CN109575528A - Low dielectric high tenacity enhancing PBT/PPO composition and preparation method thereof - Google Patents
Low dielectric high tenacity enhancing PBT/PPO composition and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Abstract
The present invention relates to a kind of low dielectric high tenacity enhancing PBT/PPO compositions and preparation method thereof.The low dielectric high tenacity enhancing PBT/PPO composition includes the raw material of following parts by weight: 45~85 parts of polybutylene terephthalate (PBT) (PBT), 15~55 parts of polyphenylene oxide (PPO), the parts by weight summation of polybutylene terephthalate (PBT) and polyphenylene oxide is 100 parts, 20~40 parts of glass fibre, 6~14 parts of compatilizer, 0.6~1 part of antioxidant, 5~20 parts of polytetrafluoroethylene (PTFE), 0.2~1 part of plasticiser, 0.2~1 part of silane coupling agent, the weight ratio of plasticiser and silane coupling agent is 1:1~5:1.The PBT/PPO composition can meet the high demand in the fields such as electron and electrician, integrated circuit packaging, electromagnetic wave shielding in dielectric properties, intensity and toughness.
Description
Technical field
The present invention relates to Material Fields, more particularly to a kind of low dielectric high tenacity enhancing PBT/PPO composition and its system
Preparation Method.
Background technique
Polybutylene terephthalate (PBT) (PBT) is a kind of hemicrystalline thermoplastic polyester, has good heat resistance, resistance to
It the advantages that time property and chemical-resistant and excellent electric property, low water imbibition and good products appearance, is used extensively
In automobile, mechanical equipment, electric manufacturing industry, such as connector, transformer, fuse shell, switch, relay, energy conservation
Lamp, coil rack, motor housing etc., these industries have strict requirements to burning, safety.In addition, with application performance
Extension, demand of the PBT material in fields such as electron and electrician, integrated circuit packaging, electromagnetic wave shieldings increasingly increase.However, common
The enhancing resin notch sensitive of PBT, poor toughness, and dielectric constant, dielectric loss are difficult to meet increasingly developed 4G, 5G technology
Requirement to dielectric properties.
Polyphenylene oxide (PPO or PPE), chemical name are poly- 2,6- dimethyl-Isosorbide-5-Nitrae-phenylate, and also known as polyphenylene aoxidizes
Object or polyphenylene ether.PPO is the engineering plastics containing phenyl ring on a kind of main chain, therefore has excellent mechanical strength, proof stress
Relaxation, creep resistance, heat resistance, water resistance, water vapor resistance, dimensional stability.But pure PPO resin poor impact toughness,
Melt viscosity height, poor in processability, are usually modified it by alloying, the dielectric constant and dielectric loss of PPO raw material
It is one of the smallest kind in engineering plastics, is hardly influenced by temperature, humidity, can be used for basic, normal, high frequency electric field neck
Domain.
PBT is blended with PPO, and since PBT is crystalline polymer, it is incompatible that PPO, which is non-crystalline polymer,.PBT/PPO
The research of alloy essentially consists in compatible problem, solves the problems, such as compatible, while keeping good performance, it will be able to meet different occasions
Requirement.
Currently, having done some researchs to the compatible modification of PBT/PPO in the prior art, patent CN101759964A discloses one
Kind polybutylene terephthalate (PBT) polyphenylene oxide composite material and preparation method thereof, which essentially discloses a kind of compatibility
By force, the preparation method of low-cost compatilizer, but the composite material is the non-reinforcing scheme of alloy, intensity, toughness is inadequate,
It is not also described in terms of dielectric properties.
Patent CN102417716A is related to a kind of permanent anti-static PBT/PPO alloy and preparation method, has antistatic effect
Fruit is lasting, achievees the effect that permanent anti-static, and antistatic effect is good, and comprehensive mechanical property is higher, close to pure PBT/PPO alloy
Performance, compatilizer are the compound that maleic anhydride is grafted polyethylene glycol oxide and SEBS is grafted GMA, and the alloy is of light color to be made into respectively
Kind of color, it is at low cost, it is heat-resist the advantages that, but the composite material is the non-reinforcing scheme of alloy, and intensity, toughness is inadequate,
It is not also described in terms of dielectric properties.
Patent CN104902693A is related to circuit board technology field, and especially a kind of polytetrafluoroethyladhesive adhesive sheet contains matter
Amount percentage is the auxiliary agent of the ptfe emulsion of 35-90%, the glass fabric of 8-60%, 0.5-2%, and surplus is molten
Agent has extremely low dielectric constant and fissipation factor, and polytetrafluoroethylene (PTFE) (PTFE) dielectric in very wide frequency range is normal
Number is also quite stable, therefore the scope of application is very vast, which is field of circuit boards, and untreated only by being added
Emulsion form PTFE is not related to engineering plastic modification field.
Patent CN104830058A is related to a kind of polyimide film and preparation method thereof, has low-k and low gloss
Degree.Mainly as printed circuit board membrane material, improve the high dielectric constant and the effect of high dielectric loss of polyimide film, but only
By the way that untreated PTFE is added, engineering plastic modification field it is not related to.
Summary of the invention
Based on this, it is necessary to provide a kind of low dielectric high tenacity enhancing PBT/PPO composition.The PBT/PPO composition
The characteristics such as dielectric properties, intensity and toughness, which can meet the high of the fields such as electron and electrician, integrated circuit packaging, electromagnetic wave shielding, to be needed
It asks.
A kind of low dielectric high tenacity enhancing PBT/PPO composition, the raw material including following parts by weight:
45~85 parts of polybutylene terephthalate (PBT) (PBT),
15~55 parts of polyphenylene oxide (PPO),
The parts by weight summation of polybutylene terephthalate (PBT) and polyphenylene oxide is 100 parts,
The weight ratio of the plasticiser and silane coupling agent is 1:1~5:1.
Low dielectric high tenacity enhances PBT/PPO composition, the original including following parts by weight in one of the embodiments,
Material:
55~75 parts of PBT,
25~45 parts of PPO,
The parts by weight summation of PBT and PPO is 100 parts,
The weight ratio of the plasticiser and silane coupling agent is 2:1~4:1.
