CN105385117B - A kind of high-low temperature resistant impact for LED plastic-aluminum structural members strengthens anti-flaming PBT composite and preparation method thereof - Google Patents
A kind of high-low temperature resistant impact for LED plastic-aluminum structural members strengthens anti-flaming PBT composite 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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- 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
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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
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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
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Abstract
The invention discloses a kind of for high-low temperature resistant impact enhancing anti-flaming PBT composite of LED plastic-aluminum structural members and preparation method thereof, belong to modified plastics production technical field.PBT composite of the present invention is formed by following components by mass distribution ratio：1~4 part of 40~70 parts of PBT, 10 20 parts of composite toughing agent, 6 15 parts of fire retardant, 20 30 parts of chopped glass fiber, rosin amine tackifier and the bionical mussel adhesive of Dopaminergics, 0 0.6 parts of lubricant, 0.1 0.5 parts of antioxidant.PBT composite of the present invention not only has excellent notch impact toughness, higher rigidity, excellent heat resistance and high flame resistance, also there is the adhesive property excellent with aluminium surface and high-low temperature resistant impact thermal shock performance, after 500 cycle periods of impact that cold and heat succeed each other any cracking and dropping situations do not occur for the LED plastic-aluminums structural member of preparation.
Description
Technical field
The invention belongs to modified plastics technical field, and in particular to a kind of high-low temperature resistant for LED plastic-aluminum structural members is rushed
Hit enhancing anti-flaming PBT composite and preparation method thereof.
Background technology
Polybutylene terephthalate (PBT) (hereinafter referred to as PBT) is a kind of linear saturated polyester resin of crystal type.PBT is in work
Some application examples in industry show its superiority that can not be substituted in some aspects, it is existing it turned into after polyamide (PA) and
The third-largest general engineering plastic after makrolon (PC), and be applied widely in many fields.
Over nearly 5 years, LED illumination industrial market has a extensive future, the high speed development rank in permeability from 15% to 60%
Section.The electric energy that LED there are about 70% in use is converted into heat energy, causes operating temperature too high, and then causes chip old
The problems such as change, light transmittance efficiency decay and service life shorten.These problems are proposed to the particularly pedestal of the material for LED and Lamp cup
Thermal diffusivity high requirement.The early stage developed in LED, pedestal and Lamp cup are mainly manufactured by die casting aluminium, there is cost high, raw
The problem of producing low efficiency and poor electrical insulating property.With the fast development of LED illumination System, polybutylene terephthalate composite wood
Expect, with unique advantages such as cost is low, easy processing manufactures, to be gradually available for producing some components of the system, mainly including lamp holder,
Lamp cup, lampshade etc., wherein, the overwhelming majority of Lamp cup material occupancy.But there is lacking for capacity of heat transmission difference in the composite plastics such as PBT
Fall into.To solve this problem, the design for being developed aluminium-plastic composite structure combines the Dominant Facies of both plastics and aluminium,
Wherein aluminium is responsible for heat transfer, and plastics play the advantage of easy-formation processing and good insulating.This composite structural member substitutes tradition casting
Alumiaum article turns into the main trend of LED at this stage.However, aluminium-plastic composite structure the PBT material of application is proposed it is higher
It is required that, except must be in addition to the property such as the high tenacity that has of traditional activeness and quietness PBT composite and high intensity, it is desirable to excellent
High-low temperature resistant impact impact property, that is to say, that aluminium-plastic composite structure part colds and heat succeed each other after circulation undergoing 500 cycles,
The phenomenon can not be cracking and peeled off.Existing PBT modification technologies focus mostly in the side such as high tenacity, high intensity and fire resistance
Face, is such as prepared with the function such as high-impact, high fire-retardance, antistatic using glass, toughener, compound flame retardant, antistatic additive
The PBT composite (CN201110138967.2, CN201210370680.7, CN201210372599.2) of property.However, these
Composite does not consider the caking property with aluminium base, when these composites are used to prepare plastic-aluminum structural member, is handed over cold and hot
For be easy under effect it is cracking and peel off etc. phenomenon.
