CN106009580A - High-rigidity and wear-resisting transparent polycarbonate material and preparation method thereof - Google Patents
High-rigidity and wear-resisting transparent polycarbonate material 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/34—Silicon-containing compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/36—Silica
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention provides a high-rigidity and wear-resisting transparent polycarbonate (PC) material and a preparation method thereof. The high-rigidity and wear-resisting transparent polycarbonate material is prepared from the following components in percentage by weight: 95 percent to 99 percent of PC resin, 0.2 percent to 2 percent of a high-rigidity and wear-resisting modifying agent, 0.1 percent to 0.3 percent of a coupling agent, 0.2 percent to 0.5 percent of a stabilizer, 0.2 percent to 0.5 percent of an antioxidant, 0.1 percent to 0.3 percent of an anti-dripping agent and 0.2 percent to 1 percent of a processing aid. The polycarbonate material takes the PC resin as a main material, and the high-rigidity and wear-resisting modifying agent, the coupling agent, the thermal stabilizer, the antioxidant, the anti-dripping agent and the processing aid have synergistic effect, so that the polycarbonate material has the characteristics of high rigidity, high wear resistance and high transparency, and furthermore, the surface rigidity and the wear-resisting property of the polycarbonate material are improved; meanwhile, the transparency is kept.
Description
Technical field
The invention belongs to technical field of high polymer material physical modification, particularly relate to a kind of transparent poly-carbonic acid of high hardness wear-resisting
Ester material and preparation method thereof.
Background technology
The existing excellent tensile property of mechanical property of Merlon, has again good impact property, and heat-resisting rain is cold, resistance to
Creep properties, electrical insulating property and resistance to weathering are excellent, be widely used in riot shield, tank visor block, bulletproof glass, explosion-proof every
In the protective materials such as plate and lasing safety PC material, for keeping out the attack of hard thing, blunt and unclarified liquid, it is also possible to keep out
Low velocity slug.But the stiff chain structure due to Merlon so that it does not crystallizes in the course of processing, is easily generated stress and opens
Split, thus cause this material to notch sensitive, fatigue resistance and wearing no resistance.Manufacturer and research institution all exist both at home and abroad
Increase exploitation dynamics in PC modification, by nano material, PC is modified the most gradually causing the attention of research worker.
High hardness nanocomposite micropowder be known practical material has high rigidity, best chemical stability, high thermal conductivity and
The precious functional material of wide spectrum light transmission.There are many excellent properties, such as excellent chemical stability, wearability, good life
The thing compatibility and superpower mechanical performance and the highest surface free energy and be acknowledged as the most promising superpower composite polymeric
The additive of thing material.
Summary of the invention
It is an object of the invention to overcome above-mentioned the deficiencies in the prior art, it is provided that a kind of high hardness wear-resisting clear polycarbonate
Material and preparation method thereof, it is intended to solve existing Merlon due to its stiff chain structure so that do not tie in the course of processing
Crystalline substance, is easily generated stress cracking, thus causes it to notch sensitive, fatigue resistance and the problem worn no resistance.
On the one hand the present invention is achieved in that, it is provided that a kind of high rigidity, high abrasion, the Merlon material of high transparency
Material, the most composed of the following components:
Further, described PC resin be melt index under the conditions of 300 DEG C/1.2KG for 15-40g/min.
Further, described high hardness wear-resisting modifying agent is nano-diamond powder, nanometer jade powder, and corundum, nanometer are micro-
Spar, Spinel micropowder or containing silica additive.
Further, described high hardness wear-resisting modifying agent is through coupling agent surface treatment, and wherein, it is hard that described consumption accounts for described height
Between the 5-15% of degree abrasion resistance modifier gross mass.
Further, described heat stabilizer is the chain extender containing active group epoxy radicals, Hinered phenols antioxidant and phosphorus
Esters of gallic acid antioxidant obtains according to 1:1:1 is compounding.
