CN101781466A - Preparation method of polyolefine/polyamide alloy material with bicontinuous structure - Google Patents
Preparation method of polyolefine/polyamide alloy material with bicontinuous structure Download PDFInfo
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- CN101781466A CN101781466A CN201010125528A CN201010125528A CN101781466A CN 101781466 A CN101781466 A CN 101781466A CN 201010125528 A CN201010125528 A CN 201010125528A CN 201010125528 A CN201010125528 A CN 201010125528A CN 101781466 A CN101781466 A CN 101781466A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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Abstract
The invention provides a preparation method of a polyolefine/polyamide alloy material with a bicontinuous structure, which comprises the following steps: mixing fictionalized polybutadiene and polyolefine which is irradiated or added with peroxide initiator, wherein the weight ratio of the polybutadiene to the polyolefine is 3-20:80-97, and putting the mixture into an extruder for granulating by melt extrusion at 160-210 DEG C to obtain a first reaction product; and mixing the first reaction product and polyamide in weight ratio of 70-85:15-30, and putting the mixture into an extruder for granulating by blend extrusion at 230-300 DEG C to obtain the polyolefine/polyamide alloy material with the bicontinuous structure. By the method provided by the invention, the polyolefine/polyamide alloy material with the bicontinuous structure can be prepared under the condition of a small phase of polyamide, and the method has the advantages of simple process, low preparation cost and the like and is suitable for industrialized production.
Description
Technical field
The present invention relates to high molecule alloy material, particularly a kind of preparation method with polyolefin/polyamide alloy material of bicontinuous structure.
Background technology
The binary polymer blend is a kind of high molecule alloy material, and it is meant that the macromolecular material with two kinds of polymkeric substance mixed together form will can obtain the macromolecular material of high comprehensive performance after the polymer blending by means of the method for physics or chemistry.The binary polymer blend is divided according to its morphological structure can be divided into single-phase continuous structure and bicontinuous structure.Single-phase continuous structure is meant that in the two-phase of the co-mixing system of polymkeric substance one is external phase mutually, and another is mutually for being dispersed in the disperse phase in the external phase.Bicontinuous structure is meant that each component in the co-mixing system of polymkeric substance all can form the external phase that runs through whole co-mixing system.Compare with blend polymer with single-phase continuous structure, the blend polymer of bicontinuous structure has many advantages, for example: for material property, the tensile strength of blend polymer with bicontinuous structure is greater than the single-phase continuous structure blend polymer with similar composition, and greater than its each component intensity simply add and; For material function, what the blend polymer with bicontinuous structure can prepare high barrier material or use that selective solvent will be wherein one mixes and takes off, and obtains porous material, can use in fields such as filtering membrane, supports.
For most incompatible polymer blend system, bicontinuous structure all is to form than being easier under the situation that two kinds of component content are close.But from the angle of material modification, under the situation that the final performance of material can guarantee, in order to improve modification efficiency, the content difference of two components is apart from being the bigger the better.
Polyolefine and polymeric amide are carried out the polyolefin/polyamide alloy material with bicontinuous structure that forms after the blend, and what people can use that selective solvent will be wherein one mixes and takes off, and obtains porous material, as filtering membrane and support of the catalyst etc.But for most incompatible polymer blend system, bicontinuous structure all is to form than being easier under the situation that two kinds of component content are close.Disclose a kind of working method by melt blending as United States Patent (USP) 20070116737A1 and prepared and have bicontinuous structure A/B alloy material, wherein A is a degradable high polymer material, and B is that non-degradable macromolecular material and A/B are incompatible.This alloy material can be made into porous material, but forms two kinds of component content of bicontinuous structure A, B near equating at A or B the very difficult bicontinuous structure that forms mutually for low levels the time is arranged.People such as Leibler (Design and properties of co-continuous nanostructured polymers byreactive blending, Nature Materials, 2002,1,54) successfully prepare stable polyethylene/polyamide 6 bicontinuous structure, wherein the content of polyamide 6 is 20wt%.It at first is with ethene, ethyl propenoate and maleic anhydride radical initiator initiated polymerization formation molecular weight under the condition of High Temperature High Pressure is 9300 polyethylene, making molecular weight by polycondensation then is 2500 polyamide 6, at last with the preparation polyethylene and polyamide 6 by extruding at 220 ℃ of melt blendings in the forcing machine, obtain having the polyethylene/polyamide 6 alloy material of bicontinuous structure, but in the polyethylene with bicontinuous structure/polyamide 6 co-mixing system of his preparation, then can't form bicontinuous structure if the molecular weight of polyethylene and polyamide 6 is too high, therefore to the raw material polyamide 6, poly molecular weight requires comparatively harsh, wherein the molecular weight of polyamide 6 is 2500, poly molecular weight 9300, and complicated process of preparation, cost is higher, is not suitable for suitability for industrialized production.