The content of the invention
The problem of existing for prior art, primary and foremost purpose of the invention, which is to design, provides a kind of for LED plastic-aluminum knots
The high-low temperature resistant impact enhancing anti-flaming PBT composite of component.The composite of the present invention is contained by being introduced in compound system
There is the bionical mussel adhesive of rosin amine tackifier and Dopaminergics of amido and carboxyl, while from epoxy and acid anhydrides
Deng the toughener of group, the chemistry of PBT composite and aluminium base surface is realized by the radical reaction of tackifier and toughener
Key is connected, and greatly improves both adhesions, when overcoming the composite of prior art preparation for aluminium-plastic composite structure part
With aluminium base cohesive force it is inadequate the problem of, it is cracking under high/low-temperature impact, peel off the problems such as, be prepared for high-performance PBT answer
Condensation material, promotes the application of PBT material in the led.
It is fire-retardant another object of the present invention is to provide the above-mentioned high-low temperature resistant impact enhancing for LED plastic-aluminum structural members
The preparation method of PBT composite.
The above-mentioned purpose of the present invention is achieved through the following technical solutions：A kind of high-low temperature resistant for LED plastic-aluminum structural members
Impact enhancing anti-flaming PBT composite, is formed by following components by mass distribution ratio：PBT40~70 part, composite toughing agent 10-
20 parts, 6-15 parts of fire retardant, 20-30 parts of chopped glass fiber, rosin amine tackifier and the bionical mussel adhesive 1~4 of Dopaminergics
Part, 0-0.6 parts of lubricant, 0.1-0.5 parts of antioxidant.
Described composite toughing agent is grafted (ethylene-octene copolymer), ethylene-methyl acrylate-methyl by maleic anhydride
Glycidyl acrylate terpolymer, maleic anhydride grafting (ethylene-propylene-diene terpolymer) copolymer, ethene-
Vinyl acetate co-polymer, maleic anhydride grafting (SBS), Itaconic Acid Grafted (second
Alkene-octene copolymer) in two or three；The mass ratio range of two kinds of composite toughing agents is 1:5~5:1, three kinds are combined
The mass fraction scope of every kind of toughener is 10~70 in toughener.
Described fire retardant is antimony oxide and brominated Polystyrene using quality proportioning as 1:3 mixture.
Described chopped glass fiber is that length is 4~30mm.
Described rosin amine tackifier and the bionical mussel adhesive of Dopaminergics is in rosin acid, rosin amine or dopamines
At least one.
The preparation method of the above-mentioned high-low temperature resistant impact enhancing anti-flaming PBT composite for LED plastic-aluminum structural members, bag
Include following processing step：
1) by PBT and composite toughing agent, fire retardant, chopped glass fiber, rosin amine tackifier and the bionical mussel of Dopaminergics
Adhesive, lubricant and antioxidant mixing；
2) mixture obtains composite through double screw extruder melting extrusion.
Step 1) described in mixing using high-speed mixer mix, 400~800 turns/min of speed of agitator, temperature of charge
40-80℃。
Step 2) in 215-255 DEG C of extrusion temperature, screw speed 200-500 turns/min.
The high-low temperature resistant impact enhancing anti-flaming PBT composite for LED plastic-aluminum structural members of the present invention not only has excellent
Good notch impact toughness, higher rigidity, excellent heat resistance and high flame resistance, also with excellent viscous of aluminium surface
Performance and high-low temperature resistant impact thermal shock performance are tied, with the LED plastic-aluminums structural member of its preparation through the impact (- 40 that colds and heat succeed each other
DEG C -100 DEG C of each half an hour) after 500 cycle periods, any cracking and dropping situations do not occur, available for making high performance lED
Lamp pedestal and shell.
The advantage of the invention is that：
1) elastomer with acid anhydrides, acid, epoxy isoreactivity group is used to answer in the PBT composite prepared by the present invention
Close toughener, wherein ethylene-methyl acrylate-glyceryl methacrylate terpolymer, maleic anhydride grafting (second
Alkene-propylene diene copolymerized thing), maleic anhydride grafting (ethylene-octene copolymer) and Itaconic Acid Grafted (ethylene-octene copolymerization
Thing) etc. be typical compatilizer component, these toughener are not only good with PBT compatibilities, moreover it is possible to form strong phase with aluminium base surface
Interaction, in addition, rosin amine tackifier and amido or carboxyl in the bionical mussel adhesive of Dopaminergics with compatilizer
Epoxide group or anhydride group react, and further promote the interaction of PBT composite and aluminium base, particularly DOPA
The bionical mussel adhesive of amine, its amido and toughener formation chemical bond, the other end is connected chemically with aluminium base formation, so that greatly
It is big to improve PBT composite and the cohesive force of aluminium base.
