CN106433112A - PA (polyamide)/AS (acrylonitrile-styrene) based resin compound and preparation method thereof - Google Patents
PA (polyamide)/AS (acrylonitrile-styrene) based resin compound 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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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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
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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
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Abstract
The invention discloses a PA (polyamide)/AS (acrylonitrile-styrene) based resin compound. The PA/AS based resin compound is prepared from 30-70 parts of PA resin, 5-60 parts of AS based resin, 2-10 parts of a compatilizer, 0.05-0.5 parts of an antioxidant and 0.1-0.6 parts of a nucleating agent, wherein the compatilizer is a styrene-maleimide copolymer. The invention further discloses a preparation method of the PA/AS based resin compound. Compared with the prior art, the PA/AS based resin compound has a remarkably improved mechanical property, and particularly, the heat deflection temperature of the PA/AS based resin compound is greatly increased.
Description
Technical field
The present invention relates to polymeric material field, particularly to a kind of PA/AS base resin complexes and preparation method thereof.
Background technology
Polyamide (PA) has excellent mechanical performance, self lubricity, chemical-resistant, workability, heat oxygen aging resistance
Performance, makes them be usually used in the machinery harsher to operating environment requirements, electronic apparatus, motor vehicles industry, but also has many
Shortcoming, such as water absorption are big, poor dimensional stability, dry state and the low defect of low temperature impact strength, and its melt viscosity is big, note
Sialorrhea is easily caused when molded.And PA and AS base mixed with resin are prepared complex, both obtain that PA height is heat-resisting, high intensity, Gao Gang
Property and chemicals-resistant characteristic, the toughness of PA, weatherability, dimensional stability, this kind of complex can be improved by AS base resin again
Material is applied to the industries such as machinery, electronic apparatus, electric tool, motor vehicles, building.But because PA is a kind of crystallinity, strong
The very low polymer of polarity, melt viscosity, and AS base resin is the polymer of a kind of amorphism, low pole, the dissolving of the two
Degree parameter difference is larger, and it is incompatible to belong to thermodynamics, and simple blending leads to two-phase interface tension force very big, thus leading to mechanical property
Can be poor, thus PA/AS base resin alloy material with practical value to be obtained it is necessary to carry out morphology Control and interface modification.
Although general compatilizer of the prior art can alleviate the compatibility between PA resin and AS base resin, the complex obtaining
Poor-performing.
Content of the invention
It is simply that provide a kind of PA/AS base resin complexes to solve the above problems, this is combined the purpose of the present invention
The mechanical performance of thing substantially increases, and especially its heat distortion temperature greatly improves.
Another object of the present invention also resides in the preparation method providing a kind of PA/AS base resin complexes.
For achieving the above object, technical scheme enforcement is as follows：
A kind of PA/AS base resin complexes, including following components and its weight portion：
Described compatilizer is styrene-maleimide copolymer.
Preferably, described styrene-maleimide copolymer is binary copolymerization or multiple copolymer, and maleimide
Nitrogen N position on replaced by alkyl.
Preferably, described styrene-maleimide copolymer is St-co-NPMI copolymer, benzene
Ethylene-propylene nitrile-N-phenylmaleimide copolymer, styrene-acrylonitrile-N-phenylmaleimide-cyclopentenes copolymerization
At least one in thing and styrene-N-phenylmaleimide-copolymer-maleic anhydride.
Preferably, maleic anhydride comonomer in described styrene-N-phenylmaleimide-copolymer-maleic anhydride
Molar percentage is less than or equal to 5%, and the molar percentage of maleimide comonomer is more than or equal to 30%.When maleic anhydride is common
When poly- monomer is higher than 5%, PA/AS base resin complexes are declined by water and heat activated interface adhesion in high temperature environments, lead
Cause performance degradation.When the molar percentage of maleimide comonomer is less than 30%, provide the official with PA molecule chain reaction
Quantity can be rolled into a ball reduce, two-phase interface adhesion declines, the mechanical performance of material and thermal level decline.
