CN106543622A - Polyester is as flow improver additive in the purposes for improving enhancing ASA composition glossiness - Google Patents

Polyester is as flow improver additive in the purposes for improving enhancing ASA composition glossiness Download PDF

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Publication number
CN106543622A
CN106543622A CN201610914707.2A CN201610914707A CN106543622A CN 106543622 A CN106543622 A CN 106543622A CN 201610914707 A CN201610914707 A CN 201610914707A CN 106543622 A CN106543622 A CN 106543622A
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China
Prior art keywords
polyester
asa
purposes
flow improver
improver additive
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CN201610914707.2A
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Chinese (zh)
Inventor
陈志凤
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Kingfa Science and Technology Co Ltd
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陈志凤
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Priority to CN201610914707.2A priority Critical patent/CN106543622A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00Compositions 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
    • C08L51/003Compositions 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00Compositions 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
    • C08L51/04Compositions 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 rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/003Additives being defined by their diameter
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The invention discloses a kind of polyester strengthens the purposes of ASA composition glossiness as flow improver additive in raising.The present invention is found surprisingly that by research, it is added to polyester as flow improver additive in enhancing ASA compositions, mobility when strengthening the melting of ASA compositions can be significantly improved, make polyester resin that cortex is formed in injection moulding process, ASA and glass fiber material form core, so typical skin-core structure can effectively prevent glass from leaking outside and so that Injection moulded part surface presents higher gloss, so as to widen significantly polyester resin range of application in the market.