In one of the embodiments, the number-average molecular weight of the polybutylene terephthalate (PBT) be 30000~
50000, the number-average molecular weight of polyphenylene oxide is 30000~50000.
In one of the embodiments, the compatilizer be one of PE-g-MAH, PPO-g-MAH, PP-g-GMA or
It is two or more.
The preparation method of the PE-g-MAH includes the following steps: polyethylene (PE), horse in one of the embodiments,
Carry out acid anhydrides (MAH) according to weight ratio (95.5~98.5): (1.5~4.5) mixing；It is added in twin-screw machine, prepares work
Skill temperature: the first 180 DEG C of area~200 DEG C, the second 190 DEG C of area~210 DEG C, 190 DEG C~210 DEG C of third area, the 4th 190 DEG C of area~
210 DEG C, the 5th 190 DEG C of area~210 DEG C, the 6th 190 DEG C of area~210 DEG C, 190 DEG C~210 DEG C of District 7,190 DEG C of Section Eight~
210 DEG C, driving screw revolving speed is 150r/min~200r/min；It is squeezed out, cooling, pelletizing forms, and grafting rate is 0.5~1.0.
In one of the embodiments, in the preparation method of the PE-g-MAH, the mixed method are as follows: stirred in low speed
It mixes in machine and is mixed according to 100r/min~300r/min.
In one of the embodiments, the preparation method of the PPO-g-MAH include the following steps: by polyphenylene oxide (PPO),
Maleic anhydride (MAH) is according to weight ratio (95.5~98.5): (1.5~4.5) mixing；It is added in twin-screw machine, preparation
Technological temperature: the first 180 DEG C of area~200 DEG C, the second 250 DEG C of area~280 DEG C, 260 DEG C~280 DEG C of third area, the 4th 260 DEG C of area
~280 DEG C, the 5th 260 DEG C of area~280 DEG C, the 6th 260 DEG C of area~280 DEG C, 260 DEG C~280 DEG C of District 7,260 DEG C of Section Eight
~280 DEG C, driving screw revolving speed is 150r/min~200r/min；It is squeezed out, cooling, pelletizing forms, and grafting rate is 0.5~1.0.
In one of the embodiments, in the preparation method of the PPO-g-MAH, the mixed method are as follows: in low speed
It is mixed in blender according to 100r/min~300r/min.
The preparation method of the PP-g-MAH includes the following steps: polypropylene (PP), horse in one of the embodiments,
Carry out acid anhydrides (MAH) according to weight ratio (95.5~98.5): (1.5~4.5) mixing；It is added in twin-screw machine, prepares work
Skill temperature: the first 180 DEG C of area~200 DEG C, the second 190 DEG C of area~210 DEG C, 190 DEG C~210 DEG C of third area, the 4th 190 DEG C of area~
210 DEG C, the 5th 190 DEG C of area~210 DEG C, the 6th 190 DEG C of area~210 DEG C, 190 DEG C~210 DEG C of District 7,190 DEG C of Section Eight~
210 DEG C, driving screw revolving speed is 150r/min~200r/min；It is squeezed out, cooling, pelletizing forms, and grafting rate is 0.5~1.0.
In one of the embodiments, in the preparation method of the PP-g-MAH, the mixed method are as follows: stirred in low speed
It mixes in machine and is mixed according to 100r/min~300r/min.
The antioxidant is Hinered phenols antioxidant, in phosphite ester antioxidant in one of the embodiments,
It is one or more kinds of.Preferably pentaerythritol esters (antioxidant 1010) and phosphorous acid esters (irgasfos 168) composition is mixed
Object is closed, preferred weight ratio is 1:0.5~1.5.
The PTFE molecular weight is 150000~350000 in one of the embodiments, 20~35 μm of partial size.
The plasticiser is diisononyl phthalate (DINP), phthalic acid two in one of the embodiments,
One or more of monooctyl ester (DOP), dibutyl phthalate (DBP).Preferably DOP.
The silane coupling agent is gamma-aminopropyl-triethoxy-silane, γ-(2,3- epoxies in one of the embodiments,
Third oxygen) propyl trimethoxy silicane, one or more of γ-(methacryloxypropyl) propyl trimethoxy silicane.It is excellent
It is selected as gamma-aminopropyl-triethoxy-silane.
The glass fibre is short glass fiber in one of the embodiments, and diameter is 10~15 μm, length 4~
5mm。
The present invention also provides the preparation methods of low dielectric high tenacity enhancing PBT/PPO composition, including walk as follows
It is rapid:
(1) polybutylene terephthalate (PBT), polyphenylene oxide, antioxidant are sequentially added into premix pot, are stirred；
(premix pot is added in the compatilizer, polytetrafluoroethylene (PTFE) (PTFE), silane coupling agent, plasticiser by (2), and stirring is mixed
It closes, to be pre-processed to the polytetrafluoroethylene (PTFE)；
(3) step (1) and the pre- mixed raw material of step (2) are distinguished into blanking from two premix pots, is added to twin-screw and squeezes
Out in machine, the twin-screw extrusion is added by the 5th section of the double screw extruder of side feed feeder in the glass fibre
Machine, melting extrusion are granulated.
The melting extrusion technique of the double screw extruder is as follows in one of the embodiments: area's temperature be 180~
230 DEG C, two area's temperature: 230~260 DEG C, three area's temperature are 240~270 DEG C, and four Qu Wendu: 240~270 DEG C, five area's temperature are
240~270 DEG C, six Qu Wendu: 220~240 DEG C, District 7 temperature: 220~240 DEG C, die head temperature: 230~250 DEG C, main spiral shell
Bar revolving speed are as follows: 300~500r/min.
The principle of the present invention and advantage are as follows:
Low dielectric high tenacity enhancing PBT/PPO composition of the invention adds on the basis of reasonable disposition each raw material component
Enter plasticiser, silane coupling agent, adjusts its ratio, then auxiliary with the lower PTFE of dielectric constant, obtaining has superior dielectric performance
With the alloy of mechanical property, it is right to can satisfy special occasions (such as electron and electrician, integrated circuit packaging, electromagnetic wave shielding field)
The high request of material.
