CN102181133A - Metal fiber reinforced polybutylene terephthalate (PBT) resin and preparation method thereof - Google Patents

Metal fiber reinforced polybutylene terephthalate (PBT) resin and preparation method thereof Download PDF

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Publication number
CN102181133A
CN102181133A CN2011100296327A CN201110029632A CN102181133A CN 102181133 A CN102181133 A CN 102181133A CN 2011100296327 A CN2011100296327 A CN 2011100296327A CN 201110029632 A CN201110029632 A CN 201110029632A CN 102181133 A CN102181133 A CN 102181133A
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Prior art keywords
pbt resin
steel fiber
strengthens
pbt
resin
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CN2011100296327A
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Chinese (zh)
Inventor
胡沁
丁宗勤
许本刚
李强
罗明华
辛敏琦
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GUANGDONG KUMBO SUNNY POLYMER MATERIAL CO Ltd
Shanghai Kumho Sunny Plastics Co Ltd
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GUANGDONG KUMBO SUNNY POLYMER MATERIAL CO Ltd
Shanghai Kumho Sunny Plastics Co Ltd
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Application filed by GUANGDONG KUMBO SUNNY POLYMER MATERIAL CO Ltd, Shanghai Kumho Sunny Plastics Co Ltd filed Critical GUANGDONG KUMBO SUNNY POLYMER MATERIAL CO Ltd
Priority to CN2011100296327A priority Critical patent/CN102181133A/en
Publication of CN102181133A publication Critical patent/CN102181133A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92704Temperature
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92819Location or phase of control
    • B29C2948/92857Extrusion unit
    • B29C2948/92876Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895Barrel or housing

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a metal fiber reinforced polybutylene terephthalate (PBT) resin and a preparation method thereof. The metal fiber reinforced PBT resin contains 60 to 80 weight percent of PBT resin, 10 to 30 weight percent of metal fiber, 0 to 10 weight percent of toughening agent, 0 to 1 weight percent of antioxidant and 0.5 to 2 weight percent of processing auxiliary agent. The preparation method comprises the following steps of: drying the PBT resin till the moisture of the PBT resin is less than 0.02 percent, uniformly dispersing the PBT resin, the toughening agent, the antioxidant and other processing auxiliary agent, performing high-speed mixing, adding the metal fiber at the downstream of an extruder, melting, mixing, extruding, cooling and drying to obtain the metal fiber reinforced PBT resin. By adding one or more metal fiber fillers into the PBT resin, the thermal shock resistance of the metal fiber reinforced PBT resin is effectively improved.

