CN103897383A - Polyamide resin composition with excellent ductility and flexible fatigability, and pneumatic tire and flexible pipe using same - Google Patents
Polyamide resin composition with excellent ductility and flexible fatigability, and pneumatic tire and flexible pipe using same Download PDFInfo
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- CN103897383A CN103897383A CN201410115441.6A CN201410115441A CN103897383A CN 103897383 A CN103897383 A CN 103897383A CN 201410115441 A CN201410115441 A CN 201410115441A CN 103897383 A CN103897383 A CN 103897383A
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- polyamide resin
- resin composition
- polymer
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- nylon
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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
- C08L51/06—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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0008—Compositions of the inner liner
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
- C08L23/0861—Saponified vinylacetate
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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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)
- General Engineering & Computer Science (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a polyamide resin composition, which has excellent ductility and flexible fatigability. The polyamide resin composition is prepared from polyamide resin (A) used as a matrix, and a modified polymer (C), which is dispersed into the polyamide resin and has a functional group (B) having reactivity with the polyamide resin (A), wherein the tensile stress at break of the modified polymer (C) is 30-70% of the tensile stress at break of the polyamide resin (A); the tensile break extension rate of the modified polymer (C) is 100-500% of that of the polyamide resin (A). The invention also discloses a pneumatic tire and a flexible pipe using the composition.
Description
Technical field
The application is the divisional application of Chinese patent application 200780050088.6.The present invention relates to Amilan polyamide resin composition and use pneumatic tyre and the flexible pipe of said composition.The pneumatic tyre and the flexible pipe that relate more specifically to there is the Amilan polyamide resin composition of excellent ductility and flexing fatigue and use said composition.
Background technology
Polyamide resin has excellent workability (or workability), chemical resistant properties and thermotolerance and low gas permeability, and therefore it is widely used in injection-molded product, extruded product, blowing product, film of utilizing these character etc.But, be enough because polyamide resin is also unnecessary at the aspect such as shock resistance, fatigue resistance, under the environment for use of accepting dynamic tension, require to improve these character.As the method for the shock resistance for improvement of polyamide resin, known in the state of the art for the properties-correcting agent blend that is become to be grouped into by elastomerics (for example, referring to U.S. patent No.4,174,358 and U.S. patent No.4,594,386).But, for fatigue resistance, depend on environment for use, the complicated mechanism of its destruction, improved enough effects can not be only by obtaining with elastomer blended.Producer has advised the different properties-correcting agent, particularly nylon for polyamide resin.But under the environment of extension and flexing fatigue, large bearing capacity acts on the interface of polymeric amide-properties-correcting agent and the inside of properties-correcting agent, the destruction of interfacial failure and properties-correcting agent occurs thus, and can not obtain enough improvement effects by properties-correcting agent.
Summary of the invention
Therefore, the object of the present invention is to provide a kind of pneumatic tyre and flexible pipe that there is the Amilan polyamide resin composition of good ductility and flexing fatigue and use said composition.
According to the present invention, a kind of daiamid composition is provided, it comprises the polyamide resin (A) as matrix and is scattered in have polymer-modified (C) that polyamide resin (A) be to reactive functional group (B) wherein, wherein the tensile stress at break of polymer-modified (C) be polyamide resin (A) tensile stress at break 30 to 70%, the tensile fracture elongation rate of polymer-modified (C) be polyamide resin (A) tensile fracture elongation rate 100 to 500%, the pneumatic tyre and the flexible pipe that use said composition are also provided.
In the present invention, can be enough to polymer-modified (C) of the functional group (B) of reacting with polyamide resin (A) to strengthen interface by mixing to have in Amilan polyamide resin composition, the properties-correcting agent about polyamide resin (A) by blend with enough strong tensile property, has improved extension and flexing fatigue character.
Realize optimal mode of the present invention
The inventor goes in for the study and addresses the above problem and as a result of, successfully address these problems by Amilan polyamide resin composition, said composition comprises polyamide resin (A) and is scattered in polymer-modified (C) with the functional group (B) that can react with polyamide resin (A) wherein, wherein polymer-modified (C) of blend has for 30% to 70% of the tensile stress at break of polyamide resin (A), be preferably 40 to 70% tensile stress at break, have for 100% to 500% of the tensile fracture elongation rate of polyamide resin (A), be preferably 110 to 500% tensile fracture elongation rate.