Preferably, described PA resin is PA6 resin；The relative viscosity of described PA6 resin is 2.0-3.0, and described PA6 tree
In fat, the molar concentration of amino is higher than the molar concentration of carboxyl.Viscosity is more than 3.0, is unfavorable for that PA6 and AS base resin are realized good
Dispersion, compatilizer by the end group with PA6 react formation PA6 graft copolymer, reduce PA6 and AS base resin interface open
Power, realizes having complementary functions of two kinds of resins, the therefore concentration impact compatible role of PA6 end group, therefore selects relatively low viscosity
PA6 be conducive to improve compatible role.
Preferably, described AS base resin is SAN, styrene-acrylonitrile-acrylic ester copolymer
At least one in thing and ABS.It is furthermore preferred that described AS base resin be styrene-
AN-AE.Wherein, described styrene-acrylonitrile-acrylate copolymer and styrene-acrylonitrile-fourth
Diene copolymers, have the rubber phase being not less than 10% it is preferred that rubber-phase content is 30-70%.
Preferably, described antioxidant is Hinered phenols antioxidant, phosphite ester kind antioxidant, thioether kind antioxidant and Duo Fang
At least one in fragrant amine antioxidants.
It is furthermore preferred that described hindered phenol is 1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyl) butane (CAS：
1843-03-4), 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid (CAS：27676-62-6), 4,4'- is sub-
Double (6- the tert-butyl-m-cresol) (CAS of butyl：85-60-9), β-(3,5- di-tert-butyl-hydroxy phenyl) positive octadecanol of propanoic acid
Ester (CAS：2082-79-3), four [β-(3,5- di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester (CAS：6683-19-
8), double [1,1- dimethyl -2- [(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionyloxy] ethyl] -2,4,8,10- of 3,9-
Four oxaspiros [5.5] hendecane (CAS：90498-90-1) and 1,3,5- trimethyl -2,4,6- three (3,5- di-t-butyl -4- hydroxyl
Base benzyl) benzene (CAS：At least one in 1709-70-2)；Described phosphite ester is double octadecyl tetramethylolmethane diphosphite
Ester (CAS：3806-34-6), double (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate (CAS：80693-00-
1), 2-2 '-di-2-ethylhexylphosphine oxide (4,6- dibutyl-benzyl) -2- ethylhexyl phosphite ester (CAS:126050-54-2), phosphorous acid
Three (2,4- di-tert-butyl-phenyl) ester (CAS:31570-04-4), trisnonyl phenyl phosphite (CAS：26523-78-4) and 4,
4'- split isopropyl diphenyl base C12-15- alcohol phosphite ester (CAS:At least one in 96152-48-6)；Described thioesters is season
Penta tetrol four (3- lauryl thiopropionate) (CAS:29598-76-3)；Described many aromatic amines are 4,4'- bis- (propyloxy phenyl
Base) diphenylamines (CAS:10081-67-1).
Preferably, described nucleator is less than at least in 1 μm of inorganic nucleator and organic nucleating agent for grain diameter
Kind；Described inorganic nucleator is at least one in Pulvis Talci, montmorillonite and Calcium Carbonate；Described organic nucleating agent is benzoic acid
At least one in sodium, Sorbitol dibenzyl ester and carboxylic acid sodium salt.