Description

Steel fiber strengthens PBT resin and preparation method thereof
Technical field
The present invention relates to the PBT resin, particularly relate to a kind of steel fiber and strengthen PBT resin and preparation method thereof.
Background technology
Material behavior is as material coefficient of thermal expansion coefficient, thermal conductivity, Young's modulus, material inherent strength, fracture toughness property etc.Generally speaking, thermal expansivity is more little, and material is little because of the volume change that temperature variation causes, the thermal stress of corresponding generation is little, and heat-shock resistance is good more; Thermal conductivity is big, and the temperature difference of material internal is more little, and the stress-difference that is caused by the temperature difference is more little, and heat-shock resistance is good more; The material inherent strength is high more, bears thermal stresses and unlikely destructive intensity is big more, good thermal shock; Young's modulus is big more, material production recoverable deformation and alleviate with the ability of rejected heat stress by force more, and heat-shock resistance is good more.In addition, shape is simple relatively, the uniform relatively member thermal shock resistance of profile is better than complex-shaped, the uneven member of structure.
The new crackle that material produces in thermal shock, and the cracking that causes of new crackle and original crack expansion, peel off, situation such as fracture, be called thermal shock and damage.The thermal shock damage is the result of thermal stresses effect.Material is when temperature variation, and it is thermal stresses that distortion is suppressed the stress that is produced.The different heterogeneous object of thermal linear expansion coefficient is when temperature variation, and the object of homogeneous thermal expansion is subjected to thermograde and does the time spent, and during phase transformation, all can produce thermal stresses.Thermal stresses is directly proportional with the springform tribute and the recoverable strain of material, and recoverable strain equals the product of linear expansivity and temperature variation.
Along with the incremental development of plastic industry, increasing plastic prod requires also more and more high to its structure design, dimensional precision, dimensional stability, assembling and fastening.On the one hand,, in goods, place the metal insert that is fit to, can improve the partial physical strength of plastic, wear resistance, electrical property, increase the stability of plastics size and dimension, improve the product precision according to the plastics application target; On the other hand, can reduce the weight of metallic article, reduce the possibility that metallic article is corroded, improve product work reliability etc.Yet, plastics are with after metal insert combines, easily produce big stress, under high low temperature recurrent state, cause the goods cracking after the stress relief, particularly more obvious after adding the inorganic materials enhancing in the plastics, after adding glass fibre, plastics combine the back goods and are very easy to cracking, rupture with metal insert.The performance of this cracking resistance of material is referred to as heat-shock resistance, refers to that material is bearing dramatic temperature when changing, and estimates the important indicator of its resisting breakage ability.At present present situation easy to crack, need improve heat-shock resistance.
This invention is that one or more steel fiber fill compositions are joined in the PBT resin, to improve the thermal shock resistance of PBT resin.
Summary of the invention
The object of the present invention is to provide a kind of steel fiber to strengthen the PBT(polybutylene terephthalate) resin, make the PBT resin have good heat-shock resistance, reduce PBT resin and metal insert goods rimose phenomenon.
Another object of the present invention is to provide this steel fiber to strengthen the preparation method of PBT resin.
Steel fiber of the present invention strengthens the PBT resin, contains following component:
60 ~ 80wt%PBT resin;
10 ~ 30wt% steel fiber;
0 ~ 10wt% toughner;
0 ~ 1wt% oxidation inhibitor;
0.5 ~ 2wt% processing aid.
Steel fiber of the present invention strengthens the PBT resin, and described PBT resin is that limiting viscosity is one or more the compound among 0.74,0.84,1.0 or 1.2 the PBT.
Steel fiber of the present invention strengthens the PBT resin, and described steel fiber is one or more a compound in Stainless Steel Fibre, aluminum fiber, copper fiber, nickel fiber, the copper alloy fiber.
Steel fiber of the present invention strengthens the PBT resin, and the diameter of described steel fiber is the 0.5-50 micron, and mean length is the 0.5-3 micron.
Steel fiber of the present invention strengthens the PBT resin, and described steel fiber is for carrying out the surface-treated steel fiber through coupling agent; Described coupling agent is silane coupling agent, titanate coupling agent, one or more compounds of aluminate coupling agent etc.
Steel fiber of the present invention strengthens the PBT resin, and described toughner is one or more the compound in ethylene-methyl acrylate-glycidyl methacrylate random terpolymer, ethylene-methyl acrylate copolymer, the ethylene-vinyl acetate copolymer.
Steel fiber of the present invention strengthens the PBT resin, and described oxidation inhibitor is one or more the compound in Hinered phenols antioxidant, phosphite ester kind antioxidant, the organosulfur oxidation inhibitor.As 246,264,1010,1076,168 etc., prevent to process with long-time actual use in the oxidation of PBT resin.
Steel fiber of the present invention strengthens the PBT resin, and described processing aid is one or more in softening agent, nucleator, lubricant, releasing agent, photostabilizer, pigment, the dyestuff.
