CN105331055A - PBT composite material used for NMT forming and preparation method thereof - Google Patents
PBT composite material used for NMT forming and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a PBT composite material used for NMT forming and a preparation method thereof. The PBT composite material used for NMT forming is characterized by being prepared from, by mass, 100 parts of polybutylene terephthalate, 10-15 parts of flexibilizers, 30-40 parts of reinforcing agents, 3-5 parts of lubricating agents, 5-8 parts of compatilizers, 0.2-0.8 part of nano materials, 0.5-1 part of antioxidants and 0.5-1 part of coupling agents. The nano materials are prepared from at least one of nano alumina, nano magnesia and nano iron oxide. The reinforcing agents are prepared from glass fibers. The PBT composite material used for NMT forming can be applied to NMT forming.
Description
Technical field
The present invention relates to technical field of polymer materials, particularly for PBT composite, its preparation method that NMT is shaping.
Background technology
NMT (NanoMoldingTechnology) is by nanometer forming technique integrated with plastics for metal, developed by Japanese great achievement plastics Co., Ltd. (Taiseiplas) the earliest, can by metal and hard resin integrated moldings such as aluminium, magnesium, stainless steel, titaniums.Current NMT forming technique large-scale application be thin, light, portable 3C Product, as notebook computer shell, projector case, phone housing, MP3 player etc.NMT forming technique core concept is combined metal, plastics, replaces at present conventional embedding injection, zinc-aluminium, magnalium die casting, provides one to have price advantage, high performancely mould golden integrated product.
The treatment process of NMT comprises flow process as follows: by needs combine metal carry out base extraction, acid treatment, T liquid (ester propylhomoserin) process, clean up with water again after carry out drying, injection moulding.Metallic surface after treatment, countless apertures will be formed in metallic surface and be about 20nm micropore, that is, can think the metallic surface after passing through process defines much small concaveconvex structure, the resin of injection enters in these concaveconvex structures, produces anchoring effect.Meanwhile, when resin injection to process after metallic surface time, the resin containing ester group will react with T liquid generation ester amine, thus is closely linked.
At present, can be used for the shaping metallic substance of NMT and mainly concentrate on aluminium, magnesium material, also have copper, stainless steel, titanium, iron, red copper various metals to bond simultaneously.Spendable resin also has PBT, PPS, nylon 6, nylon66 fiber.Saturated linear hemicrystalline polyester PBT has excellent mechanical property, good resistance to fatigue, preferably impelling strength, lower frictional coefficient, good thermotolerance and good moulding processability.
In recent years, domestic and international researchist's many employings fiberglass reinforced modified PBT material, not only can promote the physical and mechanical properties of PBT material, solves the fatigue resistance of PBT material simultaneously, weathering resistance, frictional behaviour aspect also have and improve effect preferably.But glass fiber reinforcement PBT material still has weak point, namely when injection moulding large product or thin-walled parts, have larger warpage and occur, this not only affects the outward appearance of goods, affects the work-ing life of modified PBT material simultaneously.The research paper retrieving a large amount of patent documentations and publish, there is not yet the research report being applied to the shaping PBT material of NMT, particularly have no and adopt polybutylene terephthalate (PBT) to be raw material, add ethylene-octene segmented copolymer OBC, nano-sized iron oxide, nano magnesia or nano aluminium oxide, flat alkali free glass fibre and shortly cut alkali free glass fibre, preparation can be used for shaping poly-to stupid dioctyl phthalate butanediol ester (PBT) matrix material of NMT.
Summary of the invention
Based on this, be necessary that providing a kind of can be applied to shaping PBT composite of NMT and preparation method thereof.
For the PBT composite that NMT is shaping, according to massfraction meter, comprise following component:
Wherein, described nano material is selected from least one in nano aluminium oxide, nano magnesia and nano-sized iron oxide, and described toughener is glass fibre.
Wherein in an embodiment, described toughner is ethylene-octene segmented copolymer, and in described toughner, the mass content of octene is 47% ~ 53%.
Wherein in an embodiment, described toughener is selected from flat alkali free glass fibre and short at least one of cutting in alkali free glass fibre.
Wherein in an embodiment, described lubricant is polysiloxane.
Wherein in an embodiment, described compatilizer is glycidyl ester, ethene and methyl esters methyl acrylate terpolymer.