Description

Polyester is as flow improver additive in the purposes for improving enhancing ASA composition glossiness
Technical field
The present invention relates to the new application of polyester, more particularly to polyester are improving enhancing ASA compositions as flow improver additive The purposes of glossiness.
Background technology
ASA(ACM, acrylonitrile, styrol copolymer)With being easily worked, it is adapted to injection, extrusion molding, blowing Etc. various forming methods, and there is preferable comprehensive mechanical property, therefore be widely used in packaging, commodity, electronics electricity The fields such as device, toy, instrument, transport and machine manufacture.But for the structural fabrication of some high strengths requirements, such as refrigerator Catch, television frame and support base of television etc., ASA are difficult to meet mechanical property and dimensionally stable requirement.Generally adopt Mechanical performance is remarkably improved with fiberglass reinforced ASA, improves heat resistance, at the same can by reduce thermal linear expansion coefficient and Molding shrinkage, and then improve its dimensional stability.
There is on consumption market bloom effect appearance part to have visual aesthetic feeling, can more cause the favor of consumer, But in fiberglass reinforced product injection moulding process, there is glass flow orientation, there is obvious glass fibre flow liner, cause note Plastic surface has floating fibre leakage occur can affect Injection moulded part surface smoothness, greatly reduce surface gloss.And for outer For seeing product, it is desirable to which product surface is smooth, smooth, not existing defects.But, can not meet more than existing fiberglass reinforced ASA The appearance requirement of product, limits its application.
In the research that " floating fibre " phenomenon is eliminated, spraying is common place's science and engineering that plastic products are carried out with incrustation Skill.But spraying is present as environmental pollution, overall high cost, the long efficiency of production procedure are low, paint film is de- in transport and using existing Fall probability;In addition, existing researcher is developed from equipment and material prescription improves glass fiber reinforced materials surface, such as patent CN 103483761 A report a kind of fiber reinforcement ABS materials and preparation method thereof, and subsequent forming technique is molded for high-speed and high-temperature Technology(RHCM), obtain bloom fiber glass reinforced ABS product, but RHCM technical equipment input be big, high energy consumption, do not meet low-carbon (LC), The environmental protection concept of energy-saving and emission-reduction;Patent CN101469107 B discloses a kind of excellent surface, high flowing glass fiber reinforcement PBT/ ABS composites, improve surface effect and patent CN by adding substantial amounts of lubricant in single polyester system PBT 101864117 B are reported and are added small molecule plasticizer such as bisphenol-A pair in reinforced ABS system(Diphenyl phosphate), increase body It is that mobility reduces glass leakage to obtain excellent surface, but these lubricants or phosphate compound equimolecular quantity is low, hold Easily place and surface precipitation with product, there is hidden danger of quality, while glossiness is still less than 80 °, improvement is still undesirable; 103275454 A of patent CN anticipates glass microballoon using coupling agent and adds SAN in resin, improves ABS plastics Glossiness and intensity.But due to glass microballoon early stage activation process complicated and time consumption, and enhancing effect can not show a candle to glass, and application is received Limit.Therefore, how under the spraying or high-speed and high-temperature forming technique for avoiding high energy consumption, obtaining has good mechanical properties, height simultaneously The high fiberglass reinforced ASA products of dimensional stability and appearance glossiness, are industry facing technical barrier urgently to be resolved hurrily.
The content of the invention
To solve the above problems, it is an object of the invention to provide a kind of polyester is improving enhancing as flow improver additive The purposes of ASA composition glossiness.
0.6 ~ 1.5 dL/g of inherent viscosity of the polyester, preferably 0.7 ~ 1.0 dL/g, inherent viscosity is according to standard ISO 1638-5 is with phenol-carbon tetrachloride(3:2)As solvent using Ubbelohde viscometer test gained.
Preferably, the polyester is made up of the amorphism polyester of the crystalline polyester and 10-40wt% of 60-90wt%, excellent Polyester is selected to be made up of the amorphism polyester of the crystalline polyester and 15-30wt% of 70-85wt%.
The crystalline polyester is selected from polyethylene terephthalate, PTT, gathers to benzene two The mixing of one or more in formic acid butanediol ester, PEN, PBN;
The amorphism polyester is selected from Merlon, poly terephthalic acid 1,4- cyclohexane dicarboxylates, poly terephthalic acid second The mixing of one or more in diol ester -1,4 cyclohexane dimethanol ester.
