CN106867211A - A kind of low haze is high heat-resisting to exempt from PBT composite of primary coat and preparation method thereof - Google Patents
A kind of low haze is high heat-resisting to exempt from PBT composite of primary coat and preparation method thereof Download PDFInfo
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- CN106867211A CN106867211A CN201710165623.8A CN201710165623A CN106867211A CN 106867211 A CN106867211 A CN 106867211A CN 201710165623 A CN201710165623 A CN 201710165623A CN 106867211 A CN106867211 A CN 106867211A
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- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C08K5/00—Use of organic ingredients
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- C08K5/098—Metal salts of carboxylic acids
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- C08K5/00—Use of organic ingredients
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- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92514—Pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
Abstract
Heat-resisting exempt from PBT composite of primary coat and preparation method thereof the invention discloses a kind of low haze is high, it is therefore intended that solve existing PBT classes and exempt from the heat distortion temperature of primary coat product below 160 DEG C, it is impossible to meet the problem of car light decoration high-fire resistance requirement.One of goal of the invention of the invention is to provide a kind of low haze, PBT material that is heat-resisting, exempting from primary coat high, and another purpose is to provide the preparation method of this PBT composite.After measured, the PBT composite obtained by the present invention has good surface smoothness, and the moulding prepared using the PBT composite can directly carry out vacuum aluminum-coated;Meanwhile, the present invention efficiently solves the phenomenon that mist is sent out on aluminized products surface during long-term use under high ambient conditions.In addition, product prepared by the present invention has heat distortion temperature very high, use requirement higher can be met, compared with the prior art with significant progressive.
Description
Technical field
The present invention relates to Material Field, especially material modified field, specially a kind of low haze is high heat-resisting to exempt from primary coat
PBT composite and preparation method thereof.The present invention relates to a kind of PBT composite and preparation method thereof, PBT composite tool
Have low haze, it is high it is heat-resisting, the characteristics of exempt from primary coat.
Background technology
Polybutylene terephthalate (PBT), abbreviation PBT is a kind of engineering plastics of function admirable, and it has superior mechanical
Performance and fatigue resistance, heat-resisting, weatherability and dissolubility resistent are good, and electrical property is good, the low multinomial excellent characteristic of water absorption rate, because
This, is widely used in the fields such as automobile, electronic product, industrial equipment, illumination.But in some special occasions, such as exempt from primary coat
In the application of automobile lamp escutcheon, then require that PBT material has lower mist degree, and heat resistance higher;However, pure PBT
Material can not meet this requirement, therefore, pure PBT material need to be modified.
Chinese patent application CN 102660109A disclose a kind of high fluidity, best bright finish exempt from primary coat PBT material and its
Preparation method, which employs a kind of silicon systems mesoporous material as the mode of the absorbent of small-molecule substance, prepares best bright finish
PBT material, its principle be physical absorption principle.But in thermal histories, small-molecule substance is easily desorbed prepared material,
And then surface is moved to, and cause product surface that hair mist, general color phenomenon occur, influence outward appearance and use.Therefore, this kind of method cannot
Fundamentally solve the problems, such as that product surface sends out mist.
Chinese patent application CN 101838444A disclose a kind of primer-free polyester material for decorating pieces and its preparation side
Method, its successfully solve the problems, such as car light decoration surface gloss it is not high and cannot be vacuum aluminum-coated, but the patent is not directed to
Aluminized decoration hair mist general color problem in surface during subsequent high temperature use to car light.
In recent years, with the high speed development of Hyundai Motor industry, the heat resistant requirements to car light decoration are further improved,
And existing PBT classes exempt from the heat distortion temperature of primary coat product below 160 DEG C, it is difficult to meet the application requirement of automotive lamp product.
Therefore, in the urgent need to a kind of new material, to solve the above problems.
The content of the invention
Goal of the invention of the invention is:For existing PBT classes exempt from the heat distortion temperature of primary coat product 160 DEG C with
Under, it is impossible to meet the problem of car light decoration high-fire resistance requirement, there is provided a kind of low haze heat-resisting PBT composite woods for exempting from primary coat high
Material and preparation method thereof.One of goal of the invention of the invention is to provide a kind of low haze, PBT material that is heat-resisting, exempting from primary coat high,
Another purpose is to provide the preparation method of this PBT composite.After measured, the PBT composite obtained by the present invention has
Good surface smoothness, the moulding prepared using the PBT composite can directly carry out vacuum aluminum-coated;Meanwhile, the present invention
Efficiently solve the phenomenon that mist is sent out on aluminized products surface during long-term use under high ambient conditions.In addition, present invention system
Standby product has heat distortion temperature very high, can meet use requirement higher, compared with the prior art with significant progressive.
