CN106566159A - Application of polyamide acting as flow accelerant in improving glossiness of reinforced ASA composite - Google Patents
Application of polyamide acting as flow accelerant in improving glossiness of reinforced ASA composite Download PDFInfo
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- CN106566159A CN106566159A CN201610950633.8A CN201610950633A CN106566159A CN 106566159 A CN106566159 A CN 106566159A CN 201610950633 A CN201610950633 A CN 201610950633A CN 106566159 A CN106566159 A CN 106566159A
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- Prior art keywords
- polyamide
- asa
- compositionss
- glossiness
- strengthens
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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
-
- 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
-
- 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
-
- 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
- B29C2948/92514—Pressure
-
- 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
- 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
-
- 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)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an application of polyamide acting as a flow accelerant in improving the glossiness of a reinforced ASA composite. Through research, an unexpected finding is that after polyamide acting as the flow accelerant is added to the reinforced ASA composite, the fluidity of the reinforced ASA composite during fusion can be improved significantly, polyamide resin forms a skin layer in an injection molding process, and ASA and a glass fiber material form a core material, so a typical skin-core structure can effectively prevent glass fiber from leaking outside, the surface of an injection molding piece presents superior luster, and the application scope of the polyamide resin in the market is widened substantially.
Description
Technical field
The present invention relates to the new application of polyamide, more particularly to polyamide are improving enhancing ASA groups as flow improver additive
The purposes of compound glossiness.
Background technology
ASA（Acrylate rubber, acrylonitrile, styrol copolymer）With being easily worked, it is adapted to injection, extrusion molding, blowing
Etc. various forming methods, and with preferable comprehensive mechanical property, therefore it is widely used in packaging, article of everyday use, 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., common ASA is difficult to meet mechanical property and dimensionally stable requirement.It is logical
Mechanical performance is remarkably improved frequently with fiberglass reinforced ASA, improves heat resistance, while can be by reducing linear thermal expansion system
Number and molding shrinkage, and then improve its dimensional stability.
There is bloom effect appearance part to have visual aesthetic feeling on consumption market, can more cause the favor of consumer,
But there are problems that glass flow orientation in fiberglass reinforced product injection moulding process, and 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 incrustation is carried out to plastic
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 high-speed and high-temperature molding
Technology（RHCM）, obtain bloom fiber glass reinforced ABS product, but RHCM technical equipment input is 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, by adding, substantial amounts of lubricant improves surface effect and the B of patent CN 101864117 is reported and increased
Add small molecule plasticizer such as bisphenol-A in strong ABS systems double（Diphenyl phosphate）, increase system mobility and reduce glass and leak outside
Excellent surface is obtained, but these lubricants or phosphate compound equimolecular quantity are low, easily place and surface precipitation with product,
There is hidden danger of quality, while glossiness is still less than 80 °, improvement is still undesirable；The A of patent CN 103275454 is utilized
Coupling agent is anticipated glass microballoon and SAN is added in resin, improves the glossiness and intensity of ABS plastics.But due to glass
Microballon early stage activation processing complicated and time consumption, and reinforced effects can not show a candle to glass, application is limited.Therefore, how high energy consumption is being avoided
Spraying or high-speed and high-temperature forming technique under, obtain has good mechanical properties, high-dimensional stability and appearance glossiness high simultaneously
Fiberglass reinforced modified rubber ASA products, be industry facing and 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 polyamide is improving enhancing as flow improver additive
The purposes of ASA compositionss glossiness.
Between 1.0-3.4, between preferred 1.6-2.7, relative viscosity is according to standard for the relative viscosity of the polyamide
ISO307 is using the concentrated sulphuric acid of 96% concentration as solvent using Ubbelohde viscometer test gained.
Preferably, the polyamide is by the crystallinity polyamide of 60-90wt% and the amorphism polyamide group of 10-40wt%
Into preferred polyamide is made up of the crystallinity polyamide of 70-85wt% and the amorphism polyamide of 15-30wt%.
The crystallinity polyamide selected from polysebacate decamethylenediamineand (nylon 1010), nylon 11 (nylon 11), poly- ten
Diamides (nylon 12), polycaprolactam (nylon 6), polyhexamethylene sebacamide (NYLON610), nylon 612
One kind in (nylon 612), polyhexamethylene adipamide (nylon66 fiber), poly-caprylamide (nylon 8), poly- 9 aminononanoic acid (nylon 9)
Or several mixing.