Further, described processing aid is that inside and outside lubricant agent, releasing agent and dispersant are multiple according to weight ratio 1:2:2～4
Join and obtain.
On the other hand, it is provided that a kind of high hardness wear-resisting transparent polycarbonate material preparation method, including step:
(1) recipe ingredient is weighed
PC resin, high rigidity is weighed respectively according to the hardness abrasion-resistant clear makrolon material formula described in claim 1
Abrasion resistance modifier, coupling agent, heat stabilizer, antioxidant, anti-dripping agent and processing aid；
(2) mixture is prepared
By the described PC resin weighed in step (1), high hardness wear-resisting modifying agent, coupling agent, heat stabilizer, antioxidant,
Anti-dripping agent and processing aid add high mixer high speed and mix 2-10 minute, obtain mixture；
(3) melt extrude
The mixture obtained in step (2) is added in meshing co rotating twin screw extrusion by main feed system, through melted
React, extrude, cool down, pelletizing, be dried, obtain injection raw material finished product.The process conditions of double screw extruder are: twin-screw extrusion
Machine feeding section temperature is 180-225 DEG C, and fluxing zone temperature is 235 DEG C-245 DEG C, and homogenizing zone temperature is 230 DEG C-240 DEG C, head
Temperature 215 DEG C-230 DEG C, main frame frequency is set to 20-45Hz, screw speed 400-600rpm, and vacuum is-0.04-0.1MPa.
Injection mold temperature should control at 110-140 DEG C.
The invention has the beneficial effects as follows: makrolon material of the present invention is with PC resin as major ingredient, and passes through high hardness wear-resisting
Modifying agent, coupling agent, heat stabilizer, antioxidant, anti-dripping agent and processing aid generation synergism, thus impart this poly-carbon
Acid esters material has a feature of high rigidity, high abrasion, high transparency, thus improves the case hardness of makrolon material and wear-resisting
Performance, keeps its transparency simultaneously, effectively overcomes existing Merlon due to its stiff chain structure so that in the course of processing
In do not crystallize, be easily generated stress cracking, thus cause it to notch sensitive, fatigue resistance and the problem worn no resistance.
Detailed description of the invention
Below the technical scheme in the embodiment of the present invention is clearly and completely described.
The embodiment of the present invention provide a kind of high rigidity, high abrasion, the makrolon material of high transparency, by weight percentage by
Following components forms:
Further, described PC resin be melt index under the conditions of 300 DEG C/1.2KG for 15-40g/min, preferably 15-
25g/min。
Further, described high hardness wear-resisting modifying agent is nano-diamond powder, nanometer jade powder, and corundum, nanometer are micro-
Spar, Spinel micropowder or containing silica additive, wherein, the index of refraction of above-mentioned high hardness nanocomposite micropowder is close to PC.
Further, described high hardness wear-resisting modifying agent is through coupling agent surface treatment, and wherein, it is hard that described consumption accounts for described height
Between the 5-15% of degree abrasion resistance modifier gross mass.Wherein, concrete processing method is: take 7.5g (0.03M) KH-570 coupling
Agent is injected in conical flask, adds 2.7g (0.3M) redistilled water, drip 4 glacial acetic acid and regulates pH values, magnetic agitation about 40min, with
Emulsion the most as clear as crystal (pH value is about 4.7) is as hydrolysis complement mark.KH-570 after having hydrolyzed should make immediately
Join for surface modifier in the suspension of high hardness wear-resisting modifying agent micropowder；2g high hardness wear-resisting modifying agent is joined
In 800ml dehydrated alcohol, ultrasonic disperse 30min, then press the KH-570 after 10% addition hydrolysis of diadust quality,
50 DEG C of stirring reaction 8h, then centrifugal dry, then with dehydrated alcohol for solvent by centrifugal 3 times of washing, finally very at 80 DEG C
The empty 12h that is dried i.e. obtains modified high hardness wear-resisting modifying agent.