2) glass is used in PBT composite prepared in the present invention, fire retardant etc. strengthens and provides fire resistance,
Realize the high performance of composite.
3) composite is prepared using blending, the scheme of extruding pelletization, technique is easy, easily realizes industrialized production.
4) composite has the characteristics such as high tenacity, high cold-resistant thermal shock, while having high fluidity, easy injection molding etc.
Property, has widened its application significantly.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Comparative example 1：
By PBT, ethylene-vinyl acetate copolymer, fire retardant, chopped glass fiber, lubricant and antioxidant are with mass fraction
Than for 54:15:10:20:0.5:0.5 mixing, with 500 turns/min in high-speed mixer, mixes 3min, compound warp at 60 DEG C
Double screw extruder is at 240 DEG C, and screw speed is 200 turns of lower melting extrusions, granulations.
Comparative example 2
Will be by PBT, maleic anhydride grafting (ethylene-propylene-diene terpolymer), fire retardant, chopped glass fiber, lubricant
With antioxidant using mass fraction ratio as 54:15:10:20:0.5:0.5 mixing, with 500 turns/min in high-speed mixer, 60 DEG C
Lower mixing 3min, compound is through double screw extruder at 215 DEG C, and screw speed is 200 turns of lower melting extrusions, granulations.
Embodiment 1
PBT, maleic anhydride grafting (ethylene-propylene-diene terpolymer) and ethylene-vinyl acetate copolymer is mixed
(mass fraction ratio is 1 for conjunction：1), fire retardant, chopped glass fiber, rosin acid and antioxidant are using mass fraction ratio as 52:15:10:
20:2.5:0.5 mixing, with 800 turns/min in high-speed mixer, mixes 3min, compound is through double screw extruder at 40 DEG C
At 230 DEG C, screw speed is melting extrusion, granulation under 400 turns/min.
Embodiment 2
By PBT, maleic anhydride grafting (ethylene-propylene-diene terpolymer) and ethylene-methyl acrylate-methyl-prop
(mass fraction ratio is 1 to the mixing of olefin(e) acid glycidyl ester copolymer：5), fire retardant, chopped glass fiber, dopamine, antioxidant are with quality
Score ratio is 42:15:10:30:2.5:0.5 mixing, with 800 turns/min in high-speed mixer, 3min is mixed at 40 DEG C, is mixed
Material is through double screw extruder at 240 DEG C, and screw speed is melting extrusion, granulation under 200 turns/min.
Embodiment 3
By PBT, maleic anhydride grafting (ethylene-propylene-diene terpolymer) and ethylene-methyl acrylate-methyl-prop
(mass fraction ratio is 5 to the mixing of olefin(e) acid ethylene oxidic ester terpolymer：1), fire retardant, chopped glass fiber, dopamine and rosin amine
(mass fraction ratio is 1:5), lubricant, antioxidant are using mass fraction ratio as 51.5:10:6:30:1：1:0.5 mixing, at a high speed
With 400 turns/min in mixer, 3min is mixed at 50 DEG C, compound is through double screw extruder at 255 DEG C, and screw speed is 500
Turn/min under melting extrusion, granulation.
Embodiment 4
PBT, maleic anhydride grafting (ethylene-octene copolymer) and ethylene-methyl acrylate-Glycidyl methacrylate is sweet
(mass fraction ratio is 1 to the mixing of grease terpolymer：1), fire retardant, chopped glass fiber, dopamine and rosin amine (mass fraction ratio
For 1:5), lubricant, antioxidant are using mass fraction ratio as 47.5:20:6:20:3：3:0.5 mixing, in high-speed mixer with
3min is mixed at 400 turns/min, 50 DEG C, compound is through double screw extruder at 240 DEG C, and screw speed is molten under 300 turns/min
Melt extrusion, granulation.