Present invention also offers a kind of preparation method of PA/AS base resin complexes, including following preparation process：
Step 1：Prepare raw material according to following components and its weight portion：PA resin 30-70 part, AS base resin 5-60 part,
Compatilizer 2-10 part, antioxidant 0.05-0.5 part, nucleator 0.1-0.6 part；
Step 2：The quality of the PA resin drying in step 1 to moisture is accounted for the 0-0.15% of PA resin quality；
Step 3：By PA resin dried in step 2, AS base resin in step 1, compatilizer, nucleator and antioxygen
After agent mixing, put in double screw extruder, melt extrude, simultaneously through supercooling and pelletize, that is, obtain the PA/AS base of the present invention
Resin complexes；
Described double screw extruder is divided into 9th area, and each area temperature is：One 230 DEG C of area's temperature, two 230 DEG C of area's temperature, three
230 DEG C of area's temperature, four 230 DEG C of area's temperature, five 230 DEG C of area's temperature, six 240 DEG C of area's temperature, seven 240 DEG C of area's temperature, eight area's temperature
245 DEG C, nine 250 DEG C of area's temperature；250 revs/min of engine speed.
Beneficial effects of the present invention are as follows：
The PA/AS base resin complexes of the present invention, obtain as compatilizer by using styrene-maleimide copolymer
Obtain unexpected effect, the styrene-maleimide copolymer that the present invention uses contains aromatic ring due to molecular backbone, and
Can be replaced by N atom and introduce the side chain of aromatic structure so as to molecule segment rigidity substantially increases, excellent machinery can be obtained
Performance.Common PA/AS base resin complexes reduce the heat-resisting of PA due to the PA system that is introduced to of non crystalline structure AS base resin
Property, styrene-maleimide copolymer is improving the interface binding power of PA and AS base resin, is improving the resistance to of PA/ASA complex
Heat distortion temperature.The PA/AS base resin complexes of the present invention are used styrene-maleimide copolymer as compatilizer, with
Traditional maleic anhydride compatilizer contrast, has more high anti-hydrolysis ability；Meanwhile, maleimide structure is at high temperature than Malaysia
Anhydride is more stable, is not susceptible to chain break, and the ability of therefore interface binding power opposing high temperature impact is substantially better than and uses horse
Maleic anhydride grafted thing is as the complex of compatilizer.
Specific embodiment
Below in conjunction with embodiment, the invention will be further described.
Comparative example and embodiment be see table using the manufacturer of raw material and model：
Comparative example 1-2 and embodiment 1-3 preparation method as described below, can be further illustrated this by these examples
Compared with prior art, the mechanical performance of the PA/AS base resin complexes being obtained is more excellent for invention.
Comparative example 1
Step 1：Prepare raw material according to following components and its weight portion：62kgPA6,31kgASA, 0.1kg Pulvis Talci,
0.05kg1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyl) butane；
Step 2：By PA6, ASA, Pulvis Talci, 1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyl) fourth in step 1
After alkane mixing, put in double screw extruder, melt extrude, simultaneously through supercooling and pelletize, that is, obtain the product of comparative example 1.
Wherein, double screw extruder is divided into 9th area, and each area temperature is：One 230 DEG C of area's temperature, two 230 DEG C of area's temperature, three
230 DEG C of area's temperature, four 230 DEG C of area's temperature, five 230 DEG C of area's temperature, six 240 DEG C of area's temperature, seven 240 DEG C of area's temperature, eight area's temperature
245 DEG C, nine 250 DEG C of area's temperature；250 revs/min of engine speed.
Comparative example 2
Step 1：Prepare raw material according to following components and its weight portion：The traditional Malaysia of 83kgPA6,10kgASA, 5kg
Anhydride compatilizer, 0.1kg Pulvis Talci, 0.05kg1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyl) butane；
Step 2：By PA6, ASA, traditional maleic anhydride compatilizer, Pulvis Talci, 1,1,3- tri- (2- methyl -4- in step 1
Hydroxyl -5- tert-butyl-phenyl) butane mixing after, put into double screw extruder in, melt extrude, simultaneously through supercooling and pelletize,
Obtain the product of comparative example 2.
