CN106009554A - High-fluidity glass fiber reinforced PET/ABS resin composition and preparation method thereof - Google Patents
High-fluidity glass fiber reinforced PET/ABS resin composition and preparation method thereof Download PDFInfo
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- CN106009554A CN106009554A CN201610637902.5A CN201610637902A CN106009554A CN 106009554 A CN106009554 A CN 106009554A CN 201610637902 A CN201610637902 A CN 201610637902A CN 106009554 A CN106009554 A CN 106009554A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- 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
- B29C2948/9258—Velocity
-
- 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
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a high-fluidity glass fiber reinforced PET/ABS resin composition and a preparation method thereof. The composition comprises 10-84.4 parts of low-melting point PET resin, 10-84.4 parts of ABS resin, 0-15 parts of a flexibilizer, 5-50 parts of glass fibers and 0.6 parts of an antioxidant, wherein the low-melting point PET resin is special PET resin with the melting point of 190-230DEG C; and the flexibilizer is at least one of ethylene-vinyl acetate, ethylene-methyl acrylate, ethylene-ethyl acrylate, ethylene-butyl acrylate, low density polyethylene, a maleic anhydride grafted ethylene-octylene copolymer, an ethylene-ethyl acrylate-glycidyl ester copolymer and an ethylene-butyl acrylate-glycidyl ester copolymer. The glass fiber reinforced PET/ABS resin composition prepared through optimizing the variety and the use amount of the ABS resin, the low-melting point PET resin, the flexibilizer and the glass fibers has the characteristics of low melting point and high toughness, and can be widely applied to injection molded products.
Description
Technical field
The present invention relates to engineering plastics technical field, glass fiber reinforcement PET/ABS resin combination being specifically related to a kind of high fluidity and preparation method thereof.
Background technology
Conventional polybutylene terephthalate (PBT) (PET) is the engineering plastics of a kind of hemicrystalline, and it has good mechanical property, electrical property, thermostability and chemical resistance etc., is widely used in the industries such as automobile, electronics, electrical equipment；Also in polyester bottles, fiber, the field such as thin film is widely used.But at injection molding art, owing to PET resin can crystallize in melting process, its crystallisation by cooling speed is relatively slow, and cool time is longer, limits its application.
By introducing copolymerization units in polymerization process, it is possible to reduce the cold crystallization of PET and crystallizing power, even synthesizing the PET resin of amorphous, this resin has relatively low fusing point.As patent CN103102473 A discloses a kind of by introducing 10-30% M-phthalic acid, the crystallization modifier of 5-29% and the branched regulator of 0.03-2%, low melting point, transparent PET resin are finally synthesized.Patent CN 103102646 A discloses a kind of fusing point regulator by introducing 5-10% and the crystallization promoter of 7-20%, has synthesized a kind of low melting point, the PET resin of high crystallization temperature.And patent CN 104987498 A discloses a kind of by introducing 2-methyl isophthalic acid, ammediol (MPO) and M-phthalic acid, having synthesized PTT and the polyethylene terephthalate of low melting point, its melting range is between 190 DEG C to 250 DEG C.
Copolyester with low melting point application currently mainly is textile industry, and it can carry out composite spinning with conventional polyester, and the core-skin composite fiber of gained can be used for and wool blended the worn performance improving worsted fabric；And copolyester with low melting point also has wide application prospect in non-woven fabrics, hot-melt prepreg machine, building materials and paint field.
PET is Crystalline plastics, and ABS is non-Crystalline plastics, notable difference is all there is in both in terms of crystal habit and solubility parameter, currently mainly rely on and select suitable compatilizer, improve the adhesion of two kinds of system boundaries, improve the morphological stability of blend, mechanical property and processing characteristics, meanwhile, overcome the shortcoming bigger to processing conditions degree of dependence that binary blend morphosis instability is caused.Utilize low-melting point PET resin for improving the processability of PET/ABS alloy, compared to traditional PET and ABS compositions, significant advantage can be had in terms of processing fluidity in order to avoid compatilizer selects the problem of aspect, particularly fiberglass reinforced PET/ABS alloy, the advantage of its mobility is more aobvious prominent.Therefore, this patent develops the glass fiber reinforcement PET/ABS resin alloy of high fluidity, can solve current fiberglass reinforced PET/ABS alloy problem in terms of injection.
