CN1098896C - High-toughness polyphenylether/polyamide composition and its preparing process - Google Patents
High-toughness polyphenylether/polyamide composition and its preparing process Download PDFInfo
- Publication number
- CN1098896C CN1098896C CN98117713A CN98117713A CN1098896C CN 1098896 C CN1098896 C CN 1098896C CN 98117713 A CN98117713 A CN 98117713A CN 98117713 A CN98117713 A CN 98117713A CN 1098896 C CN1098896 C CN 1098896C
- Authority
- CN
- China
- Prior art keywords
- toughness
- polyphenylether
- polyamide composition
- ppo
- nylon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
The present invention relates to an elastomeric composition with high toughness, which is prepared from polyphenylether (5 to 75 wt%), polyamide (10 to 85 wt%) and functional rubber (5 to 50 wt %) which are processed by melting blending granulation and melting injection molding. The prepared composition has high toughness and high specific elongation.
Description
The present invention relates to relevant high-toughness polyphenylether (PPO), polyamide (PA) or claim nylon and the prescription and the preparation thereof of the blend alloy that rubber elastomer is formed.
The prescription of PPO and PA blend alloy has had United States Patent (USP) U.S.Pat.No.3, and 379,792 and 4,338,421, the report of Japanese Patent No.997/1970, they disclose, and can improve the processing characteristics of PPO and the thermotolerance and the chemically-resistant solvent of raising blend with polymeric amide.But above-mentioned blend is not because fragility has practicality.
European patent EP 255,184 and U.S. GE company at the patent announcement of China registration numbers 1141319, adopt vinylaromatic hydrocarbon (as polystyrene PS) and conjugated dienes (as divinyl, isoprene etc. and derivative thereof, through hydrogenation or not hydrogenation) through the segmented copolymer of functionalized composition, can improve the toughness of PPO/PA blend alloy.
United States Patent (USP) U.S.Pat.4,315,086, U.S.Pat.4,654,405 and international applications patent PCT/US86/01511, once disclose the toughness that adopts functionalized polyphenylene ether and polymeric amide and impact modifying agent such as SBS can improve the PPO/PA blend alloy.
International applications patent WO88/08433 disclose to adopt functionalized polyphenylene ether and the first blend of functionalized ethylene-propylene rubber (m-EPR), then with this blend again with nylon 6 mixing, can improve the notched Izod impact strength of blend greatly.Here functionalized is necessary.But because PPO and elastomerics all need to carry out functionalized processing respectively, it operates relative complex.
The present invention has overcome the complicacy of operating in the prior art, and proposes a kind of high-toughness polyphenylether/polyamide/functionalized rubber elastic composition and its preparation method.
The component of high-toughness polyphenylether/polyamide of the present invention/functionalized rubber elastic composition and prescription are as table 1 (the following meter of percentage ratio by weight): table 1
Component concentration scope (Wt.%)
Polyphenylene oxide 5～75 is preferably in 5～50
Polymeric amide 85～10 is preferably in 80～20 functionalised polyolefin elastomericss 5～50
The molecular structural formula of polyphenylene oxide (PPO) is as follows:
R wherein
2And R
6Can be alkyl, as methyl, ethyl, propyl group etc., also can be phenyl or the halohydrocarbon be made up of fluorine, chlorine, bromine, iodine, can also one of them be the H atom.R
3And R
5Can be the H atom, also can be methyl.Work as R
2, R
6And R
5Be H atomic time, R
3Be that methyl is exactly the 3-methyl isophthalic acid, 4 polyphenylene oxide.Being with halohydrocarbon mainly is to make polyphenylene oxide have more flame retardant resistance.N is the polymerization degree.Here used PPO, the n value is at least more than 50.
Above-mentioned polymeric amide (PA nylon) can be nylon 6, nylon 66, nylon 46, NYLON610 and other general nylon-type superpolymer that uses etc., but two amidos wherein must be excessive.Its number-average molecular weight from 15,000 to 40,000.
