WO2022110673A1 - 一种减震阻尼有卤阻燃增强pbt材料及其制备方法 - Google Patents

一种减震阻尼有卤阻燃增强pbt材料及其制备方法 Download PDF

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WO2022110673A1
WO2022110673A1 PCT/CN2021/092854 CN2021092854W WO2022110673A1 WO 2022110673 A1 WO2022110673 A1 WO 2022110673A1 CN 2021092854 W CN2021092854 W CN 2021092854W WO 2022110673 A1 WO2022110673 A1 WO 2022110673A1
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parts
resin
pbt
shock
damping
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PCT/CN2021/092854
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French (fr)
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朱文
黄险波
叶南飚
莫文杰
姚华侠
龚德君
付学俊
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金发科技股份有限公司
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Publication of WO2022110673A1 publication Critical patent/WO2022110673A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C08J2425/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C08J2433/16—Homopolymers or copolymers of esters containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing 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
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass

Definitions

  • the invention relates to a shock absorbing and damping halogenated flame retardant reinforced PBT material and a preparation method thereof, in particular to a shock absorbing halogenated flame retardant reinforced PBT material used in the fields of cooling fan frames, motor casings, speaker shells and the like in the electrical and electronic industries , belonging 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 sheet, surface material, pipe, profile, liner, etc.
  • CN200710100042 obtains polyurethane-vinyl polymer IPN (blending, Copolymerization and interpenetrating polymer network) two-component damping material;
  • CN201110025089 discloses adding calcium carbonate or carbon black and mixing calcium stearate into epoxidized natural rubber to obtain high damping composition for bridge construction, production machinery, etc.
  • 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 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, reducing Shock materials, automobile buffer parts, sports protective products, fitness equipment protective parts, etc.
  • the purpose of the present invention is to overcome the above-mentioned shortcomings of the prior art and provide a shock-absorbing and damping halogenated 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 halogenated flame retardant reinforced PBT material, the PBT material comprises the following components in parts by weight: 30-40 parts of PBT resin, 10-15 parts of PC resin parts, 7-12 parts of sheet filler, 6-15 parts of shock-absorbing polymer, 1-4 parts of compatibilizer, 20-30 parts of glass fiber, 10-20 parts of brominated flame retardant and antimony white compound and Processing aid 0.1 to 2 parts.
  • the shock-absorbing polymer and the sheet-like filler are used in combination, and the amount of the shock-absorbing polymer is not less than 6 parts, and the amount of the sheet-shaped filler is not less than 7 parts. It has the effect of shock absorption and damping, and then add 10 to 15 parts of PC resin to enhance the shock absorption and damping.
  • a shock absorbing polymer is added as the second component, combined with flake filler mica and a multi-block copolymerized elastomer, and a bromine-containing halogenated flame retardant is used to obtain high mechanical properties and reduced energy consumption through glass fiber reinforcement.
  • PBT material for shock damping effect.
  • the mass ratio of the brominated flame retardant and the antimony white compound is 3:1 to 5.2:1.
  • the PBT material comprises the following components in parts by weight: 30-40 parts of PBT resin, 10-13 parts of PC resin, 7-10 parts of flake filler, and shock-absorbing polymer 6-12 parts, 1-2 parts of compatibilizer, 20-30 parts of glass fiber, 12.5-15.5 parts of brominated flame retardant and antimony white compound and 1-1.5 parts of processing aid.
  • the intrinsic viscosity of the PBT resin is 0.8-1.2 dl/g; the melt flow rate of the PC resin is 3-22 g/10min, and the melt flow rate of the PC resin is 3-22 g/10min.
  • the flow rate was measured according to ISO 1133-2011 using a weight of 1.2 kg and a temperature of 300°C; the flake filler was mica powder, and the mesh number of the mica powder was 40-400 mesh.
  • 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 an ethylene-methyl acrylate binary copolymer, ethylene - At least one of acrylate-glycidyl methacrylate terpolymers.
  • the glass fiber is an alkali-free glass fiber, and the glass fiber has a diameter of 10-13 ⁇ m and a length of 3-5 mm.
  • the brominated flame retardant is brominated epoxy resin, brominated polystyrene, brominated polycarbonate, decabromodiphenylethane, and polyacrylic acid pentabromobenzyl At least one of esters; the processing aid is at least one of lubricants, transesterification inhibitors, antioxidants, and pigments.
  • the lubricant is an aliphatic carboxylate-based wax lubricant or a polyolefin-based wax lubricant
  • the antioxidant is a hindered phenolic antioxidant, a phosphite At least one of antioxidants and organic sulfur antioxidants.
  • the present invention provides a method for preparing the above-mentioned PBT material, comprising the following steps:
  • 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 absorption damping halogenated flame retardant reinforced PBT material.
  • 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 sections of the twin-screw extruder from the feeding port to the die head are The screw temperature is 220 ⁇ 230°C in the feeding section, 230 ⁇ 240°C in the conveying section, 203 ⁇ 240°C in the first section of melt mixing, 240 ⁇ 250°C in the second section of melt mixing, 250 ⁇ 260°C in the natural exhaust section, and 240°C in the first section of mixing.