Further, described heat stabilizer is the chain extender containing active group epoxy radicals, Hinered phenols antioxidant and phosphorus
Esters of gallic acid antioxidant obtains according to 1:1:1 is compounding, and wherein, heat stabilizer can block strand under high temperature and hydrolysising condition and move
The strand that wriggling causes is damaged, catches the free little molecule of link, and reduces the decomposition of little molecule auxiliary agent, surface floating, from
And improve PC product surface, and increasing and extend the materials'use life-span, this heat stabilizer is the chain extension containing active group epoxy radicals
Agent, Hinered phenols antioxidant and phosphoric acid ester antioxidant obtain according to 1:1:1 is compounding, and wherein, chain extender can recover and improve
The balance of mechanical performance, hot property, processing characteristics and optics that processing is reduced, this chain extender is commercially available is placed in BASF chain extender
ADR-4370S, ADR-4380, ADR-4370S, ADR-4368C or commercially available liter SAG-005, the SAG-008 being placed in day of this chain extender
Deng, and Hinered phenols antioxidant, the mixture of phosphoric acid ester antioxidant can select the H161 of Brueggemann company, concrete real
Executing in example, the weight/mass percentage composition of this heat stabilizer can be the concrete component such as 0.2%, 0.3%, 0.4%, 0.5%..
Further, described processing aid is that inside and outside lubricant agent, releasing agent and dispersant are multiple according to weight ratio 1:2:2～4
Joining and obtain, wherein, processing aid can effectively improve the dispersibility of each component in processing and forming process, reduce harmful rubbing
Scrape along increases the glossiness etc. of material, in a particular embodiment, the weight/mass percentage composition of this processing aid can be 0.2%,
0.4%, the concrete component such as 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.5%, 1.7%, 2%.
Makrolon material of the present invention is with PC resin as major ingredient, and by high hardness wear-resisting modifying agent, coupling agent, thermally-stabilised
Agent, antioxidant, anti-dripping agent and processing aid generation synergism, thus impart this makrolon material have high rigidity,
High abrasion, the feature of high transparency, thus improve case hardness and the anti-wear performance of makrolon material, keep it transparent simultaneously
Degree, effectively overcomes existing Merlon due to its stiff chain structure so that do not crystallize in the course of processing, be easily generated stress
Cracking, thus cause it to notch sensitive, fatigue resistance and the problem worn no resistance.
Correspondingly, the embodiment of the present invention also provides for a kind of high hardness wear-resisting transparent polycarbonate material preparation method, including
Step:
(1) recipe ingredient is weighed
PC resin, high rigidity is weighed respectively according to the hardness abrasion-resistant clear makrolon material formula described in claim 1
Abrasion resistance modifier, coupling agent, heat stabilizer, antioxidant, anti-dripping agent and processing aid；
(2) mixture is prepared
By the described PC resin weighed in step (1), high hardness wear-resisting modifying agent, coupling agent, heat stabilizer, antioxidant,
Anti-dripping agent and processing aid add high mixer high speed and mix 2-10 minute, obtain mixture；
(3) melt extrude
The mixture obtained in step (2) is added in meshing co rotating twin screw extrusion by main feed system, through melted
React, extrude, cool down, pelletizing, be dried, obtain injection raw material finished product.The process conditions of double screw extruder are: twin-screw extrusion
Machine feeding section temperature is 180-225 DEG C, and fluxing zone temperature is 235 DEG C-245 DEG C, and homogenizing zone temperature is 230 DEG C-240 DEG C, head
Temperature 215 DEG C-230 DEG C, main frame frequency is set to 20-45Hz, screw speed 400-600rpm, and vacuum is-0.04-0.1MPa.
Injection mold temperature should control at 110-140 DEG C.
Above-mentioned high hardness wear-resisting transparent polycarbonate material preparation method only need to be incorporated in mixed for each component suitably by formula
At a temperature of melt extrude and i.e. can get product, during melt extruding, only need to control the temperature and time that melt extrudes i.e.