To achieve these goals, the present invention is adopted the following technical scheme that:
A kind of low haze heat-resisting PBT composite for exempting from primary coat high, is prepared using the raw material including following percentage by weight
Form:
The relative density of the polybutylene terephthalate (PBT) is 1.28~1.35g/cm3, inherent viscosity be 0.8~
1.2Pa.S, melt temperature is 220~235 DEG C.
The lubricant is N, N'- ethylene bis stearamides, pentaerythritol stearate, calcium stearate, Tissuemat E, is had
One or more in machine silicon class.
The nucleator is Sodium Benzoate, long-chain linear saturated carboxylic acid sodium salt, talcum powder, kaolin, calcium sulfate, barium sulfate
In one or more.
The antioxidant is β-(3,5- di-t-butyl -4- hydroxy benzenes) propionic acid octadecanol ester, four [β-(3,5- bis- tertiary fourths
Base -4- hydroxy phenyls) propionic acid] pentaerythritol ester, N, N ' -1,6- inferior hexyls-bis- [3- (3,5- di-tert-butyl-hydroxy phenyls)
One or more in propionamide, three (2,4- di-tert-butyl-phenyls) phosphite esters.
The pigment is one or more in carbon black, organic color masterbatch.
The preparation method of the foregoing low haze heat-resisting PBT composite for exempting from primary coat high, comprises the following steps:
(1) dispensing
Polybutylene terephthalate (PBT), lubricant, nucleator, antioxidant, pigment are weighed respectively by proportioning, are mixed
Material, adds mixture into high speed dispensing mixer, and mixed at high speed is uniform, obtains premix;
(2) extrude
Premix prepared by step 1 is placed in carries out melting extrusion granulation in extruder, and the material cooling that will be extruded, then
Pelletizing in feeding pelleter, obtains final product product.
In the step 2, extruder is double screw extruder, and the screw slenderness ratio of extruder is 36~48:1, vacuum port
Number be 1-2.
In the step 2, premix prepared by step 1 is placed in carries out melting extrusion granulation in extruder, its extrusion bar
Part is as follows:
Dual-screw-stem machine humidity province is as follows:One section of temperature is 190~220 DEG C, and two sections of temperature are 220~250 DEG C, three sections of temperature
It it is 220~260 DEG C, four sections of temperature are 210~260 DEG C, and five sections of temperature are 210~260 DEG C, and head temperature is 220~270 DEG C;
Screw speed is 250~450rpm/min;Pelleter rotating speed is 300~500r/min;Vacuum is -0.01~0.1MPa.
In the step 1, incorporation time is 1~3min.
For foregoing problems, the present invention provides a kind of low haze heat-resisting PBT composite for exempting from primary coat high and its preparation side
Method.Wherein, the PBT composite uses the component for including following percentage by weight to be made:Polybutylene terephthalate (PBT)
(PBT) 89-99.74%, lubricant 0.1-3%, nucleator 0.01-1.5%, antioxidant 0.1-1.5%, pigment 0.05-5%.
Further, the present invention provides the preparation method of foregoing PBT composite.One of them specific example is as follows, should
Method comprises the following steps:
1st, batching step
Each component is weighed as following weight percent:Polybutylene terephthalate (PBT) (PBT) 89-99.74%, lubricant
0.1-3%, nucleator 0.01-1.5%, antioxidant 0.1-1.5%, pigment 0.05-5%.The component that will be weighed is added matches somebody with somebody at a high speed
In material mixer, mixed at high speed 1-3 minutes, premix is obtained;
2nd, extrusion step
Mixed premix is placed in twin-screw and is granulated through melting extrusion, the screw slenderness ratio of double screw extruder is
36-48:1, the number of vacuum port is 1-2, and its expressing technique is:Dual-screw-stem machine humidity province:One section of 190-220 DEG C of temperature, two
Duan Wendu 220-250 DEG C, three sections of 220-260 DEG C of temperature, four sections of 210-260 DEG C of temperature, five sections of 210-260 DEG C of temperature, head temperature
220-270 DEG C of degree;Screw speed is 250-450rpm/min;Pelleter rotating speed:300-500r/min;Vacuum:- 0.01~-
0.1MPa;The material cooling that will be extruded, pelletizing in feeding pelleter, the particle packing that will be cut is obtained low haze, high resistance to
Heat, exempts from the PBT material of primary coat.
After measured, the haze value as little as 2.0% of the PBT material prepared by the present invention, heat distortion temperature (0.45MPa) is up to
170 DEG C, product surface hair mist and general color phenomenon are greatly improved, efficiently solve existing PBT platings aluminum products in use
There is the problem of high temperature hair mist, general coloured silk etc., improve the range of application of PBT composite.
