CN105924876A - Glass fiber reinforced ASA (acrylonitrile-styrene-acrylate copolymer)/PETG (polyethylene terephthalate glycol) alloy material and preparation method thereof - Google Patents

Glass fiber reinforced ASA (acrylonitrile-styrene-acrylate copolymer)/PETG (polyethylene terephthalate glycol) alloy material and preparation method thereof Download PDF

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Publication number
CN105924876A
CN105924876A CN201610420531.5A CN201610420531A CN105924876A CN 105924876 A CN105924876 A CN 105924876A CN 201610420531 A CN201610420531 A CN 201610420531A CN 105924876 A CN105924876 A CN 105924876A
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Prior art keywords
petg
asa
alloy material
fiberglass reinforced
resin
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CN201610420531.5A
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CN105924876B (en
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周中玉
李强
罗明华
辛敏琦
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Shanghai Kumho Sunny Plastics Co Ltd
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Shanghai Kumho Sunny Plastics Co Ltd
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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
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a glass fiber reinforced ASA (acrylonitrile-styrene-acrylate copolymer)/PETG (polyethylene terephthalate glycol) alloy material and a preparation method thereof. The ASA/PETG alloy material is prepared from, by weight, 30-60 parts of ASA resin, 30-60 parts of PETG resin, 10-30 parts of glass fibers, 0.5-2 parts of a compatilizer, 0.1-1 part of an antioxidant and 0.1-1 part of a lubricant. The preparation method includes steps: (a) adding the ASA resin, the PETG resin, the compatilizer, the antioxidant and the lubricant into a mixer to realize mixing; (b) after side feeding of the glass fibers and main feeding of a mixture obtained at the step through a double-screw extruder, blending and granulating to obtain the material. The method is simple and feasible; by the compatilizer, the ASA, the PETG and the glass fibers are combined more steadily, and the glass fiber reinforced ASA/PETG alloy material has excellent mechanical properties, fluidity and dimensional stability and suitable for automotive complex structural interior decoration parts such as speaker covers and defogging grilles.