The mechanism of action of plasticiser is that plasticizing agent molecule is inserted between polymer molecular chain, weakens polymer molecular chain
Between stress, increase the mobility of polymer molecular chain, reduce the crystallinity of polymer molecular chain, to make polymer
Moulding increase.Plasticiser dosage is very little, and the effect of plasticizing is not achieved, and the scope of activities of strand is too small, and resin is compatible not enough,
Dosage is too big, make strand to move freely range excessive, lesser intermolecular force can make identical strand that group occur
It is poly-, to the compatible unfavorable of two kinds of polymer.
Siloxy in silane coupling agent has reactivity to inorganic matter, and organic functional base has reactivity to organic matter
Or compatibility.When silane coupling agent between inorganic between organic interface, the inorganic base of organic matrix-silane coupling agent-can be formed
The binder course of body.
PPO melt viscosity is big, and pure PPO is difficult to, and a certain amount of plasticiser is added, and so that PPO strand is become soft, is promoted and added
Work is conducive to polymer and is uniformly dispersed.In addition, 327 DEG C of PTFE fusing point or so, in the composition in the form of powder particle
In the presence of as inorganic filler existence form, and PTFE is due to excellent " non-stick ", in the big PPO tree of melt viscosity
It is difficult to disperse in rouge, reunite, it, can be in resin and PTFE product after the surface treatment of plasticiser by silane coupling agent
Connection is formed, the reunion of powder particle can be prevented, be conducive to have the characteristics that the PTFE of low dielectric is evenly dispersed in resin,
It is preferably combined with resin, further decreases the dielectric constant and dielectric loss of composition.
The present invention uses silane coupling agent, the plasticiser of special ratios range, both can guarantee the plasticizing effect of PPO, and had reached
The effect of anakmetomeres chain, and can guarantee the surface treatment effect of PTFE, and do not influence composition other performance, make two kinds of resins
It is evenly dispersed, guarantee that dielectric material performance is uniform and stable.
Further, the compatible of PBT/PPO alloy is solved the problems, such as by using suitable compatilizer, to the technique of compatilizer
Condition is groped, and is selected optimised process to make compatilizer by oneself, can be optimized the compatibility between PBT and PPO.Preferably with PPO
For the compatilizer PPO-g-MAH of substrate preparation, which not only meets the Interfacial compatibilization effect of two kinds of Immiscible Polymer Blends of PBT/PPO
Fruit, and the dielectric constant and dielectric loss of composition can be further decreased.
The preparation method of low dielectric high tenacity enhancing PBT/PPO composition of the invention, by by the polytetrafluoroethyl-ne
Premix pot is added in alkene, silane coupling agent, plasticiser, is stirred, carries out premix processing to polytetrafluoroethylene (PTFE), can make it easier to add
Work.Each step is comprehensive, guarantees the dielectric properties, intensity and toughness of composition.
Specific embodiment
Below in conjunction with specific embodiment to low dielectric high tenacity enhancing PBT/PPO composition and preparation method thereof of the invention
It is described in further detail.
In following specific embodiments, if all raw materials derive from commercially available without other explanations.
PPO, number-average molecular weight 30000, Ruicheng branch company, Xingchen Synthetic Matrials Co., Ltd., Nantong；
PPO, number-average molecular weight 40000, Ruicheng branch company, Xingchen Synthetic Matrials Co., Ltd., Nantong；
PPO, number-average molecular weight 50000, Ruicheng branch company, Xingchen Synthetic Matrials Co., Ltd., Nantong；
PBT, number-average molecular weight 30000, Taiwan Changchun resin Co., Ltd；
PBT, number-average molecular weight 40000, Taiwan Changchun resin Co., Ltd；
PBT, number-average molecular weight 50000, Taiwan Changchun resin Co., Ltd；
Gamma-aminopropyl-triethoxy-silane (KH550), Mitugao New Material Group；
Diisononyl phthalate (DINP), Pu Weilun Chemical Co., Ltd.；
Dioctyl phthalate (DOP), Pu Weilun Chemical Co., Ltd.；
Dibutyl phthalate (DBP), Pu Weilun Chemical Co., Ltd.；
PTFE, Daikin；
Glass fibre is short glass fiber, and diameter is 13 μm, length 4.5mm, PPG industrial group.
PPO-g-MAH preparation process: by PPO, MAH according to weight ratio 98:2 mix, in low-speed mixer according to
200r/min mixing；It is added in twin-screw machine, preparation process temperature: the first 180 DEG C of area, the second 260 DEG C of area, third area 280
DEG C, the 4th 280 DEG C of area, the 5th 280 DEG C of area, the 6th 280 DEG C of area, 280 DEG C of District 7,280 DEG C of Section Eight, driving screw revolving speed is
150r/min；It is squeezed out, cooling, pelletizing forms, grafting rate 0.7.
PE-g-MAH preparation process: by PE, MAH according to weight ratio 98:2 in low-speed mixer according to 200r/min
Mixing；It is added in twin-screw machine, preparation process temperature: the first 180 DEG C of area, the second 200 DEG C of area, 210 DEG C of third area, the 4th area
210 DEG C, the 5th 210 DEG C of area, the 6th 210 DEG C of area, 210 DEG C of District 7,210 DEG C of Section Eight, driving screw revolving speed is 150r/min；Through
It squeezes out, cooling, pelletizing forms, grafting rate 0.7.
PP-g-MAH preparation process: by PP, MAH according to weight ratio 98:2 in low-speed mixer according to 200r/min
Mixing；It is added in twin-screw machine, preparation process temperature: the first 180 DEG C DEG C of area, the second 1200 DEG C of area, third, 210 DEG C, the 4th
210 DEG C of area, the 5th 210 DEG C of area, the 6th 210 DEG C of area, 210 DEG C of District 7,210 DEG C of Section Eight, driving screw revolving speed is 150r/
minr/min；It is squeezed out, cooling, pelletizing forms, grafting rate 0.7.