Above-mentioned functionalised polyolefin rubber elastomer can be second-third rubber (EPR), ethylene-octene copolymer rubber (POE), also can be ethylene-propylene-dienes copolymer rubber elastomerics (EPDM).Wherein best with EPDM.These elastomericss must pass through functionalized processing, and its reactive group can be carboxylic-acid such as fumaric acid etc., acid anhydrides such as maleic anhydride etc., can also be epoxide group etc.The preparation method of PPO/PA/ elastic composition:
It is that step is carried out in the following order: 1. melt blending extruding pelletization
The blend granulation can adopt granulation stage by stage and two kinds of methods of disposable granulation to carry out.(1) segmentation comminution granulation: by the blend overall weight percent PPO 5～75 (or nylon 10～85) can be changed elastomerics 5～50 with the palace and carry out the melt blending extruding pelletization at 230-285 ℃, then above-mentioned pellet is carried out the melt blending extruding pelletization with nylon 10～85 (or PPO 5～75) at 230-285 ℃ again, obtain the blend pellet.(2) disposable comminution granulation: be with PPO, nylon and three components of functionalized elastomeric body together by weight percentage ratio 5～75: 10～85: 5～50 (be preferably 5～50: 20～80: 5～50) carry out the disposable granulation that melt extrudes, obtain the blend pellet at 240-285 ℃.
The blend extruding pelletization adopts twin screw extruder, also can adopt single screw extrusion machine.2. fusion injection moulding
With the above-mentioned blend pellet that obtains, at 240-285 ℃, injection pressure 6-8MPa, die temperature is 70-90 ℃, is injected into sample or parts with injection moulding machine.
High-toughness polyphenylether/polyamide of the present invention/functionalised polyolefin elastomerics can obtain the blend alloy of high tenacity, high-elongation.Performance sees Table 2.Table 2
| Example | PPO (％) | PA-6 (％) | m-EPDM (％) | Tensile strength (MPa) | Elongation at break (%) | Bending strength (MPa) | Composite bending modulus (MPa) | Brinell hardness (HB) | 23 ℃ of Izod notched Izod impact strength (J/m) |
| 4 | 5 | 80 | 15 | 62 | 440 | 50 | 1200 | 6.2 | 460 |
| 5 | 10 | 75 | 15 | 64 | 450 | 40 | 1020 | 6.5 | 640 |
| 6 | 50 | 35 | 15 | 36 | 100 | 50 | 1012 | 5.5 | 230 |
| 7 | 75 | 10 | 15 | 40 | 72 | 80 | 1420 | 5.5 | 60 |
| 8 | 10 | 85 | 5 | 62 | 410 | 64 | 1327 | - | 92 |
| 9 | 10 | 70 | 20 | 47 | 373 | 44 | 864 | - | 790 |
| 10 | 10 | 40 | 50 | 16 | 152 | 9 | 153 | - | 463 |
| 11 | 30 | 50 | 20 | 46 | 349 | 45 | 854 | - | 676 |
| 12 | 30 | 20 | 50 | 14 | 70 | 10 | 165 | - | 293 |
The sample of following blend prescription and preparation carries out mechanics performance determining by the ASTM standard.Adopt the tensile strength and the tension set of D-638 standard test sample; Adopt the bending strength and the modulus of D-790 standard test sample; Adopt socle girder (Izod) notched Izod impact strength of D-256 standard test sample; Adopt the Brinell hardness number of homemade PHB-625 type engineering plastics sclerometer working sample.
Used PPO is 2,6 dimethyl-1,4 polyphenylene oxide in all Formulation Examples, and polymeric amide is a nylon 6, and EPDM is through the toxilic acid anhydridization with the EPR elastomerics that is used for comparison.
Embodiment 1(Comparative Examples)
After PPO powder and nylon 6 pellet dryings, be 10: 90 by PPO/ nylon 6 weight ratios, carry out the blend granulation at SHJ-30 type twin screw extruder.Screw diameter is 30mm, and length-to-diameter ratio is 23.2, and rotating speed is 50 rev/mins.Barrel temperature is respectively 240,270,285 and 285 ℃ from the 1-4 section.
After the above-mentioned blend pellet drying that obtains, on SZ-160/80 type injection moulding machine, be injected into standard model, the condition of barrel temperature and extruding pelletization is together.The mould temperature is 80 ℃, and injection pressure is 7MPa, injection cycle 40 seconds, pressurize 20 seconds.Sample after the injection in moisture eliminator 23 ℃ deposit more than 40 hours, carry out mechanics performance determining again.It the results are shown in Table 3.