According to the preferred embodiment of the invention, the volume fraction of polymer-modified by making (C) is 40% or more, is preferably 40 to 80%, more preferably 50 to 80%, and can obtain and there is excellent spreading resistance and the Amilan polyamide resin composition of flexing fatigue.Here " volume fraction (%) " represents to be included in the volume fraction of polymer-modified (C) in Amilan polyamide resin composition.In addition, when polymer-modified (C) and the volume fraction of polyamide resin (A) and the satisfied following formula (I) (α >l) of the ratio of melt viscosity, likely polymer-modified (C) is dispersed in polyamide resin (A) more uniformly.
α＝（Φd/Φm）×（ηm/ηd）<1 （I）
Wherein Φ d represents the volume fraction of polymer-modified (C);
Φ m represents the volume fraction of polyamide resin (A);
η d represents the melt viscosity (attention: measuring condition: Toyo Seiki Capillary Rheometer is for temperature and 1200sec at 240 DEG C of polymer-modified (C)
-1shearing rate under the measurement of capillary viscosity);
η m represents the melt viscosity (attention: measuring condition: Toyo Seiki Capillary Rheometer is for temperature and 1200sec at 240 DEG C of polyamide resin (A)
-1shearing rate under the measurement of capillary viscosity).
As the polyamide resin (A) can be used in the present invention, it can refer to nylon 6, nylon 66, nylon 6.66, nylon 612, nylon 11, nylon 12, nylon 46, nylon 6.66.610, nylon MXD 6 etc.These materials can use separately or with any they combine use.
Of the present invention polyamide resin (A) is to reactive functional group (B) as can be used for, for example it can refer to anhydride group, epoxide group, halogen group, carboxylic group, amino group, oh group and other functional group.Use anhydride group, for example, preferably use maleic anhydride group.
As polymer-modified (C) with anhydride group that can be used in the present invention, it can refer to homopolymer or the multipolymer of alkene.From the viewpoint of elongation at break and breaking tenacity, particularly preferably use ethene and at least one to be selected from the multipolymer of the alpha-olefin of propylene, butylene, hexene and octene.
As mentioned above, in Amilan polyamide resin composition, important part is that the value (all measuring according to JISK6251 at-20 DEG C) of tensile stress at break that polymer-modified (C) has and tensile fracture elongation rate is respectively 30 to 70% and 100 to 500% of polyamide resin (A).If the value of tensile stress at break is lower than above value, the material damage of polymer-modified (C) and load are not preferably produced by polyamide resin (A) matrix.In addition, if tensile fracture elongation rate is less than above value, similar to tensile stress at break, the material damage of polymer-modified (C) does not preferably occur.
Amilan polyamide resin composition according to the present invention can also comprise the carbon black being conventionally blended in rubber combination and resin combination except above component, silicon-dioxide, or other filler, vulcanizing agent or linking agent, vulcanization accelerator or crosslinking accelerator, dissimilar oil, oxidation inhibitor, softening agent, oil, tinting material and other dissimilar additive.These additives can be mixed into them in composition by common method.In the time mixing, the amount of mixing can be also conventional common amount, only otherwise can affect conversely object of the present invention.
Embodiment
Embodiment
Embodiment will be used for further explaining the present invention, but scope of the present invention is not intended to be limited to these embodiment.
Embodiment 1 to 9 and comparative example 1 to 9
The preparation of sample
By Table I to the composition in IV according to following mixing to obtain Amilan polyamide resin composition.
Table V is filled in twin screw extruder (TEX44, Japan Steel Works manufactures) and melting mixing to the polymer-modified pellet shown in VII and polyamide resin pellet.The condition of mixing is 220 DEG C and mixes 3 minutes and 1200sec
-1shearing rate.Material, with continuous the discharging from forcing machine of form of bar, by water cooling, then obtains the Amilan polyamide resin composition of pellet shape by cutters cutting.In order to obtain the sheet material for Fatigue Test, the Amilan polyamide resin composition pellet of preparation is injected in the single screw extrusion machine that provides compressing tablet die head and forms sheet form.
Then thus obtained Amilan polyamide resin composition is carried out to Fatigue Test by testing method shown below.Result is if Table I is to as shown in IV.
The testing method of evaluating for physical properties
Fatigue Test: the Amilan polyamide resin composition that is shaped to sheet material by compressing tablet die head is struck out to the shape (JIS K6251) of JIS dumbbell No.3, then after Fatigue Test, the sample of dumb-bell shape enclosed and carried out constant strain and deflection test.Under the condition of the repetition rate of this chuck at 54mm interval, 20% tensile strain rate, 20% compressive strain speed, 6.67Hz and the probe temperature of-20 DEG C, carry out, in the time of sample breakage, finish test.
