CN106832863B - A kind of the regeneration PC alloy material and its production method of anti-stress cracking - Google Patents
A kind of the regeneration PC alloy material and its production method of anti-stress cracking Download PDFInfo
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- CN106832863B CN106832863B CN201710116525.5A CN201710116525A CN106832863B CN 106832863 B CN106832863 B CN 106832863B CN 201710116525 A CN201710116525 A CN 201710116525A CN 106832863 B CN106832863 B CN 106832863B
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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
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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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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- 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
- B29C2948/92704—Temperature
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses the regeneration PC alloy materials and its production method of a kind of anti-stress cracking, preparation method includes broken, mixing, the operating procedures such as granulation, and the PC alloy material is by regenerating PC raw material, ASA resin, SMA resin, silicone oil, chain extender, compatilizer, toughener and age resister composition, the above raw material is put into batch mixer according to certain feed ratio and is stirred, by step made above, finally obtain the regeneration PC alloy material of anti-stress cracking required for the present invention, the present invention is by carrying out chain extension to regeneration PC material and other materials, it is modified, form macromolecular link, improve the interface affinity between high molecular material and inorganic filler, improve the binding force between regeneration PC material and the compatibility and substrate molecule of anti-stress cracking agent, improve the anti-stress cracking of material Performance.Method of the invention is easy to operate, and processing fluidity is good, and controllability is strong, favorable reproducibility, stable product quality, and high production efficiency is easy to industrialized production.
Description
Technical field
The present invention relates to Material Field more particularly to the regeneration PC alloy materials and its producer of a kind of anti-stress cracking
Method.
Background technique
Polycarbonate (PC) is a kind of thermoplastic engineering plastic of excellent combination property, have impact strength height, creep resistant,
Good stability of the dimension, heat-resisting, transparent, dielectric properties are good etc., is widely used.And PC is a kind of macromolecule polymeric material, molecule
Amount distribution is very vast, and polymer molecular weight is bigger, and molecular chain structure is bigger, and molecule interchain active force and entanglement degree increase, and resists
Stress cracking ability is stronger;Polymer molecular weight is small, and molecular chain structure is small, and polymer molecular weight distribution is wide, low molecular weight compositions
Bigger, anti-stress cracking ability is weak, and microcosmic tearing easy to form causes stress to concentrate, product is caused to crack, seriously constrains PC
The application of alloy material.Currently, solving the problems, such as PC alloy material stress cracking, PC conjunction is mainly improved by modified method
The anti-stress cracking of golden material, common method are that compatilizer, antioxidant, toughener etc. are added in PC alloy material to solve
Certainly, a variety of anti-stress cracking agent products are also accordingly developed, effect is not very ideal.Such as: a kind of its system of anti-stress cracking agent
Preparation Method and application and a kind of resistance to stress PC polyester (number of patent application 201310393082.6), a kind of PC anti-stress cracking agent
Preparation method and its usage (number of patent application 201410428806.0) develops different PC alloy material anti-stress crackings
Agent, but essence is also that the anti-stress cracking performance of PC alloy material is improved by method of modifying, especially regenerates the PC of application
Material, by repeatedly processing, molecular chain structure is substantially reduced, and anti-stress cracking ability is weaker, how to improve regeneration PC
The problem of alloy material anti-stress cracking, becomes our focus of attention.
The present invention in view of the deficiencies of the prior art, passes through addition ASA resin (styrene, acrylonitrile and acryl rubber etc.