Description

Fiberglass reinforced ASA/PETG alloy material and preparation method thereof
Technical field
The invention belongs to polymer blended, Polymer Processing field, be specifically related to a kind of fiberglass reinforced ASA/PETG Alloy material and preparation method thereof.
Background technology
ASA resin (acrylonitrile-styrene-butyl acrylate copolymer) is a kind of intensity height, good toughness, resistance to actinic Good, easily processed into type thermoplastics type's Polymer Materials ' Structure.
PETG is a kind of transparent, non-crystalline type copolyesters, and comonomer conventional for PETG is 1,4-CHDM Full name is polyethylene terephthalate-1,4 cyclohexane dimethanol ester.It is by p-phthalic acid (PTA), ethylene glycol (EG) and three kinds of monomer products of ester-interchange method polycondensation of 1,4-CHDM (CHDM), compare with PET Many 1,4-CHDM comonomers, with PCT than many ethylene glycol comonomer, therefore, the performance of PETG Differ widely with PET, PCT.PETG sheet material has prominent toughness and high impact strength, and its impact strength is 3～10 times of modified polyacrylate class, and there is the widest range of work, high mechanical strength and excellent flexibility, Easily print and there is environment-friendly advantage.
Through retrieval, CN104845284A discloses a kind of modified PET/PTT/PETG composite, but in patent not Mention the preparation method of fiberglass reinforced.CN 102911487 A disclose a kind of fiber glass reinforced PBT/ASA alloy material and Its preparation method, but the toughness of PBT resin is the poorest, and the range of application of material is restricted.CN 104693767 A Disclose a kind of glass fibre reinforced PC alloy material and preparation method thereof, but the processing forming of PC is poor, answering of material With being restricted.
Summary of the invention
For the defect of prior art, it is an object of the invention to provide a kind of fiberglass reinforced ASA/PETG alloy material, There is mechanical performance, mobility and the dimensional stability of excellence, be suitable for the interior trim product that vehicle structure is complicated, such as loudspeaker Cover, except mist grid etc..ABS/PETG alloy can increase through glass further in conjunction with the excellent specific property of ABS and PETG The strong ASA/PETG alloy material improved has mechanical performance, mobility and the dimensional stability of excellence, is suitable for vapour The interior trim product that bassinet structure is complicated, such as horn cover, except mist grid etc..Another object of the present invention is to provide this alloy material The preparation method of material.
It is an object of the invention to by following technical scheme realization:
First aspect, the present invention provides a kind of fiberglass reinforced ASA/PETG alloy material, comprises and have following weight portion Component:
Preferably, described ASA resin is the graft copolymer of acrylonitrile-styrene-butyl acrylate composition；Wherein, third The content of olefin(e) acid butyl ester is 15～55wt%.
Preferably, described PETG resin is p-phthalic acid, ethylene glycol and the contracting of three kinds of monomers of 1,4-CHDM Polymers；Wherein, 1,4-CHDM content is 30～40wt%.
Preferably, described glass a diameter of 7～13um.
Preferably, one or both the mixing during described compatilizer is AS-g-MAH copolymer, AS-g-GMA copolymer.
Preferably, described antioxidant is double [β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propanoic acid of triethylene-glycol Ester], four [β-(3,5-di-t-butyl 4-hydroxy phenyl) propanoic acid] pentaerythritol ester, three (2,4-di-tert-butyl-phenyls) The mixing of one or more in phosphite ester, double stearyl alcohol pentaerythritol diphosphites.
Preferably, described lubricant be liquid paraffin, hard paraffin, silane polymer, soap, fatty acid amide, In zinc stearate, calcium stearate, stearic amide, methylene bis stearic amide, N, N-ethylene bis stearic acid amide The mixing of one or more.
Second aspect, the invention still further relates to the preparation method of aforementioned fiberglass reinforced ASA/PETG alloy material, including as follows Step:
ASA resin, PETG resin, compatilizer, antioxidant, mix lubricant are obtained mixture；
Being fed by twin-screw extrusion owner by described mixture, glass is fed by side, and pelletize is blended.
Preferably, described mixing refers specifically in stirrer for mixing.
Compared with prior art, the invention have the advantages that
The method of the present invention is simple, and fiberglass reinforced ASA/PETG alloy material has the mechanical performance of excellence, flowing Property and dimensional stability, be suitable for the interior trim product that vehicle structure is complicated, such as horn cover, except mist grid etc..