Steel fiber of the present invention strengthens the preparation method of PBT resin, the PBT resin is following dry 4 ~ 6 hours at 120 ~ 140 ℃, make its moisture less than 0.02%, with the PBT resin, toughner, behind oxidation inhibitor and other processing aid high speed thorough mixing, send into twin screw extruder through measuring apparatus, conveying by screw rod, shearing and mixing, material melting, compound, add steel fiber in the forcing machine downstream, again through extruding, cooling, dry back obtains described steel fiber and strengthens the PBT resin, wherein, the feeding rotating speed is controlled at 250 ~ 350rpm, and each subregion temperature of screw extrusion press remains on 200 ~ 240 ℃, screw speed 250rpm ~ 350rpm, vacuum pump on the forcing machine is extracted small molecules low-boiling point material and moisture out, and the vacuum tightness in the control forcing machine is lower than 0.06MPa.
The present invention is base material with PBT, adds steel fiber, makes the PBT resin have good heat-shock resistance, reduce PBT glass-fibre reinforced resin and metal insert goods rimose phenomenon, a kind of high strength is provided, the steel fiber of high thermal conductivity, good thermal shock resistance energy strengthens the PBT resin.
Description of drawings
Fig. 1 is thermal shock resistance test standard inserts synoptic diagram.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described.Should be understood that following examples only are used to the present invention to be described but not to be used to limits the scope of the invention.
Embodiment 1 ~ 8
At first with the PBT resin, limiting viscosity 1.0 is carried out drying treatment, in 120 ~ 140 ℃ of down dry 4 ~ 6h, makes its moisture content be lower than 0.02%.Then place the high speed mixing machine to stir, disperse, mix dried PBT resin, toughner, oxidation inhibitor and other processing aid, send in the twin screw extruder through measuring apparatus.Each feed composition is as shown in table 1.Open vacuum pump, small molecules low-boiling point material and moisture are extracted out, the vacuum tightness in the forcing machine is maintained be lower than 0.06Mpa.By conveying, the shearing and mixing of screw rod, material melting, compound adds Stainless Steel Fibre in the forcing machine downstream, and diameter is the 0.5-50 micron, and mean length is the 0.5-3 micron, again through extrude, cool off, dry back obtains described steel fiber enhancing PBT resin.Wherein, the feeding rotating speed is controlled at 250 ~ 350rpm, screw speed 250rpm ~ 350rpm, screw extrusion press 1 district ~ 10 districts, each subregion temperature remains on 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 240 ℃, 240 ℃, 240 ℃, 240 ℃, 230 ℃ respectively.Steel fiber strengthens the PBT resin through pelletizing, and the packing back is stand-by.
Table 1 feed composition and thermal shock resistance
Figure 2011100296327100002DEST_PATH_IMAGE001
Embodiment 9
With the PBT resin, (limiting viscosity 1.0) and conveying, the shearing and mixing of glass fibre by screw rod, material melting, compound, add glass fibre in the forcing machine downstream, the feeding rotating speed is controlled at 200 ~ 350rpm, screw speed 200rpm ~ 350rpm, screw extrusion press 1 district ~ 10 districts, each subregion temperature remains on 200 ℃, 220 ℃, 230 ℃, 230 ℃, 240 ℃, 240 ℃, 240 ℃, 240 ℃, 240 ℃, 220 ℃ respectively, and through pelletizing, the packing back is stand-by.
The resin of embodiment 1 ~ 9 preparation is made the standard inserts that the heat-shock resistance evaluation test is used by shown in Figure 1 after injection moulding, carry out the thermal shock resistance evaluation, the result is as shown in table 1.Concrete experiment condition: low temperature-40 ℃, 1 hour time, 140 ℃ of high temperature, 1 hour time, high low temperature circulation primary is an one-period, writes down its cycle index until standard inserts generation cracking phenomena, and cycle index is high more, and material heat-shock resistance performance is good more.As shown in Table 1, the present invention is base material with PBT, add steel fiber, make the PBT resin have good heat-shock resistance, reduce PBT glass-fibre reinforced resin and metal insert goods rimose phenomenon, a kind of high strength is provided, and the steel fiber of high thermal conductivity, good thermal shock resistance energy strengthens the PBT resin.
Should be noted that at last, above embodiment is only in order to illustrate technical scheme of the present invention, but not limiting the scope of the invention, although the present invention has been done to explain with reference to above embodiment, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement technical scheme of the present invention, one or more compound replaces Stainless Steel Fibre in aluminum fiber, copper fiber, nickel fiber, the copper alloy fiber as adopting; Steel fiber adopts through coupling agent and carries out the surface-treated steel fiber, and described coupling agent is silane coupling agent, titanate coupling agent, one or more compounds of aluminate coupling agent.It is one or more compound among 0.74,0.84,1.0 or 1.2 the PBT that the PBT resin is adopted as limiting viscosity.Toughner is one or more the compound in ethylene-methyl acrylate-glycidyl methacrylate random terpolymer, ethylene-methyl acrylate copolymer, the ethylene-vinyl acetate copolymer.Described oxidation inhibitor is one or more the compound in Hinered phenols antioxidant, phosphite ester kind antioxidant, the organosulfur oxidation inhibitor.As 246,264,1010,1076,168 etc., prevent to process with long-time actual use in the oxidation of PBT resin.Processing aid is one or more in softening agent, nucleator, lubricant, releasing agent, photostabilizer, pigment, the dyestuff.