Embodiment 1
A kind of low dielectric high tenacity of the present embodiment enhances PBT/PPO composition, is prepared by the raw material of following parts by weight:
| PBT | 45 |
| PPO | 55 |
| Glass fibre | 20 |
| Compatilizer | 6 |
| Antioxidant | 0.6 |
| PTFE | 5 |
| Plasticiser | 1 |
| Silane coupling agent | 1 |
PBT number-average molecular weight is that 30000, PPO number-average molecular weight is 30000, compatilizer PE-g-MAH, and plasticiser is
DINP, silane coupling agent are γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, and antioxidant is pentaerythritol esters (antioxygen
Agent 1010) and phosphorous acid esters (irgasfos 168) composition mixture (weight ratio 1:1), PTFE molecular weight be 150000, partial size
It is 20 μm, the weight ratio of plasticiser and silane coupling agent is 1:1.
The preparation process of above-mentioned low dielectric high tenacity enhancing PBT/PPO composition is as follows:
(1) PBT, PPO, antioxidant are sequentially added into premix pot, high-speed stirred mixing；By compatilizer, PTFE, silane coupled
Premix pot, high-speed stirred mixing is added in agent, plasticiser；
(2) the pre- mixed raw material of step (1) is distinguished into blanking from two premix pots, be added in double screw extruder, glass
The double screw extruder is added at the 5th section of extruder, by side feeder in glass fiber, and melting extrusion is granulated, and technological parameter is such as
Under: area's temperature is 180 DEG C, two area's temperature: 230 DEG C, three area's temperature are 240 DEG C, and four Qu Wendu: 240 DEG C, five area's temperature are
240 DEG C, six Qu Wendu: 220 DEG C, District 7 temperature: 220 DEG C, die head temperature: 230 DEG C, driving screw revolving speed are as follows: 300r/min.
Embodiment 2
A kind of low dielectric high tenacity of the present embodiment enhances PBT/PPO composition, is prepared by the raw material of following parts by weight:
| PBT | 55 |
| PPO | 45 |
| Glass fibre | 25 |
| Compatilizer | 8 |
| Antioxidant | 0.7 |
| PTFE | 10 |
| Plasticiser | 0.8 |
| Silane coupling agent | 0.4 |
PBT number-average molecular weight is that 40000, PPO number-average molecular weight is 40000, compatilizer PPO-g-MAH, and plasticiser is
DOP, silane coupling agent are gamma-aminopropyl-triethoxy-silane, and antioxidant is pentaerythritol esters (antioxidant 1010) and phosphorous
The mixture (weight ratio 1:1) of esters of gallic acid (irgasfos 168) composition, PTFE molecular weight are 200000, and partial size is 30 μm, plasticiser
Weight ratio with silane coupling agent is 2:1.
The preparation process of above-mentioned low dielectric high tenacity enhancing PBT/PPO composition is as follows:
(1) PBT, PPO, antioxidant are sequentially added into premix pot, high-speed stirred mixing；By compatilizer, PTFE, silane coupled
Premix pot, high-speed stirred mixing is added in agent, plasticiser；
(2) the pre- mixed raw material of step (1) is distinguished into blanking from two premix pots, be added in double screw extruder, glass
The double screw extruder is added at the 5th section of extruder, by side feeder in glass fiber, and melting extrusion is granulated, and technological parameter is such as
Under: area's temperature is 200 DEG C, two area's temperature: 240 DEG C, three area's temperature are 250 DEG C, and four Qu Wendu: 250 DEG C, five area's temperature are
250 DEG C, six Qu Wendu: 230 DEG C, District 7 temperature: 230 DEG C, die head temperature: 240 DEG C, driving screw revolving speed are as follows: 400r/min.
Embodiment 3
A kind of low dielectric high tenacity of the present embodiment enhances PBT/PPO composition, is prepared by the raw material of following parts by weight:
| PBT | 65 |
| PPO | 35 |
| Glass fibre | 30 |
| Compatilizer | 10 |
| Antioxidant | 0.8 |
| PTFE | 20 |
| Plasticiser | 0.9 |
| Silane coupling agent | 0.3 |
PBT number-average molecular weight is that 50000, PPO number-average molecular weight is 50000, compatilizer PP-g-MAH, and plasticiser is
DBP, silane coupling agent are γ-(methacryloxypropyl) propyl trimethoxy silicane, and antioxidant is pentaerythritol esters (antioxidant
1010) and the mixture (weight ratio 1:1) of phosphorous acid esters (irgasfos 168) composition, PTFE molecular weight are 350000, and partial size is
35 μm, the weight ratio of plasticiser and silane coupling agent is 3:1.
The preparation process of above-mentioned low dielectric high tenacity enhancing PBT/PPO composition is as follows:
(1) PBT, PPO, antioxidant are sequentially added into premix pot, high-speed stirred mixing；By compatilizer, PTFE, silane coupled
Premix pot, high-speed stirred mixing is added in agent, plasticiser；
(2) the pre- mixed raw material of step (1) is distinguished into blanking from two premix pots, be added in double screw extruder, glass
The double screw extruder is added at the 5th section of extruder, by side feeder in glass fiber, and melting extrusion is granulated, and technological parameter is such as
Under: area's temperature is 220 DEG C, two area's temperature: 260 DEG C, three area's temperature are 270 DEG C, and four Qu Wendu: 270 DEG C, five area's temperature are
270 DEG C, six Qu Wendu: 240 DEG C, District 7 temperature: 240 DEG C, die head temperature: 250 DEG C, driving screw revolving speed are as follows: 500r/min.
Embodiment 4
A kind of low dielectric high tenacity of the present embodiment enhances PBT/PPO composition, is prepared by the raw material of following parts by weight:
| PBT | 75 |
| PPO | 25 |
| Glass fibre | 35 |
| Compatilizer | 12 |
| Antioxidant | 0.9 |
| PTFE | 10 |
| Plasticiser | 0.8 |
| Silane coupling agent | 0.2 |
PBT number-average molecular weight is that 40000, PPO number-average molecular weight is 40000, compatilizer PPO-g-MAH, and plasticiser is
DOP, silane coupling agent are gamma-aminopropyl-triethoxy-silane, and antioxidant is pentaerythritol esters (antioxidant 1010) and phosphorous
The mixture (weight ratio 1:1) of esters of gallic acid (irgasfos 168) composition, PTFE molecular weight are 200000, and partial size is 20 μm, plasticiser
Weight ratio with silane coupling agent is 4:1.
The preparation process of above-mentioned low dielectric high tenacity enhancing PBT/PPO composition is as follows:
(1) PBT, PPO, antioxidant are sequentially added into premix pot, high-speed stirred mixing；By compatilizer, PTFE, silane coupled
Premix pot, high-speed stirred mixing is added in agent, plasticiser；
(2) the pre- mixed raw material of step (1) is distinguished into blanking from two premix pots, be added in double screw extruder, glass
The double screw extruder is added at the 5th section of extruder, by side feeder in glass fiber, and melting extrusion is granulated, and technological parameter is such as
Under: area's temperature is 200 DEG C, two area's temperature: 240 DEG C, three area's temperature are 250 DEG C, and four Qu Wendu: 250 DEG C, five area's temperature are
250 DEG C, six Qu Wendu: 230 DEG C, District 7 temperature: 230 DEG C, die head temperature: 240 DEG C, driving screw revolving speed are as follows: 400r/min.
Embodiment 5
A kind of low dielectric high tenacity of the present embodiment enhances PBT/PPO composition, is prepared by the raw material of following parts by weight:
| PBT | 85 |
| PPO | 15 |
| Glass fibre | 40 |
| Compatilizer | 14 |
| Antioxidant | 1 |
| PTFE | 10 |
| Plasticiser | 1 |
| Silane coupling agent | 0.2 |
PBT number-average molecular weight is that 40000, PPO number-average molecular weight is 40000, compatilizer PPO-g-MAH, and plasticiser is
DOP, silane coupling agent are gamma-aminopropyl-triethoxy-silane, and antioxidant is pentaerythritol esters (antioxidant 1010) and phosphorous
The mixture (weight ratio 1:1) of esters of gallic acid (irgasfos 168) composition, PTFE molecular weight are 200000, and partial size is 20 μm, plasticiser
Weight ratio with silane coupling agent is 5:1.
The preparation process of above-mentioned low dielectric high tenacity enhancing PBT/PPO composition is as follows:
(1) PBT, PPO, antioxidant are sequentially added into premix pot, high-speed stirred mixing；By compatilizer, PTFE, silane coupled
Premix pot, high-speed stirred mixing is added in agent, plasticiser；
(2) the pre- mixed raw material of step (1) is distinguished into blanking from two premix pots, be added in double screw extruder, glass
The double screw extruder is added at the 5th section of extruder, by side feeder in glass fiber, and melting extrusion is granulated, and technological parameter is such as
Under: area's temperature is 200 DEG C, two area's temperature: 240 DEG C, three area's temperature are 250 DEG C, and four Qu Wendu: 250 DEG C, five area's temperature are
250 DEG C, six Qu Wendu: 230 DEG C, District 7 temperature: 230 DEG C, die head temperature: 240 DEG C, driving screw revolving speed are as follows: 400r/min.
Comparative example 1
A kind of PBT composition of this comparative example, is prepared by the raw material of following parts by weight:
| PBT | 100 |
| Glass fibre | 25 |
| Compatilizer | 8 |
| Antioxidant | 0.7 |
| PTFE | 10 |
| Plasticiser | 0.8 |
| Silane coupling agent | 0.4 |
PBT number-average molecular weight is 40000, compatilizer PPO-g-MAH, plasticiser DOP, and silane coupling agent is γ-ammonia
Propyl-triethoxysilicane, antioxidant is pentaerythritol esters (antioxidant 1010) and phosphorous acid esters (irgasfos 168) form
Mixture (weight ratio 1:1), PTFE molecular weight be 200000, partial size be 20 μm, the weight ratio of plasticiser and silane coupling agent
For 2:1.
The preparation process of above-mentioned PBT composition is as follows:
(1) PBT, antioxidant are sequentially added into premix pot, high-speed stirred mixing；By compatilizer, PTFE, silane coupling agent,
Premix pot, high-speed stirred mixing is added in plasticiser；
(2) the pre- mixed raw material of step (1) is distinguished into blanking from two premix pots, be added in double screw extruder, glass
The double screw extruder is added at the 5th section of extruder, by side feeder in glass fiber, and melting extrusion is granulated, and technological parameter is such as
Under: area's temperature is 200 DEG C, two area's temperature: 240 DEG C, three area's temperature are 250 DEG C, and four Qu Wendu: 250 DEG C, five area's temperature are
250 DEG C, six Qu Wendu: 230 DEG C, District 7 temperature: 230 DEG C, die head temperature: 240 DEG C, driving screw revolving speed are as follows: 400r/min.
Comparative example 2
A kind of PBT/PPO composition of this comparative example, is prepared by the raw material of following parts by weight:
| PBT | 55 |
| PPO | 45 |
| Glass fibre | 25 |
| Compatilizer | 8 |
| PTFE | 10 |
| Antioxidant | 0.8 |
| Silane coupling agent | 0.8 |
PBT number-average molecular weight is that 40000, PPO number-average molecular weight is 40000, compatilizer PPO-g-MAH, silane coupled
Agent is gamma-aminopropyl-triethoxy-silane, and antioxidant is pentaerythritol esters (antioxidant 1010) and phosphorous acid esters (antioxidant
168) mixture (weight ratio 1:1) the PTFE molecular weight formed is 200000, and partial size is 20 μm.
The preparation process of above-mentioned PBT/PPO composition is as follows:
(1) PBT, PPO, antioxidant are sequentially added into premix pot, high-speed stirred mixing；By compatilizer, PTFE, silane coupled
Premix pot, high-speed stirred mixing is added in agent；
(2) the pre- mixed raw material of step (1) is distinguished into blanking from two premix pots, be added in double screw extruder, glass
The double screw extruder is added at the 5th section of extruder, by side feeder in glass fiber, and melting extrusion is granulated, and technological parameter is such as
Under: area's temperature is 200 DEG C, two area's temperature: 240 DEG C, three area's temperature are 250 DEG C, and four Qu Wendu: 250 DEG C, five area's temperature are
250 DEG C, six Qu Wendu: 230 DEG C, District 7 temperature: 230 DEG C, die head temperature: 240 DEG C, driving screw revolving speed are as follows: 400r/min.