Summary of the invention
In view of above problem, the technical problem that the present invention solves is to provide a kind of preparation method who prepares the polyolefin/polyamide alloy material with bicontinuous structure with polymeric amide as minority and polyolefine by the mode of melt blending, and it is simple to adopt described method to prepare the technology of polyolefin/polyamide alloy material, is applicable to suitability for industrialized production.
The invention provides a kind of preparation method, comprising with polyolefin/polyamide alloy material of bicontinuous structure:
Be 3～20: 80～97 functionalized poly divinyl with weight ratio and after irradiation or the polyolefine that is added with peroxide initiator mix, put into forcing machine and melt extrude granulation, obtain first reaction product at 160 ℃～210 ℃;
With weight ratio is to put into forcing machine at 230 ℃～300 ℃ blend extruding pelletizations after 70～85: 15～30 described first reaction product and polymeric amide mix, and obtains having the polyolefin/polyamide alloy material of bicontinuous structure.
Preferably, described functionalized polyhutadiene is that the polyhutadiene of 600～10000 1,4 structure and/or the polyhutadiene of 1,2 structure make by molecular weight.
Preferably, the functionalized group of described functionalized poly divinyl is maleic anhydride, acrylic or methacrylic acid glycidyl ester.
Preferably, the irradiation source of described irradiation is gamma-ray radiation source or rumbatron electron radiation source.
Preferably, the dosage of described irradiation is 10kGy～50kGy.
Preferably, described peroxide initiator is a dicumyl peroxide, 2,5-dimethyl-2,5-di-t-butyl hexane peroxide.
Preferably, described peroxide initiator and described polyolefinic weight ratio are 0.5～1.5: 800～1000.
Preferably, described polymeric amide is polyamide 6, polyamide 66, polyamide 1010 or polymeric amide 46.
Preferably, described polyolefine is multipolymer or the polyethylene and the polyacrylic mixture of polyethylene, polypropylene, ethene and propylene.
The invention provides a kind of preparation method with polyolefin/polyamide alloy material of bicontinuous structure, it is to melt extrude at 160 ℃～210 ℃ with functionalized polyhutadiene with through irradiation or the polyolefine that is added with peroxide initiator earlier to obtain first reaction product, contain the functionalized poly divinyl graft polyolefin that functionalized poly divinyl and polyolefine generation graft reaction form in described first reaction product, also contain in described first reaction product simultaneously do not take place graft reaction, free functionalized poly divinyl; Be that minority is mixed the back at 230 ℃～300 ℃ melt blending extruding pelletizations with described first reaction product then with the polymeric amide.In the process that frit reaction is extruded, since the functionalized group on the functionalized poly divinyl can with amido generation chemical reaction in the polymeric amide, so functionalized poly divinyl graft polyolefin and polymeric amide generation graft reaction, the graft copolymer that forms the high molecular trunk is the polymeric amide graft polyolefin; Free functionalized poly divinyl can be a polymeric amide grafting polyhutadiene with the graft copolymer of polymeric amide generation graft reaction formation lower molecular weight trunk also in the reaction system simultaneously.Wherein the graft copolymer of high molecular trunk has played the enhancing interface, has promoted the stress transfer function in the process that forms bicontinuous structure, so more helps the dispersion of polymeric amide; And the lower molecular weight trunk graft copolymer that exists together more promotes to form the polyolefin/polyamide interface of larger radius of curvature, helps polymeric amide and is elongated mutually.Therefore, even be also can form bicontinuous structure under the situation of minority phase at polymeric amide, and preparation technology is simple, and cost is low, is applicable to suitability for industrialized production.
Description of drawings
Fig. 1 is the sem photograph of the polyolefin/polyamide alloy material of embodiment 1 preparation;
Fig. 2 is the sem photograph of the polyolefin/polyamide alloy material of embodiment 2 preparations;
Fig. 3 is the sem photograph of the polyolefin/polyamide alloy material of embodiment 3 preparations;
Fig. 4 is the sem photograph of the polyolefin/polyamide alloy material of embodiment 4 preparations;
Fig. 5 is the sem photograph of the polyolefin/polyamide alloy material of embodiment 5 preparations;
Fig. 6 is the sem photograph of the polyolefin/polyamide alloy material of embodiment 6 preparations;
Fig. 7 is the sem photograph of the polyolefin/polyamide alloy material of embodiment 7 preparations;
Fig. 8 is the sem photograph of the polyolefin/polyamide alloy material of comparative example 1 preparation;
Fig. 9 is the sem photograph of the polyolefin/polyamide alloy material of comparative example 2 preparations.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, but should be appreciated that these describe just to further specifying the features and advantages of the present invention, rather than to the restriction of claim of the present invention.
The embodiment of the invention discloses a kind of preparation method, comprising with polyolefin/polyamide alloy material of bicontinuous structure:
With weight ratio is 3～20: 80～97 functionalized poly divinyl and through irradiation or be added with and put into forcing machine after the peroxide initiator polyolefine mixes and melt extrude granulation at 160 ℃～210 ℃, obtains first reaction product;
With weight ratio is to put into forcing machine at 230 ℃～300 ℃ melt blending extruding pelletizations after 70～85: 15～30 described first reaction product and polymeric amide mix, and obtains having the polyolefin/polyamide alloy material of bicontinuous structure.
According to the present invention, described functionalized polyhutadiene is that the compound that graft reaction obtains takes place for polyhutadiene and functionalized monomer, it is high by 1 that the polymerization of preferred employing ligand complex catalytic way is produced, 4 infrastructure products, or contain 50%-80%1 by what the polymerization of anionic initiation mode was produced, 2 constructed products, the molecular weight of described polyhutadiene is preferably 600～10000, if the polyhutadiene molecular weight is too high, the high molecular trunk graft copolymer that then functionalized polyhutadiene and polyamide reaction generate is the polyolefin/polyamide interface that polymeric amide grafting polyhutadiene will be unfavorable for forming larger radius of curvature, and then is difficult to form the polyolefin/polyamide alloy material with bicontinuous structure.Described functionalized monomer is preferably maleic anhydride, acrylic or methacrylic acid glycidyl ester.Preparation method for the functionalized poly divinyl is a method well known to those skilled in the art, is specifically as follows polyhutadiene and functionalized monomer are prepared by direct heat adduction method.
The purpose of polyolefine being carried out irradiation or being added with peroxide initiator is to make polyolefine produce free radical, is easy to and functionalized poly divinyl generation graft reaction.Described polyolefine is preferably multipolymer or the polyethylene and the polyacrylic mixture of polyethylene, polypropylene, ethene and propylene.The irradiation source that polyolefine is carried out irradiation can be gamma-ray radiation source, alpha radiation source, β ray radiation source, x ray radiation source or rumbatron electron radiation source, according to the present invention, preferred gamma-ray radiation source or the rumbatron electron radiation source of adopting, irradiation dose is preferably 10kGy～50kGy, more preferably 15kGy～45kGy.Described peroxide initiator can be dicumyl peroxide, di-t-butyl peroxide or 2,5-dimethyl-2, the 5-di-t-butyl hexane peroxide, the preferred dicumyl peroxide or 2 that adopts, 5-dimethyl-2, the 5-di-t-butyl hexane peroxide, described peroxide initiator is preferably 0.5～1.5 with polyolefinic weight ratio: 800～1000.
Extrude 160 ℃～210 ℃ blend with functionalized polyhutadiene with through irradiation or the polyolefine that is added with peroxide initiator, melt extrude functionalized poly divinyl and polyolefine generation graft reaction in the process, generate functionalized poly divinyl graft polyolefin, percentage of grafting is 1%～20%, also comprises free functionalized poly divinyl in first reaction product that forms after the grafting.With functionalized polyhutadiene with through irradiation or be added with the process that the polyolefine of peroxide initiator melt extrudes and be preferably: be 3～20: 80～97 functionalized poly divinyl with weight ratio and after irradiation or the polyolefine that is added with peroxide initiator mix, put into forcing machine, melt extrude granulation at 160 ℃～210 ℃, rotating speed is preferably 30 rev/mins～400 rev/mins, more preferably 50 rev/mins～360 rev/mins, can be equipment well known to those skilled in the art for forcing machine, there is no particular restriction to this in the present invention.
According to the present invention, described polymeric amide is preferably polyamide 6, polyamide 66, polyamide 1010 or polymeric amide 46.
Described first reaction product and polymeric amide are extruded at 230 ℃～300 ℃ melt blendings, in the process that melt blending is extruded, described first reaction product comprises functionalized poly divinyl graft polyolefin and free functionalized poly divinyl, since the functionalized group on the functionalized poly divinyl can with the amido generation chemical reaction in the polymeric amide, so functionalized poly divinyl graft polyolefin and polymeric amide generation graft reaction, the graft copolymer that forms the high molecular trunk is the polymeric amide graft polyolefin, and free functionalized poly divinyl can be a polymeric amide grafting polyhutadiene with the graft copolymer of polymeric amide generation graft reaction formation lower molecular weight trunk also in the reaction system simultaneously.Wherein the graft copolymer of high molecular trunk has played the enhancing interface, has promoted the stress transfer function in the process that forms bicontinuous structure, so more helps the dispersion of polymeric amide; And the lower molecular weight trunk graft copolymer that exists together more promotes to form the polyolefin/polyamide interface of larger radius of curvature, helps polymeric amide and is elongated mutually.Therefore even under polymeric amide is the situation of minority phase, also can form bicontinuous structure.
Described first reaction product and polymeric amide are carried out the process that blend extrudes to be preferably: with weight ratio is to put into single screw rod or twin screw extruder after 70～85: 15～30 described first reaction product and polymeric amide mix, at 230 ℃～300 ℃ melt blending extruding pelletizations, screw speed is preferably 30 rev/mins～400 rev/mins, more preferably 50 rev/mins～360 rev/mins, can be equipment well known to those skilled in the art for forcing machine, there is no particular restriction to this in the present invention.
In order further to understand the present invention, a kind of preparation method with polyolefin/polyamide alloy of bicontinuous structure provided by the invention is described below in conjunction with embodiment.The forcing machine that uses in following examples is the SHJ-30 twin screw extruder that the Fengyang Industry ﹠ Trade Group, Beijing produces, and screw diameter is 30mm, and length-to-diameter ratio is 40; Maleic anhydride graft polyhutadiene in following examples is provided by Beijing Yanshan Petrochemical Company, and percentage of grafting is 15% or 20%, and molecular weight is 3200; Acrylic acid-grafted polyhutadiene in following examples is provided by Beijing Yanshan Petrochemical Company, and percentage of grafting is 20%, and molecular weight is 3200; Glycidyl methacrylate graft polyhutadiene in following examples is provided by Beijing Yanshan Petrochemical Company, and percentage of grafting is 15%, and molecular weight is 3200; Polyethylene in following examples is the linear low density polyethylene LLDPE that Jilin Petrochemical company produces, melting index be 2g/10min (190 ℃, 2.16kg); Polypropylene in following examples is all for being provided by Panjin ethylene industry company, melting index be 3.3g/10min (230 ℃, 2.16kg); Ethylene-propylene copolymer in following examples is contained the grand plastic material company limited of ytterbium by Dongguan City and is provided, melting index be 21g/10min (230 ℃, 2.16kg); Polyamide 6 in following examples is newly understood U.S.A by Guangdong and is reached plastic cement company limited and provide, and limiting viscosity is 2.5dl/g; Polyamide 66 in following examples is provided by Heilungkiang nylon factory, and limiting viscosity is 2dl/g.
Embodiment 1
1, be to put into the twin screw extruder extruding pelletization after 20% maleic anhydride graft polyhutadiene and 1g dicumyl peroxide mix with 900g polyethylene, 100g percentage of grafting, extrusion temperature is controlled to be 195 ℃, and screw speed is 80 rev/mins.
2, put into the twin screw extruder extruding pelletization after getting product that 750g step 1 obtains and the 250g polyamide 6 mixing, extrusion temperature is controlled to be 235 ℃, screw speed is 100 rev/mins, obtain the polyolefin/polyamide alloy material, referring to the sem photograph of Fig. 1 for the polyolefin/polyamide alloy material of present embodiment preparation, as can be seen from the figure each component in the alloy material all forms the external phase that runs through whole co-mixing system.
Embodiment 2
1, with 450g polyethylene, 550g polypropylene, 50g percentage of grafting is 15% maleic anhydride graft polyhutadiene and 0.06g2,5-dimethyl-2, the 5-di-t-butyl hexane peroxide is put into the twin screw extruder extruding pelletization after mixing, extrusion temperature is controlled to be 200 ℃, and screw speed is 80 rev/mins.
2, put into the twin screw extruder extruding pelletization after getting product that 800g step 1 obtains and the 200g polyamide 6 mixing, extrusion temperature is controlled to be 235 ℃, screw speed is 100 rev/mins, obtain the polyolefin/polyamide alloy material, referring to the sem photograph of Fig. 2 for the polyolefin/polyamide alloy material of present embodiment preparation, as can be seen from the figure each component in the alloy material all forms the external phase that runs through whole co-mixing system.
1, be to put into the twin screw extruder extruding pelletization after 20% maleic anhydride graft polyhutadiene and 1g dicumyl peroxide mix with 850g ethylene-propylene copolymer, 150g percentage of grafting, extrusion temperature is controlled to be 195 ℃, and screw speed is 80 rev/mins.
2, put into the twin screw extruder extruding pelletization after getting product that 800g step 1 obtains and the 200g polyamide 66 mixing, extrusion temperature is controlled to be 265 ℃, screw speed is 100 rev/mins, obtain having the polyolefin/polyamide alloy material of bicontinuous structure, referring to the sem photograph of Fig. 3 for the polyolefin/polyamide alloy material of present embodiment preparation, as can be seen from the figure each component in the alloy material all forms the external phase that runs through whole co-mixing system.
Embodiment 4
1, be to put into the twin screw extruder extruding pelletization after 15% maleic anhydride graft polyhutadiene and 1g dicumyl peroxide mix with 900g polypropylene, 50g percentage of grafting, extrusion temperature is controlled to be 195 ℃, and screw speed is 80 rev/mins.
2, put into the twin screw extruder extruding pelletization after getting product that 750g step 1 obtains and the 250g polyamide 66 mixing, extrusion temperature is controlled to be 265 ℃, screw speed is 100 rev/mins, obtain having the polyolefin/polyamide alloy material of bicontinuous structure, referring to the sem photograph of Fig. 4 for the polyolefin/polyamide alloy material of present embodiment preparation, as can be seen from the figure each component in the alloy material all forms the external phase that runs through whole co-mixing system.
Embodiment 5
1, the 900g polyethylene is used rumbatron electron radiation source irradiation, irradiation dose is 20kGy.
2, will put into the twin screw extruder extruding pelletization after irradiated polyethylene of step 1 and the acrylic acid-grafted mixed with polybutadiene of 100g, extrusion temperature is controlled to be 195 ℃, and screw speed is 80 rev/mins.
3, put into the twin screw extruder extruding pelletization after getting product that 750g step 2 obtains and the 250g polyamide 66 mixing, extrusion temperature is controlled to be 265 ℃, screw speed is 100 rev/mins, obtain having the polyolefin/polyamide alloy material of bicontinuous structure, referring to the sem photograph of Fig. 5 for the polyolefin/polyamide alloy material of present embodiment preparation, as can be seen from the figure each component in the alloy material all forms the external phase that runs through whole co-mixing system.
Embodiment 6
1, with 900g polypropylene gamma-ray radiation source irradiation, irradiation dose is 15kGy.
2, will put into the twin screw extruder extruding pelletization after irradiated polypropylene of step 1 and 100g glycidyl methacrylate graft mixed with polybutadiene, extrusion temperature is controlled to be 195 ℃, and screw speed is 80 rev/mins.
3, put into the twin screw extruder extruding pelletization after getting product that 750g step 2 obtains and the 250g polyamide 66 mixing, extrusion temperature is controlled to be 265 ℃, screw speed is 100 rev/mins, obtain having the polyolefin/polyamide alloy material of bicontinuous structure, referring to the sem photograph of Fig. 6 for the polyolefin/polyamide alloy material of present embodiment preparation, as can be seen from the figure each component in the alloy material all forms the external phase that runs through whole co-mixing system.
Embodiment 7
1, with 900g polypropylene gamma-ray radiation source irradiation, irradiation dose is 15kGy.
2, will put into the twin screw extruder extruding pelletization after the irradiated polypropylene of step 1 and 100g percentage of grafting are 20% maleic anhydride graft mixed with polybutadiene, extrusion temperature is controlled to be 195 ℃, and screw speed is 100 rev/mins.
3, put into the twin screw extruder extruding pelletization after getting product that 750g step 2 obtains and the 250g polyamide 66 mixing, extrusion temperature is controlled to be 265 ℃, screw speed is 100 rev/mins, obtain having the polyolefin/polyamide alloy material of bicontinuous structure, referring to the sem photograph of Fig. 7 for the polyolefin/polyamide alloy material of present embodiment preparation, as can be seen from the figure each component in the alloy material all forms the external phase that runs through whole co-mixing system.
Comparative example 1
700 gram polyethylene and 300 are restrained put into the twin screw extruder extruding pelletization after polyamide 6s mix, extrusion temperature is controlled to be 220 ℃, screw speed is 60 rev/mins, obtain with the polyethylene is that external phase, polyamide 6 are the polyolefin/polyamide alloy material of disperse phase, referring to the sem photograph that Figure 8 shows that the polyolefin/polyamide alloy material that this comparative example makes, as can be seen from the figure co-mixing system does not form bicontinuous structure.
Comparative example 2
1, obtain maleic anhydride grafted polyethylene with putting into the twin screw extruder extruding pelletization after 980g polyethylene, 20g maleic anhydride and the mixing of 1g dicumyl peroxide, extrusion temperature is controlled to be 195 ℃, and screw speed is 80 rev/mins.
2, put into the twin screw extruder extruding pelletization after getting product that 700g step 1 obtains and the 300g polyamide 6 mixing, extrusion temperature is controlled to be 235 ℃, screw speed is 100 rev/mins, obtain the polyolefin/polyamide alloy material, referring to the sem photograph that Figure 9 shows that the polyolefin/polyamide alloy material that this comparative example makes, as can be seen from the figure co-mixing system does not form bicontinuous structure.
By The above results as can be known, adopt method provided by the invention to prepare the polyolefin/polyamide alloy material, can make the polyolefin/polyamide alloy material with bicontinuous structure, and described preparation technology is simple, preparation cost is low, applicable to suitability for industrialized production.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined herein General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (9)
1. preparation method with polyolefin/polyamide alloy material of bicontinuous structure comprises:
Be 3～20: 80～97 functionalized poly divinyl with weight ratio and after irradiation or the polyolefine that is added with peroxide initiator mix, put into forcing machine and melt extrude granulation, obtain first reaction product at 160 ℃～210 ℃;
With weight ratio is to put into forcing machine at 230 ℃～300 ℃ blend extruding pelletizations after 70～85: 15～30 described first reaction product and polymeric amide mix, and obtains having the polyolefin/polyamide alloy material of bicontinuous structure.
2. preparation method according to claim 1 is characterized in that, described functionalized polyhutadiene is that the polyhutadiene of 600～10000 1,4 structure and/or the polyhutadiene of 1,2 structure make by molecular weight.
3. preparation method according to claim 1 is characterized in that, the functionalized group of described functionalized poly divinyl is maleic anhydride, acrylic or methacrylic acid glycidyl ester.
4. preparation method according to claim 1 is characterized in that, the irradiation source of described irradiation is: gamma-ray radiation source or rumbatron electron radiation source.
5. preparation method according to claim 4 is characterized in that, the dosage of described irradiation is 10kGy～50kGy.
6. preparation method according to claim 1 is characterized in that, described peroxide initiator is dicumyl peroxide or 2,5-dimethyl-2,5-di-t-butyl hexane peroxide.
7. preparation method according to claim 6 is characterized in that, described peroxide initiator and described polyolefinic weight ratio are 0.5～1.5: 800～1000.
8. preparation method according to claim 1 is characterized in that, described polymeric amide is polyamide 6, polyamide 66, polyamide 1010 or polymeric amide 46.
9. according to any described preparation method of claim 1 to 7, it is characterized in that described polyolefine is multipolymer or the polyethylene and the polyacrylic mixture of polyethylene, polypropylene, ethene and propylene.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775784A (en) * | 2012-03-12 | 2012-11-14 | 东莞市信诺橡塑工业有限公司 | Polyamide 66/high-density polyethylene composition prepared by in-situ reaction compatibilization method and preparation method thereof |
| CN102796368A (en) * | 2012-07-25 | 2012-11-28 | 四川大学 | Preparation method of semi-aromatic polyamide alloy |
| CN103044909A (en) * | 2012-11-25 | 2013-04-17 | 安徽六方重联机械股份有限公司 | Packaging plastic substrate thin film containing nylon PA6 |
| CN106883599A (en) * | 2012-06-22 | 2017-06-23 | 丰田纺织株式会社 | Resin combination |
| CN110475605A (en) * | 2017-03-30 | 2019-11-19 | 东丽株式会社 | The manufacturing method of seperation film and seperation film |
| CN110983527A (en) * | 2019-12-29 | 2020-04-10 | 江苏恒力化纤股份有限公司 | Nylon 6 composite fiber and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5663229A (en) * | 1993-03-24 | 1997-09-02 | Ems-Inventa Ag | Ternary polymer mixture and its use |
| CN1175968A (en) * | 1995-10-27 | 1998-03-11 | 埃勒夫阿托化学有限公司 | Mixture of polyolefin and polyamide alloy, and fabrication process |
| CN1290594A (en) * | 1999-06-24 | 2001-04-11 | 中国科学院长春应用化学研究所 | Method for preparing polyamide polynropylene alloy |
| EP1465308A2 (en) * | 2003-04-04 | 2004-10-06 | REHAU AG + Co | Heat shrinkable protection tube |
-
2010
- 2010-03-17 CN CN2010101255283A patent/CN101781466B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5663229A (en) * | 1993-03-24 | 1997-09-02 | Ems-Inventa Ag | Ternary polymer mixture and its use |
| CN1175968A (en) * | 1995-10-27 | 1998-03-11 | 埃勒夫阿托化学有限公司 | Mixture of polyolefin and polyamide alloy, and fabrication process |
| CN1290594A (en) * | 1999-06-24 | 2001-04-11 | 中国科学院长春应用化学研究所 | Method for preparing polyamide polynropylene alloy |
| EP1465308A2 (en) * | 2003-04-04 | 2004-10-06 | REHAU AG + Co | Heat shrinkable protection tube |
Non-Patent Citations (2)
| Title |
|---|
| 《polymer》 19851130 Souheng Wu Phase structure and adhesion in polymer blends: A criterion for rubber toughening 第1855-1863页 1-9 第26卷, * |
| 《polymer》 20060312 Cong Wang Phase morphology and toughening mechanism of polyamide 6/EPDM-g-MA blends obtained via dynamic packing injection molding 第3197-3206页 1-9 第47卷, * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775784A (en) * | 2012-03-12 | 2012-11-14 | 东莞市信诺橡塑工业有限公司 | Polyamide 66/high-density polyethylene composition prepared by in-situ reaction compatibilization method and preparation method thereof |
| CN102775784B (en) * | 2012-03-12 | 2014-02-26 | 东莞市信诺橡塑工业有限公司 | Polyamide 66/high-density polyethylene composition prepared by in-situ reaction compatibilization method and preparation method thereof |
| CN106883599A (en) * | 2012-06-22 | 2017-06-23 | 丰田纺织株式会社 | Resin combination |
| CN102796368A (en) * | 2012-07-25 | 2012-11-28 | 四川大学 | Preparation method of semi-aromatic polyamide alloy |
| CN103044909A (en) * | 2012-11-25 | 2013-04-17 | 安徽六方重联机械股份有限公司 | Packaging plastic substrate thin film containing nylon PA6 |
| CN110475605A (en) * | 2017-03-30 | 2019-11-19 | 东丽株式会社 | The manufacturing method of seperation film and seperation film |
| US11446611B2 (en) | 2017-03-30 | 2022-09-20 | Toray Industries, Inc. | Separating membrane and method for manufacturing separating membrane |
| CN110983527A (en) * | 2019-12-29 | 2020-04-10 | 江苏恒力化纤股份有限公司 | Nylon 6 composite fiber and preparation method thereof |
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