The amorphism polyamide is selected from poly- paraphenylene terephthalamide's trimethylhexane diamine, poly- heptamethylene diamine 3- tertiary butyl adipic acids
In one or both mixing.
The addition of the polyamide is accounted for strengthens the 2 ~ 60%, preferably 10 ~ 40% of ASA composition total weights, more preferably
15~30%。
The enhancing ASA compositionss 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, Pulvis Talci, 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 compositionss of the present invention can be obtained by known method, be comprised the following steps that：
In addition to reinforcing agent, by each component in high-speed stirred batch mixer mix homogeneously, then the material of mix homogeneously is placed in double
In screw extruder, wherein reinforcing agent is fed system and is added by side, and the melting of Jing dual-screw-stem machines, extrusion, pelletize is 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 is 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 polyamide as flow improver additive in enhancing ASA compositionss, can be with
Mobility when strengthening the melting of ASA compositionss is significantly improved, makes polyamide that cortex, ASA and glass are formed in injection moulding process
Glass fibrous material forms core, and so typical skin-core structure can effectively prevent glass from leaking outside, and causes Injection moulded part table
Face presents higher gloss, so as to widen polyamide range of application in the market significantly.
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 is very beautiful, melt flow rate (MFR) 5g/10min；
ASA2, Luran S 777K, Ben Ling companies, melt flow rate (MFR) 15g/10min；
PA6（1）：Relative viscosity 2.5；
PA6（2）：Relative viscosity 1.2；
Poly- paraphenylene terephthalamide's trimethylhexane diamine（Transparent nylon）：Relative viscosity 2.7；
Reinforcing agent, glass fibre, ECS13-4.5-534A, Tongxiang megalith, a diameter of 13 μm；
The preparation of the enhancing ASA compositionss containing polyamide：
In addition to reinforcing agent, by the proportioning of table 1 by each component the mix homogeneously in high-speed stirred batch mixer, then by the thing of mix homogeneously
Material is placed in double screw extruder, and wherein reinforcing agent is fed system and added by side, and the melting of Jing dual-screw-stem machines, extrusion, pelletize is obtained final product
ASA compositionss containing polyamide, then Jing injection machines obtain product by injection mo(u)lding being not less than under 80 DEG C of mold temperatures,
Results of property is shown in Table 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 is less than 0.1MPa.
The testing standard of glossiness：ASTM D523, take 60 ° of angle test values.
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 each composition of 1 embodiment of table 1 ~ 14（Weight portion）
Can be seen that by the data of table 1 and be added to polyamide as flow improver additive in ASA enhancing composition, can be effective
Prevent glass from leaking outside, and cause Injection moulded part surface to present higher glossiness, especially by crystallinity polyamide and noncrystalline
Property polyamide compounding composition polyamide the glossiness on Injection moulded part surface is significantly improved as flow improver additive.
Claims (8)
1. polyamide strengthens the purposes of ASA compositionss glossiness as flow improver additive in raising.
2. polyamide according to claim 1 is improving enhancing ASA compositionss gloss as flow improver additive
The purposes of degree, it is characterised in that the relative viscosity of the polyamide between 1.0-3.4, between preferred 1.6-2.7, phase
Gained is tested using Ubbelohde viscometer as solvent using the concentrated sulphuric acid of 96% concentration according to standard ISO307 to viscosity.
3. polyamide according to claim 1 strengthens the purposes of ASA compositionss glossiness as flow improver additive in raising,
Characterized in that, the polyamide is made up of the crystallinity polyamide of 60-90wt% and the amorphism polyamide of 10-40wt%,
Preferred polyamide is made up of the crystallinity polyamide of 70-85wt% and the amorphism polyamide of 15-30wt%.
4. polyamide according to claim 3 strengthens the purposes of ASA compositionss glossiness as flow improver additive in raising,
Characterized in that, the crystallinity polyamide is selected from polysebacate decamethylenediamineand, nylon 11, poly-lauramide, polycaprolactam
In amine, polyhexamethylene sebacamide, nylon 612, polyhexamethylene adipamide, poly-caprylamide, poly- 9 aminononanoic acid
The mixing of one or more；The amorphism polyamide is special selected from poly- paraphenylene terephthalamide's trimethylhexane diamine, poly- heptamethylene diamine 3-
The mixing of the one or both in butyl adipic acid.