Comparative example 3
A kind of PBT/PPO composition of this comparative example, is prepared by the raw material of following parts by weight:
| PBT | 55 |
| PPO | 45 |
| Glass fibre | 25 |
| Compatilizer | 8 |
| Antioxidant | 0.7 |
| PTFE | 10 |
| Plasticiser | 0.4 |
PBT number-average molecular weight is that 40000, PPO number-average molecular weight is 40000, compatilizer PPO-g-MAH, and plasticiser is
DOP, antioxidant are the mixture (weight that pentaerythritol esters (antioxidant 1010) and phosphorous acid esters (irgasfos 168) form
Than 1:1), PTFE molecular weight is 200000, and partial size is 20 μm.
The preparation process of above-mentioned PBT/PPO composition is as follows:
(1) PBT, PPO, antioxidant are sequentially added into premix pot, high-speed stirred mixing；Compatilizer, PTFE, plasticiser are added
Enter and premixes pot, high-speed stirred mixing；
(2) the pre- mixed raw material of step (1) is distinguished into blanking from two premix pots, be added in double screw extruder, glass
The double screw extruder is added at the 5th section of extruder, by side feeder in glass fiber, and melting extrusion is granulated, and technological parameter is such as
Under: area's temperature is 200 DEG C, two area's temperature: 240 DEG C, three area's temperature are 250 DEG C, and four Qu Wendu: 250 DEG C, five area's temperature are
250 DEG C, six Qu Wendu: 230 DEG C, District 7 temperature: 230 DEG C, die head temperature: 240 DEG C, driving screw revolving speed are as follows: 400r/min.
Comparative example 4
A kind of PBT/PPO composition of this comparative example, is prepared by the raw material of following parts by weight:
| PBT | 55 |
| PPO | 45 |
| Glass fibre | 25 |
| Compatilizer | 8 |
| Antioxidant | 0.7 |
| PTFE | 10 |
| Plasticiser | 0.5 |
| Silane coupling agent | 1 |
PBT number-average molecular weight is that 40000, PPO number-average molecular weight is 40000, compatilizer PPO-g-MAH, and plasticiser is
DOP, silane coupling agent are gamma-aminopropyl-triethoxy-silane, and antioxidant is pentaerythritol esters (antioxidant 1010) and phosphorous
The weight ratio of the mixture (weight ratio 1:1) of esters of gallic acid (irgasfos 168) composition, plasticiser and silane coupling agent is 1:2, PTFE
Molecular weight is 200000, and partial size is 20 μm,.
The preparation process of above-mentioned PBT composition is as follows:
(1) PBT, PPO, antioxidant are sequentially added into premix pot, high-speed stirred mixing；By compatilizer, PTFE, silane coupled
Premix pot, high-speed stirred mixing is added in agent, plasticiser；
(2) the pre- mixed raw material of step (1) is distinguished into blanking from two premix pots, be added in double screw extruder, glass
The double screw extruder is added at the 5th section of extruder, by side feeder in glass fiber, and melting extrusion is granulated, and technological parameter is such as
Under: area's temperature is 200 DEG C, two area's temperature: 240 DEG C, three area's temperature are 250 DEG C, and four Qu Wendu: 250 DEG C, five area's temperature are
250 DEG C, six Qu Wendu: 230 DEG C, District 7 temperature: 230 DEG C, die head temperature: 240 DEG C, driving screw revolving speed are as follows: 400r/min.
Comparative example 5
A kind of PBT/PPO composition of this comparative example, is prepared by the raw material of following parts by weight:
| PBT | 100 |
| PPO | 45 |
| Glass fibre | 25 |
| Compatilizer | 8 |
| Antioxidant | 0.7 |
| PTFE | 10 |
| Plasticiser | 1.2 |
| Silane coupling agent | 0.2 |
PBT number-average molecular weight is that 40000, PPO number-average molecular weight is 40000, compatilizer PPO-g-MAH, and plasticiser is
DOP, silane coupling agent are gamma-aminopropyl-triethoxy-silane, and antioxidant is pentaerythritol esters (antioxidant 1010) and phosphorous
The weight ratio of the mixture (weight ratio 1:1) of esters of gallic acid (irgasfos 168) composition, plasticiser and silane coupling agent is 6:1, PTFE
Molecular weight is 200000, and partial size is 20 μm.
The preparation process of above-mentioned PBT composition is as follows:
(1) PBT, PPO, antioxidant are sequentially added into premix pot, high-speed stirred mixing；By compatilizer, silane coupling agent, modeling
Premix pot, high-speed stirred mixing is added in agent；
(2) the pre- mixed raw material of step (1) is distinguished into blanking from two premix pots, be added in double screw extruder, glass
The double screw extruder is added at the 5th section of extruder, by side feeder in glass fiber, and melting extrusion is granulated, and technological parameter is such as
Under: area's temperature is 200 DEG C, two area's temperature: 240 DEG C, three area's temperature are 250 DEG C, and four Qu Wendu: 250 DEG C, five area's temperature are
250 DEG C, six Qu Wendu: 230 DEG C, District 7 temperature: 230 DEG C, die head temperature: 240 DEG C, driving screw revolving speed are as follows: 400r/min.
Comparative example 6
A kind of PBT/PPO composition of this comparative example, is prepared by the raw material of following parts by weight:
PBT number-average molecular weight is that 40000, PPO number-average molecular weight is 40000, compatilizer PPO-g-MAH, and plasticiser is
DOP, silane coupling agent are gamma-aminopropyl-triethoxy-silane, and antioxidant is pentaerythritol esters (antioxidant 1010) and phosphorous
The weight ratio of the mixture (weight ratio 1:1) of esters of gallic acid (irgasfos 168) composition, plasticiser and silane coupling agent is 2:1.
