CN103772613A - Method and device for producing polymer with high grafting rate - Google Patents
Method and device for producing polymer with high grafting rate Download PDFInfo
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- CN103772613A CN103772613A CN201310072578.3A CN201310072578A CN103772613A CN 103772613 A CN103772613 A CN 103772613A CN 201310072578 A CN201310072578 A CN 201310072578A CN 103772613 A CN103772613 A CN 103772613A
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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
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
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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
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/375—Plasticisers, homogenisers or feeders comprising two or more stages
- B29C48/385—Plasticisers, homogenisers or feeders comprising two or more stages using two or more serially arranged screws in separate barrels
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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
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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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
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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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
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
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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
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92695—Viscosity; Melt flow index [MFI]; Molecular weight
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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
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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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
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
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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
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
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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
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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Abstract
The invention provides a method and device for producing polymer with a high grafting rate. The device comprises an equidirectional double-screw extruder and a different-direction double-screw extruder, wherein a supercritical fluid feeding opening is formed in a second heating zone of the different-direction double-screw extruder. The method comprises the following steps: adding a first component comprising polymer resin from a polymer resin feeding opening of the equidirectional double-screw extruder, adding a second component comprising liquid of a polar monomer and a graft accelerating agent from a liquid feeding opening of the equidirectional double-screw extruder, and performing mixing and plasticization in the equidirectional double-screw extruder; conveying the mixed mixture into the different-direction double-screw extruder to be extruded. By the adoption of the method and the device, provided by the invention, polymer resin with the high grafting rate can be produced, and the grafting rate of the product can reach up to 3.5-5%.
Description
Technical field
The present invention relates to a kind of method of producing polymkeric substance, relate in particular to a kind of production method of high percentage of grafting fluoropolymer resin and the device for the production of described high percentage of grafting fluoropolymer resin.
Background technology
Graft copolymerization is the common technology that polymkeric substance is carried out to modification, grafting can increase polymkeric substance bond strength, improve polymer blending alloy consistency, make polymer surfaces hydrophobic or hydrophilic, for crosslinked position etc. is provided.
Generally, graft copolymerization is, under existing by reactive macromole, graft copolymerization monomer, by radical polymerization, ionic polymerization or ring-opening polymerization, to be grafted on macromole, forms side chain; It is as follows that chain shifts graft copolymerization principle:
Or
Main graft copolymerization comprises solution graft copolymerization, fusion-grafting and solid phase grafting method.
The method temperature of reaction of solution graft copolymerization is low, percentage of grafting is high, as the preparation method that patent CN1259354C discloses a kind of polyolefine and polyoxyethylene graft copolymer, prepares the polyolefine that contains p-methylstyrene, then methyl is refined, then in organic solvent, carry out graft reaction.Although solution grafting can obtain higher percentage of grafting, due in a large number with an organic solvent, aftertreatment complexity, environmental pollution is serious, and cost is high.
Solid phase grafting method temperature of reaction is low; solvent load is few; reaction is easily controlled; cost is low, pollute little, as patent CN1133669C discloses the method for polyolefine solid phase grafting; polyolefine, polar monomer are under peroxide initiator, azo-compound initiator or redox system effect; dimethylbenzene is interfacial agent, under nitrogen protection, reacts, and makes the polyolefin graft copolymer that side chain comprises three kinds of monomeric units.Solid phase grafting reaction, cannot make graft copolymerization monomer evenly be grafted on polymkeric substance conventionally.
Patent US5140074, patent EP0519341A etc. have reported the method that uses porous polyolefin and vinyl monomer-grafted, and the method need to be prepared the polyolefine in specific pore rate and aperture, and cost is higher, and grafts use range is narrower.
Fusion-grafting method technique is simple, can produce continuously, if patent US5650468 is by fusion-grafting, utilize continuous extruding technology, the graft product that to have obtained percentage of grafting be 0.4-1.7%, but traditional fusion-grafting method percentage of grafting is lower.
In supercritical environment, prepare graftomer and can improve grafting efficiency, reduce the degraded of polymkeric substance, as the polyacrylic method of solid phase grafting in patent CN101386668B, CN102863588A, the disclosed supercritical co environment of CN102838710A, the disclosed method of carrying out maleic anhydride graft polyisobutene in supercritical environment of patent CN101284897B etc., aforesaid method is all to carry out in autoclave, and the production intermittent phase is long.
Reaction is extruded the chemical reaction of polymkeric substance and the course of processing is combined, make reinforced in the synthetic and modifying process of polymkeric substance, mix, reaction and devolatilization etc. are combined into a continuous process, twin screw extruder is modal reaction extrusion equipment, patent CN101143946A discloses a kind of supercritical reaction and has extruded the method and apparatus of preparing maleic anhydride, the screw slenderness ratio of screw extrusion press is 24: 1-48: 1, supercritical co is in forcing machine side entry feed, can generate the maleic anhydride inoculated polypropylene that percentage of grafting is 0.3-1.2%, but percentage of grafting is too low.
Therefore, still lack a kind of apparatus and method that use supercutical fluid to react the high percentage of grafting polymkeric substance of extrusion.
Summary of the invention
To be solved by this invention is the low problem of percentage of grafting existing in current fusion-grafting method.
The object of this invention is to provide a kind of method of producing high percentage of grafting polymkeric substance, and for the production of the device of described high percentage of grafting polymkeric substance.