Claims (9)

1. a steel fiber strengthens the PBT resin, it is characterized in that, contains following component:
60 ~ 80wt%PBT resin;
10 ~ 30wt% steel fiber;
0 ~ 10wt% toughner;
0 ~ 1wt% oxidation inhibitor;
0.5 ~ 2wt% processing aid.
2. steel fiber according to claim 1 strengthens the PBT resin, it is characterized in that, described PBT resin is that limiting viscosity is one or more the compound among 0.74,0.84,1.0 or 1.2 the PBT.
3. steel fiber according to claim 1 strengthens the PBT resin, it is characterized in that, described steel fiber is one or more a compound in Stainless Steel Fibre, aluminum fiber, copper fiber, nickel fiber, the copper alloy fiber.
4. steel fiber according to claim 1 strengthens the PBT resin, it is characterized in that the diameter of described steel fiber is the 0.5-50 micron, and mean length is the 0.5-3 micron.
5. steel fiber according to claim 1 strengthens the PBT resin, it is characterized in that, described steel fiber is for carrying out the surface-treated steel fiber through coupling agent; Described coupling agent is silane coupling agent, titanate coupling agent, one or more compounds of aluminate coupling agent.
6. steel fiber according to claim 1 strengthens the PBT resin, it is characterized in that described toughner is one or more the compound in ethylene-methyl acrylate-glycidyl methacrylate random terpolymer, ethylene-methyl acrylate copolymer, the ethylene-vinyl acetate copolymer.
7. steel fiber according to claim 1 strengthens the PBT resin, it is characterized in that, described oxidation inhibitor is one or more the compound in Hinered phenols antioxidant, phosphite ester kind antioxidant, the organosulfur oxidation inhibitor.
8. steel fiber according to claim 1 strengthens the PBT resin, it is characterized in that described processing aid is one or more in softening agent, nucleator, lubricant, releasing agent, photostabilizer, pigment, the dyestuff.
9. strengthen the preparation method of PBT resin according to each described steel fiber of claim 1 ~ 7, it is characterized in that, may further comprise the steps:
(a), with the PBT resin 120 ~ 140 ℃ dry 4 ~ 6 hours down, make its moisture less than 0.02%;
(b), with behind PBT resin, toughner, oxidation inhibitor and other processing aid high speed thorough mixing, send into twin screw extruder through measuring apparatus, by conveying, the shearing and mixing of screw rod, material melting, compound;
(c), add steel fiber in the forcing machine downstream, again through extrude, cool off, dry back obtains described steel fiber enhancing PBT resin;
Wherein, the feeding rotating speed is controlled at 250 ~ 350rpm, and each subregion temperature of screw extrusion press remains on 200 ~ 240 ℃, and the vacuum tightness in the screw speed 250rpm ~ 350rpm, forcing machine is lower than 0.06MPa.
CN2011100296327A 2011-01-27 2011-01-27 Metal fiber reinforced polybutylene terephthalate (PBT) resin and preparation method thereof Pending CN102181133A (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102746623A (en) * 2011-11-24 2012-10-24 南京鸿瑞塑料制品有限公司 Preparation method for insulating heat conduction material
CN103450676A (en) * 2013-08-07 2013-12-18 上海日之升新技术发展有限公司 Continuous long aluminum fiber reinforced PA66 composite and preparation method thereof
CN103467931A (en) * 2013-08-07 2013-12-25 上海日之升新技术发展有限公司 Continuous long aluminum fiber reinforced PBT complex and preparation method thereof
CN103819863A (en) * 2014-03-03 2014-05-28 上海瀚氏模具成型有限公司 High temperature-resistant fiber-reinforced ASA/PC plastic for automotive upholstery and preparation method of fiber-reinforced ASA/PC plastic
CN103834148A (en) * 2014-03-03 2014-06-04 上海瀚氏模具成型有限公司 High heat-proof fiber-reinforced PBT plastic for automotive interior parts and preparation method thereof
CN104552970A (en) * 2013-10-25 2015-04-29 中国石油化工股份有限公司 Polymer composite fiber containing superfine metal fibers and preparation method of polymer composite fiber
CN105131545A (en) * 2015-09-18 2015-12-09 安徽创业机电设备有限公司 High-strength and high-ductility bristle
CN107353455A (en) * 2017-08-22 2017-11-17 江苏鑫鼎瑞运动用品科技有限公司 One kind has dulcet environment-friendly type rope skipping material
CN107650295A (en) * 2016-07-26 2018-02-02 江苏和伟美科技发展有限公司 It is a kind of to prepare equipment for exempting to spray PBT and preparation method thereof
CN109206922A (en) * 2017-07-04 2019-01-15 镇江市睿泽文化传播有限公司 A kind of high impact resins plastics
CN109206923A (en) * 2017-07-04 2019-01-15 镇江市睿泽文化传播有限公司 A kind of flame-retardant resin plastics
CN109206921A (en) * 2017-07-04 2019-01-15 镇江市睿泽文化传播有限公司 A kind of anti-oxidation resin plastics