The addition of the polyester is accounted for strengthens the 2 ~ 60% of ASA composition total weights, elect 10 ~ 40%, more preferably 20 as ~ 35%。
The enhancing ASA compositions also include ASA resin and reinforcing agent, wherein, the addition of reinforcing agent accounts for enhancing ASA groups The 5 ~ 40% of compound gross weight.
At 220 DEG C, the melt flow rate (MFR) under 10kg load-up conditions is 5~120g/10min to the ASA resin, preferably 8 ~ 40g/10min。
The one kind or several of the reinforcing agent in glass fibre, carbon fiber, talcum powder, wollastonite, whisker, glass microballoon The mixture planted, preferred glass fibre or carbon fiber, more preferably a diameter of 6 ~ 20 microns of glass fibre.
Enhancing ASA compositions of the present invention can be obtained by known method, comprised the following steps that:
In addition to reinforcing agent, each component is well mixed in high-speed stirred batch mixer, then the material being well mixed is placed in double In screw extruder, wherein reinforcing agent is fed system by side and is added, and the melting of Jing dual-screw-stem machines, extrusion, granulation are obtained final product.
Preferably, the feeding rotating speed of the double screw extruder is 200 ~ 350 rpm;Each section of screw rod of double screw extruder Temperature of the temperature from charge door to head is respectively preferably 220~250 DEG C of an area, two 220~270 DEG C of areas, and three areas 210~ 260 DEG C, four 210~260 DEG C of areas, five 210~260 DEG C of areas, 220~260 DEG C of die temperature, engine speed is 100~ 500r/min, vacuum are less than 0.1MPa.
The present invention compared with prior art, has the advantages that:
The present invention is found surprisingly that by research, is added to polyester as flow improver additive in enhancing ASA compositions, Ke Yixian Write and improve the mobility strengthened when ASA compositions are melted, make polyester resin that cortex, ASA and glass fibers are formed in injection moulding process Dimension material forms core, and so typical skin-core structure can effectively prevent glass from leaking outside, and so that Injection moulded part surface is in Reveal higher gloss, so as to widen significantly polyester resin range of application in the market.
Specific embodiment
The present invention is further illustrated below by specific embodiment, following examples are the present invention preferably embodiment party Formula, but embodiments of the present invention are not limited by following embodiments.
Raw material used in the present invention is as follows:
ASA1, ASA PW-997, Taiwan are very beautiful, melt flow rate (MFR) 5g/10min;
ASA2, Luran S 777K, Ben Ling companies, melt flow rate (MFR) 15g/10min;
Polyethylene terephtalate 1:Inherent viscosity is 0.8 dL/g,
Polyethylene terephtalate 2:Inherent viscosity is 0.6 dL/g,
Polycarbonate:Inherent viscosity is 1.2 dL/g,
Reinforcing agent, glass fibre, ECS13-4.5-534A, Tongxiang megalith, a diameter of 13 μm.
The preparation of the enhancing ASA compositions containing polyester:
In addition to reinforcing agent, each component is well mixed in high-speed stirred batch mixer by 1 proportioning of table, then by the thing being well mixed Material is placed in double screw extruder, and wherein reinforcing agent is fed system by side and added, and the melting of Jing dual-screw-stem machines, extrusion, granulation are obtained final product ASA compositions containing polyester, then Jing injection machines obtain product by injection mo(u)lding being not less than under 80 DEG C of mold temperatures, property Can the results are shown in Table shown in 1.
Wherein, the feeding rotating speed of the double screw extruder is 200 ~ 350 rpm;Each section of screw rod temperature of double screw extruder Temperature of the degree from charge door to head is respectively preferably 220~250 DEG C of an area, two 220~270 DEG C of areas, and three areas 210~ 260 DEG C, four 210~260 DEG C of areas, five 210~260 DEG C of areas, 220~260 DEG C of die temperature, engine speed is 100~ 500r/min, vacuum are less than 0.1MPa.
The testing standard of glossiness:ASTM D523, take 60 ° of angle test values, and glossiness is bigger, and it is more smooth to represent surface, Floating fibre is fewer.
Floating fibre:Surface floating fiber is assessed using square plate, model is observed in Quadratic Finite Element optical microphotograph Microscopic observation, by fine grade It is divided into 3 grades:
Grade 1:Surface is without floating fibre;
Grade 2:There is slight floating fibre on surface;
Grade 3:There is substantially floating fibre on surface;
The concrete proportioning and its test performance result of 1 each composition of 1 embodiment 1 ~ 14 of table and comparative example(Weight portion)
Can be seen that by 1 data of table and be added to polyester as flow improver additive in enhancing ASA compositions, effectively can prevent Only glass leakage, and cause Injection moulded part surface to present higher glossiness, especially crystalline polyester and amorphism are gathered The polyester of ester compounding composition is significantly improved to the glossiness on Injection moulded part surface as flow improver additive.