Embodiment 5
By PBT, maleic anhydride grafting (ethylene-propylene-diene terpolymer), ethylene-methyl acrylate-metering system
Acid glycidyl ester terpolymer mixed with ethylene-vinyl acetate copolymer (mass fraction ratio be 20：60:20) it is, fire-retardant
Agent, chopped glass fiber, dopamine and rosin amine (mass ratio 5:1), antioxidant is using mass fraction ratio as 48.5:15:12:20:4:0.5
Mixing, with 400 turns/min in high-speed mixer, mixes 3min, compound is through double screw extruder in 240 DEG C, spiral shell at 80 DEG C
Bar rotating speed is melting extrusion, granulation under 400 turns/min.
Embodiment 6
PBT, maleic anhydride grafting (ethylene-octene copolymer), ethylene-methyl acrylate-Glycidyl methacrylate is sweet
Grease terpolymer mixed with ethylene-vinyl acetate copolymer (mass fraction ratio be 20：20:60), fire retardant, chopped glass
Fine, rosin acid and rosin amine (mass ratio 1:1), antioxidant is using mass fraction ratio as 45.5:20:8:20:4:0.5 mixing, in height
With 400 turns/min in fast mixer, 3min is mixed at 50 DEG C, compound is through double screw extruder at 240 DEG C, and screw speed is
Melting extrusion, granulation under 200 turns/min.
Embodiment 7
By PBT, Itaconic Acid Grafted (ethylene-octene copolymer), ethylene-methyl acrylate-methyl propenoic acid glycidyl
Ester terpolymer mixed with ethylene-vinyl acetate copolymer (mass fraction ratio be 60：20:20), fire retardant, chopped glass
(mass fraction ratio is 1 for fine, rosin acid and dopamine:1), lubricant and antioxidant are using mass fraction ratio as 47:15:12:20:
2.5:3:0.5 mixing, with 400 turns/min in high-speed mixer, mixes 3min, compound exists through double screw extruder at 50 DEG C
240 DEG C, screw speed is melting extrusion, granulation under 500 turns/min.
Embodiment 8
PBT, maleic anhydride grafting (ethylene-octene copolymer), ethylene-methyl acrylate-Glycidyl methacrylate is sweet
Grease terpolymer mixed with ethylene-vinyl acetate copolymer (mass fraction ratio be 30：30:40), fire retardant, chopped glass
(mass fraction ratio is 1 for fine, rosin acid and rosin amine:1), lubricant and antioxidant are using mass fraction ratio as 39:15:10:30:4:
1:0.5 mixing, with 400 turns/min in high-speed mixer, mixes 3min, compound is through double screw extruder 250 at 40 DEG C
DEG C, screw speed is melting extrusion, granulation under 300 turns/min.
Composite property prepared by the embodiment of table 1 and comparative example 1,2
The high-low temperature resistant impact enhancing anti-flaming PBT composite for LED plastic-aluminum structural members of the present invention not only has excellent
Good notch impact toughness, higher rigidity, excellent heat resistance and high flame resistance, also with excellent viscous of aluminium surface
Performance and high-low temperature resistant impact thermal shock performance are tied, with the LED plastic-aluminums structural member of its preparation through the impact (- 40 that colds and heat succeed each other
DEG C -100 DEG C of each half an hour) after 500 cycle periods, any cracking and dropping situations do not occur, available for making high performance lED
Lamp pedestal and shell.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention
Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (7)
1. a kind of high-low temperature resistant impact enhancing anti-flaming PBT composite for LED plastic-aluminum structural members, it is characterised in that：By with
Lower component is formed by mass distribution ratio：40~70 parts of PBT, 10-20 parts of composite toughing agent, 6-15 parts of fire retardant, chopped glass fiber
20-30 parts, 1~4 part of rosin amine tackifier and the bionical mussel adhesive of Dopaminergics, 0-0.6 parts of lubricant, antioxidant 0.1-
0.5 part；Described composite toughing agent is grafted (ethylene-octene copolymer), ethylene-methyl acrylate-methyl-prop by maleic anhydride
Olefin(e) acid ethylene oxidic ester terpolymer, maleic anhydride grafting (ethylene-propylene-diene terpolymer) copolymer, ethene-vinegar
Vinyl acetate copolymer, maleic anhydride grafting (SBS), Itaconic Acid Grafted (ethene-
Octene copolymer) in two or three；Described rosin amine tackifier and the bionical mussel adhesive of Dopaminergics are rosin
At least one of amine or dopamine.