Wherein in an embodiment, described coupling agent is silane coupling agent.
Wherein in an embodiment, the particle diameter of described nano material is 104nm ~ 157nm.
Wherein in an embodiment, described oxidation inhibitor is phenolic antioxidant.
For a preparation method for the shaping PBT composite of NMT, comprise the steps:
According to massfraction meter, take following raw material: polybutylene terephthalate 100 parts, toughner 10 ~ 15 parts, toughener 30 ~ 40 parts, lubricant 3 ~ 5 parts, compatilizer 5 ~ 8 parts, nano material 0.2 ~ 0.8 part, 0.5 ~ 1 part, oxidation inhibitor and coupling agent 0.5 ~ 1.0 part, wherein, described nano material is selected from least one in nano aluminium oxide, nano magnesia and nano-sized iron oxide, and described toughener is glass fibre;
In described coupling agent 1% ~ 3% and ethanol are hybridly prepared into the first solution, and by described nano material and described first solution, high-speed stirring at 62 DEG C ~ 86 DEG C obtains the first material;
Remaining described coupling agent and ethanol are hybridly prepared into the second solution, and by described toughener and described second solution, stirring at low speed at 57 DEG C ~ 76 DEG C obtains the second material;
Compound is obtained by after described polybutylene terephthalate, described toughner, described lubricant, described compatilizer and described oxidation inhibitor high-speed mixing, described compound is added in forcing machine as the first material, described first material is added by main feed system, the second material is added by side feed system, extrudes rear granulation and obtains for the shaping PBT composite of NMT.
Wherein in an embodiment, in described first solution and in described second solution, the mass ratio of described coupling agent and described ethanol is 1 ~ 3:2.3 ~ 7.
The above-mentioned PBT composite shaping for NMT by adding the glass fibre of 10 parts ~ 15 parts as toughener in the polybutylene terephthalate of 100 parts, the nano material adding 0.2 ~ 0.8 part is carried out composite, the coefficient of linear expansion for the shaping PBT composite of NMT can be reduced significantly, thus with metal base, there is in coefficient of linear expansion good matching, effectively solve the two in the problem occurring to peel off in conjunction with section, thus it is shaping to be widely used in NMT.
Embodiment
Mainly below to be described in further detail for shaping PBT composite of NMT and preparation method thereof in conjunction with specific embodiments.
The PBT composite shaping for NMT of one embodiment, according to massfraction meter, comprises following component:
Wherein, nano material is selected from least one in nano aluminium oxide, nano magnesia and nano-sized iron oxide, and toughener is glass fibre.
Polybutylene terephthalate (PBT) is main raw material.Preferably, PBT resin limiting viscosity is 1.15 ~ 1.18dL/g, and density is 1.31 ~ 1.33g/cm
3, fusing point 223 ~ 227 DEG C, quality melt flow rate (MFR) 27 ~ 29g/10min, tensile strength 55.2MPa, flexural strength 81.7MPa.
Preferably, toughner is ethylene-octene segmented copolymer, and in toughner, the mass content of octene is 47% ~ 53%.Preferred further, toughner quality melt flow rate (MFR) 0.482 ~ 0.882g/10min.Toughner is preferably at least one in INFUSE9000 and INFUSE9007 of DOW chemical company
Preferably, toughener is selected from flat alkali free glass fibre and short at least one of cutting in alkali free glass fibre.Concrete, the aspect ratio of flat alkali free glass fibre is 4:1, and length is 3 ~ 6 millimeters; The short diameter cutting alkali free glass fibre is 9 ~ 13 microns, and length is 3 ~ 6 millimeters.
Preferably, lubricant is polysiloxane.Being preferably the German Wa Ke company trade mark is PA445200 watt of gram silicone.
Preferably, compatilizer is glycidyl ester, ethene and methyl esters methyl acrylate terpolymer.Be more preferably the product of French Arkema, the trade mark is AX-8900.
Preferably, coupling agent is silane coupling agent.Be more preferably German BASF TU169 glycidyl ether oxygen propyl trimethoxy silicane coupling agent.
Preferably, oxidation inhibitor is phenolic antioxidant.Be more preferably BASF IRGANOX1010 oxidation inhibitor
Preferably, the particle diameter of nano material is 104nm ~ 157nm.
