CN103897383B - Amilan polyamide resin composition with excellent ductility and flexing fatigue and the pneumatic tire and hose using said composition - Google Patents
Amilan polyamide resin composition with excellent ductility and flexing fatigue and the pneumatic tire and hose using said composition Download PDFInfo
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- CN103897383B CN103897383B CN201410115441.6A CN201410115441A CN103897383B CN 103897383 B CN103897383 B CN 103897383B CN 201410115441 A CN201410115441 A CN 201410115441A CN 103897383 B CN103897383 B CN 103897383B
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- polyamide
- modified
- break
- pneumatic tire
- composition
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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 atoms other than carbon or hydrogen
- C08L23/0853—Ethene vinyl acetate copolymers
- C08L23/0861—Saponified copolymers, e.g. ethene vinyl alcohol copolymers
-
- 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
A kind of Amilan polyamide resin composition, with excellent ductility and flexing fatigue, by the polyamide as matrix（A）Have with what is be dispersed therein to polyamide（A）Reactive functional group（B）It is polymer-modified（C）Composition, wherein polymer-modified（C）Tensile stress at break be polyamide（A）Tensile stress at break 30 to 70%, it is polymer-modified（C）Tensile elongation at break be polyamide（A）Tensile elongation at break 100 to 500% and using said composition pneumatic tire and hose.
Description
Technical field
The application is the divisional application of Chinese patent application 200780050088.6.The present invention relates to polyamide combinations
Object and the pneumatic tire and hose using said composition.Relate more specifically to the polyamides with excellent ductility and flexing fatigue
Polyimide resin composition and the pneumatic tire and hose using said composition.
Background technology
Polyamide has excellent workability（Or machinability）, chemical resistance and heat resistance and low gas
Permeability, and therefore it is widely used in and utilizes the injection molding product of these properties, extruded product, blown product, film etc..
But since polyamide in impact resistance, fatigue resistance etc. is not necessarily enough, receiving dynamic tension
Requirement improves these properties under use environment.As for improving the method for the impact resistance of polyamide, in the prior art
It is known as being blended with the modifying agent being made of elastomer components（For example, see U.S. patent No.4,174,358 and U.S. patents
No.4,594,386）.But for fatigue resistance, depending on use environment, the complicated mechanism of destruction, improved enough effects
Fruit can not only by with it is elastomer blended and obtain.Producer suggested the different modifying agent for polyamide, special
It is not nylon.But extending in the environment of flex fatigue, big bearing capacity acts on interface and the modification of polyamide-modifier
The inside of agent, thus occurs the destruction of interfacial failure and modifying agent, and enough improvement effects can not be obtained by modifying agent.
The content of the invention
Therefore, it is an object of the invention to provide a kind of polyamides with excellent ductility and flexing fatigue
Composition and the pneumatic tire and hose using said composition.
According to the present invention, a kind of daiamid composition is provided, it includes the polyamides as matrix（A）With it is scattered
Have in therein to polyamide（A）Reactive functional group（B）It is polymer-modified（C）, wherein polymer-modified
（C）Tensile stress at break be polyamide（A）Tensile stress at break 30 to 70%, it is polymer-modified（C）Fracture
Tensile elongation is polyamide（A）Tensile elongation at break 100 to 500%, additionally provide using said composition
Pneumatic tire and hose.
In the present invention, can be enough and polyamide by mixing to have in Amilan polyamide resin composition（A）Instead
The functional group answered（B）It is polymer-modified（C）To enhance interface, i.e., by being blended on polyamide（A）With sufficiently strong
Tensile property modifying agent, improve extension and flexing fatigue properties.
Realize the optimal mode of the present invention
The present inventor, which goes in for the study, to solve the above problems and as a result, successfully by Amilan polyamide resin composition solution
Certainly these problems, said composition include polyamide（A）Be dispersed therein have can be with polyamide（A）Reaction
Functional group（B）It is polymer-modified（C）, wherein what is be blended is polymer-modified（C）With for polyamide（A）Fracture draw
30% to the 70% of stress is stretched, is preferably 40 to 70% tensile stress at break, has for polyamide（A）Break-draw
100% to the 500% of elongation is preferably 110 to 500% Tensile elongation at break.
Preferred embodiment according to the present invention, it is polymer-modified by making（C）Volume fraction for 40% or more, it is excellent
Elect 40 to 80% as, more preferably 50 to 80%, the polyamide with excellent spreading resistance and flexing fatigue can be obtained
Resin combination.Here " volume fraction（%）" represent be included in it is polymer-modified in Amilan polyamide resin composition（C）Body
Fraction.In addition, when polymer-modified（C）And polyamide（A）Volume fraction and melt viscosity ratio meet it is following
Formula（I）（α>l）, it is possible to it will be polymer-modified（C）Evenly be dispersed in polyamide（A）In.
α=（Φd/Φm）×（ηm/ηd）<1 （I）
Wherein Φ d represent polymer-modified（C）Volume fraction；
Φ m represent polyamide（A）Volume fraction；
η d represent polymer-modified（C）Melt viscosity（Pay attention to：Measuring condition：Toyo Seiki Capillary
Rheometer is for the temperature and 1200sec at 240 DEG C-1Shear rate under capillary viscosity measurement）；
η m represent polyamide（A）Melt viscosity（Pay attention to：Measuring condition：Toyo Seiki Capillary
Rheometer is for the temperature and 1200sec at 240 DEG C-1Shear rate under capillary viscosity measurement）.
As the polyamide that can be used in the present invention（A）, also refer to nylon 6, nylon66 fiber, nylon
6.66th, nylon 612, nylon 11, nylon 12, nylon 46, nylon 6.66.610, nylon MXD 6 etc..These substances can individually make
With or with it is any they be used in combination.
As for use in the present invention to polyamide（A）Reactive functional group（B）, such as it also refers to
Anhydride group, epoxide group, halogen group, carboxylic group, amino group, hydroxyl group and other functional groups.Use anhydride group
Group, such as it is preferable to use maleic groups.
There is the polymer-modified of anhydride group as what be can be used in the present invention（C）, also refer to the equal of alkene
Polymers or copolymer.From the viewpoint of elongation at break and fracture strength, particularly preferably it is selected from using ethylene and at least one
Propylene, butylene, hexene and octene alpha-olefin copolymer.
As described above, it is important that polymer-modified in Amilan polyamide resin composition（C）The break-draw having
The value of stress and Tensile elongation at break（It is measured at -20 DEG C all in accordance with JISK6251）Respectively polyamide（A）30
To 70% and 100 to 500%.If the value of tensile stress at break is less than values above, polymer-modified（C）Material damage and negative
It carries not preferably by polyamide（A）Matrix generates.In addition, if Tensile elongation at break is less than values above, drawn with fracture
Stress similitude is stretched, it is polymer-modified（C）Material damage preferably do not occur.
Amilan polyamide resin composition according to the present invention can also include usually being blended into rubber in addition to more than component
Carbon black in composition and resin combination, silica or other fillers, vulcanizing agent or crosslinking agent, vulcanization accelerator or friendship
Join accelerating agent, different types of oil, antioxidant, plasticizer, oil, colorant and different types of other additives.These additions
They can be mixed into composition by agent by common method.When mixing, the amount of mixing can also be conventional common
Amount, as long as the purpose of the present invention will not be influenced in turn.
Specific embodiment
Embodiment
Embodiment will be used to that the present invention to be explained further, but the scope of the present invention is not intended to be limited to these embodiments.
Embodiment 1 to 9 and comparative example 1 to 9
The preparation of sample
Ingredient in Table I to IV is mixed to obtain Amilan polyamide resin composition according to following.
Table V is filled into double screw extruder to the polymer-modified pellet shown in VII and polyamide resin pellet
（TEX44, Japan Steel Works are manufactured）In and melting mixing.The condition of mixing for 220 DEG C mix 3 minutes and
1200sec-1Shear rate.Material is continuously discharged in the form of item from extruder, by water cooling, then passes through cutting
Knife cuts to obtain the Amilan polyamide resin composition of pellet shape.In order to obtain the sheet material for testing fatigue, the polyamides of preparation
Polyimide resin composition pellet is injected into the single screw extrusion machine for being provided with sheet die and forms sheet form.
Then testing fatigue is carried out by test method as shown below to thus obtained Amilan polyamide resin composition.Knot
Fruit is as shown in Table I to IV.
For the test method of evaluation of physical properties
Testing fatigue：The Amilan polyamide resin composition that sheet material is shaped to by sheet die is struck out into JIS dumbbells No.3
Shape（JIS K6251）, then the sample of dumb-bell shape is enclosed after testing fatigue and carries out constant strain and bend to test.
This chuck at 54mm intervals, 20% tensile strain rate, 20% compression strain rate, the repetition rate of 6.67Hz and-
It is carried out under conditions of 20 DEG C of test temperature, terminates to test when sample is broken.
Judge：Well ... until the repetition rate of fracture is more than 500000（It is cut off under 1000000X）.
Difference ... is less than 500,000X until the repetition rate of fracture.
Table I
*1：Referring to Table V；*2：Referring to Table VI；*3：Referring to Table VII
*4：Break-draw polymer-modified TBd=（It is measured according to JIS K6251）
The break-draw of TBm=polyamides（It is measured according to JIS K6251）
*5：Elongation at break polymer-modified EBd=（It is measured according to JIS K6251）
The elongation at break of EBm=polyamides（It is measured according to JIS K6251）
Table II
| Polymer type | Comparative example 4 |
| Formula（Parts by weight） | |
| 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 (public formula (I)) | 0.58 |
| TBd/TBm*4 | 0.21 |
| EBd/EBm*4 | 1.47 |
| Testing fatigue | 80000 |
| Judge | Difference |
*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（Parts by weight） | ||||
| 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 (public 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 |
| Testing fatigue | 1000000 cut-outs | 1000000 cut-outs | 3000 | 50000 |
| Judge | It is good | It is good | Difference | Difference |
*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 capillary viscosity of the polyamide at -20 DEG C
*1：It is measured according to JIS K-6251 methods
*2：It is measured according to JIS K-6251 methods
*3：It is measured according to JIS K-7199 methods
Table VI：Polymer-modified tensile property and capillary viscosity at -20 DEG C
Table VII：Tensile property and capillary viscosity of the rubber constituent at -20 DEG C
*1：Preparation method：The brombutyl of specified rate, antioxidant, maleic anhydride and magnesia are injected into 70
In the pressure kneader heated at DEG C, then by the predetermined time（7 minutes）Interior mixing obtains desired product.It is introduced into
The amount of maleic anhydride in butyl rubber is 1.5mol%, is analyzed and measured by 1H-NMR.
*2：Referring to the footnote of Table V.
Industrial applicibility
Amilan polyamide resin composition according to the present invention may be used as the liner of pneumatic tire etc. and can further use
Make for example for the outer tube material of hose, inside tube inner layer materials and inside tube outer layer materials.
Claims (5)
1. a kind of pneumatic tire, used as the Amilan polyamide resin composition of liner, the Amilan polyamide resin composition includes
As matrix polyamide (A) and be dispersed therein have to polyamide (A) reactive anhydride functional group
(B) modified copolymer (C), the wherein tensile stress at break of modified copolymer (C) should for the break-draw of polyamide (A)
The Tensile elongation at break of 30 to 70% and the modified copolymer (C) of power is the Tensile elongation at break of polyamide (A)
100 to 500%, wherein modified copolymer (C) has 40 to 80% volume fraction, the polyamide based on 100 volume %
Composition and wherein modified copolymer (C) change for (i) maleic anhydride modified ethylene-butene copolymer or (ii) maleic anhydride
The ethylene-octene copolymer of property.
2. pneumatic tire as described in claim 1, wherein modified copolymer (C) are maleic anhydride modified Ethylene/Butylene
Copolymer.
3. the pneumatic tire as described in claim 1 or 2, wherein modified copolymer (C) have 50 to 80% volume fraction.
4. the volume integral of the pneumatic tire as described in claim 1 or 2, wherein modified copolymer (C) and polyamide (A)
The ratio of number and melt viscosity meets the following formula (I)：
α=(Φ d/ Φ m) × (η m/ η d)<1 (I)
Wherein Φ d：The volume fraction of modified copolymer (C)
Φm：The volume fraction of polyamide (A)
ηd：The melt viscosity of modified copolymer (C)
ηm：The melt viscosity of polyamide (A).
5. the pneumatic tire as described in claim 1 or 2, wherein polyamide (A) are selected from nylon 6, nylon66 fiber, nylon
6/66th, at least one of nylon 6/12, nylon 11 and nylon 12 resin.
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 CN103897383A (en) | 2014-07-02 |
| CN103897383B true 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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Families Citing this family (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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3054968B2 (en) * | 1991-12-26 | 2000-06-19 | 横浜ゴム株式会社 | Pneumatic tire |
| JP2003128845A (en) * | 2001-10-18 | 2003-05-08 | Bridgestone Corp | Rubber composition and pneumatic tire using the same |
-
2007
- 2007-01-18 CN CN201410115441.6A patent/CN103897383B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| Publication number | Publication date |
|---|---|
| CN103897383A (en) | 2014-07-02 |
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