Wherein, double screw extruder is divided into 9th area, and each area temperature is：One 230 DEG C of area's temperature, two 230 DEG C of area's temperature, three
230 DEG C of area's temperature, four 230 DEG C of area's temperature, five 230 DEG C of area's temperature, six 240 DEG C of area's temperature, seven 240 DEG C of area's temperature, eight area's temperature
245 DEG C, nine 250 DEG C of area's temperature；250 revs/min of engine speed.
Embodiment 1
Step 1：Prepare raw material according to following components and its weight portion：62kgPA6,31kgASA, 5kg styrene-N- benzene
Base maleimide copolymer, 0.1kg Pulvis Talci, 0.05kg1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyl) fourth
Alkane；
Step 2：The quality of the PA6 resin drying in step 1 to moisture is accounted for the 0-0.15% of PA6 resin quality；
Step 3：By PA6 dried in step 2, the ASA in step 1, styrene-N-phenylmaleimide copolymerization
After thing, Pulvis Talci, 1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyl) butane mix, put in double screw extruder,
Melt extrude, simultaneously through supercooling and pelletize, that is, obtain the product of embodiment 1.
Wherein, double screw extruder is divided into 9th area, and each area temperature is：One 230 DEG C of area's temperature, two 230 DEG C of area's temperature, three
230 DEG C of area's temperature, four 230 DEG C of area's temperature, five 230 DEG C of area's temperature, six 240 DEG C of area's temperature, seven 240 DEG C of area's temperature, eight area's temperature
245 DEG C, nine 250 DEG C of area's temperature；250 revs/min of engine speed.
Embodiment 2
Step 1：Prepare raw material according to following components and its weight portion：62kgPA6,31kgASA, 5kg styrene-propene
Nitrile-N-phenylmaleimide copolymer, 0.1kg Pulvis Talci, 0.05kg1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl benzene
Base) butane；
Step 2：The quality of the PA6 resin drying in step 1 to moisture is accounted for the 0-0.15% of PA6 resin quality；
Step 3：By PA6 dried in step 2, the ASA in step 1, styrene-acrylonitrile-N- benzyl maleimide
After amine copolymer thing, Pulvis Talci, 1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyl) butane mix, put into twin-screw extrusion
In machine, melt extrude, simultaneously through supercooling and pelletize, that is, obtain the product of embodiment 2.
Wherein, double screw extruder is divided into 9th area, and each area temperature is：One 230 DEG C of area's temperature, two 230 DEG C of area's temperature, three
230 DEG C of area's temperature, four 230 DEG C of area's temperature, five 230 DEG C of area's temperature, six 240 DEG C of area's temperature, seven 240 DEG C of area's temperature, eight area's temperature
245 DEG C, nine 250 DEG C of area's temperature；250 revs/min of engine speed.
Embodiment 3
Step 1：Prepare raw material according to following components and its weight portion：62kgPA6,31kgASA, 2.5kg styrene-N-
Phenyl maleimide copolymers, 2.5kg styrene-acrylonitrile-N-phenylmaleimide copolymer, 0.1kg Pulvis Talci,
0.05kg1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyl) butane；
Step 2：The quality of the PA6 resin drying in step 1 to moisture is accounted for the 0-0.15% of PA6 resin quality；
Step 3：By PA6 dried in step 2, the ASA in step 1, styrene-N-phenylmaleimide copolymerization
Thing, styrene-acrylonitrile-N-phenylmaleimide copolymer, Pulvis Talci, 1,1,3- tri- (the tertiary fourth of 2- methyl -4- hydroxyl -5-
Base phenyl) butane mixing after, put into double screw extruder in, melt extrude, simultaneously through supercooling and pelletize, that is, obtain embodiment
3 product.
Wherein, double screw extruder is divided into 9th area, and each area temperature is：One 230 DEG C of area's temperature, two 230 DEG C of area's temperature, three
230 DEG C of area's temperature, four 230 DEG C of area's temperature, five 230 DEG C of area's temperature, six 240 DEG C of area's temperature, seven 240 DEG C of area's temperature, eight area's temperature
245 DEG C, nine 250 DEG C of area's temperature；250 revs/min of engine speed.
It is shown experimentally that the special compatilizer of the present invention to PA/AS base resin complexes anti-hydrolytic performance and heat resistance
Impact.