The above-mentioned PBT composite shaping for NMT has the following advantages:
(1), glycidyl ester, ethene and methyl esters methyl acrylate terpolymer is used.
As compatilizer, glycidyl ester, methyl acrylate segment in ethene and methyl esters methyl acrylate terpolymer to melt extrude in process can with polybutylene terephthalate generation transesterification reaction, simultaneously with reacting property of the hydroxyl increase-volume on simple glass fiber and flat glass fiber surface, to realize dispersed in polybutylene terephthalate of simple glass fiber and flat glass fiber, thus effectively improve that resist warping performance of matrix material, improve the warpage issues of matrix material, the notched Izod impact strength of PBT material can be improved significantly, consistency, mobility, crystallization velocity, surface luster etc.
(2), by adding the glass fibre of 10 parts ~ 15 parts as toughener in the polybutylene terephthalate of 100 parts, the nano material adding 0.2 ~ 0.8 part is carried out composite, the coefficient of linear expansion for the shaping PBT composite of NMT can be reduced significantly, thus with metal base, there is in coefficient of linear expansion good matching, effectively solve the two in the problem occurring to peel off in conjunction with section, thus it is shaping to be widely used in NMT.
The preparation method of the above-mentioned PBT composite shaping for NMT, comprises the steps:
Step S110, according to massfraction meter, take following raw material: polybutylene terephthalate 100 parts, toughner 10 ~ 15 parts, toughener 30 ~ 40 parts, lubricant 3 ~ 5 parts, compatilizer 5 ~ 8 parts, nano material 0.2 ~ 0.8 part, 0.5 ~ 1 part, oxidation inhibitor and coupling agent 0.5 ~ 1.0 part, wherein, nano material is selected from least one in nano aluminium oxide, nano magnesia and nano-sized iron oxide, and toughener is glass fibre.
Polybutylene terephthalate (PBT) is main raw material.Preferably, PBT resin limiting viscosity is 1.15 ~ 1.18dL/g, and density is 1.31 ~ 1.33g/cm
3, fusing point 223 ~ 227 DEG C, quality melt flow rate (MFR) 27 ~ 29g/10min, tensile strength 55.2MPa, flexural strength 81.7MPa.
Preferably, toughner is ethylene-octene segmented copolymer, and in toughner, the mass content of octene is 47% ~ 53%.Preferred further, toughner quality melt flow rate (MFR) 0.482 ~ 0.882g/10min.Toughner is preferably at least one in INFUSE9000 and INFUSE9007 of DOW chemical company
Preferably, toughener is selected from flat alkali free glass fibre and short at least one of cutting in alkali free glass fibre.Concrete, the aspect ratio of flat alkali free glass fibre is 4:1, and length is 3 ~ 6 millimeters; The short diameter cutting alkali free glass fibre is 9 ~ 13 microns, and length is 3 ~ 6 millimeters.
Preferably, lubricant is polysiloxane.Being preferably the German Wa Ke company trade mark is PA445200 watt of gram silicone.
Preferably, compatilizer is glycidyl ester, ethene and methyl esters methyl acrylate terpolymer.Be more preferably the product of French Arkema, the trade mark is AX-8900.
Preferably, coupling agent is silane coupling agent.Be more preferably German BASF TU169 glycidyl ether oxygen propyl trimethoxy silicane coupling agent.
Preferably, oxidation inhibitor is phenolic antioxidant.Be more preferably BASF IRGANOX1010 oxidation inhibitor
Preferably, the particle diameter of nano material is 104nm ~ 157nm.
Step S120,1% ~ 3% in coupling agent and ethanol are hybridly prepared into the first solution, by nano material and the first solution, high-speed stirring at 62 DEG C ~ 86 DEG C obtains the first material.
Preferably, in the first solution, the mass ratio of coupling agent and ethanol is 1 ~ 3:2.3 ~ 7.
Preferably, ethanol is dehydrated alcohol.
Preferably, coupling agent and ethanol are at room temperature stirred within 2 ~ 3 minutes, make the first solution.
Preferably, the rotating speed of high-speed stirring is 800 ~ 1200rpm.
Preferably, the time of high-speed stirring is 8 minutes ~ 10 minutes.