Embodiment 2(Comparative Examples)
With PPO and nylon 6 weight ratios is 20: 80 material, prepares sample and carries out performance measurement by the processing condition of embodiment 1.It the results are shown in Table 3.
Embodiment 3(Comparative Examples)
With PPO and nylon 6 weight ratios is 30: 70 material, prepares sample and carries out performance measurement by the processing condition of embodiment 1.It the results are shown in Table 3.Table 3 is the mechanical property of toughening modifying PPO/PA-6 blend alloy not
With the pure nylon 6 of embodiment 1 same process condition preparation be 40 (J/m) 23 ℃ Izod notched Izod impact strength, and pure PPO is 39 (J/m).
| Example | PPO (％) | PA (％) | Tensile strength (MPa) | Bending strength (MPa) | Composite bending modulus (MPa) | Hardness (HB) | 23 ℃ of Izod notched Izod impact strength (J/m) |
| 1 | 10 | 90 | 71 | 72 | 1456 | 7.6 | 63 |
| 2 | 20 | 80 | 73 | 76 | 1586 | 8.8 | 32 |
| 3 | 30 | 70 | 73 | 78 | 1620 | 8.4 | 32 |
By last explanation, not adding toughner, to remove the PPO/PA-6 proportioning be that 10: 90 shock strength is slightly higher than pure PPO and pure nylon, and other proportioning is all low than pure component.In a word, blend alloy is crisp.
Embodiment 4
With PPO, nylon 6 and m-EPDM proportioning is to carry out disposable blend granulation at 5: 80: 15, is injected into standard model then.The processing condition of granulation and injected sample and embodiment 1 are together.Results of property sees Table 2.
Embodiment 5
With PPO, nylon 6 and m-EPDM proportioning is to carry out disposable blend granulation (embodiment 4) at 10: 75: 15, and carries out granulation, is injection molded into sample and carries out performance measurement by the processing condition of embodiment 1.The results are shown in Table 2.
Embodiment 6
With PPO, nylon 6 and m-EPDM proportioning is to carry out disposable blend granulation (embodiment 4) at 50: 35: 15, and carries out granulation, is injection molded into sample and carries out performance measurement by the processing condition of embodiment 1.The results are shown in Table 2.
Embodiment 7
With PPO, nylon 6 and m-EPDM proportioning is to carry out disposable blend granulation (embodiment 4) at 75: 10: 15, and carries out granulation, is injection molded into sample and carries out performance measurement by the processing condition of embodiment 1.The results are shown in Table 2.
Embodiment 8
With PPO, nylon 6 and m-EPDM proportioning is to carry out disposable blend granulation (embodiment 4) at 10: 85: 5, and carries out granulation, is injection molded into sample and carries out performance measurement by the processing condition of embodiment 1.The results are shown in Table 2.
Embodiment 9
With PPO, nylon 6 and m-EPDM proportioning is to carry out disposable blend granulation (embodiment 4) at 10: 70: 20, and carries out granulation, is injection molded into sample and carries out performance measurement by the processing condition of embodiment 1.The results are shown in Table 2.
Embodiment 10
With PPO, nylon 6 and m-EPDM proportioning is to carry out disposable blend granulation (embodiment 4) at 10: 40: 50, and carries out granulation, is injection molded into sample and carries out performance measurement by the processing condition of embodiment 1.The results are shown in Table 2.
Embodiment 11
With PPO, nylon 6 and m-EPDM proportioning is to carry out disposable blend granulation (embodiment 4) at 30: 50: 20, and carries out granulation, is injection molded into sample and carries out performance measurement by the processing condition of embodiment 1.The results are shown in Table 2.
Embodiment 12
With PPO, nylon 6 and m-EPDM proportioning is to carry out disposable blend granulation (embodiment 4) at 30: 20: 50, and carries out granulation, is injection molded into sample and carries out performance measurement by the processing condition of embodiment 1.The results are shown in Table 2.
By table 2 explanation, elastomer content is in 5%～50% toughness that can improve blend alloy, and its elongation at break is also high.But too high not only shock strength of elastomer content and elongation at break descend, and other mechanical properties are lowered.