In sum, the PBT composite prepared by the present invention has good surface smoothness, and is answered using the PBT
Condensation material prepare moulding can directly carry out it is vacuum aluminum-coated, efficiently solve PBT composite preparation aluminized products in height
The phenomenon of mist is sent out on surface during long-term use under warm environmental condition.Meanwhile, PBT composite of the invention has heat very high
Deformation temperature, can meet use requirement higher, effectively expand the range of application of PBT composite.
Specific embodiment
All features disclosed in this specification, or disclosed all methods or during the step of, except mutually exclusive
Feature and/or step beyond, can combine by any way.
Any feature disclosed in this specification, unless specifically stated otherwise, can be equivalent or with similar purpose by other
Alternative features are replaced.I.e., unless specifically stated otherwise, each feature is an example in a series of equivalent or similar characteristics
.
Embodiment 1
Using the component of following weight percents in the present embodiment:Polybutylene terephthalate (PBT) (PBT) 90.5%, season
Penta tetrol stearate 3%, talcum powder 0.5%, β-(3,5- di-t-butyl -4- hydroxy benzenes) propionic acid octadecanol ester 1.0%, charcoal
Black 5.0%.During each component of aforementioned proportion added into high speed dispensing mixer, mixed at high speed 1 minute;By mixed premix
It is placed in twin-screw and is granulated through melting extrusion, the screw slenderness ratio of double screw extruder is 36:1, vacuum port number is 1, its
Expressing technique is:Dual-screw-stem machine humidity province:One section of 210 DEG C, two sections of temperature, 240 DEG C, three sections of temperature, 240 DEG C, four sections temperature of temperature
240 DEG C, five sections of 240 DEG C of temperature, 250 DEG C of head temperatures;Vacuum is -0.03MPa;Screw speed is 300rpm/min;Pelletizing
Machine rotating speed:300r/min;The material cooling that will be extruded, pelletizing in feeding pelleter, the particle packing that will be cut is obtained ground fog
Degree, it is high heat-resisting, exempt from the PBT material of primary coat.
Embodiment 2
Using the component of following weight percents in the present embodiment:Polybutylene terephthalate (PBT) (PBT) 90.5%, season
Penta tetrol stearate 3%, talcum powder 0.5%, four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester
1.0%th, carbon black 5.0%.During each component of aforementioned proportion added into high speed dispensing mixer, mixed at high speed 1 minute;After mixing
Premix be placed in twin-screw and granulated through melting extrusion, the screw slenderness ratio of double screw extruder is 40:1, vacuum port number
It it is 1, its expressing technique is:Dual-screw-stem machine humidity province:One section of 210 DEG C, two sections of temperature, 240 DEG C, three sections of temperature, 240 DEG C of temperature,
Four sections of temperature, 240 DEG C, five sections 240 DEG C of temperature, 250 DEG C of head temperature;Vacuum is -0.05MPa;Screw speed is 300rpm/
min;Pelleter rotating speed:300r/min;The material cooling that will be extruded, pelletizing in feeding pelleter, the particle packing that will be cut, i.e.,
Low haze is obtained, it is high heat-resisting, exempt from the PBT material of primary coat.
Embodiment 3
Using the component of following weight percents in the present embodiment:Polybutylene terephthalate (PBT) (PBT) 90.5%, season
Penta tetrol stearate 3%, talcum powder 0.5%, N, N ' -1,6- inferior hexyls-bis- [3- (3,5- di-tert-butyl-hydroxy phenyls)
Propionamide 1.0%, color masterbatch 5.0%.During each component of aforementioned proportion added into high speed dispensing mixer, mixed at high speed 1 minute;
Mixed premix is placed in twin-screw and is granulated through melting extrusion, the screw slenderness ratio of double screw extruder is 48:1, very
Number of eating dishes without rice or wine is 2, and its expressing technique is:Dual-screw-stem machine humidity province:One section of 210 DEG C, two sections of temperature, 240 DEG C, three sections of temperature temperature
240 DEG C of degree, four sections of temperature, 240 DEG C, five sections 240 DEG C of temperature, 250 DEG C of head temperature;Vacuum is -0.1MPa;Screw speed is
400rpm/min;Pelleter rotating speed:400r/min;The material cooling that will be extruded, pelletizing, the particle that will be cut in feeding pelleter
Packing, that is, be obtained low haze, high heat-resisting, exempts from the PBT material of primary coat.