Judgement: good ... until being greater than 500000(, the repetition rate of fracture cuts off under 1000000X).
Poor ... until the repetition rate of fracture is less than 500,000X.
Table I
* 1: referring to Table V; * 2: referring to Table VI; * 3: referring to Table VII
* the polymer-modified fracture stretching (measuring according to JIS K6251) of 4:TBd=
The fracture stretching (measuring according to JIS K6251) of TBm=polyamide resin
* the polymer-modified elongation at break (measuring according to JIS K6251) of 5:EBd=
The elongation at break (measuring according to JIS K6251) of EBm=polyamide resin
Table II
| Polymer type | Comparative example 4 |
| Formula (weight part) | |
| BESNOTL (nylon 11) *1 | － |
| BMNO (nylon 11) *1 | 30 |
| MA8510(Mah-EB) *2 | － |
| MP0620(Mah-EP) *2 | － |
| VA1840(Mah-EO) *2 | － |
| AR201(Mah-EEA) *2 | － |
| Dumilan C1550 (EVA of saponification) *2 | － |
| Yokohama rubber IIR (Mah-IIR) *3 | － |
| EPDM *3 | － |
| X2(Br-IIR) *3 | － |
| ENR25(E-NR) *3 | 70 |
| Φd/Φm | 2.3 |
| ηm/ηd | 0.25 |
| α (formula (I)) | 0.58 |
| TBd/TBm*4 | 0.21 |
| EBd/EBm*4 | 1.47 |
| Fatigue Test | 80000 |
| Judgement | Poor |
* 1: referring to Table V; * 2: referring to Table VI
* 3: referring to Table VII; * 4: referring to the footnote of Table I
Table III
| Polymer type | Embodiment 6 | Embodiment 7 | Comparative example 5 | Comparative example 6 |
| Formula (weight part) | ||||
| 3030XA (nylon 12) *1 | 40 | 50 | 45 | 45 |
| MA8510(Mah-EB) *2 | 60 | － | － | － |
| VA1840(Mah-EO) *2 | － | 50 | － | － |
| EPDM *3 | － | － | 55 | － |
| ENR25(E-NR) *3 | － | － | － | 56 |
| Φd/Φm | 1.5 | 1.0 | 1.22 | 1.22 |
| ηm/ηd | 0.30 | 0.39 | 0.69 | 0.703 |
| α (formula (I)) | 0.45 | 0.39 | 0.84 | 0.86 |
| TBd/TBm*4 | 0.52 | 0.41 | 0.07 | 0.17 |
| EBd/EBm*4 | 1.19 | 1.15 | 1.38 | 1.25 |
| Fatigue Test | 1000000 cut off | 1000000 cut off | 3000 | 50000 |
| Judgement | Good | Good | Poor | Poor |
* 1: referring to Table V; * 2: referring to Table VI
* 3: referring to Table VII; * 4: referring to the footnote of Table I
Table IV
* 1: referring to Table V; * 2: referring to Table VI
* 3: referring to Table VII; * 4: referring to the footnote of Table I
Table V: tensile property and the capillary viscosity of polyamide resin at-20 DEG C
* 1: measure according to JIS K-6251 method
* 2: measure according to JIS K-6251 method
* 3: measure according to JIS K-7199 method
Table VI: polymer-modified tensile property and capillary viscosity at-20 DEG C
Table VII: tensile property and the capillary viscosity of rubber constituent at-20 DEG C
* 1: preparation method: the brominated butyl rubber of specified rate, oxidation inhibitor, maleic anhydride and magnesium oxide are injected in the pressurization kneader of heating at 70 DEG C, then obtain by mixing the product of expecting within predetermined time (7 minutes).The amount that is incorporated into the maleic anhydride in isoprene-isobutylene rubber is 1.5mol%, analyzes mensuration by 1H-NMR.
* 2: referring to the footnote of Table V.
Industrial applicibility
Can be as the liner of pneumatic tyre etc. and can be further as for example outer tube material, inner tube inner layer material and the inner tube cladding material for flexible pipe according to Amilan polyamide resin composition of the present invention.
Claims (8)
1. an Amilan polyamide resin composition, it comprises the polyamide resin (A) as matrix and is scattered in have polymer-modified (C) that polyamide resin (A) be to reactive functional group (B) wherein, wherein the tensile stress of polymer-modified (C) be polyamide resin (A) tensile stress at break 30 to 70%, and the tensile fracture elongation rate of polymer-modified (C) be polyamide resin (A) tensile fracture elongation rate 100 to 500%.