A kind of Resin Used As Impact Modifier made of ter-polymers combined polymerization), SMA resin (phenylethylene-maleic anhydride), silicone oil and anti-ageing
The substances such as agent, and mixed according to a certain amount of weight ratio, be kneaded, the present invention passes through to regeneration PC material and other materials
Material carries out chain extension, modification, forms macromolecular link, improves the interface affinity between high molecular material and inorganic filler, improves
Binding force between regeneration PC material and the compatibility and substrate molecule of anti-stress cracking agent, improves the anti-stress cracking of material
Performance.Method of the invention is easy to operate, and processing fluidity is good, and controllability is strong, favorable reproducibility, stable product quality, production effect
Rate is high, easy to industrialized production.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of regeneration PC alloy materials of anti-stress cracking
And its production method, it is not high to regeneration PC utilization rate in the prior art to solve, regenerate the technology of PC alloy material resistance to stress difference
Problem, the present invention is achieved by the following technical solutions:
The invention discloses a kind of production methods that can improve regeneration PC alloy material anti-stress cracking, including following operation
Step:
1) it is crushed, by the cleaning of renewable PC raw material, is broken into powder powder of the largest particles no more than 3mm;
2) mixing, by PC particle powder broken in step 1) put into batch mixer in, then be separately added into ASA resin and
SMA resin is stirred, and silicone oil is added in whipping process, and chain extender, phase is added into the batch mixer again after mixing evenly
Hold agent, toughener and age resister, obtains mixture;
3) it is granulated, mixture obtained in step 2) is transferred in double screw extruder and carries out melting mixing, is granulated;
The regeneration PC raw material, ASA resin, SMA resin, silicone oil, chain extender, compatilizer, toughener and age resister
Components by weight percent are as follows:
Wherein, the revolving speed control of the stirring of batch mixer described in step 2) is at 300~400 revs/min, mixing time 5
~10min;
Further, in order to preferably realize PC alloy material anti-stress cracking performance, chain extender RPS-1005
Type chain extender or ADR-4368 type chain extender;The compatilizer is EMA1913AC type compatilizer or EMA1125AC type compatilizer;
The toughener is one of MBS E-920 type toughener, MBS S-6720 type toughener or MBS EM500 type toughener;
Further, the age resister in the present invention is by 4,4'- thiobis (6- tert-butyl -3- methylphenol), 2- first
Base -4- hydroxyl -5- 2-methyl-2-phenylpropane base butane and the double octadecyls of thio-2 acid mix, wherein 4,4'- thiobis (the tertiary fourth of 6-
Base -3- methylphenol), the components by weight percent of the double octadecyls of 2- methyl -4- hydroxyl -5- 2-methyl-2-phenylpropane base butane and thio-2 acid
Are as follows:
30~50 parts of 4,4'- thiobis (6- tert-butyl -3- methylphenol)
30~50 parts of butane of -5- 2-methyl-2-phenylpropane base of -4- hydroxyl of 2- methyl
Double 10~30 parts of the octadecyls of thio-2 acid.
Further, mixture is transferred in double screw extruder in step 3) and carries out melting mixing, is granulated, twin-screw squeezes
Machine barrel temperature when squeezing out is divided into ten temperature regions out, and the temperature of ten temperature regions controls respectively: the first humidity province
It is 180-220 DEG C;Second temperature area is 230-250 DEG C;Third humidity province is 240-260 DEG C;4th humidity province is 230-250
℃;5th humidity province is 250-260 DEG C;6th humidity province is 230-250 DEG C;7th humidity province is 200-220 DEG C;8th temperature
Area is 190-210 DEG C;9th humidity province is 210-230 DEG C;Tenth humidity province is 220-240 DEG C;Extrusion pressure is 4.0-
5.0MPa, extruding pelletization is to get regeneration PC alloy material.
Routine, which resists, should split modified PC and product of the present invention regeneration PC alloy Experimental comparison's data are as follows:
The obtained regeneration PC alloy material of production method disclosed by the invention is big with molecular weight, resistance to stress is strong,
The feature high to regeneration PC stock utilization, while method of the invention is easy to operate, processing fluidity is good, and controllability is strong, weight
Existing property is good, stable product quality, and high production efficiency is easy to industrialized production.
Detailed description of the invention
Fig. 1 is barrel temperature region distribution schematic diagram.
Specific embodiment
It elaborates below to the embodiment of the present invention, the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
Present embodiment discloses a kind of regeneration PC alloy material of anti-stress cracking, production stage is as follows:
1) it is crushed, is broken into the powder that the largest particles is no more than 3mm with crusher after renewable PC raw material is cleaned up
Powder;
2) mixing weighs in 84 parts of broken PC particle powder (component proportion by weight) investment batch mixer, then distinguishes
3 parts of ASA resins are added and 3 parts of SMA resins are stirred, in whipping process be added 1 part of 201 silicone oil, after mixing evenly again to
0.3 part of RPS-1005 type chain extender, 2.7 parts of EMA1913AC type compatilizers, 1 part of MBS E-920 type toughener are added in batch mixer
With 5 parts of age resisters, mixture is obtained;The revolving speed control of batch mixer stirring is at 300 revs/min, mixing time 5min;
3) it is granulated, mixture obtained in step 2) is transferred in double screw extruder and carries out melting mixing, is granulated;
Age resister in embodiment is by 40 parts of (by weight) 4,4'- thiobis (6- tert-butyl -3- methylbenzene
Phenol), 40 parts of 2- methyl -4- hydroxyl -5- 2-methyl-2-phenylpropane base butane and the double octadecyls of 20 parts of thio-2 acid mix, walk
It is rapid 3) in by mixture be transferred in double screw extruder carry out melting mixing, be granulated, double screw extruder squeeze out when, barrel temperature
Degree is divided into ten temperature regions, as shown in Figure 1, the temperature of ten temperature regions controls respectively: the first humidity province is 180-220
℃;Second temperature area is 230-250 DEG C;Third humidity province is 240-260 DEG C;4th humidity province is 230-250 DEG C;5th temperature
Area is 250-260 DEG C;6th humidity province is 230-250 DEG C;7th humidity province is 200-220 DEG C;8th humidity province is 190-210
℃;9th humidity province is 210-230 DEG C;Tenth humidity province (head) is 220-240 DEG C;Extrusion pressure is 4.0MPa, and extrusion is made
Grain is to get regeneration PC alloy material.Regeneration PC alloy material in embodiment 1 is strong stretching compared with secondary alloy PC material
Degree, bending strength, the deformation of dimension card and glacial acetic acid have a significant effect in terms of impregnating destructive test.