Embodiment 13
With PPO, nylon 6 and elastomerics m-EPR proportioning is to carry out disposable blend granulation (embodiment 4) at 5: 80: 15, and carries out granulation, is injection molded into the sample of blend alloy and carries out performance measurement by the processing condition of embodiment 1.Its result compares with the PPO/ nylon blending alloy (embodiment 4) that identical proportioning, same process condition are made up of the m-EPDM elastomerics.See Table 4.
Embodiment 14
With PPO, nylon 6 and elastomerics m-EPR proportioning is to carry out disposable blend granulation (embodiment 4) at 10: 75: 15, and carries out granulation, is injection molded into the sample of blend alloy and carries out performance measurement by the processing condition of embodiment 1.Its result compares with the PPO/ nylon blending alloy (embodiment 5) that identical proportioning, same process condition are made up of the m-EPDM elastomerics.See Table 4.
Embodiment 15
With PPO, nylon 6 and elastomerics m-EPR proportioning is to carry out disposable blend granulation (embodiment 4) at 50: 35: 15, and carries out granulation, is injection molded into the sample of blend alloy and carries out performance measurement by the processing condition of embodiment 1.Its result compares with the PPO/ nylon blending alloy (embodiment 6) that identical proportioning, same process condition are made up of the m-EPDM elastomerics.See Table 4.The mechanical property that the different elastomericss of table 4 (content is fixed as 15%) are formed blend alloy compares
| Example | PPO ％ | PA-6 ％ | M-elastomerics 15% | Tensile strength (MPa) | Elongation at break (%) | Bending strength (MPa) | Composite bending modulus (MPa) | Brinell hardness (HB) | 23 ℃ of Izod notched Izod impact strength (J/m) |
| 13 4 | 5 | 80 | m-EPR m-EPDM | 62 62 | 435 440 | 58 50 | 1300 1200 | 5.9 6.2 | 98 460 |
| 14 5 | 10 | 75 | m-EPR m-EPDM | 61 64 | 455 450 | 46 40 | 1125 1020 | 6.6 6.5 | 127 640 |
| 15 6 | 50 | 35 | m-EPR m-EPDM | 55 36 | 120 100 | 56 50 | 1092 1012 | 5.4 5.5 | 88 230 |
Find out by table 4, better with m-EPDM MODIFIED PP O/ blend of nylon effect than m-EPR, good toughness not only, other performance difference is very not big yet.
Claims (6)
1. high-toughness polyphenylether/polyamide composition is characterized in that described composition comprises following component and content (weight percentage):
Polyphenylene oxide 5～75
Polymeric amide 85～10
Functionalised polyolefin elastomerics 5～50
2. high-toughness polyphenylether/polyamide composition according to claim 1 is characterized in that described composition comprises following component and content (weight percentage):
Polyphenylene oxide 5～50
Polymeric amide 80～20
Functionalised polyolefin elastomerics 5～50
3. high-toughness polyphenylether/polyamide composition according to claim 1 is characterized in that described polyphenylene oxide is 2,6 dimethyl-1,4 polyphenylene oxide.
4. high-toughness polyphenylether/polyamide composition according to claim 1 is characterized in that described polymeric amide is a nylon 6.
5. high-toughness polyphenylether/polyamide composition according to claim 1 is characterized in that described functionalised polyolefin elastomerics is toxilic acid anhydridization second-propylene-dienes ternary alkene class rubbery copolymer m-EPDM or toxilic acid anhydridization ethylene-propylene rubber multipolymer m-EPR.