Claims (8)

1. polyester strengthens the purposes of ASA composition glossiness as flow improver additive in raising.
2. polyester according to claim 1 is improving enhancing ASA compositions pool degree as flow improver additive
Purposes, it is characterised in that the inherent viscosity of the polyester is 0.6 ~ 1.5 dL/g, preferably 0.7 ~ 1.0 dL/g, special Property viscosity is according to standard ISO 1638-5 with phenol-carbon tetrachloride 3:2 test gained using Ubbelohde viscometer as solvent.
3. polyester according to claim 1 strengthens the purposes of ASA composition glossiness as flow improver additive in raising, its It is characterised by, the polyester is made up of the amorphism polyester of the crystalline polyester and 10-40wt% of 60-90wt%, preferred polyester It is made up of the amorphism polyester of the crystalline polyester and 15-30wt% of 70-85wt%.
4. polyester according to claim 3 strengthens the purposes of ASA composition glossiness as flow improver additive in raising, its It is characterised by, the crystalline polyester is selected from polyethylene terephthalate, PTT, gathers to benzene two The mixing of one or more in formic acid butanediol ester, PEN or PBN, it is described Amorphism polyester is selected from Merlon, poly terephthalic acid 1,4- cyclohexane dicarboxylates, polyethylene terephthalate -1, The mixing of one or more in 4- cyclohexanedimethanoester esters.
5. polyester according to claim 1 strengthens the purposes of ASA composition glossiness as flow improver additive in raising, its It is characterised by, the addition of the polyester is accounted for and strengthens 2 ~ 60%, preferably 10 ~ 40%, more preferably the 20 of ASA composition total weights ~35%。
6. polyester according to claim 1 strengthens the purposes of ASA composition glossiness as flow improver additive in raising, its It is characterised by, the enhancing ASA compositions also include ASA resin and reinforcing agent, wherein, the addition of reinforcing agent accounts for enhancing ASA The 5 ~ 40% of composition total weight.
7. polyester according to claim 6 strengthens the purposes of ASA composition glossiness as flow improver additive in raising, its It is characterised by, at 220 DEG C, the melt flow rate (MFR) under 10kg load-up conditions is 5~120g/10min to the ASA resin, preferably 8 ~40g/10min。
8. polyester according to claim 6 strengthens the purposes of ASA composition glossiness as flow improver additive in raising, its Be characterised by, the reinforcing agent selected from glass fibre, carbon fiber, talcum powder, wollastonite, whisker, the one kind in glass microballoon or Several mixtures, preferred glass fibre or carbon fiber, more preferably a diameter of 6 ~ 20 microns of glass fibre.
CN201610914707.2A 2016-10-20 2016-10-20 Polyester is as flow improver additive in the purposes for improving enhancing ASA composition glossiness Pending CN106543622A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106566158A (en) * 2016-10-25 2017-04-19 谢湘 Reinforced ASA composition and application thereof
WO2018072583A1 (en) * 2016-10-20 2018-04-26 金发科技股份有限公司 Use of polyester as flow promoter for increasing gloss of enhanced aromatic vinyl copolymer composition
CN107974020A (en) * 2016-10-25 2018-05-01 金发科技股份有限公司 A kind of reinforced aromatic vinyl copolymer compositions and its application
CN110079062A (en) * 2019-03-29 2019-08-02 苏州威瑞成新材料有限公司 A kind of high rigidity weather resistant PC T/ASA alloy

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CN101875772A (en) * 2010-07-14 2010-11-03 深圳市科聚新材料有限公司 Glass fiber reinforced PC composite material and preparation method thereof
CN104672846A (en) * 2013-11-28 2015-06-03 上海杰事杰新材料(集团)股份有限公司 Glass fiber reinforced polycarbonate (PC) composite material and preparation method thereof
CN105264017A (en) * 2013-06-04 2016-01-20 沙特基础全球技术有限公司 Blended thermoplastic compositions with improved impact strength and flow

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
WO2010003914A1 (en) * 2008-07-09 2010-01-14 Lanxess Deutschland Gmbh Thermoplastics having improved flow
CN101875772A (en) * 2010-07-14 2010-11-03 深圳市科聚新材料有限公司 Glass fiber reinforced PC composite material and preparation method thereof
CN105264017A (en) * 2013-06-04 2016-01-20 沙特基础全球技术有限公司 Blended thermoplastic compositions with improved impact strength and flow
CN104672846A (en) * 2013-11-28 2015-06-03 上海杰事杰新材料(集团)股份有限公司 Glass fiber reinforced polycarbonate (PC) composite material and preparation method thereof

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018072583A1 (en) * 2016-10-20 2018-04-26 金发科技股份有限公司 Use of polyester as flow promoter for increasing gloss of enhanced aromatic vinyl copolymer composition
CN106566158A (en) * 2016-10-25 2017-04-19 谢湘 Reinforced ASA composition and application thereof
CN107974020A (en) * 2016-10-25 2018-05-01 金发科技股份有限公司 A kind of reinforced aromatic vinyl copolymer compositions and its application
CN110079062A (en) * 2019-03-29 2019-08-02 苏州威瑞成新材料有限公司 A kind of high rigidity weather resistant PC T/ASA alloy

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Effective date of registration: 20190701

Address after: 510663 Guangzhou science and Technology Development Zone, Guangdong, China, 33

Applicant after: Kingfa Technology Co., Ltd.

Address before: 510635 No. 69, Longkou West Road, Tianhe District, Guangzhou City, Guangdong Province, 602

Applicant before: Chen Zhifeng

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