Anti-hydrolytic performance is evaluated：
According to ISO 527-2/1A, by the 4mm thickness test bar of molded preparation, width 10mm, test speed 5mm/
Min, the aerial hydrolysis of 23 DEG C of test is front and hydrolyzes after-drawing intensity (TS) (or tensile strength TS conservation rate) (at least 5
Same composition and the meansigma methodss of shaped samples test result).Hydrolyze and by the addition glycol/water ratio toward in autoclave be
1：1 mixed solution, adds molded test bar, adjusts temperature and is tested for 100 DEG C, in the hydrolysis reaching setting
Between autoclave temperature is cooled to taking-up test bar after room temperature after 1000h, by the solvent rub on its surface, with aluminium foil bag heat
Sealing, prevents from carrying out humidity exchange with air before evaluating mechanical property.Compare with the corresponding mechanical property before hydrolysis, calculate
Go out the conservation rate of tensile strength, and as a percentage.
Heat resistance impact is evaluated：
Heat distortion temperature HDT under 1.8MPa load for the material is evaluated according to ISO 75 standard.
Compare comparative example 1, comparative example 2, styrene-maleimide copolymer is used as embodiment 1-3 of compatilizer
Obtain higher tensile strength and heat-resistant deforming temperature, by the glycol/water mixed solution of same time as medium
After high temperature ageing, embodiment 1-3 has higher stretching strength retentivity, illustrates to use styrene-maleimide copolymer
Improve the performance of the resistant to hydrolysis (anti-alcoholysis) of material as compatilizer.
Embodiment is used for illustrative purposes only, rather than limitation of the present invention, person skilled in the relevant technique,
In the case of the spirit and scope of the present invention, various conversion or modification, therefore all equivalent technology can also be made
Scheme also should belong to scope of the invention, should be limited by each claim.
Claims (10)
1. a kind of PA/AS base resin complexes are it is characterised in that include following components and its weight portion：
Described compatilizer is styrene-maleimide copolymer.
2. as claimed in claim 1 a kind of PA/AS base resin complexes it is characterised in that described styrene-maleimide
Copolymer is to be replaced by alkyl on binary copolymerization or multiple copolymer, and the nitrogen N position of maleimide.
3. as claimed in claim 2 a kind of PA/AS base resin complexes it is characterised in that described styrene-maleimide
Copolymer is St-co-NPMI copolymer, styrene-acrylonitrile-N-phenylmaleimide copolymer, benzene
Ethylene-propylene nitrile-N-phenylmaleimide-cyclopentenes copolymer and styrene-N-phenylmaleimide-maleic anhydride
At least one in copolymer.
4. as claimed in claim 3 a kind of PA/AS base resin complexes it is characterised in that described styrene-N- phenyl Malaysia
In acid imide-copolymer-maleic anhydride, the molar percentage of maleic anhydride comonomer is less than or equal to 5%, maleimide amine copolymer
The molar percentage of monomer is more than or equal to 30%.
5. as claimed in claim 1 a kind of PA/AS base resin complexes it is characterised in that described PA resin be PA6 resin；
The relative viscosity of described PA6 resin is the molar concentration of amino in 2.0-3.0, and described PA6 resin is higher than the mole dense of carboxyl
Degree.
6. as claimed in claim 1 a kind of PA/AS base resin complexes it is characterised in that described AS base resin be styrene-
In acrylonitrile copolymer, styrene-acrylonitrile-acrylate copolymer and ABS extremely
Few one kind.
7. as claimed in claim 1 a kind of PA/AS base resin complexes it is characterised in that described antioxidant be Hinered phenols
At least one in antioxidant, phosphite ester kind antioxidant, thioether kind antioxidant and many aromatic amines antioxidant.