The preparation process of above-mentioned low dielectric high tenacity enhancing PBT/PPO composition is as follows:
(1) PBT, PPO, antioxidant are sequentially added into premix pot, high-speed stirred mixing；By compatilizer, silane coupling agent, modeling
Premix pot, high-speed stirred mixing is added in agent；
(2) the pre- mixed raw material of step (1) is distinguished into blanking from two premix pots, be added in double screw extruder, glass
The double screw extruder is added at the 5th section of extruder, by side feeder in glass fiber, and melting extrusion is granulated, and technological parameter is such as
Under: area's temperature is 200 DEG C, two area's temperature: 240 DEG C, three area's temperature are 250 DEG C, and four Qu Wendu: 250 DEG C, five area's temperature are
250 DEG C, six Qu Wendu: 230 DEG C, District 7 temperature: 230 DEG C, die head temperature: 240 DEG C, driving screw revolving speed are as follows: 400r/min.
The following are comparative examples and embodiment list:
1 comparative example of table and embodiment raw material form parts by weight list
Performance test:
The sample of above-described embodiment 1-5 and comparative example 1-6 preparation presses ASTM testing standard through identical drying, Shooting Technique
Mechanics Performance Testing batten is prepared, then through identical humidity, temperature, each case of time adjustment, the physical property measurement number measured
According to such as table 2.
Above-mentioned comparative example and the made sample of embodiment are subjected to following performance test:
Dielectric properties: 243 standard testing of IEC, size of sample 60mm*60mm*1.5mm are pressed；
Tensile property: ASTM D638 standard testing, rate of extension 50mm/min are pressed；
Bending property: ASTM D790 standard testing, rate of extension 2mm/min are pressed；
Impact property: ASTM D256 standard testing is pressed, batten is with a thickness of 3.2mm.
The performance of table 2 embodiment 1-5 and comparative example 1-6
Embodiment 1 can be seen that the increasing with PBT and PPO molecular weight, glass, compatible dosage to embodiment 3 from table 1
Add, the intensity of PBT/PPO composition improves, and notch impact strength improves, and dielectric properties are excellent, the best performance of embodiment 2.
From embodiment 1 to embodiment 3, gamma-aminopropyl-triethoxy-silane, γ-(2,3- rings are respectively adopted in silane coupling agent
The third oxygen of oxygen) propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane；Plasticiser be respectively adopted DINP,
DOP,DBP；PE-g-MAH, PPO-g-MAH, PP-g-MAH is respectively adopted in compatilizer.From the point of view of performance, γ-aminopropyl three is used
Ethoxysilane is as silane coupling agent, and DOP is as plasticiser, and PBT/PPO composition is comprehensive when PPO-g-MAH is as compatilizer
Close best performance.
Embodiment 1 can be seen that embodiment 3 as the weight ratio of plasticiser and silane coupling agent improves from table 1,
The plasticizing effect of PBT and PPO gradually shows, and is all significantly increased to mechanical property, the dielectric properties of composition, embodiment 2
Best performance.
Embodiment 4 and embodiment 2 compare, and as PPO amount reduces, glass amount increases, the weight of plasticiser and silane coupling agent
Than increasing, notch impact strength reduces amount, and dielectric constant improves, and dielectric loss increases.
Embodiment 5 and embodiment 2 compare, and as PPO amount continues to reduce, glass amount is continued growing, and plasticiser and silane are even
The weight ratio of connection agent continues to increase, and the notch sensitive embodiment of PBT is more and more obvious, and notch shock continues to reduce.
Compared with Example 2, the not addition of PPO, in dielectric properties, notch impact strength, PBT's lacks comparative example 1
It falls into and highlights.Compared with Example 2, in the case where no addition plasticiser, PBT, PPO plasticizing effect are bad for comparative example 2, although
There is compatilizer, but still com-patibilising effect is bad, the characteristics of PPO low dielectric is difficult to embody in the composition.Comparative example 3 with
Embodiment 2 is compared, in the case where no addition silane coupling agent, resin deficiency compatible with two phase surfaces of glass, and resin pair
The lack of fill-out of glass, intensity is lower, and dielectric properties are also decreased obviously.Comparative example 4 compared with Example 2, plasticiser and silane
The weight ratio of coupling agent is less than 1:1, is 1:2, and the dielectric properties of comparative example 4 are obviously deteriorated, and impact property is poor.Comparative example 5 with
Embodiment 2 is compared, and it is 6:1 that the weight ratio of plasticiser and silane coupling agent, which is greater than 5:1, and the dielectric properties of comparative example 5 obviously become
Difference.PPO is not added compared with comparative example 1, comparative example 2, comparative example 3, comparative example 4, comparative example 5, comparative example 6 for integrated embodiment 2
Or it is single using the ratio of silane coupling agent or plasticiser or silane coupling agent and plasticiser not in the range of 1:1~5:1
Or it is added without PTFE, it is not enough to reach the requirement of the low dielectric of composition.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of low dielectric high tenacity enhances PBT/PPO composition, which is characterized in that the raw material including following parts by weight:
The weight ratio of the plasticiser and silane coupling agent is 1:1~5:1.
2. low dielectric high tenacity according to claim 1 enhances PBT/PPO composition, which is characterized in that including following heavy
Measure the raw material of part:
The weight ratio of the plasticiser and silane coupling agent is 2:1~4:1.
3. low dielectric high tenacity according to claim 1 enhances PBT/PPO composition, which is characterized in that the number of the PBT
The number-average molecular weight that average molecular weight is 30000~50000, PPO is 30000~50000.