  • the present invention firstly reports that the polyester containing glass fiber and halogen flame retardant system in engineering plastics has shock absorption and damping effect;
  • the shock-absorbing damping halogenated flame-retardant reinforced polyester material obtained by the present invention has a tensile strength of over 80 MPa and a notched impact strength of over 6.5 kJ/m 2 (ISO standard);
  • the shock-absorbing and damping halogenated 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.
  • PBT resin and PC resin after drying treatment are mixed with brominated flame retardant and antimony white compound, flake filler, shock-absorbing polymer, compatibilizer, glass fiber, and processing aid in proportion.
  • the high-speed mixing mixer mixes evenly or enters the pre-mixer through the metering feeder alone to obtain the mixed material;
  • the above-mentioned mixed material is fed into the twin-screw extruder, and the feeding amount is adjusted to be 450 ⁇ 800kg/hour, and the temperature of the screw of each section of the twin-screw extruder from the feed port to the die head is 230 in the feed section.
  • the metering section is 230°C, and the screw speed is 400rpm.
  • twin-screw extruder Under the conveying and shearing action of the twin-screw extruder, it is fully melted and plasticized, kneaded and mixed, extruded through the head, drawn, cooled, pelletized, and dried. The final packaging is to obtain the PBT material.
  • 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; A3: Yizheng Chemical Fiber GL234, the intrinsic viscosity is 1.2dl /g;
  • B. PC resin respectively choose B1: LG Chemical PC 1300 03NP, melt flow rate 3g/10min (@300°C, 1.2kg); B2: LG Chemical PC 1300 10NP, melt flow rate 10g/10min (@300°C , 1.2kg); B3: LG Chemical PC 1300 22NP, melt flow rate 22g/10min (@300°C, 1.2kg);
  • C. Glass fiber choose C1: ECS13-3.0-T436W (glass fiber diameter 13 ⁇ m, length 3.0cm, Taishan Glass Fiber Co., Ltd.); C2: ECS11-4.5-534A (glass fiber diameter 11 ⁇ m, length 4.5cm, Jushi Group );
  • D. Mica powder select D1: AY-03N (Jingda Mica Material Co., Ltd., 40 mesh); select D2: mica powder 400 mesh (Dachao Chemical Co., Ltd.);
  • E. Brominated flame retardants E1: Brominated epoxy F-2100, Israel ICL; E2: Brominated polystyrene Saytex 621, Albemarle; E3: Brominated polycarbonate BC-58, Chemtura ; E4: Decabromodiphenylethane 8010, Albemarle; E5: Pentabromobenzyl acrylate FR-1025, Israel ICL;
  • Antimony white choose S-05N, Chenzhou Antimony Industry
  • G. 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);
  • H. Compatibilizer select respectively H1: ethylene-acrylate-glycidyl methacrylate terpolymer, trade mark PTW (DuPont); H2: ethylene-methyl acrylate binary copolymer, trade mark ELVALOY AC 1125 (DuPont) );
  • Processing aids select antioxidants (1010, 168, 412S, Rianlong), pigments (zinc sulfide, Huntsman; black mother PE2718, Cabot), lubricants (PED 521, Clariant; PETS) respectively , hair base), transesterification inhibitor (sodium dihydrogen phosphate, Wuhan Huachuang), antioxidants account for 25wt% of processing aids, pigments are 10-30wt%, lubricants are 30-40wt%, esters The exchange inhibitor ratio is 15-40wt%.
  • the components and amounts of the PBT materials in Examples 1 to 11 are shown in Table 1.
  • the processing aids in Examples 1 and 8 are antioxidant 1010 12.5wt%, antioxidant 168 12.5wt%, black masterbatch PE2718 10wt% %, lubricant PETS 40wt%, sodium dihydrogen phosphate 25wt%; in Example 2, the processing aids are antioxidant 1010 12.5wt%, antioxidant 168 12.5wt%, zinc sulfide 30wt%, lubricant PETS 30wt%, Sodium dihydrogen phosphate 15wt%; in Example 3 and Example 10, the processing aids are antioxidant 1010 12.5wt%, antioxidant 412s 12.5wt%, lubricant PETS 40wt%, sodium dihydrogen phosphate 35wt%; Examples 4-6, the processing aids in Example 7, Example 9, and Example 11 are antioxidant 1010 12.5wt%, antioxidant 168 12.5wt%, lubricant PETS 35wt%, sodium dihydrogen phosphate 40
  • 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 and comparative example 3 do not contain PC resin, and their shock absorption and damping are not as good as the present invention; comparative example 2 does not contain PC resin and shock-absorbing polymer, and their shock absorption and damping are not as good as the present invention; comparative example 4 does not contain tablets As the filler, its shock absorption and damping are not as good as that of the present invention.
  • test groups 1-5 and control groups 1-4 were set up.
  • test groups 1-5 and control groups 1-4 only the amount of shock absorbing polymer, flake filler and PC resin 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 PC resin is 10-13 parts
  • the flake filler is 7-10 parts
  • the shock-absorbing polymer is 6-12 parts
  • the PBT material has better shock-absorbing and damping effect.
  • the amount of shock-absorbing polymer, flake filler and PC resin is not all within the scope of the present invention, and its shock-absorbing and damping effect is not as good as that of the test group 1; the control group 3 does not contain PC resin, and its shock-absorbing and damping effect is The effect is not as good as that of the experimental group 1; It is indicated that the compounding of the shock-absorbing polymer and the sheet filler in the present invention has a synergistic effect, which can greatly improve the shock-absorbing and damping performance; on this basis, adding PC resin can enhance the shock-absorbing and damping.