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.Following example will assist in those skilled in the art Member is further appreciated by the present invention, but limits the present invention the most in any form.It should be pointed out that, the common skill to this area For art personnel, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement.These broadly fall into Protection scope of the present invention.
Embodiment 1
The present embodiment provide the component of fiberglass reinforced ASA/PETG alloy material and the part by weight of each component be:
Preparation method is as follows:
A (), by ASA resin, PETG resin, compatilizer, antioxidant, mixes in lubricant addition mixing and blending machine Closing, the time is 10 minutes；
B step a gained mixture is fed by () by twin-screw extrusion owner, glass is fed by side, and blended pelletize prepares glass Fine enhancing ASA/PETG alloy material.
Embodiment 2
The present embodiment provide the component of fiberglass reinforced ASA/PETG alloy material and the part by weight of each component be:
Preparation method is as follows:
A (), by ASA resin, PETG resin, compatilizer, antioxidant, mixes in lubricant addition mixing and blending machine Closing, the time is 15 minutes；
B step a gained mixture is fed by () by twin-screw extrusion owner, glass is fed by side, and blended pelletize prepares glass Fine enhancing ASA/PETG alloy material.
Embodiment 3
The present embodiment provide the component of fiberglass reinforced ASA/PETG alloy material and the part by weight of each component be:
Preparation method is as follows:
A (), by ASA resin, PETG resin, compatilizer, antioxidant, mixes in lubricant addition mixing and blending machine Closing, the time is 20 minutes；
B step a gained mixture is fed by () by twin-screw extrusion owner, glass is fed by side, and blended pelletize prepares glass Fine enhancing ASA/PETG alloy material.
Embodiment 4
The present embodiment provide the component of fiberglass reinforced ASA/PETG alloy material and the part by weight of each component be:
Preparation method is as follows:
A (), by ASA resin, PETG resin, compatilizer, antioxidant, mixes in lubricant addition mixing and blending machine Closing, the time is 10 minutes；
B step a gained mixture is fed by () by twin-screw extrusion owner, glass is fed by side, and blended pelletize prepares glass Fine enhancing ASA/PETG alloy material.
Comparative example 1
This comparative example provide the component of fiberglass reinforced ASA/PETG alloy material and the part by weight of each component be:
Preparation method is as follows:
A ASA resin, PETG resin, antioxidant, lubricant are added in mixing and blending machine and mix by (), the time It it is 10 minutes；
B step a gained mixture is fed by () by twin-screw extrusion owner, glass is fed by side, and blended pelletize prepares glass Fine enhancing ASA/PETG alloy material.
Fiberglass reinforced ASA/PETG alloy material component prepared by embodiment and comparative example is shown in Table 1.
Table 1
Implementation result
The fiberglass reinforced ASA/PETG alloy material performance of embodiment 1～4 preparation is shown in Table 2.
Table 2 fiberglass reinforced ASA/PETG alloy material performance
In sum, the method for the present invention is simple, and fiberglass reinforced ASA/PETG alloy material has the machinery of excellence Performance, mobility and dimensional stability, be suitable for the interior trim product that vehicle structure is complicated, such as horn cover, except mist grid Deng.
Comparative example 2～9
Comparative example 2～9 is the comparative example of embodiment 1, is respectively in place of contrast:
The content of comparative example 2:ASA resin is 80 parts, PETG resin content is 20 parts；(beyond content range of the present invention Limit)；
The content of comparative example 3:ASA resin is 20 parts, PETG resin content is 80 parts；
Comparative example 4:ASA resin content is 25 parts, PETG resin content is 70 parts, the content of glass is 5 parts；
Comparative example 5:ASA resin content is 40 parts, PETG resin content is 20 parts, the content of glass is 40 parts；
Comparative example 6:ASA resin content is 65 parts, and PETG resin content is 20 parts, and glass fiber content is 5 parts；
Comparative example 7:CN104845284A disclosed embodiment 1 technical scheme；
Comparative example 8:CN 102911487 A disclosed embodiment 1 technical scheme；
Comparative example 9:CN 104693767 A disclosed embodiment 1 technical scheme；
Table 3 comparative example alloy material performance
Above the specific embodiment of the present invention is described.It is to be appreciated that the invention is not limited in Stating particular implementation, those skilled in the art can make various deformation or amendment within the scope of the claims, This has no effect on the flesh and blood of the present invention.