Summary of the invention
The purpose of the present invention, it is simply that glass fiber reinforcement PET/ABS resin combination providing a kind of high fluidity in order to solve the problems referred to above and preparation method thereof.
The object of the present invention is achieved like this:
A kind of glass fiber reinforcement PET/ABS resin combination of the high fluidity of the present invention, this PET/ABS resin combination includes following components and weight portion content:
The glass fiber reinforcement PET/ABS resin combination of above-mentioned a kind of high fluidity, wherein, the repetitive of described low-melting point PET resin is made up of following components:
Component A: account for the dicarboxylic acid units of the repetitive 45-55mol% of resin；
Component B: account for the diol units that carbon number is 2～14 of the repetitive 45-55mol% of resin；
Wherein, described component A is made up of with the M-phthalic acid or O-phthalic acid unit A2 accounting for its 0-20mol% terephthalic acid units A1 accounting for its 80-100mol%；Wherein, described component B is formed by accounting for the ethylene glycol unit B 1 of its 80-100mol%, the aliphatic diol that carbon number is 2～9 accounting for its 0-20mol% or cycloaliphatic diol units B2 that carbon number is 2～9；And meet in component A or component B at least any one component, comprise two or more different unit.
The glass fiber reinforcement PET/ABS resin combination of above-mentioned a kind of high fluidity, wherein, its melting range of low-melting point PET resin is between 190-230 DEG C, between preferably 210-230 DEG C, between most preferably 215-225 DEG C.Described low-melting point PET resin, its intrinsic viscosity is between 0.55-0.95ml/g, between preferably 0.65-0.85ml/g, between most preferably 0.7-0.8ml/g.
The glass fiber reinforcement PET/ABS resin combination of above-mentioned a kind of high fluidity, wherein, at least one in acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene-acrylate copolymer, MBS and acrylonitrile-ethylene propylene diene rubber-styrol copolymer of ABS resin, preferred version is acrylonitrile-butadiene-styrene copolymer.
The glass fiber reinforcement PET/ABS resin combination of above-mentioned a kind of high fluidity, wherein, at least one during toughener is ethylene-vinyl acetate, ethylene-methyl acrylate, ethylene-ethylacrylate, Ethylene-butyl acrylate, Low Density Polyethylene, maleic anhydride grafted ethene-octene copolymer, ethylene-ethylacrylate-glycidyl ester copolymer, Ethylene-butyl acrylate-glycidyl ester copolymer
The glass fiber reinforcement PET/ABS resin combination of above-mentioned a kind of high fluidity, wherein, glass fibre is alkali-free short glass fiber or continuous alkali-free glass fibre, and wherein glass fiber diameter is 10～25 μm.
The glass fiber reinforcement PET/ABS resin combination of above-mentioned a kind of high fluidity, wherein, antioxidant is pentaerythritol ester and phosphite ester, and the two weight ratio is 1:1.
Present invention also offers the preparation method of the glass fiber reinforcement PET/ABS resin combination of a kind of high fluidity, comprise the following steps:
(1) according to following components and weight portion content preparation raw material:
(2) double screw extruder will be entered after ABS resin, low-melting point PET resin, toughener, the even mixing of antioxidant, between in an extruder, position adds glass fibre, processing technique is as follows: district's temperature 210-220 DEG C, two district's temperature 230-240 DEG C, three district's temperature 235-245 DEG C, four district's temperature 235-245 DEG C, five district's temperature 235-245 DEG C, six district's temperature 235-245 DEG C, seven district's temperature 240-250 DEG C, eight district's temperature 240-250 DEG C, nine district's temperature 230-240 DEG C；Engine speed 300-400 rev/min；；
(3) discharging, cools down after extrusion, is dried, pelletizing, can prepare the glass fiber reinforcement PET/ABS resin combination of high fluidity of the present invention.
Compared with prior art, the glass fiber reinforcement PET/ABS resin combination of the high fluidity in the present invention is compared to traditional PET and ABS compositions, having significant advantage, particularly fiberglass reinforced PET/ABS alloy in terms of processing fluidity, the advantage of its mobility is more aobvious prominent
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described.