Embodiment 2
Embodiment 2 discloses a kind of regeneration PC alloy material of anti-stress cracking, and production stage is as follows:
1) it is crushed, is broken into the powder that the largest particles is no more than 3mm with crusher after renewable PC raw material is cleaned up
Powder;
2) mixing weighs in 90 parts of broken PC particle powder (component proportion by weight) investment batch mixer, then distinguishes
3 parts of ASA resins are added and 1 part of SMA resin is stirred, 0.5 part of 201 silicone oil are added in whipping process, after mixing evenly again
0.3 part of ADR-4368 type chain extender, 1.2 parts of EMA1125AC type compatilizers, 1 part of MBS S-6720 type are added into batch mixer to increase
Tough dose and 3 parts of age resisters, obtain mixture;The revolving speed control of batch mixer stirring is at 400 revs/min, mixing time
10min;
3) it is granulated, mixture obtained in step 2) is transferred in double screw extruder and carries out melting mixing, is granulated;
Age resister in embodiment is by 30 parts of (by weight) 4,4'- thiobis (6- tert-butyl -3- methylbenzene
Phenol), 40 parts of 2- methyl -4- hydroxyl -5- 2-methyl-2-phenylpropane base butane and the double octadecyls of 30 parts of thio-2 acid mix, walk
It is rapid 3) in by mixture be transferred in double screw extruder carry out melting mixing, be granulated, double screw extruder squeeze out when, barrel temperature
Degree is divided into ten temperature regions, and the temperature of ten temperature regions controls respectively: the first humidity province is 180-220 DEG C;Second temperature
Spending area is 230-250 DEG C;Third humidity province is 240-260 DEG C;4th humidity province is 230-250 DEG C;5th humidity province is 250-
260℃;6th humidity province is 230-250 DEG C;7th humidity province is 200-220 DEG C;8th humidity province is 190-210 DEG C;9th
Humidity province is 210-230 DEG C;Tenth humidity province (head) is 220-240 DEG C;Extrusion pressure is 4.0MPa, extruding pelletization to get
Regenerate PC alloy material.Regeneration PC alloy material in embodiment 2 is compared with secondary alloy PC material, in tensile strength, bending
Intensity, the deformation of dimension card and glacial acetic acid also have a significant effect in terms of impregnating destructive test.
Embodiment 3
Embodiment 3 discloses a kind of regeneration PC alloy material of anti-stress cracking, and production stage is as follows:
1) it is crushed, is broken into the powder that the largest particles is no more than 3mm with crusher after renewable PC raw material is cleaned up
Powder;
2) mixing weighs in 85 parts of broken PC particle powder (component proportion by weight) investment batch mixer, then distinguishes
4 parts of ASA resins are added and 2 parts of SMA resins are stirred, in whipping process be added 1 part of 201 silicone oil, after mixing evenly again to
0.5 part of RPS-1005 type chain extender, 1.5 parts of EMA1125AC type compatilizers, 2 parts of MBS EM500 type toughener are added in batch mixer
With 4 parts of age resisters, mixture is obtained;The revolving speed control of batch mixer stirring is at 400 revs/min, mixing time 8min;
3) it is granulated, mixture obtained in step 2) is transferred in double screw extruder and carries out melting mixing, is granulated;
Age resister in embodiment is by 35 parts of (by weight) 4,4'- thiobis (6- tert-butyl -3- methylbenzene
Phenol), 35 parts of 2- methyl -4- hydroxyl -5- 2-methyl-2-phenylpropane base butane and the double octadecyls of 30 parts of thio-2 acid mix, walk
It is rapid 3) in by mixture be transferred in double screw extruder carry out melting mixing, be granulated, double screw extruder squeeze out when, barrel temperature
Degree is divided into ten temperature regions, and the temperature of ten temperature regions controls respectively: the first humidity province is 180-220 DEG C;Second temperature
Spending area is 230-250 DEG C;Third humidity province is 240-260 DEG C;4th humidity province is 230-250 DEG C;5th humidity province is 250-
260℃;6th humidity province is 230-250 DEG C;7th humidity province is 200-220 DEG C;8th humidity province is 190-210 DEG C;9th
Humidity province is 210-230 DEG C;Tenth humidity province (head) is 220-240 DEG C;Extrusion pressure is 5.0MPa, extruding pelletization to get
Regenerate PC alloy material.Regeneration PC alloy material in embodiment 3 is compared with secondary alloy PC material, in tensile strength, bending
Intensity, the deformation of dimension card and glacial acetic acid also have a significant effect in terms of impregnating destructive test.