2. the high-low temperature resistant impact enhancing anti-flaming PBT composite according to claim 1 for LED plastic-aluminum structural members,
It is characterized in that：Described composite toughing agent is grafted (ethylene-octene copolymer), ethylene-methyl acrylate-first by maleic anhydride
Base glycidyl acrylate terpolymer, maleic anhydride grafting (ethylene-propylene-diene terpolymer) copolymer, second
Alkene-vinyl acetate co-polymer, maleic anhydride grafting (SBS), Itaconic Acid Grafted
Two or three in (ethylene-octene copolymer)；The mass ratio range of two kinds of composite toughing agents is 1:5~5:1, three kinds multiple
The mass fraction scope for closing every kind of toughener in toughener is 10~70%.
3. the high-low temperature resistant impact enhancing anti-flaming PBT composite according to claim 1 for LED plastic-aluminum structural members,
It is characterized in that：Described fire retardant is antimony oxide and brominated Polystyrene using quality proportioning as 1:3 mixture.
4. the high-low temperature resistant impact enhancing anti-flaming PBT composite according to claim 1 for LED plastic-aluminum structural members,
It is characterized in that：The length of described chopped glass fiber is 4~30mm.
5. the high-low temperature resistant impact enhancing flame-retardant PBT for LED plastic-aluminum structural members described in any one of Claims 1 to 4 is combined
The preparation method of material, it is characterised in that：Comprise the following steps that：
1) by PBT and composite toughing agent, fire retardant, chopped glass fiber, rosin amine tackifier and the bionical mussel gluing of Dopaminergics
Agent, lubricant and antioxidant mixing；
2) mixture obtains fire-retardant for the high-low temperature resistant impact enhancing of LED plastic-aluminum structural members through double screw extruder melting extrusion
PBT composite.
6. the high-low temperature resistant impact enhancing anti-flaming PBT composite according to claim 5 for LED plastic-aluminum structural members
Preparation method, it is characterised in that：Step 1) described in mixing using high-speed mixer mix, 400~800 turns of speed of agitator/
Min, 40-80 DEG C of temperature of charge.
7. the high-low temperature resistant impact enhancing anti-flaming PBT composite according to claim 5 for LED plastic-aluminum structural members
Preparation method, it is characterised in that：Step 2) in 215-255 DEG C of extrusion temperature, screw speed 200-500 turns/min.
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| CN112679917B (en) * | 2020-12-09 | 2022-11-25 | 中广核瑞胜发（厦门）新材料有限公司 | Cold-heat-resistant high-strength high-toughness PBT (polybutylene terephthalate) composite material suitable for full-shading lamp and preparation and application thereof |
| EP4043526A1 (en) | 2021-02-12 | 2022-08-17 | SABIC Global Technologies B.V. | Thermoplastic composition of polycarbonate and polyester |
| CN113295603B (en) * | 2021-05-21 | 2024-04-16 | 厦门强力巨彩光电科技有限公司 | Experimental method for verifying stripping of epoxy glue and bracket of outdoor lamp bead |
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| CN102786779A (en) * | 2011-05-16 | 2012-11-21 | 山东道恩高分子材料股份有限公司 | High-impact glass fiber reinforced halogen-free flame retardation PBT material |
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Denomination of invention: The invention relates to a high and low temperature impact resistant reinforced flame retardant PBT composite for LED aluminum-plastic structural parts and a preparation method thereof Effective date of registration: 20211220 Granted publication date: 20170901 Pledgee: Dongyang sub branch of Bank of China Ltd. Pledgor: HENGDIAN GROUP DEBANG ENGINEERING PLASTIC CO.,LTD. Registration number: Y2021330002568 |