4. low dielectric high tenacity according to claim 1 enhances PBT/PPO composition, which is characterized in that the compatilizer
For one or more of PE-g-MAH, PPO-g-MAH, PP-g-GMA；
The preparation method of the PE-g-MAH includes the following steps: PE, MAH according to weight ratio (95.5~98.5): (1.5
~4.5) it is mixed in low-speed mixer according to 100r/min~300r/min；It is added in twin-screw machine, preparation process temperature:
First 180 DEG C of area~200 DEG C, the second 190 DEG C of area~210 DEG C, 190 DEG C~210 DEG C of third area, the 4th 190 DEG C of area~210 DEG C,
5th 190 DEG C of area~210 DEG C, the 6th 190 DEG C of area~210 DEG C, 190 DEG C~210 DEG C of District 7,190 DEG C~210 DEG C of Section Eight,
Driving screw revolving speed is 150r/min~200r/min；It is squeezed out, cooling, pelletizing forms, and grafting rate is 0.5~1.0；
The preparation method of the PPO-g-MAH includes the following steps: PPO, MAH according to weight ratio (95.5~98.5):
(1.5~4.5) mix in low-speed mixer according to 100r/min~300r/min；It is added in twin-screw machine, preparation process
Temperature: the first 180 DEG C of area~200 DEG C, the second 250 DEG C of area~280 DEG C, 260 DEG C~280 DEG C of third area, the 4th 260 DEG C of area~
280 DEG C, the 5th 260 DEG C of area~280 DEG C, the 6th 260 DEG C of area~280 DEG C, 260 DEG C~280 DEG C of District 7,260 DEG C of Section Eight~
280 DEG C, driving screw revolving speed is 150r/min~200r/min；It is squeezed out, cooling, pelletizing forms, and grafting rate is 0.5~1.0；
The preparation method of the PP-g-MAH includes the following steps: PP, MAH according to weight ratio (95.5~98.5): (1.5
~4.5) it is mixed in low-speed mixer according to 100r/min~300r/min；It is added in twin-screw machine, preparation process temperature:
First 180 DEG C of area~200 DEG C, the second 190 DEG C of area~210 DEG C, 190 DEG C~210 DEG C of third area, the 4th 190 DEG C of area~210 DEG C,
5th 190 DEG C of area~210 DEG C, the 6th 190 DEG C of area~210 DEG C, 190 DEG C~210 DEG C of District 7,190 DEG C~210 DEG C of Section Eight,
Driving screw revolving speed is 150r/min~200r/min；It is squeezed out, cooling, pelletizing forms, and grafting rate is 0.5~1.0.
5. low dielectric high tenacity according to claim 1 enhances PBT/PPO composition, which is characterized in that the polytetrafluoro
Ethylene molecule amount be 150000~350000,20~35 μm of partial size.
6. low dielectric high tenacity according to claim 1 enhances PBT/PPO composition, which is characterized in that the plasticiser
For one or more of diisononyl phthalate, dioctyl phthalate, dibutyl phthalate.
7. low dielectric high tenacity according to claim 1 enhances PBT/PPO composition, which is characterized in that the silane is even
Connection agent is gamma-aminopropyl-triethoxy-silane, γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, γ-(methacryl
One or more of oxygen) propyl trimethoxy silicane.
8. low dielectric high tenacity according to claim 1-6 enhances PBT/PPO composition, which is characterized in that institute
The antioxidant stated is one or more of Hinered phenols antioxidant, phosphite ester antioxidant；And/or the glass
Fiber is short glass fiber, and diameter is 10~15 μm, 4~5mm of length.
9. the preparation method of the described in any item low dielectric high tenacity enhancing PBT/PPO compositions of claim 1-8, feature exist
In including the following steps:
(1) the PBT, PPO, antioxidant are sequentially added into premix pot, are stirred；
(2) premix pot is added in the compatilizer, polytetrafluoroethylene (PTFE), silane coupling agent, plasticiser, be stirred, to described
Polytetrafluoroethylene (PTFE) is pre-processed；
(3) step (1) and the pre- mixed raw material of step (2) are distinguished into blanking from two premix pots, is added to double screw extruder
In, the double screw extruder is added by the 5th section of the double screw extruder of side feed feeder in the glass fibre, melts
Melt extruding pelletization.
10. a kind of preparation method of low dielectric high tenacity enhancing PBT/PPO composition, feature exist according to claim 9
In the melting extrusion technique of the double screw extruder is as follows: area's temperature is 180~230 DEG C, two area's temperature: 230~260
DEG C, three area's temperature be 240~270 DEG C, four Qu Wendu: 240~270 DEG C, five area's temperature be 240~270 DEG C, six Qu Wendu: 220
~240 DEG C, District 7 temperature: 220~240 DEG C, die head temperature: 230~250 DEG C, driving screw revolving speed are as follows: 300~500r/min.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111057362A (en) * | 2019-12-31 | 2020-04-24 | 天津万塑新材料科技有限公司 | Low-dielectric-constant modified plastic for 5G mobile phone printed circuit board |
| CN111234478A (en) * | 2020-03-16 | 2020-06-05 | 深圳市高科塑化有限公司 | Low-dielectric glass fiber reinforced PBT (polybutylene terephthalate) composite material and preparation method thereof |
| CN112625406A (en) * | 2020-12-07 | 2021-04-09 | 上海金发科技发展有限公司 | Cold-heat shock resistant polybutylene terephthalate composition |
| CN113372692A (en) * | 2021-06-23 | 2021-09-10 | 广东虹勤通讯技术有限公司 | Polyester composite material and flexible cover sheet base material |
| CN113444352A (en) * | 2021-06-23 | 2021-09-28 | 广东虹勤通讯技术有限公司 | Low dielectric composite material and antenna assembly |
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2018
- 2018-10-22 CN CN201811230206.8A patent/CN109575528A/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111057362A (en) * | 2019-12-31 | 2020-04-24 | 天津万塑新材料科技有限公司 | Low-dielectric-constant modified plastic for 5G mobile phone printed circuit board |
| CN111234478A (en) * | 2020-03-16 | 2020-06-05 | 深圳市高科塑化有限公司 | Low-dielectric glass fiber reinforced PBT (polybutylene terephthalate) composite material and preparation method thereof |
| CN111234478B (en) * | 2020-03-16 | 2022-05-06 | 深圳市高科塑化有限公司 | Low-dielectric glass fiber reinforced PBT (polybutylene terephthalate) composite material and preparation method thereof |
| CN112625406A (en) * | 2020-12-07 | 2021-04-09 | 上海金发科技发展有限公司 | Cold-heat shock resistant polybutylene terephthalate composition |
| CN112625406B (en) * | 2020-12-07 | 2023-04-07 | 上海金发科技发展有限公司 | Cold-heat shock resistant polybutylene terephthalate composition |
| CN113372692A (en) * | 2021-06-23 | 2021-09-10 | 广东虹勤通讯技术有限公司 | Polyester composite material and flexible cover sheet base material |
| CN113444352A (en) * | 2021-06-23 | 2021-09-28 | 广东虹勤通讯技术有限公司 | Low dielectric composite material and antenna assembly |
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