Preferably, nano material is placed in homogenizer, temperature is set to 62 DEG C ~ 86 DEG C, and is set to low-speed mode, adds entrance at the uniform velocity add the first solution from liquid, high-speed stirring 8 ~ 10 minutes after reinforced end.Wherein, the rotating speed of low-speed mode is 80 ~ 120rpm.
Step S130, remaining coupling agent and ethanol are hybridly prepared into the second solution, by toughener and the second solution, stirring at low speed at 57 DEG C ~ 76 DEG C obtains the second material.
Preferably, in the second solution, the mass ratio of coupling agent and ethanol is 1 ~ 3:2.3 ~ 7.
Preferably, ethanol is dehydrated alcohol.
Preferably, coupling agent and ethanol are at room temperature stirred within 2 ~ 3 minutes, make the second solution.
Preferably, the rotating speed of stirring at low speed is 80 ~ 120rpm.
Preferably, the time of stirring at low speed is 6 minutes ~ 8 minutes.
Preferably, toughener is placed in homogenizer, temperature is set to 57 DEG C ~ 76 DEG C, and is set to low-speed mode, adds entrance at the uniform velocity add the first solution from liquid, stirring at low speed 6 minutes ~ 8 minutes after reinforced end.
Step S140, obtain compound by after polybutylene terephthalate, toughner, lubricant, compatilizer and oxidation inhibitor high-speed mixing, compound is added in forcing machine, first material is added by main feed system, simultaneously the second material added by side feed system, extrude rear granulation and obtain for the shaping PBT composite of NMT.
Preferably, polybutylene terephthalate first toasts 1 hour ~ 2 hours before mixing at 102 DEG C ~ 118 DEG C.
Preferably, polybutylene terephthalate, toughner, lubricant, compatilizer and oxidation inhibitor are placed in high-speed mixer high speed mixing 5 ~ 7 minutes.
Preferably, forcing machine is twin screw extruder.Preferred, the design parameter of twin screw extruder is, one district's temperature 181 ~ 198 DEG C, two district's temperature 218 ~ 229 DEG C, three district's temperature 223 ~ 237 DEG C, four district's temperature 235 ~ 247 DEG C, five district's temperature 236 ~ 244 DEG C, six district's temperature 219 ~ 232 DEG C, seven district's temperature 211 ~ 223 DEG C, eight district's temperature 210 ~ 223 DEG C, nine district's temperature 210 ~ 225 DEG C, die temperature 238 ~ 246 DEG C, the residence time is 1 ~ 2 minute, and pressure is 5 ~ 7MPa.
The preparation method of the above-mentioned PBT composite shaping for NMT is simple to operate, is easy to industrialization; The PBT composite shaping for NMT and the metal base of preparation have good matching in coefficient of linear expansion, effectively solve the two in the problem occurring to peel off in conjunction with section, thus it are shaping to be widely used in NMT.
Be below specific embodiment part:
Embodiment 1
The preparation process of the PBT composite shaping for NMT of the present embodiment is as follows:
(1) component in table 1, according to the mass fraction, is taken:
Table 1
(2) nano material is placed in homogenizer, 1 part of silane coupling agent is placed in beaker A, by silane coupling agent: dehydrated alcohol is that 1:2.3 takes dehydrated alcohol and is placed in beaker A, and stirring at room temperature X minute, makes it mix simultaneously; Start homogenizer, temperature is set to 70 DEG C, and be placed in low-speed mode, add entrance in upper end liquid and at the uniform velocity add the silane coupling agent ethanolic soln be equipped with, fast mode is started after coupling agent adds, high-speed stirring 8 minutes, obtains the first material, and wherein the rotating speed of high-speed stirring is 950rpm.
(3), by glass fibre be placed in homogenizer, 1 part of silane coupling agent is placed in beaker B, by silane coupling agent: dehydrated alcohol is that 1:2.3 takes dehydrated alcohol and is placed in beaker B, and stirring at room temperature 8 minutes, makes it mix simultaneously; Start homogenizer, temperature is set to 65 DEG C, and is placed in low-speed mode, add entrance in upper end liquid and at the uniform velocity add the silane coupling agent ethanolic soln be equipped with, after coupling agent adds, stirring at low speed 3 minutes, obtain the second material, wherein the rotating speed of stirring at low speed is 110rpm.