Claims (9)

1. a fiberglass reinforced ASA/PETG alloy material, it is characterised in that comprise the component with following weight portion:
Fiberglass reinforced ASA/PETG alloy material the most according to claim 1, it is characterised in that described ASA tree Fat is the graft copolymer of acrylonitrile-styrene-butyl acrylate composition；Wherein, the content of butyl acrylate be 15～ 55wt%.
Fiberglass reinforced ASA/PETG alloy material the most according to claim 1, it is characterised in that described PETG Resin is p-phthalic acid, ethylene glycol and the condensation polymer of three kinds of monomers of 1,4 cyclohexane dimethanol；Wherein, Isosorbide-5-Nitrae-hexamethylene Dimethanol content is 30～40wt%.
Fiberglass reinforced ASA/PETG alloy material the most according to claim 1, it is characterised in that described glass is straight Footpath is 7～13um.
Fiberglass reinforced ASA/PETG alloy material the most according to claim 1, it is characterised in that described compatilizer For one or both the mixing in AS-g-MAH copolymer, AS-g-GMA copolymer.
Fiberglass reinforced ASA/PETG alloy material the most according to claim 1, it is characterised in that described antioxidant For triethylene-glycol double [β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester], four [β-(3,5-bis-uncles Butyl 4-hydroxy phenyl) propanoic acid] pentaerythritol ester, three (2,4-di-tert-butyl-phenyl) phosphite ester, double stearyl alcohol The mixing of one or more in pentaerythritol diphosphites.
Fiberglass reinforced ASA/PETG alloy material the most according to claim 1, it is characterised in that described lubricant For liquid paraffin, hard paraffin, silane polymer, soap, fatty acid amide, zinc stearate, calcium stearate, The mixing of one or more in stearic amide, methylene bis stearic amide, N, N-ethylene bis stearic acid amide.
8. according to a preparation method for fiberglass reinforced ASA/PETG alloy material described in any one of claim 1 to 7, It is characterized in that, comprise the steps:
ASA resin, PETG resin, compatilizer, antioxidant, mix lubricant are obtained mixture；
Being fed by twin-screw extrusion owner by described mixture, glass is fed by side, and pelletize is blended.
The preparation method of fiberglass reinforced ASA/PETG alloy material the most according to claim 8, it is characterised in that Described mixing refers specifically in stirrer for mixing.
CN201610420531.5A 2016-06-13 2016-06-13 Fiberglass reinforced ASA/PETG alloy materials and preparation method thereof Active CN105924876B (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106751327A (en) * 2016-12-12 2017-05-31 芜湖市天雄新材料科技有限公司 Low smell high durable ASA/PC/PETG alloy materials and preparation method thereof
CN107641281A (en) * 2017-08-17 2018-01-30 常州中英科技股份有限公司 A kind of ASA resin mixture of high wave transmission rate and its antenna house of preparation
CN108314869A (en) * 2018-02-12 2018-07-24 金发科技股份有限公司 A kind of ASA/ polyester alloys material and its preparation method and application
CN108587030A (en) * 2018-05-18 2018-09-28 中广核俊尔（上海）新材料有限公司 The glass fibre reinforced modified Resin A SA composite material and preparation methods of low smell
CN110256797A (en) * 2019-06-20 2019-09-20 江苏金发科技新材料有限公司 Resist cold weather-proof low smell glass fibre reinforced composite material and preparation method thereof
CN112430383A (en) * 2020-11-19 2021-03-02 中广核俊尔（上海）新材料有限公司 High-fluidity reinforced PET/ASA material and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101418111A (en) * 2008-11-14 2009-04-29 上海金发科技发展有限公司 Weather resistant halogen-free flame retardant ABS resin and preparation process thereof
CN102911487A (en) * 2012-08-23 2013-02-06 上海金发科技发展有限公司 Glass fiber reinforced polybutylece terephthalate (PBT)/acrylonitrile styrene acrylate (ASA) alloy material and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101418111A (en) * 2008-11-14 2009-04-29 上海金发科技发展有限公司 Weather resistant halogen-free flame retardant ABS resin and preparation process thereof
CN102911487A (en) * 2012-08-23 2013-02-06 上海金发科技发展有限公司 Glass fiber reinforced polybutylece terephthalate (PBT)/acrylonitrile styrene acrylate (ASA) alloy material and preparation method thereof

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106751327A (en) * 2016-12-12 2017-05-31 芜湖市天雄新材料科技有限公司 Low smell high durable ASA/PC/PETG alloy materials and preparation method thereof
CN107641281A (en) * 2017-08-17 2018-01-30 常州中英科技股份有限公司 A kind of ASA resin mixture of high wave transmission rate and its antenna house of preparation
CN108314869A (en) * 2018-02-12 2018-07-24 金发科技股份有限公司 A kind of ASA/ polyester alloys material and its preparation method and application
WO2019153988A1 (en) * 2018-02-12 2019-08-15 金发科技股份有限公司 Asa/polyester alloy material, preparation method therefor and application thereof
CN108314869B (en) * 2018-02-12 2020-09-29 金发科技股份有限公司 ASA/polyester alloy material and preparation method and application thereof
CN108587030A (en) * 2018-05-18 2018-09-28 中广核俊尔（上海）新材料有限公司 The glass fibre reinforced modified Resin A SA composite material and preparation methods of low smell
CN108587030B (en) * 2018-05-18 2021-04-20 中广核俊尔（上海）新材料有限公司 Low-odor glass fiber reinforced modified resin ASA composite material and preparation method thereof
CN110256797A (en) * 2019-06-20 2019-09-20 江苏金发科技新材料有限公司 Resist cold weather-proof low smell glass fibre reinforced composite material and preparation method thereof
CN112430383A (en) * 2020-11-19 2021-03-02 中广核俊尔（上海）新材料有限公司 High-fluidity reinforced PET/ASA material and preparation method thereof
CN112430383B (en) * 2020-11-19 2023-06-30 中广核俊尔（上海）新材料有限公司 High-fluidity reinforced PET/ASA material and preparation method thereof

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