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CN1566248A (en) * 2003-06-13 2005-01-19 赵立民 Weathering-resistant and permeable adhesive for paving a road and its constitutional body
CN1810879A (en) * 2005-11-07 2006-08-02 温州市华兴托辊制造有限公司 Roller of composite polymer material
CN101469109A (en) * 2007-12-28 2009-07-01 上海杰事杰新材料股份有限公司 Polyester / metal fibre conductive, heat conducting and fast crystallization composite material and preparation thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1566248A (en) * 2003-06-13 2005-01-19 赵立民 Weathering-resistant and permeable adhesive for paving a road and its constitutional body
CN1810879A (en) * 2005-11-07 2006-08-02 温州市华兴托辊制造有限公司 Roller of composite polymer material
CN101469109A (en) * 2007-12-28 2009-07-01 上海杰事杰新材料股份有限公司 Polyester / metal fibre conductive, heat conducting and fast crystallization composite material and preparation thereof

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102746623B (en) * 2011-11-24 2014-09-03 南京鸿瑞塑料制品有限公司 Preparation method for insulating heat conduction material
CN102746623A (en) * 2011-11-24 2012-10-24 南京鸿瑞塑料制品有限公司 Preparation method for insulating heat conduction material
CN103450676A (en) * 2013-08-07 2013-12-18 上海日之升新技术发展有限公司 Continuous long aluminum fiber reinforced PA66 composite and preparation method thereof
CN103467931A (en) * 2013-08-07 2013-12-25 上海日之升新技术发展有限公司 Continuous long aluminum fiber reinforced PBT complex and preparation method thereof
CN103467931B (en) * 2013-08-07 2016-01-13 上海日之升新技术发展有限公司 Continuous long aluminum fiber strengthens PBT mixture and preparation method thereof
CN104552970B (en) * 2013-10-25 2018-11-30 中国石油化工股份有限公司 A kind of polymer composite fibrous preparation method and its preparation containing ultrafine metal fibers it is polymer composite fibrous
CN104552970A (en) * 2013-10-25 2015-04-29 中国石油化工股份有限公司 Polymer composite fiber containing superfine metal fibers and preparation method of polymer composite fiber
CN103819863A (en) * 2014-03-03 2014-05-28 上海瀚氏模具成型有限公司 High temperature-resistant fiber-reinforced ASA/PC plastic for automotive upholstery and preparation method of fiber-reinforced ASA/PC plastic
CN103834148A (en) * 2014-03-03 2014-06-04 上海瀚氏模具成型有限公司 High heat-proof fiber-reinforced PBT plastic for automotive interior parts and preparation method thereof
CN103834148B (en) * 2014-03-03 2015-10-14 上海瀚氏模具成型有限公司 The resistance to high thermal fiber of a kind of automotive upholstery strengthens PBT plastic and preparation method thereof
CN103819863B (en) * 2014-03-03 2016-08-17 上海瀚氏模具成型有限公司 A kind of automotive upholstery high heat resistance fiber reinforcement ASA/PC plastics and preparation method thereof
CN105131545A (en) * 2015-09-18 2015-12-09 安徽创业机电设备有限公司 High-strength and high-ductility bristle
CN107650295A (en) * 2016-07-26 2018-02-02 江苏和伟美科技发展有限公司 It is a kind of to prepare equipment for exempting to spray PBT and preparation method thereof
CN109206922A (en) * 2017-07-04 2019-01-15 镇江市睿泽文化传播有限公司 A kind of high impact resins plastics
CN109206923A (en) * 2017-07-04 2019-01-15 镇江市睿泽文化传播有限公司 A kind of flame-retardant resin plastics
CN109206921A (en) * 2017-07-04 2019-01-15 镇江市睿泽文化传播有限公司 A kind of anti-oxidation resin plastics
CN107353455A (en) * 2017-08-22 2017-11-17 江苏鑫鼎瑞运动用品科技有限公司 One kind has dulcet environment-friendly type rope skipping material

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Application publication date: 20110914