Can, therefore, its preparation method technique is simple, and condition is easily-controllable, with low cost, feature low for equipment requirements, is suitable to industry metaplasia
Produce.
Below in conjunction with specific embodiment, the present invention done a detailed elaboration.
Embodiment 1
High hardness wear-resisting transparent polycarbonate material in this embodiment, content by weight percentage, by following components group
Become: PC resin 98.2 parts, nano-diamond powder 1 part, coupling agent 0.2 part, heat stabilizer 0.2 part, 0.2 part of antioxidant, processing helps
Agent 0.2 part.
Its preparation method is as follows:
(1) each component is weighed by above-mentioned parts by weight
(2) the described PC resin that will weigh in step (1), nano-diamond powder, coupling agent, heat stabilizer, antioxidant, add
Work auxiliary agent adds high mixer high speed and mixes 2-10 minute；
(3) mixture obtained in step (2) is added in meshing co rotating twin screw extrusion by main feed system, through molten
Melt reaction, extrude, cool down, pelletizing, be dried, obtain injection raw material finished product.The process conditions of double screw extruder are: twin screw squeezes
Going out machine feeding section temperature and be 180-225 DEG C, fluxing zone temperature is 235 DEG C-245 DEG C, and homogenizing zone temperature is 230 DEG C-240 DEG C, machine
Head temperature 215 DEG C-230 DEG C, main frame frequency is set to 20-45Hz, screw speed 400-600rpm, and vacuum is-0.04-
0.1MPa.Injection mold temperature should control at 110-140 DEG C.
Embodiment 2
High hardness wear-resisting transparent polycarbonate material in this embodiment, content by weight percentage, by following components group
Become: PC resin 98.2 parts, nano crystalline stone 1 part, coupling agent 0.2 part, heat stabilizer 0.2 part, 0.2 part of antioxidant, processing aid
0.2 part.
Its preparation method such as embodiment 1.
Embodiment 3
High hardness wear-resisting transparent polycarbonate material in this embodiment, content by weight percentage, by following components group
Become: PC resin 98.2 parts, Spinel micropowder 1 part, coupling agent 0.2 part, heat stabilizer 0.2 part, 0.2 part of antioxidant, processing aid
0.2 part.
Its preparation method such as embodiment 1.
Embodiment 4
High hardness wear-resisting transparent polycarbonate material in this embodiment, content by weight percentage, by following components group
Become: PC resin 98.2 parts, 1 part of corundum, coupling agent 0.2 part, heat stabilizer 0.2 part, 0.2 part of antioxidant, processing aid 0.2
Part.
Its preparation method such as embodiment 1.
Comparative example 1
High hardness wear-resisting transparent polycarbonate material in this comparative example, content by weight percentage, by following components group
Become: PC resin 99.2 parts, coupling agent 0.2 part, heat stabilizer 0.2 part, 0.2 part of antioxidant, processing aid 0.2 part.
Performance test and evaluation:
The particle material above-described embodiment 1-5 and comparative example 1 prepared is first in convection oven under conditions of 100-120 DEG C
It is dried 4 hours, then dried particle material injection (mo(u)lding) machine is made the test of standard testing batten.
Wherein, hot strength is tested by ASTM D-638 standard.
Specimen types is I type, batten size (mm): (176 ± 2) (length) × (12.6 ± 0.2) (end portion width) × (3.05
± 0.2) (thickness), draw speed is 50mm/min；
Notch impact strength is tested by ASTM D-256 standard.
Specimen types is I type, specimen size (mm): (63 ± 2) × (12.45 ± 0.2) × (3.1 ± 0.2)；Breach type
For A class, breach residual thickness is 1.9mm.