Claims (1)
1. a kind of production method that can improve regeneration PC alloy material anti-stress cracking, including following operating procedure:
1) it is crushed, by the cleaning of renewable PC raw material, is broken into powder powder of the largest particles no more than 3mm;
2) mixing, by weight component proportion weigh 90 parts of broken PC particle powder and are separately added into 3 parts of ASA resins and 1 part again
SMA resin is stirred, and 0.5 part of 201 silicone oil is added in whipping process, is added 0.3 part into batch mixer again after mixing evenly
ADR-4368 type chain extender, 1.2 parts of EMA1125AC type compatilizers, 1 part of MBS S-6720 type toughener and 3 parts of age resisters, obtain
To mixture;The revolving speed control of batch mixer stirring is at 400 revs/min, mixing time 10min;
3) it is granulated, mixture obtained in step 2) is transferred in double screw extruder and carries out melting mixing, is granulated;
It is characterized in that, wherein age resister is specially by by weight: 30 parts of 4,4'- thiobis (6- tert-butyl -3- methyl
Phenol), 40 parts of (2- methyl -4- hydroxyl -5- 2-methyl-2-phenylpropane base) butane of 1,1,3- tri- and the double octadecyl alcolols of 30 parts of thio-2 acid
Ester mixes;
In step 3) by mixture be transferred in double screw extruder carry out melting mixing, be granulated, double screw extruder squeeze out when,
Barrel temperature is divided into ten temperature regions, and the temperature of ten temperature regions controls respectively: the first humidity province is 180-220 DEG C;
Second temperature area is 230-250 DEG C;Third humidity province is 240-260 DEG C;4th humidity province is 230-250 DEG C;5th humidity province
It is 250-260 DEG C;6th humidity province is 230-250 DEG C;7th humidity province is 200-220 DEG C;8th humidity province is 190-210
℃;9th humidity province is 210-230 DEG C;Tenth humidity province is 220-240 DEG C;Extrusion pressure is 4.0MPa, extruding pelletization to get
Regenerate PC alloy material.
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CN108997734A (en) * | 2018-07-20 | 2018-12-14 | 广东国立科技股份有限公司 | A kind of PPO alloy and preparation method thereof of the resistance to boiling of chemically-resistant |
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CN101041741A (en) * | 2006-03-20 | 2007-09-26 | 佛山市顺德区汉达精密电子科技有限公司 | PC (polycarbonate) defective material modified PC/ABS alloy (three) |
CN102276972A (en) * | 2011-08-17 | 2011-12-14 | 东莞劲胜精密组件股份有限公司 | Polychloroprene/acrylonitrile butadiene styrene (PC/ABS) defective material recovery composition and preparation method thereof |
CN104672834A (en) * | 2013-11-29 | 2015-06-03 | 青岛佳亿阳工贸有限公司 | High-performance low-cost PC (polycarbonate) modified material |
CN105237982A (en) * | 2015-10-21 | 2016-01-13 | 奉化市旭日新材料有限公司 | Glass fiber reinforcement regeneration PC composite material and preparation method thereof |
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2017
- 2017-03-01 CN CN201710116525.5A patent/CN106832863B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101041741A (en) * | 2006-03-20 | 2007-09-26 | 佛山市顺德区汉达精密电子科技有限公司 | PC (polycarbonate) defective material modified PC/ABS alloy (three) |
CN102276972A (en) * | 2011-08-17 | 2011-12-14 | 东莞劲胜精密组件股份有限公司 | Polychloroprene/acrylonitrile butadiene styrene (PC/ABS) defective material recovery composition and preparation method thereof |
CN104672834A (en) * | 2013-11-29 | 2015-06-03 | 青岛佳亿阳工贸有限公司 | High-performance low-cost PC (polycarbonate) modified material |
CN105237982A (en) * | 2015-10-21 | 2016-01-13 | 奉化市旭日新材料有限公司 | Glass fiber reinforcement regeneration PC composite material and preparation method thereof |
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