The material that the embodiment of the present invention and comparative example are used is as follows:
Low-melting point PET resin: intrinsic viscosity is 0.71ml/g, the trade mark is HS550, engineering plastics factory of Yizheng branch company of asset management company limited of SINOPEC；Wherein, terephthalic acid units content is 39mol% ratio, and isophthalic acid units content is 11mol% ratio, and ethylene glycol unit content is 50mol% ratio；
Conventional PET resin: intrinsic viscosity is 0.68ml/g, and the trade mark is SB500, engineering plastics factory of Yizheng branch company of asset management company limited of SINOPEC；
ABS resin: the trade mark is PA757, TaiWan, China Qi Mei company；
Toughener: Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer, the trade mark is PTW, du pont company；Maleic anhydride grafted ethene-octene copolymer (MPOE), the trade mark is N493D, du pont company；
Short glass fiber: the trade mark is ECS 303H-3, a diameter of 10 μm, Chongqing Polycomp International Co., Ltd.
Continuous glass fibre: the trade mark is ER14-2000-988A, diameter 13 μm, megalith group of China.
Antioxidant: four [β-(3,5-di-tert-butyl-4-hydroxy phenyl) propanoic acid] pentaerythritol ester, Irganox 1010, Ciba fine chemicals.Three [2.4-di-tert-butyl-phenyl] phosphite ester, Irganox 168, Ciba fine chemicals；The two weight ratio 1:1.
Embodiment 1～10 and comparative example 1～3:
By table 1 formula, ABS resin, PET resin, toughener and other auxiliary agents etc. are mixed in high-speed mixer and within 1～2 minute, obtains premix material, premix material is through double screw extruder, and glass fibre adds in the middle part of extruder, melt extrudes, cools down, pelletize and get final product at 210 DEG C～250 DEG C.
The performance test results is as shown in table 1.
The component (weight portion) of table 1 embodiment 1-10 and comparative example 1-3 and the performance test results
*: fusing point uses DSC method test；
Knowable to embodiment 1-10 of table 1 and the comparison of comparative example 1-3, the present invention is by preferred ABS resin, the PET resin of low melting point and toughener, use different glass fibre, can prepare the glass fiber reinforcement PET/ABS resin combination with high fluidity, this novel resin combination will be well used at Injection Industry.
Above example is used for illustrative purposes only, rather than limitation of the present invention, person skilled in the relevant technique, without departing from the spirit and scope of the present invention, various conversion or modification can also be made, the technical scheme of the most all equivalents also should belong to scope of the invention, should be limited by each claim.
Claims (9)
1. the glass fiber reinforcement PET/ABS resin combination of a high fluidity, it is characterised in that should
PET/ABS resin combination includes following components and weight portion content thereof:
The glass fiber reinforcement PET/ABS resin combination of a kind of high fluidity the most as claimed in claim 1
Thing, it is characterised in that the repetitive of described low-melting point PET resin is made up of following components:
Component A: account for the dicarboxylic acid units of the repetitive 45-55mol% of resin；
Component B: account for the diol units that carbon number is 2-14 of the repetitive 45-55mol% of resin；
Wherein, described component A is by accounting for terephthalic acid units A1 of its 80-100mol% and accounting for its 0-20mol%
M-phthalic acid or O-phthalic acid unit A2 composition；Wherein, described component B is by accounting for its 80-100mol%
Ethylene glycol unit B 1, account for the aliphatic diol that carbon number is 2-9 or alicyclic two of its 0-20mol%
Alcohol unit B 2 forms；And meet in component A or component B at least any one component, comprise two or more
Different unit.
The glass fiber reinforcement PET/ABS resin combination of a kind of high fluidity the most as claimed in claim 1
Thing, it is characterised in that described its melting range of low-melting point PET resin is between 190-230 DEG C, preferably
Between 210-230 DEG C, between most preferably 215-225 DEG C.
The glass fiber reinforcement PET/ABS resin combination of a kind of high fluidity the most as claimed in claim 1
Thing, it is characterised in that described low-melting point PET resin, its intrinsic viscosity 0.55-0.95ml/g it
Between, between preferably 0.65-0.85ml/g, between most preferably 0.7-0.8ml/g.
