 如权利要求1所述的PBT材料,其特征在于,所述PBT树脂的用量为32~40份,所述相容剂的用量为2~3份,所述磷系阻燃剂的用量为10~15份,所述含氮阻燃协效剂的用量为5~6份,所述加工助剂的用量为1~1.5份,所述减震聚合物的用量为7~10份,所述片状填料的用量为9-12份。
- 如权利要求1或2所述的PBT材料,其特征在于,所述PBT树脂的特性粘度为0.8~1.0dl/g,所述片状填料为40~400目的云母粉。
- 如权利要求1或2所述的PBT材料,其特征在于,所述减震聚合物为氢化苯乙烯-丁二烯嵌段共聚物,所述氢化苯乙烯-丁二烯嵌段共聚物的纯度大于98%,邵氏硬度为65~90;所述相容剂为丙烯酸酯类相容剂,所述丙烯酸酯类相容剂为乙烯-丙烯酸酯、乙烯-丙烯酸酯-甲基丙烯酸缩水甘油酯三元共聚物中的至少一种。
- 如权利要求1或2所述的PBT材料,其特征在于,所述玻璃纤维为无碱玻璃纤维,所述玻璃纤维的直径为10~13μm,长度为3~5mm;所述磷系阻燃剂为二乙基次膦酸铝。
- 如权利要求1或2所述的PBT材料,其特征在于,所述含氮阻燃协效剂为三聚氰胺氰尿酸盐或三聚氰胺聚磷酸盐,所述加工助剂为润滑剂、酯交换抑制剂、抗氧剂、颜料中的至少一种。
- 如权利要求6所述的PBT材料,其特征在于,所述润滑剂为脂肪族羧酸酯类蜡润滑剂、聚烯烃类蜡润滑剂中的至少一种;所述抗氧剂为受阻酚类抗氧剂、亚磷酸酯抗氧剂、有机硫抗氧剂中的至少一种。
- 如权利要求1~7任一项所述的PBT材料的制备方法,其特征在于,包括 以下步骤:(1)将PBT树脂进行预干燥处理,将预干燥后的PBT树脂、磷系阻燃剂、含氮阻燃协效剂、片状填料、减震聚合物、相容剂、玻璃纤维、加工助剂按照比例加入高速搅拌混料机,混合均匀或单独通过计量喂料器进入预混机,得混合物料;(2)将步骤(1)的混合物料送入双螺杆挤出机中,在双螺杆挤出机的输送和剪切作用下,充分熔融塑化、捏合混炼、经机头挤出、拉条、冷却、切粒、干燥,最后包装,即得减震阻尼无卤阻燃增强PBT材料。
- 如权利要求8所述的制备方法,其特征在于,所述步骤(1)中,预干燥温度为120~140℃,预干燥时间为4~6小时。
- 如权利要求8所述的制备方法,其特征在于,所述步骤(2)中,双螺杆挤出机的喂料速度为450~800kg/小时,双螺杆挤出机从加料口到机头的温度分别为加料段220~230℃、输送段230~240℃、熔融混合I段203~240℃、熔融混合II段240~250℃、自然排气段250~260℃、混炼I段240~250℃、混炼II段240~250℃、真空排气段230~240℃、挤出计量段230~240℃,螺杆转速为250~400rpm。
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