The preparation of step 3, PBT composite:
PBT resin is toasted 4h at 120 DEG C, dried PBT resin, toughner, lubricant, compatilizer, oxidation inhibitor etc. are placed in high-speed mixer mixing X minute, obtain mixture, mixture is added in twin screw extruder, first material is added by main feed system, simultaneously the second material added by side feed system, through melt extruding, water-cooled, pelletizing, obtain PBT composite.
Wherein, the design parameter of twin screw extruder is, one district's temperature 185 DEG C, two district's temperature 195 DEG C, three district's temperature 230 DEG C, four district's temperature 230 DEG C, five district's temperature 220 DEG C, six district's temperature 220 DEG C, seven district's temperature 220 DEG C, eight district's temperature 220 DEG C, nine district's temperature 230 DEG C, die temperature 235 DEG C, the residence time is 1 minute, and pressure is 4.2MPa.
Embodiment 2
The preparation process of the PBT composite shaping for NMT of the present embodiment is as follows:
(1) component in table 2, according to the mass fraction, is taken:
Table 2
(2) nano material is placed in homogenizer, 1 part of silane coupling agent is placed in beaker A, by silane coupling agent: dehydrated alcohol is that 1:7 takes dehydrated alcohol and is placed in beaker A, and stirring at room temperature 2 minutes, makes it mix simultaneously; Start homogenizer, temperature is set to 65 DEG C, and is placed in low-speed mode, add entrance in upper end liquid and at the uniform velocity add the silane coupling agent ethanolic soln be equipped with, start fast mode after coupling agent adds, high-speed stirring minute, obtain the first material, wherein the rotating speed of high-speed stirring is 950rpm.
(3), by glass fibre be placed in homogenizer, 1 part of silane coupling agent is placed in beaker B, by silane coupling agent: dehydrated alcohol is that 1:4 takes dehydrated alcohol and is placed in beaker B, and stirring at room temperature 3 minutes, makes it mix simultaneously; Start homogenizer, temperature is set to 67 DEG C, and is placed in low-speed mode, add entrance in upper end liquid and at the uniform velocity add the silane coupling agent ethanolic soln be equipped with, after coupling agent adds, stirring at low speed 3 minutes, obtain the second material, wherein the rotating speed of stirring at low speed is 95rpm.
The preparation of step 3, PBT composite:
PBT resin is toasted 4h at 120 DEG C, dried PBT resin, toughner, lubricant, compatilizer, oxidation inhibitor etc. are placed in high-speed mixer mixing 9 minutes, obtain mixture, mixture is added in twin screw extruder, first material is added by main feed system, simultaneously the second material added by side feed system, through melt extruding, water-cooled, pelletizing, obtain PBT composite.
Wherein, the design parameter of twin screw extruder is, one district's temperature 185 DEG C, two district's temperature 195 DEG C, three district's temperature 230 DEG C, four district's temperature 230 DEG C, five district's temperature 230 DEG C, six district's temperature 220 DEG C, seven district's temperature 220 DEG C, eight district's temperature 220 DEG C, nine district's temperature 220 DEG C, die temperature 235 DEG C, the residence time is 1 minute, and pressure is 4.2MPa.
Embodiment 3
The preparation process of the PBT composite shaping for NMT of the present embodiment is as follows:
(1) component in table 3, according to the mass fraction, is taken:
Table 3
(2) nano material is placed in homogenizer, 1 part of silane coupling agent is placed in beaker A, by silane coupling agent: dehydrated alcohol is that 1:2.3 takes dehydrated alcohol and is placed in beaker A, and stirring at room temperature 3 minutes, makes it mix simultaneously; Start homogenizer, temperature is set to 65 DEG C, and be placed in low-speed mode, add entrance in upper end liquid and at the uniform velocity add the silane coupling agent ethanolic soln be equipped with, fast mode is started after coupling agent adds, high-speed stirring 9 minutes, obtains the first material, and wherein the rotating speed of high-speed stirring is 950rpm.
(3), by glass fibre be placed in homogenizer, 1 part of silane coupling agent is placed in beaker B, by silane coupling agent: dehydrated alcohol is that 1:2.3 takes dehydrated alcohol and is placed in beaker B, and stirring at room temperature 3 minutes, makes it mix simultaneously; Start homogenizer, temperature is set to 65 DEG C, and is placed in low-speed mode, add entrance in upper end liquid and at the uniform velocity add the silane coupling agent ethanolic soln be equipped with, after coupling agent adds, stirring at low speed 3 minutes, obtain the second material, wherein the rotating speed of stirring at low speed is 90rpm.