8. as claimed in claim 7 a kind of PA/AS base resin complexes it is characterised in that described Hinered phenols antioxygen
Agent is 1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyl) butane, 1,3,5- tri- (3,5- di-t-butyl -4- hydroxyl benzyl
Base) isocyanuric acid, 4,4' butylidene biss (6- tert-butyl-m-cresol), β-(3,5- di-tert-butyl-hydroxy phenyl) propanoic acid positive ten
Double [1,1- dimethyl-the 2- of eight carbon alcohol esters, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester, 3,9-
[(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionyloxy] ethyl] -2,4,8,10- four oxaspiro [5.5] hendecane and 1,
At least one in 3,5- trimethyl -2,4,6- three (3,5- di-tert-butyl-4-hydroxyl benzyl) benzene；Described phosphorous acid esters antioxygen
Agent be distearyl pentaerythritol diphosphite, double (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate,
2-2 '-di-2-ethylhexylphosphine oxide (4,6- dibutyl-benzyl) -2- ethylhexyl phosphite ester, phosphorous acid three (2,4- di-tert-butyl-phenyl)
At least one in ester, trisnonyl phenyl phosphite and 4,4'- split isopropyl diphenyl base C12-15- alcohol phosphite ester；Described
Sulphur ester antioxidant is tetramethylolmethane four (3- lauryl thiopropionate)；Described many aromatic amines antioxidant is 4,4'- bis- (benzene
Base isopropyl) diphenylamines.
9. as claimed in claim 1 a kind of PA/AS base resin complexes it is characterised in that described nucleator be grain diameter
At least one in inorganic nucleator and organic nucleating agent less than 1 μm；Described inorganic nucleator is Pulvis Talci, montmorillonite and carbon
At least one in sour calcium；Described organic nucleating agent is at least one in sodium benzoate, Sorbitol dibenzyl ester and carboxylic acid sodium salt.
10. a kind of preparation method of PA/AS base resin complexes as claimed in claim 1 is it is characterised in that include following system
Standby step：
Step 1：Prepare raw material according to following components and its weight portion：PA resin 30-70 part, AS base resin 5-60 part, compatible
Agent 2-10 part, antioxidant 0.05-0.5 part, nucleator 0.1-0.6 part；
Step 2：The quality of the PA resin drying in step 1 to moisture is accounted for the 0-0.15% of PA resin quality；
Step 3：By PA resin dried in step 2, AS base resin in step 1, compatilizer, nucleator and antioxidant mix
After conjunction, put in double screw extruder, melt extrude, simultaneously through supercooling and pelletize, that is, obtain the PA/AS base resin of the present invention
Complex；
Described double screw extruder is divided into 9th area, and each area temperature is：One 230 DEG C of area's temperature, two 230 DEG C of area's temperature, three area's temperature
230 DEG C of degree, four 230 DEG C of area's temperature, five 230 DEG C of area's temperature, six 240 DEG C of area's temperature, seven 240 DEG C of area's temperature, eight area's temperature 245
DEG C, nine 250 DEG C of area's temperature；250 revs/min of engine speed.
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| CN112592583A (en) * | 2020-11-16 | 2021-04-02 | 金旸（厦门）新材料科技有限公司 | Alcoholysis-resistant enhanced PA6T material and preparation method thereof |
| CN112592583B (en) * | 2020-11-16 | 2023-03-10 | 金旸（厦门）新材料科技有限公司 | Alcoholysis-resistant enhanced PA6T material and preparation method thereof |
| CN115975366A (en) * | 2023-01-13 | 2023-04-18 | 佛山市达孚新材料有限公司 | Modified polycarbonate resin, product and preparation method thereof |
| CN115975366B (en) * | 2023-01-13 | 2024-02-13 | 佛山市达孚新材料有限公司 | Modified polycarbonate resin, product and preparation method thereof |
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