Abstract

本发明涉及一种减震阻尼有卤阻燃增强PBT材料，所述PBT材料包含如下重量份的组分：PBT树脂30～40份、PC树脂10～15份、片状填料7～12份、减震聚合物6～15份、相容剂1～4份、玻璃纤维20～30份、溴系阻燃剂和锑白复配物10～20份和加工助剂0.1～2份。本发明首次公开报道在工程塑料中含玻纤有卤阻燃体系的聚酯具有减震阻尼效果；本发明得到的减震阻尼有卤阻燃增强聚酯材料，拉伸强度在80MPa以上，缺口冲击强度在6.5kJ/m 2以上(ISO标准)。

Description

一种减震阻尼有卤阻燃增强PBT材料及其制备方法 技术领域
本发明涉及一种减震阻尼有卤阻燃增强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有卤阻燃增强PBT材料，属于工程塑料技术领域。
背景技术
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，未见公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有卤阻燃增强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：一种减震阻尼有卤阻燃增强PBT材料，所述PBT材料包含如下重量份的组分：PBT树脂30～40份、PC树脂10～15份、片状填料7～12份、减震聚合物6～15份、相容剂1～4份、玻璃纤维20～30份、溴系阻燃剂和锑白复配物10～20份和加工助剂0.1～2份。
本发明在有卤阻燃体系中，将减震聚合物与片状填料复配使用，且减震聚合物的用量不低于6份，片状填料的用量不低于7份，复配使用具有减震阻尼效果，然后添加10～15份的PC树脂，对减震阻尼起到增强的作用。
本发明加入减震聚合物作为第二组份，结合片状填料云母和多嵌段共聚的弹性体复合，采用含溴的有卤阻燃剂，通过玻纤增强来获得高机械性能且具有减震阻尼效果的PBT材料。
作为本发明所述PBT材料的优选实施方式，所述溴系阻燃剂和锑白复配物中，溴系阻燃剂和锑白复配物的质量比为3:1～5.2：1。
作为本发明所述PBT材料的优选实施方式，所述PBT材料包含如下重量份的组分：PBT树脂30～40份、PC树脂10～13份、片状填料7～10份、减震聚合物6～12份、相容剂1～2份、玻璃纤维20～30份、溴系阻燃剂和锑白复配物12.5～15.5份和加工助剂1～1.5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0.8～1.2dl/g；所述PC树脂的熔体流动速率为3～22g/10min，所述PC树脂的熔体流动速率是根据ISO 1133-2011使用1.2kg重量并在300℃的温度测量；所述片状填料为云母粉，所述云母粉的目数为40～400目。
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-丙烯酸甲酯二元共聚物、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。
作为本发明所述PBT材料的优选实施方式，所述溴系阻燃剂为溴化环氧树脂、溴化聚苯乙烯、溴化聚碳酸酯、十溴二苯乙烷、聚丙烯酸五溴苄酯中的至少一种；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或聚烯烃类蜡润滑剂，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、PC树脂进行预干燥处理，将经干燥处理后的PBT树脂、PC树脂，以及溴系阻燃剂和锑白复配物、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，即得到减震阻尼有卤阻燃增强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各段螺杆温度分别为加料段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有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有卤阻燃增强聚酯材料，拉伸强度在80MPa以上，缺口冲击强度在6.5kJ/m 2以上(ISO标准)；
(3)本发明得到的减震阻尼有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。
具体实施方式
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、PC树脂在130℃下干燥4小时，水分控制在小于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、PC树脂，与溴系阻燃剂和锑白复配物、片状填料、减震聚合物、相容剂、玻璃纤维、加工助剂按比例进行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，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，即得到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PBT材料在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ISO 180-2000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；A3：仪征化纤GL234，特性粘度为1.2dl/g；