5. polyamide according to claim 1 strengthens the purposes of ASA compositionss glossiness as flow improver additive in raising,
Characterized in that, the addition of the polyamide is accounted for strengthens the 2 ~ 60%, preferably 10 ~ 40% of ASA composition total weights, more preferably
For 15 ~ 30%.
6. polyamide according to claim 1 strengthens the purposes of ASA compositionss glossiness as flow improver additive in raising,
Characterized in that, the enhancing ASA compositionss also include ASA resin and reinforcing agent, wherein, the addition of reinforcing agent accounts for enhancing
The 5 ~ 40% of ASA composition total weights.
7. polyamide according to claim 6 strengthens the purposes of ASA compositionss glossiness as flow improver additive in raising,
Characterized in that, the ASA resin is at 220 DEG C, the melt flow rate (MFR) under 10kg load-up conditions is 5～120g/10min, excellent
Select 8 ~ 40g/10min.
8. polyamide according to claim 6 strengthens the purposes of ASA compositionss glossiness as flow improver additive in raising,
Characterized in that, the one kind of the reinforcing agent in glass fibre, carbon fiber, Pulvis Talci, wollastonite, whisker, glass microballoon
Or several mixture, preferred glass fibre or carbon fiber, more preferably a diameter of 6 ~ 20 microns of glass fibre.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610950633.8A CN106566159A (en) | 2016-10-27 | 2016-10-27 | Application of polyamide acting as flow accelerant in improving glossiness of reinforced ASA composite |
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| CN201610950633.8A CN106566159A (en) | 2016-10-27 | 2016-10-27 | Application of polyamide acting as flow accelerant in improving glossiness of reinforced ASA composite |
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| CN106566159A true CN106566159A (en) | 2017-04-19 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018076968A1 (en) * | 2016-10-27 | 2018-05-03 | 金发科技股份有限公司 | Use of polyamide as flow promoter to increase glossiness of reinforced aromatic vinyl copolymer composition |
| CN109486147A (en) * | 2018-10-14 | 2019-03-19 | 金旸（厦门）新材料科技有限公司 | A kind of anti-wire drawing fire retardation PC-ASA alloy and preparation method thereof |
| CN112646361A (en) * | 2020-12-14 | 2021-04-13 | 上海金发科技发展有限公司 | Highlight black spraying-free PA/ASA composition and preparation method thereof |
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| CN101508839A (en) * | 2008-02-13 | 2009-08-19 | 尤尼蒂卡株式会社 | Glass fiber reinforced polyamide resin composition |
| CN102206411A (en) * | 2010-03-30 | 2011-10-05 | E.I.内穆尔杜邦公司 | Flame-retardant polyamide resin composition and products containing same |
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| CN104693785A (en) * | 2015-03-20 | 2015-06-10 | 苏州威瑞成新材料有限公司 | Low-water absorption enhanced PA/ASA alloy |
| CN105143350A (en) * | 2013-04-16 | 2015-12-09 | 东洋纺株式会社 | Glass fiber-reinforced polyamide resin composition |
| CN108003548A (en) * | 2016-10-27 | 2018-05-08 | 金发科技股份有限公司 | Polyamide is improving the purposes of reinforced aromatic vinyl copolymer compositions glossiness as flow improver additive |
-
2016
- 2016-10-27 CN CN201610950633.8A patent/CN106566159A/en active Pending
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| CN101508839A (en) * | 2008-02-13 | 2009-08-19 | 尤尼蒂卡株式会社 | Glass fiber reinforced polyamide resin composition |
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Non-Patent Citations (1)
| Title |
|---|
| 索延辉 等: "《ABS树脂生产实践及应用》", 31 May 2015 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018076968A1 (en) * | 2016-10-27 | 2018-05-03 | 金发科技股份有限公司 | Use of polyamide as flow promoter to increase glossiness of reinforced aromatic vinyl copolymer composition |
| CN109486147A (en) * | 2018-10-14 | 2019-03-19 | 金旸（厦门）新材料科技有限公司 | A kind of anti-wire drawing fire retardation PC-ASA alloy and preparation method thereof |
| CN112646361A (en) * | 2020-12-14 | 2021-04-13 | 上海金发科技发展有限公司 | Highlight black spraying-free PA/ASA composition and preparation method thereof |
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