The glass fiber reinforcement PET/ABS resin combination of a kind of high fluidity the most as claimed in claim 1
Thing, it is characterised in that described ABS resin is selected from acrylonitrile-butadiene-styrene copolymer, propylene
Nitrile-butadiene-propylene acid ester copolymer, MBS and acrylonitrile
At least one in-ethylene propylene diene rubber-styrol copolymer, preferably acrylonitrile-butadiene-styrene (ABS) copolymerization
Thing.
The glass fiber reinforcement PET/ABS resin combination of a kind of high fluidity the most as claimed in claim 1
Thing, it is characterised in that described toughener is ethylene-vinyl acetate, ethylene-methyl acrylate, ethylene
-ethyl acrylate, Ethylene-butyl acrylate, Low Density Polyethylene, maleic anhydride grafted ethene-octene are common
Polymers, ethylene-ethylacrylate-glycidyl ester copolymer, Ethylene-butyl acrylate-ethylene oxidic ester are common
At least one in polymers etc..
The glass fiber reinforcement PET/ABS resin combination of a kind of high fluidity the most as claimed in claim 1
Thing, it is characterised in that described glass fibre is alkali-free short glass fiber or continuous alkali-free glass fibre,
Wherein glass fiber diameter is 10-25 μm.
The glass fiber reinforcement PET/ABS resin combination of a kind of high fluidity the most as claimed in claim 1
Thing, it is characterised in that described antioxidant is pentaerythritol ester and phosphite ester, ratio of weight and number is 1:1.
The glass fiber reinforcement PET/ABS resin combination of a kind of high fluidity the most as claimed in claim 1
The preparation method of thing, it is characterised in that comprise the following steps:
(1) according to following components and weight portion content preparation raw material:
(2) double spiral shell will be entered after ABS resin, low-melting point PET resin, toughener, the even mixing of antioxidant
Bar extruder, in an extruder between position add glass fibre, processing technique is as follows: district's temperature 210-220
DEG C, two district's temperature 230-240 DEG C, three district's temperature 235-245 DEG C, four district's temperature 235-245 DEG C, five district's temperature
Spend 235-245 DEG C, six district's temperature 235-245 DEG C, seven district's temperature 240-250 DEG C, eight district's temperature 240-250
DEG C, nine district's temperature 230-240 DEG C；Engine speed 300-400 rev/min；
(3) discharging, cools down after extrusion, is dried, pelletizing, can prepare high fluidity of the present invention
Glass fiber reinforcement PET/ABS resin combination.
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| CN201610637902.5A CN106009554A (en) | 2016-08-05 | 2016-08-05 | High-fluidity glass fiber reinforced PET/ABS resin composition and preparation method thereof |
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| CN201610637902.5A CN106009554A (en) | 2016-08-05 | 2016-08-05 | High-fluidity glass fiber reinforced PET/ABS resin composition and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3889214A4 (en) * | 2018-11-26 | 2022-07-27 | Mitsubishi Engineering-Plastics Corporation | Thermoplastic resin composition and molded article |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101952366A (en) * | 2008-01-15 | 2011-01-19 | 沙伯基础创新塑料知识产权有限公司 | Moldable polyester compositions, processes of manufacture, and articles thereof |
| CN102134369A (en) * | 2011-02-24 | 2011-07-27 | 金发科技股份有限公司 | ABS (acrylonitrile butadiene styrene) /PET (polyethylene terephthalate) /copolyester ternary alloy and preparation method thereof |
| CN104987498A (en) * | 2015-04-02 | 2015-10-21 | 沈阳工业大学 | Low-melting point copolyester preparation method |
-
2016
- 2016-08-05 CN CN201610637902.5A patent/CN106009554A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101952366A (en) * | 2008-01-15 | 2011-01-19 | 沙伯基础创新塑料知识产权有限公司 | Moldable polyester compositions, processes of manufacture, and articles thereof |
| CN102134369A (en) * | 2011-02-24 | 2011-07-27 | 金发科技股份有限公司 | ABS (acrylonitrile butadiene styrene) /PET (polyethylene terephthalate) /copolyester ternary alloy and preparation method thereof |
| CN104987498A (en) * | 2015-04-02 | 2015-10-21 | 沈阳工业大学 | Low-melting point copolyester preparation method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3889214A4 (en) * | 2018-11-26 | 2022-07-27 | Mitsubishi Engineering-Plastics Corporation | Thermoplastic resin composition and molded article |
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Application publication date: 20161012 |