B.PC树脂，分别选用B1：LG化学PC 1300 03NP，熔体流动速率3g/10min(@300℃，1.2kg)；B2：LG化学PC 1300 10NP，熔体流动速率10g/10min(@300℃，1.2kg)；B3：LG化学PC 1300 22NP，熔体流动速率22g/10min(@300℃，1.2kg)；
C.玻璃纤维，分别选用C1：ECS13-3.0-T436W(玻纤直径13μm，长度3.0cm，泰山玻璃纤维有限公司)；C2：ECS11-4.5-534A(玻纤直径11μm，长度4.5cm，巨石集团)；
D.云母粉，选用D1：AY-03N(精达云母材料有限公司，40目)；选用D2：云母粉400目(大潮化工有限公司)；
E.溴系阻燃剂，分别选用E1：溴化环氧F-2100，以色列ICL；E2：溴化聚苯乙烯Saytex 621，雅宝；E3：溴化聚碳酸酯BC-58，科聚亚；E4：十溴二苯乙烷8010，雅宝；E5：聚丙烯酸五溴苄酯FR-1025，以色列ICL；
F.锑白：选用S-05N，辰州锑业；
G.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)；
H.相容剂：分别选用H1：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)；H2：乙烯-丙烯酸甲酯二元共聚物，牌号ELVALOY AC 1125(杜邦)；
I.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)，酯交换抑制剂(磷酸二氢钠，武汉华创)，抗氧剂的占加工助剂比例为25wt％，颜料比例为10-30wt％，润滑剂比例30-40wt％，酯交换抑制剂比例15-40wt％。
实施例1～11
实施例1～11PBT材料的各组分及用量如表1所示，实施例1和实施例8中加工助剂为抗氧剂1010 12.5wt％，抗氧剂168 12.5wt％，黑色母PE2718 10wt％，润滑剂PETS 40wt％，磷酸二氢钠25wt％；实施例2中加工助剂为抗氧剂1010 12.5wt％，抗氧剂168 12.5wt％，硫化锌30wt％，润滑剂PETS 30wt％，磷酸二氢钠15wt％；实施例3和实施例10中加工助剂为抗氧剂1010 12.5wt％，抗氧剂412s 12.5wt％，润滑剂PETS 40wt％，磷酸二氢钠35wt％；实施例4～6、实施例7、实施例9、实施例11中的加工助剂为抗氧剂1010 12.5wt％，抗氧剂168 12.5wt％，润滑剂PETS 35wt％，磷酸二氢钠40wt％；对比例1～4中加工助剂为抗氧剂1010 12.5wt％，抗氧剂168 12.5wt％，润滑剂PETS 40wt％，磷酸二氢钠35wt％，实施例1～11PBT材料的性能测试结果如表2所示。
对比例1～4
对比例1～4PBT材料的各组分及用量如表1所示，对比例1～4PBT材料的性能测试结果如表2所示。
表1
Figure PCTCN2021092854-appb-000001
Figure PCTCN2021092854-appb-000002
表2
Figure PCTCN2021092854-appb-000003
Figure PCTCN2021092854-appb-000004
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和对比例3中不含PC树脂，其减震阻尼不如本发明；对比例2中不含PC树脂、减震聚合物，其减震阻尼不如本发明；对比例4中不含片状填料，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、PC树脂的用量对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、PC树脂的用量不同，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
Figure PCTCN2021092854-appb-000005
由表3可知，减震聚合物、片状填料、PC树脂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。当PC树脂为10～13份、片状填料为7～10份、减震聚合物为6～12份时，PBT材料具有更优的减震阻尼效果。
对照组4～6中，减震聚合物、片状填料、PC树脂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3不含PC树脂，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；在此基础上，加入PC树脂，对减震阻尼起到增强的作用。
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)