The performance test results table:
Makrolon material of the present invention is with PC resin as major ingredient, and by high hardness wear-resisting modifying agent, coupling agent, thermally-stabilised
Agent, antioxidant, anti-dripping agent and processing aid generation synergism, thus impart this makrolon material have high rigidity,
High abrasion, the feature of high transparency, thus improve case hardness and the anti-wear performance of makrolon material, keep it transparent simultaneously
Degree, effectively overcomes existing Merlon due to its stiff chain structure so that do not crystallize in the course of processing, be easily generated stress
Cracking, thus cause it to notch sensitive, fatigue resistance and the problem worn no resistance.
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications are also considered as
Protection scope of the present invention.
Claims (7)
1. a high hardness wear-resisting transparent polycarbonate material, it is characterised in that the most composed of the following components:
High hardness wear-resisting transparent polycarbonate material the most according to claim 1, it is characterised in that described PC resin is molten
Melt index under the conditions of 300 DEG C/1.2KG for 15-40g/min.
High hardness wear-resisting transparent polycarbonate material the most according to claim 1, it is characterised in that described high hardness wear-resisting
Modifying agent is nano-diamond powder, nanometer jade powder, corundum, nano crystalline stone, Spinel micropowder or containing silicon dioxide
Additive.
High hardness wear-resisting transparent polycarbonate material the most according to claim 1, it is characterised in that described high hardness wear-resisting
Modifying agent is through coupling agent surface treatment, and wherein, described consumption accounts between the 5-15% of described high hardness wear-resisting modifying agent gross mass.
High hardness wear-resisting transparent polycarbonate material the most according to claim 1, it is characterised in that described heat stabilizer is for containing
The chain extender of active group epoxy radicals, Hinered phenols antioxidant and phosphoric acid ester antioxidant obtain according to 1:1:1 is compounding.
Hardness abrasion-resistant clear makrolon material the most according to claim 1, it is characterised in that described processing aid is interior
External lubricant, releasing agent and dispersant obtain according to weight ratio 1:2:2～4 are compounding.
7. according to the hardness abrasion-resistant clear makrolon material preparation method described in any one of claim 1-6, it is characterised in that
Including step:
(1) recipe ingredient is weighed
PC resin, high hardness wear-resisting is weighed respectively according to the hardness abrasion-resistant clear makrolon material formula described in claim 1
Modifying agent, coupling agent, heat stabilizer, antioxidant, anti-dripping agent and processing aid；
(2) mixture is prepared
By the described PC resin weighed in step (1), high hardness wear-resisting modifying agent, coupling agent, heat stabilizer, antioxidant, resist and drip
Fall agent and processing aid adds high mixer high speed and mixes 2-10 minute, obtains mixture；
(3) melt extrude
The mixture that obtains in step (2) is added in meshing co rotating twin screw extrusion by main feed system, through frit reaction,
Extrusion, cooling, pelletizing, dry, acquisition injection raw material finished product.The process conditions of double screw extruder are: double screw extruder adds
Material section temperature is 180-225 DEG C, and fluxing zone temperature is 235 DEG C-245 DEG C, and homogenizing zone temperature is 230 DEG C-240 DEG C, head temperature
215 DEG C-230 DEG C, main frame frequency is set to 20-45Hz, screw speed 400-600rpm, and vacuum is-0.04-0.1MPa.Injection
Mold temperature should control at 110-140 DEG C.
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| CN111518378A (en) * | 2020-04-19 | 2020-08-11 | 东莞市骄阳塑胶科技有限公司 | Special transparent high-surface-hardness wear-resistant polycarbonate material and preparation method thereof |
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| CN106947199A (en) * | 2017-05-02 | 2017-07-14 | 湖南峰业光电有限公司 | A kind of TV high heat resistant transparent reinforcing material and its preparation method and application |
| CN106947199B (en) * | 2017-05-02 | 2018-11-30 | 湖南峰业光电有限公司 | A kind of transparent reinforcing material of TV high heat resistance and its preparation method and application |
| CN108976753A (en) * | 2018-08-03 | 2018-12-11 | 陈强挥 | A kind of plastics and preparation method thereof with Thermal conductivity |
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Application publication date: 20161012 |