2. Amilan polyamide resin composition as described in claim 1, wherein polymer-modified (C) has 40 to 80% volume fraction.
3. Amilan polyamide resin composition as described in claim 1, wherein polymer-modified (C) and the volume fraction of polyamide resin (A) and the ratio of melt viscosity meet following formula (I):
α＝（Φd/Φm）×（ηm/ηd）<1 （I）
Wherein Φ d: the volume fraction of polymer-modified (C)
Φ m: the volume fraction of polyamide resin (A)
η d: the melt viscosity of polymer-modified (C)
η m: the melt viscosity of polyamide resin (A).
4. Amilan polyamide resin composition as described in claim 1, wherein polyamide resin (A) is for being selected from least one resin in nylon 6, nylon 66, nylon 6/66, nylon 6/12, nylon 11 and nylon 12.
5. Amilan polyamide resin composition as described in claim 1, wherein functional group (B) is anhydride group.
6. Amilan polyamide resin composition as described in claim 1, wherein polymer-modified (C) is selected from the multipolymer of the alpha-olefin of propylene, butane, hexane and octane for ethene and at least one.
7. by the pneumatic tyre as liner according to the Amilan polyamide resin composition of claim 1.
8. will be used as at least flexible pipe of one deck according to the Amilan polyamide resin composition of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410115441.6A CN103897383B (en) | 2007-01-18 | 2007-01-18 | Amilan polyamide resin composition with excellent ductility and flexing fatigue and the pneumatic tire and hose using said composition |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410115441.6A CN103897383B (en) | 2007-01-18 | 2007-01-18 | Amilan polyamide resin composition with excellent ductility and flexing fatigue and the pneumatic tire and hose using said composition |
| CNA2007800500886A CN101600764A (en) | 2007-01-18 | 2007-01-18 | Have the Amilan polyamide resin composition of excellent ductility and flexing fatigue and pneumatic tyre and the flexible pipe that uses said composition |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800500886A Division CN101600764A (en) | 2007-01-18 | 2007-01-18 | Have the Amilan polyamide resin composition of excellent ductility and flexing fatigue and pneumatic tyre and the flexible pipe that uses said composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103897383A true CN103897383A (en) | 2014-07-02 |
| CN103897383B CN103897383B (en) | 2018-06-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410115441.6A Expired - Fee Related CN103897383B (en) | 2007-01-18 | 2007-01-18 | Amilan polyamide resin composition with excellent ductility and flexing fatigue and the pneumatic tire and hose using said composition |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106221106A (en) * | 2016-08-05 | 2016-12-14 | 宁波金特信钢铁科技有限公司 | A kind of preparation method of rubber tyre carcass resisting fatigue auxiliary agent |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05169909A (en) * | 1991-12-26 | 1993-07-09 | Yokohama Rubber Co Ltd:The | Pneumatic tire |
| JP2003128845A (en) * | 2001-10-18 | 2003-05-08 | Bridgestone Corp | Rubber composition and pneumatic tire using the same |
| CN1473116A (en) * | 2001-09-05 | 2004-02-04 | 横滨橡胶株式会社 | Pneumatic tire having run flat capability |
| EP1728824A2 (en) * | 2005-05-31 | 2006-12-06 | Bridgestone Corporation | Evoh composite resin and refrigerant transporting hose |
-
2007
- 2007-01-18 CN CN201410115441.6A patent/CN103897383B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05169909A (en) * | 1991-12-26 | 1993-07-09 | Yokohama Rubber Co Ltd:The | Pneumatic tire |
| CN1473116A (en) * | 2001-09-05 | 2004-02-04 | 横滨橡胶株式会社 | Pneumatic tire having run flat capability |
| JP2003128845A (en) * | 2001-10-18 | 2003-05-08 | Bridgestone Corp | Rubber composition and pneumatic tire using the same |
| EP1728824A2 (en) * | 2005-05-31 | 2006-12-06 | Bridgestone Corporation | Evoh composite resin and refrigerant transporting hose |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106221106A (en) * | 2016-08-05 | 2016-12-14 | 宁波金特信钢铁科技有限公司 | A kind of preparation method of rubber tyre carcass resisting fatigue auxiliary agent |
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| Publication number | Publication date |
|---|---|
| CN103897383B (en) | 2018-06-01 |
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