Embodiment 4
Using the component of following weight percents in the present embodiment:Polybutylene terephthalate (PBT) (PBT) 90%, season penta
Tetrol stearate 3%, Sodium Benzoate 0.8%, β-(3,5- di-t-butyl -4- hydroxy benzenes) propionic acid octadecanol ester 1.2%, color
Masterbatch 5.0%.During each component of aforementioned proportion added into high speed dispensing mixer, mixed at high speed 1 minute;By mixed premix
Material is placed in twin-screw and is granulated through melting extrusion, and the screw slenderness ratio of double screw extruder is 48:1, vacuum port number is 2,
Its expressing technique is:Dual-screw-stem machine humidity province:One section of 210 DEG C, two sections of temperature, 240 DEG C, three sections of temperature, 240 DEG C, four sections temperature of temperature
Degree 240 DEG C, five sections of 240 DEG C of temperature, 250 DEG C of head temperatures;Vacuum is -0.1MPa;Screw speed is 400rpm/min;Pelletizing
Machine rotating speed:400r/min;The material cooling that will be extruded, pelletizing in feeding pelleter, the particle packing that will be cut is obtained ground fog
Degree, it is high heat-resisting, exempt from the PBT material of primary coat.
Embodiment 5
Using the component of following weight percents in the present embodiment:Polybutylene terephthalate (PBT) (PBT) 89.9%, season
Penta tetrol stearate 3%, Sodium Benzoate 0.3%, talcum powder 0.3%, three (2,4- di-tert-butyl-phenyls) phosphite ester
1.5%th, carbon black 5.0%.During each component of aforementioned proportion added into high speed dispensing mixer, mixed at high speed 1 minute;After mixing
Premix be placed in twin-screw and granulated through melting extrusion, the screw slenderness ratio of double screw extruder is 48:1, vacuum port number
It it is 2, its expressing technique is:Dual-screw-stem machine humidity province:One section of 210 DEG C, two sections of temperature, 240 DEG C, three sections of temperature, 240 DEG C of temperature,
Four sections of temperature, 240 DEG C, five sections 240 DEG C of temperature, 250 DEG C of head temperature;Vacuum is -0.1MPa;Screw speed is 400rpm/
min;Pelleter rotating speed:400r/min;The material cooling that will be extruded, pelletizing in feeding pelleter, the particle packing that will be cut, i.e.,
Low haze is obtained, it is high heat-resisting, exempt from the PBT material of primary coat.
Embodiment 6
Using the component of following weight percents in the present embodiment:Polybutylene terephthalate (PBT) (PBT) 91.4%, N,
N'- ethylene bis stearamides 2%, long-chain linear saturated carboxylic acid sodium salt 0.3%, N, the N ' -1,6- inferior hexyls-bis- [3- (uncles of 3,5- bis-
Butyl -4- hydroxy phenyls) propionamide 1.4%, carbon black 4.9%.During each component of aforementioned proportion added into high speed dispensing mixer,
Mixed at high speed 1 minute;Mixed premix is placed in twin-screw and is granulated through melting extrusion, the screw rod of double screw extruder is long
Footpath ratio is 48:1, vacuum port number is 2, and its expressing technique is:Dual-screw-stem machine humidity province:One section of temperature, 210 DEG C, two sections temperature
240 DEG C, three sections of 240 DEG C, four sections of temperature, 240 DEG C, five sections of temperature, 240 DEG C of temperature, 250 DEG C of head temperatures;Vacuum for-
0.1MPa;Screw speed is 400rpm/min;Pelleter rotating speed:400r/min;The material cooling that will be extruded, in feeding pelleter
Pelletizing, the particle packing that will be cut is obtained low haze, high heat-resisting, exempts from the PBT material of primary coat.
Embodiment 7
Using the component of following weight percents in the present embodiment:Polybutylene terephthalate (PBT) (PBT) 92.55%,
N, N'- ethylene bis stearamide 2%, long-chain linear saturated carboxylic acid sodium salt 0.1%, talcum powder 0.25%, N, N ' -1,6- are sub-
Base-bis- [3- (3,5- di-tert-butyl-hydroxy phenyls) propionamide 1.1%, color masterbatch 4%.The each component of aforementioned proportion is added
In high speed dispensing mixer, mixed at high speed 1 minute;Mixed premix is placed in twin-screw and is granulated through melting extrusion, it is double
The screw slenderness ratio of screw extruder is 48:1, vacuum port number is 2, and its expressing technique is:Dual-screw-stem machine humidity province:One section
210 DEG C, two sections of temperature 240 DEG C, three sections of temperature 240 DEG C, four sections of temperature 240 DEG C, five sections of temperature 240 DEG C of temperature, head temperature 250
℃;Vacuum is -0.1MPa;Screw speed is 400rpm/min;Pelleter rotating speed:400r/min;The material cooling that will be extruded,
Pelletizing in feeding pelleter, the particle packing that will be cut is obtained low haze, high heat-resisting, exempts from the PBT material of primary coat.
Embodiment 8
Using the component of following weight percents in the present embodiment:Polybutylene terephthalate (PBT) (PBT) 91.4%, N,
N'- ethylene bis stearamides 2%, long-chain linear saturated carboxylic acid sodium salt 0.3%, talcum powder 0.3%, β-(3,5- di-t-butyl -4-
Hydroxy benzenes) propionic acid octadecanol ester 1.0%, color masterbatch 5%.During each component of aforementioned proportion added into high speed dispensing mixer,
Mixed at high speed 1 minute;Mixed premix is placed in twin-screw and is granulated through melting extrusion, the screw rod of double screw extruder is long
Footpath ratio is 48:1, vacuum port number is 2, and its expressing technique is:Dual-screw-stem machine humidity province:One section of temperature, 210 DEG C, two sections temperature
240 DEG C, three sections of 240 DEG C, four sections of temperature, 240 DEG C, five sections of temperature, 240 DEG C of temperature, 250 DEG C of head temperatures;Vacuum for-
0.1MPa;Screw speed is 400rpm/min;Pelleter rotating speed:400r/min;The material cooling that will be extruded, in feeding pelleter
Pelletizing, the particle packing that will be cut is obtained low haze, high heat-resisting, exempts from the PBT material of primary coat.
Embodiment 9
Using the component of following weight percents in the present embodiment:Polybutylene terephthalate (PBT) (PBT) 95.5%, N,
N'- ethylene bis stearamides 2%, talcum powder 0.5%, N, N ' -1,6- inferior hexyls-bis- [3- (3,5- di-t-butyl -4- hydroxy benzenes
Base) propionamide 1.0%, color masterbatch 1%.During each component of aforementioned proportion added into high speed dispensing mixer, 1 point of mixed at high speed
Clock;Mixed premix is placed in twin-screw and is granulated through melting extrusion, the screw slenderness ratio of double screw extruder is 48:1,
Vacuum port number is 2, and its expressing technique is:Dual-screw-stem machine humidity province:One section of 210 DEG C, two sections of temperature, 240 DEG C, three sections of temperature
240 DEG C, four sections of temperature, 240 DEG C, five sections of temperature, 240 DEG C of temperature, 250 DEG C of head temperature;Vacuum is -0.1MPa;Screw speed
It is 400rpm/min;Pelleter rotating speed:400r/min;The material cooling that will be extruded, pelletizing, the grain that will be cut in feeding pelleter
Son packing, that is, be obtained low haze, high heat-resisting, exempts from the PBT material of primary coat.
Embodiment 10
Using the component of following weight percents in the present embodiment:Polybutylene terephthalate (PBT) (PBT) 91%, season penta
Tetrol stearate 3%, long-chain linear saturated carboxylic acid sodium salt 0.3%, talcum powder 0.5%, β-(3,5- di-t-butyl -4- hydroxyls
Benzene) propionic acid octadecanol ester 1.0%, carbon black 4.5%.During each component of aforementioned proportion added into high speed dispensing mixer, at a high speed
Mixing 1 minute;Mixed premix is placed in twin-screw and is granulated through melting extrusion, the screw slenderness ratio of double screw extruder
It is 36:1, vacuum port number is 1, and its expressing technique is:Dual-screw-stem machine humidity province:One section of temperature, 210 DEG C, two sections temperature 240
DEG C, three sections of 240 DEG C, four sections of temperature, 240 DEG C, five sections of temperature, 240 DEG C of temperature, 250 DEG C of head temperatures;Vacuum is -0.03MPa;
Screw speed is 300rpm/min;Pelleter rotating speed:300r/min;The material cooling that will be extruded, pelletizing in feeding pelleter will
The particle packing for cutting, that is, be obtained low haze, high heat-resisting, exempts from the PBT material of primary coat.
Embodiment 11
Using the component of following weight percents in the present embodiment:Polybutylene terephthalate (PBT) (PBT) 91%, season penta
Tetrol stearate 3%, long-chain linear saturated carboxylic acid sodium salt 0.3%, talcum powder 0.5%, three (2,4- di-tert-butyl-phenyls) are sub-
Phosphate 1.0%, carbon black 4.5%.During each component of aforementioned proportion added into high speed dispensing mixer, mixed at high speed 1 minute;Will
Mixed premix is placed in twin-screw and is granulated through melting extrusion, and the screw slenderness ratio of double screw extruder is 48:1, vacuum
Mouth number is 2, and its expressing technique is:Dual-screw-stem machine humidity province:One section of 210 DEG C, two sections of temperature, 240 DEG C, three sections of temperature temperature
240 DEG C, four sections of temperature, 240 DEG C, five sections 240 DEG C of temperature, 250 DEG C of head temperature;Vacuum is -0.1MPa;Screw speed is
300rpm/min;Pelleter rotating speed:300r/min;The material cooling that will be extruded, pelletizing, the particle that will be cut in feeding pelleter
Packing, that is, be obtained low haze, high heat-resisting, exempts from the PBT material of primary coat.
Embodiment 12
Using the component of following weight percents in the present embodiment:It is polybutylene terephthalate (PBT) (PBT) 93.2%, poly-
Ethylene waxes 1.5%, kaolin 1.2%, four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester 0.2%, charcoal
Black 3.9%.During each component of aforementioned proportion added into high speed dispensing mixer, mixed at high speed 2 minutes;By mixed premix
It is placed in twin-screw and is granulated through melting extrusion, the screw slenderness ratio of double screw extruder is 36:1, vacuum port number is 1, its
Expressing technique is:Dual-screw-stem machine humidity province:One section of 200 DEG C, two sections of temperature, 235 DEG C, three sections of temperature, 235 DEG C, four sections temperature of temperature
235 DEG C, five sections of 235 DEG C of temperature, 250 DEG C of head temperatures;Vacuum is -0.05MPa;Screw speed is 350rpm/min;Pelletizing
Machine rotating speed:350r/min;The material cooling that will be extruded, pelletizing in feeding pelleter, the particle packing that will be cut is obtained ground fog
Degree, it is high heat-resisting, exempt from the PBT material of primary coat.
Embodiment 13
Using the component of following weight percents in the present embodiment:It is polybutylene terephthalate (PBT) (PBT) 94.1%, hard
Resin acid calcium 0.3%, calcium sulfate 0.6%, three (2,4- di-tert-butyl-phenyls) phosphite ester 0.3%, carbon black 4.7%.By above-mentioned ratio
The each component of example is added in high speed dispensing mixer, mixed at high speed 2 minutes;Mixed premix is placed in twin-screw through molten
Melt extruding pelletization, the screw slenderness ratio of double screw extruder is 48:1, vacuum port number is 2, and its expressing technique is:Twin-screw
Machine humidity province:One section of 210 DEG C, two sections of temperature, 240 DEG C, three sections of temperature, 240 DEG C, four sections of temperature, 240 DEG C, five sections of temperature temperature 240
DEG C, 250 DEG C of head temperature;Vacuum is -0.03MPa;Screw speed is 400rpm/min;Pelleter rotating speed:400r/min;Will
The material cooling of extrusion, pelletizing in feeding pelleter, the particle packing that will be cut is obtained low haze, high heat-resisting, exempts from primary coat
PBT material.
Embodiment 14
Using the component of following weight percents in the present embodiment:It is polybutylene terephthalate (PBT) (PBT) 92.8%, poly-
Ethylene waxes 0.7%, barium sulfate 0.5%, four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester 1.1%, color
Masterbatch 4.9%.During each component of aforementioned proportion added into high speed dispensing mixer, mixed at high speed 3 minutes;By mixed premix
Material is placed in twin-screw and is granulated through melting extrusion, and the screw slenderness ratio of double screw extruder is 36:1, vacuum port number is 1,
Its expressing technique is:Dual-screw-stem machine humidity province:One section of 210 DEG C, two sections of temperature, 245 DEG C, three sections of temperature, 245 DEG C, four sections temperature of temperature
Degree 245 DEG C, five sections of 245 DEG C of temperature, 260 DEG C of head temperatures;Vacuum is -0.03MPa;Screw speed is 300rpm/min;Cut
Grain machine rotating speed:300r/min;The material cooling that will be extruded, pelletizing in feeding pelleter, the particle packing that will be cut is obtained low
Mist degree, it is high heat-resisting, exempt from the PBT material of primary coat.
Embodiment 15
Using the component of following weight percents in the present embodiment:It is polybutylene terephthalate (PBT) (PBT) 93%, organic
Silicone lubricant 1.5%, barium sulfate 0.4%, β-(3,5- di-t-butyl -4- hydroxy benzenes) propionic acid octadecanol ester 0.5%, color masterbatch
4.6%.During each component of aforementioned proportion added into high speed dispensing mixer, mixed at high speed 1 minute;Mixed premix is put
Granulated through melting extrusion in twin-screw, the screw slenderness ratio of double screw extruder is 36:1, vacuum port number is 2, and it is squeezed
Going out technique is:Dual-screw-stem machine humidity province:One section of 200 DEG C, two sections of temperature, 235 DEG C, three sections of temperature, 235 DEG C, four sections temperature 235 of temperature
DEG C, five sections of 235 DEG C of temperature, 250 DEG C of head temperatures;Vacuum is -0.05MPa;Screw speed is 350rpm/min;Pelleter turns
Speed:350r/min;The material cooling that will be extruded, pelletizing in feeding pelleter, the particle packing that will be cut is obtained low haze,
It is high heat-resisting, exempt from the PBT material of primary coat.
Product prepared by above-described embodiment is tested, test result is as shown in Table 1 below.
The PBT composite performance of table 1
Embodiment | Mist degree (%) | Heat distortion temperature (DEG C) |
Embodiment 1 | 5.8 | 162 |
Embodiment 2 | 4.5 | 161 |
Embodiment 3 | 2.1 | 163 |
Embodiment 4 | 2.1 | 159 |
Embodiment 5 | 2.0 | 160 |
Embodiment 6 | 2.0 | 165 |
Embodiment 7 | 2.0 | 170 |
Embodiment 8 | 2.1 | 167 |
Embodiment 9 | 2.2 | 162 |
Embodiment 10 | 6.0 | 153 |
Embodiment 11 | 2.1 | 151 |
Embodiment 12 | 2.2 | 165 |
Embodiment 13 | 3.0 | 163 |
Embodiment 14 | 2.0 | 170 |
Embodiment 15 | 2.1 | 168 |
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, it is all in essence of the invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
The invention is not limited in foregoing specific embodiment.The present invention is expanded to and any in this manual disclosed
New feature or any new combination, and disclose any new method or process the step of or any new combination.This explanation
All features disclosed in book, in addition to mutually exclusive feature, can combine by any way.
Any feature disclosed in this specification (including any accessory claim, summary), unless specifically stated otherwise,
Equivalent by other or with similar purpose alternative features are replaced.I.e., unless specifically stated otherwise, each feature is a series of
An example in equivalent or similar characteristics.
Claims (10)
1. a kind of low haze heat-resisting PBT composite for exempting from primary coat high, it is characterised in that using including following percentage by weight
Raw material is prepared from:
Polybutylene terephthalate (PBT) 89 ~ 99.74%;
Lubricant 0.1 ~ 3%;
Nucleator 0.01 ~ 1.5%;
Antioxidant 0.1 ~ 1.5%;
Pigment 0.05 ~ 5%.
2. the low haze according to claim 1 heat-resisting PBT composite for exempting from primary coat high, it is characterised in that described poly- right
The relative density of benzene dicarboxylic acid butanediol ester is 1.28 ~ 1.35 g/cm3, inherent viscosity is 0.8 ~ 1.2 Pa.S, and melt temperature is
220~235℃。
3. the low haze according to claim 1 and 2 heat-resisting PBT composite for exempting from primary coat high, it is characterised in that the profit
Lubrication prescription is N, the one kind in N'- ethylene bis stearamides, pentaerythritol stearate, calcium stearate, Tissuemat E, organic silicon
Or it is various.
4. the low haze heat-resisting PBT composite for exempting from primary coat high according to claim 1 or 2 or 3, it is characterised in that institute
Nucleator is stated for the one kind in Sodium Benzoate, long-chain linear saturated carboxylic acid sodium salt, talcum powder, kaolin, calcium sulfate, barium sulfate or
It is various.
5. the low haze heat-resisting PBT composite for exempting from primary coat high according to claim 1 or 2 or 3 or 4, its feature exists
In, the antioxidant be β-(3,5- di-t-butyl -4- hydroxy benzenes)Propionic acid octadecanol ester, four [β-(3,5- di-t-butyls -4-
Hydroxy phenyl) propionic acid] pentaerythritol ester, N, N ' -1,6- inferior hexyls-bis- [3- (3,5- di-tert-butyl-hydroxy phenyls) propionyl
One or more in amine, three (2,4- di-tert-butyl-phenyls) phosphite esters.
6. the low haze according to claim 1 heat-resisting PBT composite for exempting from primary coat high, it is characterised in that the pigment
It is one or more in carbon black, organic color masterbatch.
7. the preparation method of the heat-resisting PBT composite for exempting from primary coat high of low haze described in any one of preceding claims 1-6, its
It is characterised by, comprises the following steps:
(1)Dispensing
Polybutylene terephthalate (PBT), lubricant, nucleator, antioxidant, pigment are weighed respectively by proportioning, obtain compound,
Add mixture into high speed dispensing mixer, mixed at high speed is uniform, obtains premix;
(2)Extrusion
Premix prepared by step 1 is placed in carries out melting extrusion granulation in extruder, and the material cooling that will be extruded, and is re-fed into
Pelletizing in pelleter, obtains final product product.
8. method according to claim 7, it is characterised in that in the step 2, extruder is double screw extruder, squeezes
The screw slenderness ratio for going out machine is 36 ~ 48:1, the number of vacuum port is 1-2.
9. the method according to claim 7 or 8, it is characterised in that in the step 2, premix prepared by step 1 is put
Melting extrusion granulation is carried out in extruder, its extrusion condition is as follows:
Dual-screw-stem machine humidity province is as follows:One section of temperature is 190 ~ 220 DEG C, and two sections of temperature are 220 ~ 250 DEG C, three sections of temperature are 220 ~
260 DEG C, four sections of temperature are 210 ~ 260 DEG C, and five sections of temperature are 210 ~ 260 DEG C, and head temperature is 220 ~ 270 DEG C;Screw speed is
250~450rpm/min;Pelleter rotating speed is 300 ~ 500r/min;Vacuum is -0.1 ~ 0.1MPa.
10. method according to claim 7, it is characterised in that in the step 1, incorporation time is 1 ~ 3min.
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109553935A (en) * | 2018-11-19 | 2019-04-02 | 江阴市宏丰塑业有限公司 | A kind of polybutylene terephthalate (PBT) modified material for exempting from linging |
CN109651770A (en) * | 2018-11-20 | 2019-04-19 | 金旸(厦门)新材料科技有限公司 | It is a kind of to exempt from priming paint PBT decorative ring of vehicle lamp material and its preparation method based on overcritical cleaning technique |
CN109943043A (en) * | 2019-04-12 | 2019-06-28 | 南京运昶高分子材料有限公司 | A kind of modified PBT suitable for exempting from priming paint plating |
CN112646332A (en) * | 2020-12-16 | 2021-04-13 | 上海金发科技发展有限公司 | Low-haze high-gloss PBT (polybutylene terephthalate) composite material and preparation method thereof |
CN113045871A (en) * | 2020-12-22 | 2021-06-29 | 上海普利特复合材料股份有限公司 | Low-precipitation, low-haze and high-weather-resistance glass fiber reinforced PBT (polybutylene terephthalate) composite material and preparation method thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02286739A (en) * | 1989-04-28 | 1990-11-26 | Dainippon Ink & Chem Inc | Polybutylene terephthalate resin composition |
JPH03163157A (en) * | 1989-11-22 | 1991-07-15 | Kanebo Ltd | Thermoplastic resin composition |
CN102464870A (en) * | 2010-11-15 | 2012-05-23 | 上海锦湖日丽塑料有限公司 | Microcrystal PBT (Polybutylece Terephthalate) resin and preparation method thereof |
CN102558791A (en) * | 2011-12-23 | 2012-07-11 | 苏州新宏隆工程塑料有限公司 | High heat resistance, high gloss, low volatility and rapid prototyping polybutylene terephthalate and preparation method thereof |
CN103232640A (en) * | 2013-04-27 | 2013-08-07 | 上海锦湖日丽塑料有限公司 | Spraying-free aesthetic resin composition with amber effect and preparation method thereof |
-
2017
- 2017-03-20 CN CN201710165623.8A patent/CN106867211A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02286739A (en) * | 1989-04-28 | 1990-11-26 | Dainippon Ink & Chem Inc | Polybutylene terephthalate resin composition |
JPH03163157A (en) * | 1989-11-22 | 1991-07-15 | Kanebo Ltd | Thermoplastic resin composition |
CN102464870A (en) * | 2010-11-15 | 2012-05-23 | 上海锦湖日丽塑料有限公司 | Microcrystal PBT (Polybutylece Terephthalate) resin and preparation method thereof |
CN102558791A (en) * | 2011-12-23 | 2012-07-11 | 苏州新宏隆工程塑料有限公司 | High heat resistance, high gloss, low volatility and rapid prototyping polybutylene terephthalate and preparation method thereof |
CN103232640A (en) * | 2013-04-27 | 2013-08-07 | 上海锦湖日丽塑料有限公司 | Spraying-free aesthetic resin composition with amber effect and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
张玉龙: "《塑料、橡胶助剂速查手册》", 31 August 2012, 中国纺织出版社 * |
李强,等: "车灯饰圈免底涂PBT材料研究", 《塑料工业》 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109553935A (en) * | 2018-11-19 | 2019-04-02 | 江阴市宏丰塑业有限公司 | A kind of polybutylene terephthalate (PBT) modified material for exempting from linging |
CN109651770A (en) * | 2018-11-20 | 2019-04-19 | 金旸(厦门)新材料科技有限公司 | It is a kind of to exempt from priming paint PBT decorative ring of vehicle lamp material and its preparation method based on overcritical cleaning technique |
CN109943043A (en) * | 2019-04-12 | 2019-06-28 | 南京运昶高分子材料有限公司 | A kind of modified PBT suitable for exempting from priming paint plating |
CN112646332A (en) * | 2020-12-16 | 2021-04-13 | 上海金发科技发展有限公司 | Low-haze high-gloss PBT (polybutylene terephthalate) composite material and preparation method thereof |
CN112646332B (en) * | 2020-12-16 | 2023-04-14 | 上海金发科技发展有限公司 | Low-haze high-gloss PBT (polybutylene terephthalate) composite material and preparation method thereof |
CN113045871A (en) * | 2020-12-22 | 2021-06-29 | 上海普利特复合材料股份有限公司 | Low-precipitation, low-haze and high-weather-resistance glass fiber reinforced PBT (polybutylene terephthalate) composite material and preparation method thereof |
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