6. the preparation method of high-toughness polyphenylether/polyamide composition according to claim 1 is characterized in that step is carried out in the following order:
(1) disposable melt blending extruding pelletization:
The percentage ratio meter is with polyphenylene oxide by weight: polymeric amide: the functionalised polyolefin elastomerics is 5～50: 80～20: 5～50 carry out the melt blending extruding pelletization at 240-285 ℃ with screw extrusion press, obtain the blend pellet,
(2) fusion injection moulding:
With above-mentioned blend pellet, be that 6-8MPa and Mo Wen are 70-90 ℃ at 240-285 ℃, injection pressure, be injected into sample or parts with injection moulding machine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98117713A CN1098896C (en) | 1998-08-31 | 1998-08-31 | High-toughness polyphenylether/polyamide composition and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98117713A CN1098896C (en) | 1998-08-31 | 1998-08-31 | High-toughness polyphenylether/polyamide composition and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1246499A CN1246499A (en) | 2000-03-08 |
| CN1098896C true CN1098896C (en) | 2003-01-15 |
Family
ID=5225658
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98117713A Expired - Fee Related CN1098896C (en) | 1998-08-31 | 1998-08-31 | High-toughness polyphenylether/polyamide composition and its preparing process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1098896C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101225214B (en) * | 2007-11-08 | 2010-04-14 | 上海交通大学 | Toughening modifying method for polyphenyl ether/nylon 6 alloy |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1879963B1 (en) * | 2005-05-12 | 2018-01-03 | JTEKT Corporation | Polyamide resin composition |
| CN103642191A (en) * | 2013-11-25 | 2014-03-19 | 常熟市蓝天新材料科技有限公司 | Antibacterial toughening modified polyphenyl ether alloy material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4315086A (en) * | 1979-08-08 | 1982-02-09 | Sumitomo Chemical Company, Limited | Resin compositions |
| WO1988008433A1 (en) * | 1987-04-24 | 1988-11-03 | Allied-Signal Inc. | Compositions of polyphenylene oxides and thermoplastic polymers |
| CN1141319A (en) * | 1995-06-07 | 1997-01-29 | 通用电气公司 | Compositions containing polyphenylene other and polyamide resins, which exhibit improved impact strength |
-
1998
- 1998-08-31 CN CN98117713A patent/CN1098896C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4315086A (en) * | 1979-08-08 | 1982-02-09 | Sumitomo Chemical Company, Limited | Resin compositions |
| WO1988008433A1 (en) * | 1987-04-24 | 1988-11-03 | Allied-Signal Inc. | Compositions of polyphenylene oxides and thermoplastic polymers |
| CN1141319A (en) * | 1995-06-07 | 1997-01-29 | 通用电气公司 | Compositions containing polyphenylene other and polyamide resins, which exhibit improved impact strength |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101225214B (en) * | 2007-11-08 | 2010-04-14 | 上海交通大学 | Toughening modifying method for polyphenyl ether/nylon 6 alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1246499A (en) | 2000-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1134507C (en) | Conductive polyphenylene ether-polyamide compositions and method for their preparation | |
| EP0262901B1 (en) | Thermoplastic resin composition | |
| CA2017563C (en) | Shaped resin article | |
| CN101104732A (en) | Nylon/acrylonitrile-butadiene-styrene resin mixing material | |
| EP0373900A2 (en) | Polyphenylene ether resin composition | |
| CN1962759A (en) | Process for preparing polycarbonate/styrene-acrylonitrile copolymer alloy | |
| CN102002233A (en) | Mixture for preparing nylon nano composite material and preparation method of composite material | |
| JP2002544308A (en) | Conductive composition whose volume resistivity is controlled by its composition | |
| CN1098896C (en) | High-toughness polyphenylether/polyamide composition and its preparing process | |
| EP0574229B1 (en) | Thermoplastic resin composition and molded article | |
| CN102807749A (en) | Polyphenyl ether/nylon/graphene compound material | |
| JP3185193B2 (en) | Resin composition | |
| EP2041223B1 (en) | Thermoplastic elastomer composition, method of making and articles thereof | |
| CN1687217A (en) | PP and ABS nano filler alloy and preparation method thereof | |
| WO2002000793A1 (en) | A modified polyamide and polycarbonate blend | |
| CN1462771A (en) | Nano composite material polyphenylene sulfide modified by rubber being mixed | |
| CN1974634A (en) | Method of improving the machinability of polyamide | |
| CN1225932A (en) | Method and compositions of compatibilized polyphenylene ether-polyamide resin blends having enhanced flow characteristic | |
| CN110591332B (en) | Polyphenylene ether/polyamide 66 composition and method for making same | |
| KR0150765B1 (en) | Natural colored polyphenylenether thermoplastic resin composition | |
| CN1285672C (en) | Ductility increased nylon composition | |
| CN1036276C (en) | Toughened polyester composition | |
| CN100349976C (en) | Rubber modified nylon composition | |
| CN1200384A (en) | High impact polyphenylene ether/styrene resin/elastomer composition | |
| CN1239605C (en) | Copolymerized formol/polyolefine or copolymerized olefine elastomeric composite modified material and its preparation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |