CN1922259A - Cross-linked composition comprising a triblock sequenced copolymer, method for the production thereof, and uses of the same - Google Patents
Cross-linked composition comprising a triblock sequenced copolymer, method for the production thereof, and uses of the same Download PDFInfo
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- CN1922259A CN1922259A CNA2005800059057A CN200580005905A CN1922259A CN 1922259 A CN1922259 A CN 1922259A CN A2005800059057 A CNA2005800059057 A CN A2005800059057A CN 200580005905 A CN200580005905 A CN 200580005905A CN 1922259 A CN1922259 A CN 1922259A
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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
- 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
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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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
- C08L21/00—Compositions of unspecified rubbers
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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
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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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
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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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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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
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
Abstract
The invention relates to a cross-linked composition comprising at least one elastomer and at least one triblock sequenced copolymer. The invention also relates to a method for obtaining one such composition, based on a system and a suitably selected cross-linking temperature. According to a preferred embodiment of the invention, the cross-linked composition can be transformed as a thermoplastic material. The inventive composition can be used in various applications, especially for producing conduits for the transfer of fluids, seals and insulation linings.
Description
The present invention relates to cross-linked composition, its preparation method and its application.The present invention discloses the cross-linked composition that contains elastomerics and three block segmented copolymers especially, it is based on hot crosslinked preparation method and its application.
Cross-linked composition of the present invention has application in the manufacturing of some goods, such as insulation strip of paper used for sealing (seal) and moulded product and also be useful on the pipeline that fluid is carried, such as being used for those of automotive industry, for example brake or cooling system in.Other application, the manufacturing such as belt (such as transmission belt), tire, cable sheath or sole can contain composition of the present invention.
The specific example of the present invention is that it is the cross-linked composition that can change as thermoplastic material.This be because, concerning some application (insulation strip of paper used for sealing and moulded product or liquid conducting pipes), the material that need be able to effectively utilize, it not only has the performance similar to elastomerics and particularly can bear sizable distortion and do not rupture and after the elongation or the strain of compression-type, even after the strain of multiple elongation or compression-type, can reply their initial geometrical shapies, and has a good thermotolerance, chemical-resistant and weathering resistance, the technology and the equipment of the work program of the enough thermoplastic materials of described material energy are processed, mainly be make these goods and make during the recycling of the refuse that generates become possibility, make this recycling needn't use elastomerics.
Therefore in US-A-4 130 535, to having taked measure based on polyolefinic " thermoplastic elastomer ", this elastomerics presents by polyacrylic non-crosslinked matrix and the trimeric crosslinked structure that irregular spherolite constituted of ethylene/propylene/diene (EPDM), so that under the service temperature that is lower than the polypropylene fusing point, demonstrate with vulcanize after the similar proterties of elastomerics, when being heated the above temperature of fusing point so far simultaneously, can use them as thermoplastic material.
Though demonstrating really, these materials are equivalent to elastomeric some performance, but they demonstrate big tensile-permanent set (elongation set) (greater than 50%) under greater than 100 ℃ temperature, this makes them not be suitable for making those a little to want the goods that use in the place more than 100 ℃ at the temperature great majority, as insulation and/or stopping property strip of paper used for sealing (leaktightness seal) and moulded product or be used for guaranteeing that pipeline that liquid carries in the starting motor-driven vehicle cabin, flexible pipe, pipe etc. may be exactly this situation.
In order to address this problem, EP 0 840 763 B1 provide a solution, this scheme is based on to use has the cross-linked elastomer that thermoplasticity changes, this elastomerics carried out crosslinked the acquisition with the blend of " Vegaprene " expression afterwards by a kind of, and this blend contains based on poly-(octene/ethene) that obtained by metallocene catalysis with the polyolefinic elastomerics of maleic anhydride graft.Though this solution is gratifying, it still is confined to some application.
This is because the performance of this blend is different from those performances of taking the simple linear interpolation method to be predicted to the performance of various components (elastomerics and plastics) respectively usually.There is synergistic effect sometimes, but also has other slightly weaker situation of performance.This perhaps with the character at the distribution of form, filler and the softening agent of each phase, interface or relevant in the distribution of each sulfuration bridge in mutually.In order to overcome these phenomenons, must rely on expensive being difficult to and blend bonded compatilizer or coagent usually.
Particularly at the aspect of performance of anti-repeated stress, the fatigue property of compound is main.This can obtain such as zinc methacrylate by using coagent.Yet because the polarity of this compound, coagent is difficult to be dispersed in the blend.In addition, it at high temperature causes blend to adhere on the mixing apparatus with the hyperergy of metal.Therefore its use range is not wide.Another favorable properties is anti-high elongation.This character is difficult to obtain by the disclosed blend of EP 0 840 763 B1.
At last, in some cases, the improvement of using in the compressive strain that method obtained (representing with CS usually) that is disclosed among EP 0 840 763 B1 is proved to be inadequate.
In order to address the above problem and a lot of other problem, applicant company has now found that the solution based on cross-linked composition, and said composition contains the segmented copolymer and the optional thermoplastic polymer that contains of at least a elastomerics and at least a three blocks.
The solution of being found by applicant company can address the above problem and other mechanical property of deterioration blend (dynamic property, loss, hardness, rebound resilience or the like) not.Disperse blend easily according to method of the present invention.In addition, it demonstrate not can adhering device advantage.
Therefore, first theme of the present invention is a cross-linked composition, and it comprises in weight part:
At least a elastomerics (I) of-20-100 weight part,
The segmented copolymer (II) of at least a three blocks of-2-50 weight part and
At least a thermoplastic polymer (III) of-0-100 weight part.
In the scope of implication of the present invention, elastomerics (I) can be selected from natural rubber (NR), synthetic rubber (BR), by metallocene catalysis polymeric elastomerics, poly-(ethylene/propene) (EPR), poly-(ethylene/propylene/diene) (EPDM), extended chain polypropylene acid esters such as poly-(butyl acrylate) or gather (2-ethylhexyl acrylate), viton (FPM) such as multipolymer and silicone elastomer based on tetrafluoroethylene.
It is poly-(conjugated diolefine) that term " synthetic rubber (BR) " is understood as the meaning, such as polyhutadiene, polyisoprene and their block or random copolymers.
In the scope of implication of the present invention, term " by the elastomerics of metallocene catalyst polymerisation " is understood as any elastomerics that the meaning is made up of homopolymer, multipolymer or trimer, it uses metallocene catalyst to carry out polymerization, such as poly-(octene/ethene), also have known poly-octene, they can be buied with trade name Engage from Du Pont DowElastomer (DDE).
According to the present invention, the segmented copolymer of three blocks (II) is corresponding to following general formula:
Y-B-Y’
Wherein, B is the block with elastomeric properties, and Y and Y ' are inconsistent on thermodynamics with B block.They can be identical or inequality on chemical constitution, and at least a in them mainly is made of the methacrylic monomer.
B block is an elastomerics, and it belongs to the family of polyolefine, polyacrylic ester, urethane, polyethers, such as polyoxyethylene or polyoxypropylene and nitrile elastomerics.Specifically, the monomer that is used for synthetic elastomeric block B can be alkene such as iso-butylene, long-chain acrylate or methacrylic ester such as butyl acrylate or 2-ethylhexyl acrylate or is selected from divinyl, isoprene, 2,3-dimethyl-1,3-divinyl, 1, the diene of 3-pentadiene or 2-phenyl-1,3 divinyl.
B advantageously is selected from poly-(diene), particularly poly-(divinyl), poly-(isopentene) and their random copolymers, or be selected from according to routine techniques partially or completely hydrogenant gather (diene).In polyhutadiene, advantageously use those with lowest glass transition temperature Tg, for example poly-(1, the 4-divinyl), its Tg (-90 ℃ approximately) is lower than the Tg (about 0 ℃) of poly-(1).
B block preferably mainly is made up of poly-(1, the 4-divinyl).
Advantageously, the Tg of B is lower than 0 ℃, and preferably is lower than-40 ℃.
Y and Y ' can obtain by at least a monomer of polymerization, and this monomer is selected from vinylbenzene and derivative and short chain methacrylic ester thereof such as methyl methacrylate.
Preferably, the Y ' that represents with M is made up of methyl methacrylate monomer subsequently, or contains the methyl methacrylate of 50wt% at least, the preferred methyl methacrylate of 70wt% at least.Other monomer that constitutes this block can the yes or no acrylic monomer, and can yes or no reactive.As the non-limitative example of reactive functional groups, can mention: oxyethane functional group, amine functional group, acid anhydride functional group or carboxylic acid functional.Reactive monomer can be the monomer that hydrolyzable becomes acid.In can constituting other monomer of Y ' block, can mention: glycidyl methacrylate, methacrylic tert-butyl acrylate or glutarimide as non-limitative example.
According to advantageous forms, Y ' block preferably contains imide functionality with the ratio of the 30-60mol% of Y '.These imide functionality can be obtained by imidization reaction.Advantageously, carry out the imidization reaction of two adjacent MMA functional groups.For example, this imidization reaction is described among patent EP 275 918, EP 315 149, EP 315 150, EP 315 151 and the EP 331 052, and its content is incorporated among the application.Composition of the present invention can prepare by the triblock copolymer (II) that use has a Y ' block, and wherein said Y ' block is imidization or can carry out imidization reaction during blend component of the present invention (I), (II) and optional (III).
M advantageously reaches 60% poly-(methyl methacrylate) at least by syndiotactic and (PMMA) forms.
When the chemical constitution of Y was different from Y ', under the situation of following embodiment, it can pass through vinyl aromatic compounds, obtained such as the polymerization of vinylbenzene, alpha-methyl styrene, Vinyl toluene or vinyl pyridine.Next represent Y with S.The Tg of Y (or S) is advantageously greater than 23 ℃, and is preferably more than 50 ℃.
Next represent according to triblock copolymer Y-B-Y ' of the present invention with S-B-M.
According to the present invention, S-B-M has 10000g/mol-500000g/mol, the number average molar weight of preferred 20000-200000g/mol.These S-B-M three blocks advantageously have following composition, represent with weight percentage, and summation is 100%:
M:10-80% and preferred 15-70%,
B:2-80% and preferred 5-70%,
S:10-88% and preferred 5-85%.
According to the present invention, segmented copolymer (II) can contain at least a S-B diblock, wherein S and B block have with S-B-M three blocks in the S character identical with the B block.They by with S-B-M three blocks in S block monomer identical and optional monomer altogether with the B block form.
The S-B diblock has 5000g/mol-500000g/mol, the number average molar weight of preferred 10000-200000g/mol.The S-B diblock advantageously is made up of with the weight percentage of the B of preferred 15-85% 5-95%.
Below represent the blend of S-B diblock and S-B-M three blocks with SBM.This blend advantageously contains the S-B diblock of 5-80% and S-B-M three blocks of 95-20% correspondingly.
An advantage of these SBM block compositions is exactly: it need be when its end of synthesis this S-B-M of purifying.
For example, thermoplastic polymer (III) is selected from modification or unmodified polyolefine, polymeric amide, polyester, thermoplastic polyurethane, fluoropolymer and chlorine-containing polymer, such as poly-(vinylchlorid) (PVC).
Thermoplastic polymer (III) advantageously is a functionalized polyolefin.Thermoplastic polymer (III) is preferably the grafted polyolefine, and it is selected from polyethylene, the polypropylene with vinylformic acid, maleic anhydride or glycidyl methacrylate graft and gathers (ethylene/propene).
Advantageously, can also comprise the polyacrylic acid elastomerics according to cross-linked composition of the present invention, trimer such as ethene, acrylate and acrylic acid trimer or vinylbenzene, vinyl cyanide and acrylate, it is as the UV stablizer with as membrane-forming agent, and work as the latter and add man-hour by extruding, it can improve the outward appearance of composition.When using above-mentioned polyacrylic acid elastomerics, in per 100 weight parts elastomerics/triblock copolymer blend, preferably use with the ratio of 2-20 weight part.
Again advantageously, composition of the present invention can comprise softening agent in addition, and its existence can increase its flowability, therefore is convenient to its processing, and can also regulates by this product hardness that processing produced according to the ideal grade value.Preferably, this softening agent is the paraffinic softening agent of being sold with trade name Plaxene by Total or sold with trade name Flexon by Exxon of that class, and in the mixture of per 100 weight part elastomerics/triblock copolymers and optional graft polyolefin, use with the ratio of 5-120 weight part.
Yet other softening agent also is suitable such as polyoxyethylene alkylphenyl.
Said composition also can comprise the filler of light earthfill rockfill concrete riprap RCC: silica, carbonate, clay, chalk, kaolin or the like, or the filler of carbon black class.The latter's application proves particularly advantageous, because they can not only regulate some mechanical property according to composition of the present invention, such as tensile strength or tensile modulus, and can give the ultraviolet light resistant of their excellences.When having above-mentioned filler in the composition, in the mixture of per 100 weight part elastomerics/triblock copolymers and optional graft polyolefin, they advantageously exist with the level of 5-100 weight part.
This cross-linked composition also can contain conventional other auxiliary material that adopts in polymer industry according to the desired performance that obtains, such as anti static additive, lubricant, oxidation inhibitor, coupling agent, tinting material, processing aid or tackifier, condition is that these auxiliary materials are compatible each other certainly.
It is because its preparation relates to the crosslinked elastomerics that is present in its component that composition according to the present invention is called " crosslinked ".
For this reason, according to composition of the present invention, before crosslinked, comprise at least a cross-linking system, this cross-linking system contain with good grounds be present in polymer property in the composition one or more linking agents of suitably selecting, with one or more crosslinking accelerators, the effect of described cross-linking system is priming reaction kinetics and increases cross-linking density.
According to preferred version of the present invention, this cross-linking system comprises: be selected from dicumyl peroxide as one or more of linking agent, 1,3-two (tertiary butyl sec.-propyl) benzene, 2,5-dimethyl-2,5-two (tertiary butyl) hexane superoxide and 1,1-two (tertiary butyl)-3,3, the organo-peroxide of 5-trimethyl-cyclohexane, with be selected from zinc oxide as one or more of crosslinking accelerator, stearic acid, N, N '-(penylene) dimaleimide, triallyl cyanurate, cyanuric acid three isoolefine propyl ester, methacrylic ester (such as methacrylic acid tetrahydrofurfuryl ester or methacrylic acid 2-phenoxy group ethyl ester), dimethacrylate is (such as Ethylene glycol dimethacrylate, dimethacrylate Tetraglycol 99 ester, dimethacrylate 1,4-butanediol ester or zinc dimethacrylate), trimethacrylate (such as trimethylolpropane trimethacrylate) and diacrylate (such as dizinc acrylate resin).
Another preferred version according to the present invention, cross-linking system is based on the system of sulphur, this system except zinc oxide and/or stearic acid as the crosslinking accelerator, also contain one or more for sulphur promotor, such as 4,4 '-dithiomorpholine, tetramethyl thiuram disulfide, two pentamethylene thiuram tetrasulfide or zinc dibutyl dithiocarbamates, with the optional anti-agent of reverting (antireversion agent), such as 1,3-two (lemon health iminomethyl (citraconimidomethyl)) benzene.
The particularly preferred scheme according to the present invention, cross-linking system contains: as the resol of linking agent, this resol is selected from reactive alkylation cresol/formaldehyde and bromo cresol/formaldehyde resin, with chlorine-containing polymer as crosslinking accelerator, polyethylene or sovprene such as chlorating or chlorosulphonation randomly use with zinc oxide and/or stearic acid.This is that this elastomerics also has the feature of aesthetic appearances except showing extremely gratifying mechanical property, tensile-permanent set and compressive set because back one cross-linking system makes it can obtain elastomerics.
With regard to all situations, in the blend of per 100 weight part elastomerics/triblock copolymers and optional graft polyolefin, linking agent preferably is present in this prescription with the level of 1-10 weight part, in per this mixture of 100 weight parts, crosslinking accelerator preferably exists with the level of 0.5-12 weight part simultaneously.
When vulcanization system was the sulfenyl system, this was for sulphur promotor, and for their part, in the blend of per 100 weight part elastomerics/triblock copolymers and optional graft polyolefin, preferably the level with the 1-7 weight part exists.
According to the present invention, the crosslinked of composition uses two kinds of cross-linking systems to carry out.For instance, can unite use based on the cross-linking system of sulphur with based on the cross-linking system of organo-peroxide, or based on the cross-linking system of resol with based on the cross-linking system of organo-peroxide.
Depend on (I) and character (III), composition of the present invention can adopt the technology of the processing that is used for thermoplastic material and equipment to change: thermoforming, and injection moulding, extrude, be shaped or the like.In this concrete example, composition of the present invention is described as " adopting thermoplasticity to process ".As the example of above-mentioned composition, can mention following those, wherein elastomerics (I) is made of homopolymer, multipolymer or trimer, its polymerization can use metallocene catalyst to carry out, and has polymkeric substance (III).Advantageously, (III) be functionalised polyolefin, preferred graft polyolefin.It can be selected from aforesaid graft polyolefin.For instance, can mention known (I) and blend (III) with trade name " Vegaprene ".
According to the cross-linked composition with thermoplasticity transformation of the present invention, those suitable mechanical propertys demonstrating aspect hardness, tensile strength and the extension at break with thermoplastic elastomer of the prior art have better compressive set and tensile-permanent set than the latter simultaneously.This advantage not only can be observed in short-term, and can long-term observation arrive, and composition exhibiting wherein according to the present invention goes out the trend that creep reduces.
Another theme of the present invention is the manufacture method of cross-linked composition as defined above, it is characterized in that it comprises: graft polyolefin, softening agent, filler and auxiliary material randomly in the presence of, elastomerics and three block segmented copolymers carry out blend and this blend carries out crosslinked under suitable selection temperature by suitable cross-linking system.
According to the embodiment of the inventive method, carrying out crosslinked temperature is 150-320 ℃ according to preferably.
According to the particularly preferred embodiment of the inventive method, this method comprises:
A) thermoplastic polymer, polyacrylic acid elastomerics, softening agent, filler and/or auxiliary material randomly in the presence of, elastomerics, triblock copolymer and cross-linking system carry out blend;
B) this blend is heated to 150-320 ℃ temperature and
C) it is kept time of 1-15 minute under this temperature.
This method can be carried out in Banbury mixer or with interchangeable form, be carried out in the kneading machine altogether at twin screw extruder or Buss type.According to environment, with gained material calendering or extrude, cool off then and carry out granulation.So the particle that obtains be easy to that these particles change in flakes by heating, the product of plate, section bar, pipe or other hope.
Another theme of the present invention is the application of cross-linked composition in insulation and/or stopping property strip of paper used for sealing and moulded product manufacturing as defined above, is used for thermal insulation or sound insulation and/or sealing water and sealing moisture, particularly is used in construction industry and the automotive industry (for example doorframe).
Another theme of the present invention is the application that this composition is made at the pipeline that is used for the liquid conveying, pipe, flexible pipe, manifold, jet pipe etc.For instance, can mention the pipeline, flexible pipe and other parts that are used to carry liquid, it is used for brake, cooling, power steering or air-conditioning system in automotive industry.
Cross-linked composition of the present invention can also be mentioned the application in belt, tire, cable sheath and sole are made.
Remaining part by means of this specification sheets will be understood the present invention better, wherein relate to the embodiment according to cross-linked composition of the present invention subsequently.
In preferred compositions of the present invention,, can mention 3 kinds of following compositions as non-limiting example:
1.NR/BR composition is used for dynamic application: braking mechanism, engine bearer,
2.EPDM composition, Vegaprene 3, are used for static application: strip of paper used for sealing,
3.Vegaprene 2 compositions are used for flexible pipe, cable coating layer class.
But, obviously provide these embodiment only to be used to set forth theme of the present invention, wherein they are construed as limiting the present invention never in any form.
Embodiment:
Prepare each prescription according to following method: will prepare the required component adding of cross-linked composition and have in the Banbury mixer of suitable shearing action.When shearing continuously, the internal temperature of Banbury mixer is transferred to 170 ℃ value, and when reaching this temperature, blend was kept under this temperature about 5 minutes.With the material that so obtains in the cooling of the exit of Banbury mixer and carry out granulation.
Carry out following mensuration:
-Shore hardness is measured according to method described in the standard NF T 46-052,
-tensile strength (TS) and the extension at break (EB) of each composition of preparation thus measured according to the method described in the standard ISO 37, and in addition:
-compressive set (CS) when 100 ℃ down 25% compression was finished in pressurization in 22 hours, according to the method described in the standard ISO 815 measure and
-apply when finishing 20% elongation in 70 hours tensile-permanent set (elongation set) (ES), measure according to the method described in the standard ISO 2285.
The research of these compositions is represented and the gained result is summarised in the following table with umber.
It should be noted that the reference group compound does not contain triblock copolymer, and therefore constitute Comparative Examples.
SEB represents: contain three blocks (II) 50wt%PMMA, that have 60000 mumber average molar masses.
Table 1: based on the composition of NR/BR
| Reference | A | B | C | D | E |
| NR | 80 | 80 | 80 | 80 | 80 |
| BR | 20 | 20 | 20 | 20 | 20 |
| SBM | 5 | 10 | 20 | 30 | |
| ZnO | 20 | 20 | 20 | 20 | 20 |
| Stearic acid | 2 | 2 | 2 | 2 | 2 |
| Carbon black | 20 | 20 | 20 | 20 | 20 |
| Softening agent | 4 | 4 | 4 | 4 | 4 |
| Anti-aging agent (protective agent) | 4.5 | 4.5 | 4.5 | 4.5 | 4.5 |
| Promotor | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Sulphur | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| DC | 7.1 | 9.26 | 8.83 | 7.73 | 5.69 |
| Hardness | 44 | 47 | 49 | 53 | 55 |
| Tensile strength (MPa) | 18.3 | 18.4 | 20.5 | 22.5 | 21.4 |
| Standard deviation (MPa) | 1.1 | 0.9 | 1.2 | 0.9 | 1.1 |
| M50％(MPa) | 0.73 | 0.89 | 0.87 | 1.07 | 1.04 |
| M100％(MPa) | 1.12 | 1.39 | 1.37 | 1.69 | 1.57 |
| M200％(MPa) | 2.09 | 2.72 | 2.78 | 3.44 | 3 |
| M300％(MPa) | 3.76 | 5.01 | 5.15 | 6.26 | 5.27 |
| Delft tears (kN/m) | 14.3 | 16.6 | 37.0 | 38.7 | 48.0 |
| Standard deviation (MPa) | 2.1 | 0.8 | 2.9 | 2.6 | 8.1 |
| CS, 100 ℃ following 22 hours, the compression 25% | 42 | 42 | 51 | 56 | 54 |
| Zwick resilience (%) | 74 | 74 | 72 | 66 | 57 |
Table 2: based on the prescription of NR
| Reference | A | B | C | D |
| NR | 100 | 100 | 100 | 100 |
| SMB | 5 | 7 | 10 | |
| ZnO | 20 | 20 | 20 | 20 |
| Stearic acid | 2 | 2 | 2 | 2 |
| Anti-aging agent | 4.5 | 4.5 | 4.5 | 4.5 |
| Promotor | 1.5 | 1.5 | 1.5 | 1.5 |
| Sulphur | 1.5 | 1.5 | 1.5 | 1.5 |
| DC | 6.76 | 6.19 | 6.64 | 5.52 |
| Hardness | 39 | 38 | 41 | 46 |
| Tensile strength (MPa) | 15.6 | 16.4 | 18.4 | 19.4 |
| Standard deviation (MPa) | 1.5 | 1.3 | 0.7 | 0.7 |
| Extension at break (%) | 650 | 620 | 660 | 670 |
| Standard deviation (%) | 20 | 25 | 10 | 10 |
| M50％(MPa) | 0.52 | 0.62 | 0.62 | 0.77 |
| M100％(MPa) | 0.77 | 0.87 | 0.88 | 1.04 |
| M200％(MPa) | 1.22 | 1.32 | 1.37 | 1.52 |
| M300％(MPa) | 1.77 | 1.94 | 2.06 | 2.22 |
| Delft tears (kN/m) | 8.5 | 9.0 | 12.1 | 15.7 |
| Standard deviation (MPa) | 1.1 | 0.3 | 1.0 | 1.1 |
| CS, 100 ℃ following 22 hours, the compression 25% | 40 | 38 | 42 | 43 |
| Zwick resilience (%) | 82 | 78 | 79 | 77 |
From table 1 and 2 as seen, significant improvement is arranged at Delft aspect tearing, it shows better fatigue property (under mechanical stress repeatedly), reaches this performance and can not change the important performance of other correspondence (CS, resilience).No matter crosslinked prescription is with or without the thermoplasticity turn model, and this all is the improvement to them.
Table 3: based on the composition of EPDM
| Reference | A | B | C | D |
| EPDM | 175 | 175 | 175 | 175 |
| SMB | 5 | 10 | 15 | |
| ZnO | 5 | 5 | 5 | 5 |
| Stearic acid | 1.5 | 1.5 | 1.5 | 1.5 |
| Carbon black | 78 | 78 | 78 | 78 |
| Softening agent | 12 | 12 | 12 | 12 |
| Promotor | 2.5 | 2.5 | 2.5 | 2.5 |
| Sulphur | 0.66 | 0.66 | 0.66 | 0.66 |
| Hardness | 48 | 45 | 44 | 43 |
| Tensile strength (MPa) | 18.7 | 20 | 18.9 | 18.7 |
| Standard deviation (MPa) | 0.4 | 0.6 | 0.7 | 0.3 |
| Extension at break (%) | 560 | 610 | 630 | 660 |
| Standard deviation (%) | 10 | 15 | 15 | 10 |
| M50％(MPa) | 0.74 | 0.65 | 0.6 | 0.6 |
| M100％(MPa) | 1.3 | 1.1 | 1 | 0.9 |
| M200％(MPa) | 3.6 | 3 | 2.5 | 2.7 |
| M300％(MPa) | 6.6 | 5.7 | 5.1 | 5 |
| Delft tears (kN/m) | 18.8 | 20 | 21.3 | 22.5 |
| Standard deviation (MPa) | 0.6 | 0.4 | 0.6 | 0.6 |
| CS, 125 ℃ following 22 hours, the compression 25% | 40 | 40 | 39 | 40 |
| Zwick resilience (%) | 63 | 62 | 61 | 60 |
Table 4:Vegaprene type prescription
| Reference | A | B |
| EPDM | 100 | 100 |
| PP | 63 | 63 |
| Carbon black | 30 | 30 |
| Softening agent | 70 | 70 |
| ZnO | 5 | 5 |
| Stearic acid | 1 | 1 |
| Superoxide | 3.5 | 3.5 |
| Anti-aging agent | 1 | 1 |
| Processing aid | 1.5 | 1.5 |
| SBM | 10 |
| Hardness | 77 | 71 |
| Tensile strength (MPa) | 5 | 5 |
| Standard deviation (MPa) | 0.15 | 0.15 |
| Extension at break (%) | 240 | 310 |
| Standard deviation (%) | 15 | 25 |
| M50％(MPa) | 3.21 | 2.48 |
| M100％(MPa) | 3.93 | 3.13 |
Table 3 and 4 is presented at elongation and Delft tears the aspect improvement is arranged, and its installation and intensity for parts is important.
Table 5:Vegaprene 2 type prescriptions
| Reference | A | B |
| EPDM | 100 | 100 |
| PP | 50 | 50 |
| Softening agent | 30 | 30 |
| Carbon black | 30 | 30 |
| ZnO | 4 | 4 |
| Superoxide | 4 | 4 |
| Processing aid | 6 | 6 |
| SBM | 15 |
| Hardness | 63 | 64 |
| Tensile strength (MPa) | 5.2 | 4.9 |
| Standard deviation (MPa) | 0.1 | 0.1 |
| Extension at break (%) | 330 | 300 |
| Standard deviation (%) | 10 | 10 |
| M50％(MPa) | 2.3 | 2.4 |
| M100％(MPa) | 3.5 | 3.6 |
| M300％(MPa) | 4.8 | 4.3 |
| Delft tears (kN/m) | 10.8 | 11.2 |
| CS, 125 ℃ following 22 hours, the compression 25% | 67 | 57 |
From this table as seen, improved the CS under the high temperature.
Claims (28)
1. cross-linked composition, it contains:
At least a elastomerics (I) of-20-100 weight part,
The segmented copolymer (II) of at least a three blocks of-2-50 weight part, wherein at least one block mainly is made of the methacrylic monomer,
At least a thermoplastic polymer (III) of-0-100 weight part.
2. as the desired composition of claim 1, it is characterized in that: the segmented copolymer of this three block (II) is corresponding to following general formula Y-B-Y ', wherein B be with Y and Y ' block thermodynamics on inconsistent elastomeric block, and Y has with Y ' or does not have and at least aly in identical chemical constitution and they mainly is made of the methacrylic monomer.
3. as the desired composition of claim 2, it is characterized in that: B be can with the elastomeric block of elastomerics (I) co-crosslinking, it is selected from polydiene, partially or completely hydrogenant polydiene, polyolefin elastomer, extended chain polypropylene acid esters, nitrile elastomerics or the acrylic copolymer that side is hung vinyl-functional that contains with low Tg value.
4. as the desired composition of claim 3, it is characterized in that: B is by at least a divinyl, the isoprene, 2 of being selected from, the polydiene that monomeric polymerization obtained of 3-dimethyl-1,3-butadiene, 1,3-pentadiene and 2-phenyl-1,3-butadiene.
5. as the desired composition of claim 2, it is characterized in that: Y and Y ' obtain by at least a monomeric polymerization, and wherein said monomer is selected from vinylbenzene and derivative, methacrylic acid short-chain alkyl ester such as methyl methacrylate or functional monomer such as vinylformic acid, methacrylic acid or glycidyl methacrylate.
6. as the desired composition of claim 5, it is characterized in that Y is the block of mainly being made up of vinylbenzene, and Y ' contains the block of 50wt% methyl methacrylate at least.
7. as the desired composition of claim 6, it is characterized in that: Y ' block contains imide functionality.
8. as the desired composition of claim 1, it is characterized in that: elastomerics (I) is to be selected from following compound: the elastomerics of natural rubber, synthetic rubber, EPR, EPDM, employing metallocene polymerization such as poly-(octene/ethene), extended chain polypropylene acid esters or polyolefin elastomer its can be modification or non-modification, extended chain polypropylene acid esters such as poly-(butyl acrylate) or gather (2-ethylhexyl acrylate), viton (FPM) such as multipolymer and silicone elastomer based on tetrafluoroethylene.
9. as the desired composition of claim 8, it is characterized in that: elastomerics (I) is poly-(octene/ethene).
10. as the desired composition of claim 9, it is characterized in that: it can change as thermoplastic material.
11. as the desired composition of claim 1, it is characterized in that: thermoplastic polymer is selected from the grafted polyolefine, such as the polyethylene of using vinylformic acid, maleic anhydride or glycidyl methacrylate graft, polypropylene and poly-(ethylene/propene).
12. each desired composition of claim as described above is characterized in that: before crosslinked, it contains at least a cross-linking system that comprises one or more linking agents and one or more crosslinking accelerators.
13. as the desired composition of claim 12, it is characterized in that: cross-linking system comprises as one or more of linking agent and is selected from dicumyl peroxide, 1,3-two (tertiary butyl sec.-propyl) benzene, 2,5-dimethyl-2,5-two (tertiary butyl) hexane superoxide and 1,1-two (tertiary butyl)-3,3, the organo-peroxide of 5-trimethylammonium-hexanaphthene, with be selected from zinc oxide as one or more of crosslinking accelerator, stearic acid, N, N '-(penylene) dimaleimide, triallyl cyanurate, cyanuric acid three isoolefine propyl ester, dimethacrylate, trimethacrylate, the compound of diacrylate and triacrylate.
14. as the desired composition of claim 12, it is characterized in that: cross-linking system is based on sulphur, and except zinc oxide and/or stearic acid as the crosslinking accelerator, also contain one or more for sulphur activators and the optional anti-agent of reverting.
15. as the desired composition of claim 12, it is characterized in that: cross-linking system contains the resol as linking agent, it is selected from reactive alkylating cresol/formaldehyde and bromo cresol/formaldehyde resin, chlorine polymkeric substance with as crosslinking accelerator randomly uses with zinc oxide and/or stearic acid.
16. as the desired composition of one of claim 13-15, it is characterized in that: in the blend of per 100 weight parts, linking agent and crosslinking accelerator exist with the content of 0.5-12 weight part.
17. each desired cross-linked composition of claim as described above, it contains the filler and/or the auxiliary material of softening agent and/or light earthfill rockfill concrete riprap RCC or carbon black class in addition.
18. desired preparation method of one of claim as described above with cross-linked composition that thermoplasticity changes, it is characterized in that this method comprises: thermoplastic polymer, softening agent, filler and auxiliary material randomly in the presence of, at least a elastomerics and at least a three block segmented copolymers are carried out blend, and make this blend under the temperature of suitably selecting, be undertaken crosslinked by suitable cross-linking system.
19., it is characterized in that as the desired method of claim 18: it be included in carry out under the 150-320 ℃ of temperature crosslinked.
20., it is characterized in that: the crosslinked 1-15 of carrying out minute time as claim 18 or 19 desired methods.
21. one kind insulate and/or stopping property strip of paper used for sealing and moulded product, it contains each desired cross-linked composition just like claim 1-17.
22. as the desired insulation of claim 21 and/or stopping property strip of paper used for sealing and the application of moulded product in construction industry.
23. as the desired insulation of claim 21 and/or stopping property strip of paper used for sealing and the application of moulded product in automotive industry.
24. a pipeline, such as pipe, flexible pipe, manifold or jet pipe, it contains each desired cross-linked composition just like claim 1-17.
25. as the application of the desired composition of one of claim 1-17 in cables manufacturing.
26. as the application of the desired composition of one of claim 1-17 in tire is made.
27. as the application of the desired composition of one of claim 1-17 in belt is made.
28. as the application of the desired composition of one of claim 1-17 in sole is made.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0401826A FR2866651A1 (en) | 2004-02-24 | 2004-02-24 | Cross linking composition, useful in e.g. joints and insulation accessories that are useful in automobile industries, comprises an elastomer, a triblock copolymer sequence and a polyolefin graft |
| FR0401826 | 2004-02-24 | ||
| FR0408713 | 2004-08-06 |
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| Publication Number | Publication Date |
|---|---|
| CN1922259A true CN1922259A (en) | 2007-02-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005800059057A Pending CN1922259A (en) | 2004-02-24 | 2005-02-23 | Cross-linked composition comprising a triblock sequenced copolymer, method for the production thereof, and uses of the same |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1922259A (en) |
| FR (1) | FR2866651A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102947381A (en) * | 2010-06-23 | 2013-02-27 | 米其林企业总公司 | Rubber composition comprising a thermoplastic filler and compatibilizer |
| CN106459503A (en) * | 2014-06-11 | 2017-02-22 | 株式会社普利司通 | Rubber compound to produce tyres |
| CN107459612A (en) * | 2017-09-11 | 2017-12-12 | 四川大学 | A kind of activeness and quietness agent, epoxy resin toughened composite and preparation method thereof |
| CN108350247A (en) * | 2015-11-16 | 2018-07-31 | 阿科玛法国公司 | Include the polymer composition of the vegetable material of dispersion |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11246192B2 (en) | 2016-12-06 | 2022-02-08 | Whirlpool Corporation | Microwave oven with full glass door |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6747094B2 (en) * | 1999-09-09 | 2004-06-08 | Asahi Kasei Kabushiki Kaisha | High impact thermoplastic resin composition |
| CN1190460C (en) * | 2000-01-14 | 2005-02-23 | 住友橡胶工业株式会社 | Low elastic macromolecule compsns. and sealing material using same |
| FR2809741B1 (en) * | 2000-05-31 | 2002-08-16 | Atofina | IMPROVED SHOCK RESISTANT MATERIALS |
-
2004
- 2004-02-24 FR FR0401826A patent/FR2866651A1/en active Pending
-
2005
- 2005-02-23 CN CNA2005800059057A patent/CN1922259A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102947381A (en) * | 2010-06-23 | 2013-02-27 | 米其林企业总公司 | Rubber composition comprising a thermoplastic filler and compatibilizer |
| CN102947381B (en) * | 2010-06-23 | 2015-05-13 | 米其林企业总公司 | Rubber composition comprising a thermoplastic filler and compatibilizer |
| CN106459503A (en) * | 2014-06-11 | 2017-02-22 | 株式会社普利司通 | Rubber compound to produce tyres |
| CN108350247A (en) * | 2015-11-16 | 2018-07-31 | 阿科玛法国公司 | Include the polymer composition of the vegetable material of dispersion |
| CN107459612A (en) * | 2017-09-11 | 2017-12-12 | 四川大学 | A kind of activeness and quietness agent, epoxy resin toughened composite and preparation method thereof |
| CN107459612B (en) * | 2017-09-11 | 2019-11-29 | 四川大学 | A kind of activeness and quietness agent, epoxy resin toughened composite material and preparation method |
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| Publication number | Publication date |
|---|---|
| FR2866651A1 (en) | 2005-08-26 |
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