The preparation of step 3, PBT composite:
PBT resin is toasted 4h at 120 DEG C, dried PBT resin, toughner, lubricant, compatilizer, oxidation inhibitor etc. are placed in high-speed mixer mixing 9 minutes, obtain mixture, mixture is added in twin screw extruder, first material is added by main feed system, simultaneously the second material added by side feed system, through melt extruding, water-cooled, pelletizing, obtain PBT composite.
Wherein, the design parameter of twin screw extruder is, one district's temperature 185 DEG C, two district's temperature 195 DEG C, three district's temperature 230 DEG C, four district's temperature 230 DEG C, five district's temperature 230 DEG C, six district's temperature 220 DEG C, seven district's temperature 220 DEG C, eight district's temperature 220 DEG C, nine district's temperature 220 DEG C, die temperature 235 DEG C, the residence time is 1 minute, and pressure is 4.2MPa.
Embodiment 4
The preparation process of the PBT composite shaping for NMT of the present embodiment is as follows:
(1) component in table 4, according to the mass fraction, is taken:
Table 4
(2) nano material is placed in homogenizer, 1 part of silane coupling agent is placed in beaker A, by silane coupling agent: dehydrated alcohol is that 1:2.3 takes dehydrated alcohol and is placed in beaker A, and stirring at room temperature 9 minutes, makes it mix simultaneously; Start homogenizer, temperature is set to 65 DEG C, and be placed in low-speed mode, add entrance in upper end liquid and at the uniform velocity add the silane coupling agent ethanolic soln be equipped with, fast mode is started after coupling agent adds, high-speed stirring 9 minutes, obtains the first material, and wherein the rotating speed of high-speed stirring is 900rpm.
(3), by glass fibre be placed in homogenizer, 1 part of silane coupling agent is placed in beaker B, by silane coupling agent: dehydrated alcohol is that 1:2.3 takes dehydrated alcohol and is placed in beaker B, and stirring at room temperature 9 minutes, makes it mix simultaneously; Start homogenizer, temperature is set to 65 DEG C, and is placed in low-speed mode, add entrance in upper end liquid and at the uniform velocity add the silane coupling agent ethanolic soln be equipped with, after coupling agent adds, stirring at low speed 3 minutes, obtain the second material, wherein the rotating speed of stirring at low speed is 95rpm.
The preparation of step 3, PBT composite:
PBT resin is toasted 4h at 120 DEG C, dried PBT resin, toughner, lubricant, compatilizer, oxidation inhibitor etc. are placed in high-speed mixer mixing 9 minutes, obtain mixture, mixture is added in twin screw extruder, first material is added by main feed system, simultaneously the second material added by side feed system, through melt extruding, water-cooled, pelletizing, obtain PBT composite.
Wherein, the design parameter of twin screw extruder is, one district's temperature 185 DEG C, two district's temperature 195 DEG C, three district's temperature 225 DEG C, four district's temperature 230 DEG C, five district's temperature 230 DEG C, six district's temperature 220 DEG C, seven district's temperature 220 DEG C, eight district's temperature 220 DEG C, nine district's temperature 220 DEG C, die temperature 235 DEG C, the residence time is 1 minute, and pressure is 4.2MPa.
Embodiment 5
The preparation process of the PBT composite shaping for NMT of the present embodiment is as follows:
(1) component in table 5, according to the mass fraction, is taken:
Table 5
(2) nano material is placed in homogenizer, 1 part of silane coupling agent is placed in beaker A, by silane coupling agent: dehydrated alcohol is that 1:2.3 takes dehydrated alcohol and is placed in beaker A, and stirring at room temperature 3 minutes, makes it mix simultaneously; Start homogenizer, temperature is set to 65 DEG C, and be placed in low-speed mode, add entrance in upper end liquid and at the uniform velocity add the silane coupling agent ethanolic soln be equipped with, fast mode is started after coupling agent adds, high-speed stirring 9 minutes, obtains the first material, and wherein the rotating speed of high-speed stirring is 950rpm.
(3), by glass fibre be placed in homogenizer, 1 part of silane coupling agent is placed in beaker B, by silane coupling agent: dehydrated alcohol is 2.3 take dehydrated alcohol and be placed in beaker B, and stirring at room temperature 3 minutes, makes it mix simultaneously; Start homogenizer, temperature is set to 65 DEG C, and is placed in low-speed mode, add entrance in upper end liquid and at the uniform velocity add the silane coupling agent ethanolic soln be equipped with, after coupling agent adds, stirring at low speed 3 minutes, obtain the second material, wherein the rotating speed of stirring at low speed is 90rpm.
The preparation of step 3, PBT composite:
PBT resin is toasted 4h at 120 DEG C, dried PBT resin, toughner, lubricant, compatilizer, oxidation inhibitor etc. are placed in high-speed mixer mixing 9 minutes, obtain mixture, mixture is added in twin screw extruder, first material is added by main feed system, simultaneously the second material added by side feed system, through melt extruding, water-cooled, pelletizing, obtain PBT composite.
Wherein, the design parameter of twin screw extruder is, one district's temperature 185 DEG C, two district's temperature 195 DEG C, three district's temperature 210 DEG C, four district's temperature 230 DEG C, five district's temperature 230 DEG C, six district's temperature 230 DEG C, seven district's temperature 220 DEG C, eight district's temperature 220 DEG C, nine district's temperature 220 DEG C, die temperature 235 DEG C, the residence time is 1 minute, and pressure is 4.2MPa.
The PBT composite that embodiment 1 ~ 5 obtains is made standard model test properties.Wherein, according to ISO527 testing standard test tensile strength and elongation at break; According to ISO178 testing standard test flexural strength and modulus in flexure; According to ISO180 testing standard test notched Izod impact strength (1/8 "); According to ISO75 testing standard test thermal distorsion temperature; The PBT composite obtained 1 ~ 5 is made standard inserts and is detected metal plastic stripping strength (MPa), and test result is in table 6.
Table 6
As can be seen from Table 6:
1, its very well bonding to the metallic article after T process of result of the present invention's 5 case study on implementation, stretch release intensity can reach more than 28Mpa.
2, known through Comprehensive Correlation result, in case study on implementation 3 mass ratio to be the short mixture cutting alkali free glass fibre and flat alkali free glass fibre of 1:3 be 40 and the comprehensive mechanical of mass ratio material when be the nano aluminium oxide of 1:1 and the mixture of nano magnesia being 0.6 for best, its stretch release intensity is maximum simultaneously; The visible selection for different glass fiber and different nano material and ratio are arranged in pairs or groups playing a role in the present invention.
3, the result based on table 6 can be found out, several embodiment of the present invention can meet for the shaping matrix material of NMT, has very high stretch release intensity and comprehensive mechanical performance.
Each technical characteristic of the above embodiment can combine arbitrarily, for making description succinct, the all possible combination of each technical characteristic in above-described embodiment is not all described, but, as long as the combination of these technical characteristics does not exist contradiction, be all considered to be the scope that this specification sheets is recorded.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be construed as limiting the scope of the patent.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. for the PBT composite that NMT is shaping, it is characterized in that, according to massfraction meter, comprise following component:
Wherein, described nano material is selected from least one in nano aluminium oxide, nano magnesia and nano-sized iron oxide, and described toughener is glass fibre.
2. the PBT composite shaping for NMT according to claim 1, is characterized in that, described toughner is ethylene-octene segmented copolymer, and in described toughner, the mass content of octene is 47% ~ 53%.
3. the PBT composite shaping for NMT according to claim 1, is characterized in that, described toughener is selected from flat alkali free glass fibre and short at least one of cutting in alkali free glass fibre.
4. the PBT composite shaping for NMT according to claim 1, is characterized in that, described lubricant is polysiloxane.
5. the PBT composite shaping for NMT according to claim 1, is characterized in that, described compatilizer is glycidyl ester, ethene and methyl esters methyl acrylate terpolymer.
6. the PBT composite shaping for NMT according to claim 1, is characterized in that, described coupling agent is silane coupling agent.
7. the PBT composite shaping for NMT according to claim 1, is characterized in that, the particle diameter of described nano material is 104nm ~ 157nm.