  1. 一种减震阻尼有卤阻燃增强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30～40份、PC树脂10～15份、片状填料7～12份、减震聚合物6～15份、相容剂1～4份、玻璃纤维20～30份、溴系阻燃剂和锑白复配物10～20份和加工助剂0.1～2份。
  2. 如权利要求1所述的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30～40份、PC树脂10～13份、片状填料7～10份、减震聚合物6～12份、相容剂1～2份、玻璃纤维20～30份、溴系阻燃剂和锑白复配物12.5～15.5份和加工助剂1～1.5份。
  3. 如权利要求1或2所述的PBT材料，其特征在于，所述溴系阻燃剂和锑白复配物中，溴系阻燃剂和锑白复配物的质量比为3:1～5.2：1。
  4. 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0.8～1.2dl/g；所述PC树脂的熔体流动速率为3～22g/10min，所述PC树脂的熔体流动速率是根据ISO 1133-2011使用1.2kg重量并在300℃的温度测量；所述片状填料为云母粉，所述云母粉的目数为40～400目。
  5. 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-丙烯酸甲酯二元共聚物、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；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。
  6. 如权利要求1或2所述的PBT材料，其特征在于，所述溴系阻燃剂为溴化环氧树脂、溴化聚苯乙烯、溴化聚碳酸酯、十溴二苯乙烷、聚丙烯酸五溴苄酯中的至少一种；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。
  7. 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 酯类蜡润滑剂或聚烯烃类蜡润滑剂，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。
  8. 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、PC树脂进行预干燥处理，将经干燥处理后的PBT树脂、PC树脂，以及溴系阻燃剂和锑白复配物、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，即得到减震阻尼有卤阻燃增强PBT材料。
  9. 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。
  10. 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各段螺杆温度分别为加料段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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