8. the PBT composite shaping for NMT according to claim 1, is characterized in that, described oxidation inhibitor is phenolic antioxidant.
9., for a preparation method for the shaping PBT composite of NMT, it is characterized in that, comprise the steps:
According to massfraction meter, take following raw material: polybutylene terephthalate 100 parts, toughner 10 ~ 15 parts, toughener 30 ~ 40 parts, lubricant 3 ~ 5 parts, compatilizer 5 ~ 8 parts, nano material 0.2 ~ 0.8 part, 0.5 ~ 1 part, oxidation inhibitor and coupling agent 0.5 ~ 1.0 part, wherein, described nano material is selected from least one in nano aluminium oxide, nano magnesia and nano-sized iron oxide, and described toughener is glass fibre;
In described coupling agent 1% ~ 3% and ethanol are hybridly prepared into the first solution, and by described nano material and described first solution, high-speed stirring at 62 DEG C ~ 86 DEG C obtains the first material;
Remaining described coupling agent and ethanol are hybridly prepared into the second solution, and by described toughener and described second solution, stirring at low speed at 57 DEG C ~ 76 DEG C obtains the second material;
Compound is obtained by after described polybutylene terephthalate, described toughner, described lubricant, described compatilizer and described oxidation inhibitor high-speed mixing, described compound is added in forcing machine, described first material is added by main feed system, the second material is added by side feed system, extrudes rear granulation and obtains for the shaping PBT composite of NMT.
10. the preparation method of the PBT composite shaping for NMT according to claim 9, is characterized in that, in described first solution and in described second solution, the mass ratio of described coupling agent and described ethanol is 1 ~ 3:2.3 ~ 7.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106995593A (en) * | 2017-04-07 | 2017-08-01 | 深圳市华盈新材料有限公司 | Nanometer injection PBT composite and its preparation technology |
| CN107337909A (en) * | 2016-12-27 | 2017-11-10 | 深圳市新合富力科技有限公司 | Modified plastic rubber and its manufacture method |
| CN108262914A (en) * | 2016-12-30 | 2018-07-10 | 广州光宝移动电子部件有限公司 | Composite construction and its manufacturing method with titanium-containing materials and plastic material |
| CN109306157A (en) * | 2018-10-08 | 2019-02-05 | 重庆国际复合材料股份有限公司 | A kind of PBT composite and preparation method thereof |
| CN110305454A (en) * | 2019-08-15 | 2019-10-08 | 深圳市兴盛迪新材料有限公司 | A kind of PBT composite and its application |
| WO2020140306A1 (en) * | 2018-12-30 | 2020-07-09 | 上海锦湖日丽塑料有限公司 | Plastic composite material capable of being polished and connected to metal, and preparation method therefor |
| CN112795193A (en) * | 2021-01-14 | 2021-05-14 | 深圳力越新材料有限公司 | PPS/PBT composite material for NMT and preparation method thereof |
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| CN104672756A (en) * | 2015-02-11 | 2015-06-03 | 深圳市兴盛迪新材料有限公司 | ABS composite flame resistant material and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107337909A (en) * | 2016-12-27 | 2017-11-10 | 深圳市新合富力科技有限公司 | Modified plastic rubber and its manufacture method |
| CN108262914A (en) * | 2016-12-30 | 2018-07-10 | 广州光宝移动电子部件有限公司 | Composite construction and its manufacturing method with titanium-containing materials and plastic material |
| CN106995593A (en) * | 2017-04-07 | 2017-08-01 | 深圳市华盈新材料有限公司 | Nanometer injection PBT composite and its preparation technology |
| CN109306157A (en) * | 2018-10-08 | 2019-02-05 | 重庆国际复合材料股份有限公司 | A kind of PBT composite and preparation method thereof |
| WO2020140306A1 (en) * | 2018-12-30 | 2020-07-09 | 上海锦湖日丽塑料有限公司 | Plastic composite material capable of being polished and connected to metal, and preparation method therefor |
| CN110305454A (en) * | 2019-08-15 | 2019-10-08 | 深圳市兴盛迪新材料有限公司 | A kind of PBT composite and its application |
| CN112795193A (en) * | 2021-01-14 | 2021-05-14 | 深圳力越新材料有限公司 | PPS/PBT composite material for NMT and preparation method thereof |
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| CN105331055B (en) | 2017-04-26 |
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