First aspect of the present invention is to provide a kind of method of producing high percentage of grafting polymkeric substance, and described method comprises the steps:
Wherein, second component can be in the 1st heating zone or the 2nd heating zone adds, and is preferably in the 2nd heating zone and adds;
Those skilled in the art can understand, and can be divided into multiple heating zone at screw extrusion press, along Flow of Goods and Materials direction, are followed successively by the 1st heating zone, the 2nd heating zone, the 3rd heating zone, and the rest may be inferred." front " of the present invention or " afterwards " all refer to material flow direction in twin screw extruder.
Wherein, in described parallel dual-screw extruding machine, screw slenderness ratio L/D is preferably at (36-52): in 1 scope.Described parallel dual-screw extruding machine rotating speed is preferably 300-600r/min, is preferably 320-550r/min, is preferably 350-500r/min, is preferably 380-450r/min, most preferably is 400r/min.
Wherein, in described counter rotation twin screw extruder, screw slenderness ratio L/D is preferably at (20-40): in 1 scope.Described parallel dual-screw extruding machine rotating speed is preferably 300-600r/min, is preferably 320-550r/min, is preferably 350-500r/min, is preferably 380-450r/min, most preferably is 400r/min.
Wherein, described supercutical fluid can be supercritical co, overcritical nitrogen, supercritical water or its arbitrary combination.
Described supercutical fluid consumption is preferably 0.2-1ml/min, more preferably 0.3-8ml/min, more preferably 0.5-5ml/min.
According to a kind of preferred embodiment of first aspect of the present invention, wherein, described polyolefine melt temperature is preferably within the scope of 70-100 ℃, and melting index (2.16kg load) is preferably within the scope of 0.5-30g/10min.
In described parallel dual-screw extruding machine and/or counter rotation twin screw extruder, temperature is preferably and is controlled within the scope of 50-100 ℃, more preferably within the scope of 80-90 ℃, more preferably within the scope of 82-88 ℃.
Described fluoropolymer resin is preferably polyolefine, can be homopolymer or multipolymer, most preferably is poly-alpha olefins homopolymer or multipolymer, and described multipolymer can be the more multiple copolymer that copolymer, terpolymer or more kinds of monomer polymerization obtain.
Alpha-olefin of the present invention is preferably α-aliphatics alkene, and described alpha-olefin is preferably α-aliphatics alkene of C2-C20, and more preferably α-aliphatics alkene of C1-C10, as ethene, propylene, 1-butylene, 1-hexene, 1-octene etc.
Described graft copolymerization monomer can be polar monomer, non-polar monomer, more preferably polar monomer.
Described polar monomer is preferably and contains the two bond polarity monomers of C=C, more preferably be selected from the comonomer that contains hydroxyl, alkoxyl group, carbonyl, carboxyl, ether, ester group, aromatic base or its combination, as the carboxylic acid, acid anhydrides, carboxylicesters and the aromatic hydrocarbon that contain the two keys of C=C, described in contain the two keys of C=C the example of carboxylic acid comprise vinylformic acid, methacrylic acid or its combination; The example of the acid anhydrides of the carboxylic acid of the two keys of the described C=C of containing comprises maleic anhydride, FUMARIC ACID TECH GRADE acid anhydride or its combination; The example of described double bond containing carboxylicesters comprises acrylate, methacrylic ester, vinyl acetate or its arbitrary combination, and described acrylate, methacrylic ester can be methyl esters, ethyl ester, propyl ester, butyl ester, glycidyl ester etc.; The example of described double bond containing aromatic hydrocarbon comprises vinylbenzene, p-methylstyrene, Vinylstyrene or its arbitrary combination.More preferably, described polar monomer is selected from: glyceryl ester, vinylbenzene, maleic anhydride described in methyl acrylate, methyl methacrylate, methacrylic acid.
Described non-polar monomer is preferably alpha-olefin, and described alpha-olefin is preferably α-fatty alkene of C2-C20, and the more preferably α of C1-C10-fatty alkene, as ethene, propylene, 1-butylene, 1-hexene, 1-octene etc.
Graft-promoting additive of the present invention can be ionic initiator (as cationic initiator, anionic initiator), radical initiator or complex metal; And being preferably radical initiator, described radical initiator is selected from: any one or a few in organo-peroxide (organic compound of contain-O-O-group), organic persulfide (organic compound of contain-S-S-group), azo-compound (organic compound of contain-N=N-group); More preferably any one or a few in superoxide.
Described organo-peroxide is selected from: peroxycarboxylic acid esters, peroxycarbonates, peroxidation two acyls, peroxidation two alkane, ketone peroxide, any one or a few in carboxylic acid peroxide, concrete example comprises: peroxyformic acid, peracetic acid, cyclohexanone peroxide, methylethyl ketone peroxide, dibenzoyl peroxide, benzoyl peroxide formic acid, peroxidized t-butyl perbenzoate, tertbutyl peroxide, ditertiary butyl peroxide, two t-amyl peroxy things, t-amyl peroxy hydrogen, dihydro is crossed Ethylene Oxide, cyclohexanone peroxide, dipropyonyl peroxide, acetylbenzoylperoxide, diacetone peroxide, tert-butyl peroxide isopropyl benzene, dicumyl peroxide, tertiary octyl group peroxy esters, 2, 5-dimethyl-2, 5-di-t-butyl peroxide hexane, more preferably be oxidized diisopropylbenzene(DIPB), tertiary octyl group peroxy esters, 2, 5-dimethyl-2, one or more in 5-di-t-butyl peroxide hexane.
The example of described azo-compound comprises: any one or a few in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile), azo-bis-iso-dimethyl, azo isobutyl cyano group methane amide, azo dicyclohexyl formonitrile HCN, azo dicyano valeric acid, azo two NSC 18620 salt.
Described graft-promoting additive can be to add with the form of monomer, or adds after graft-promoting additive is dissolved in to solvent.
According to the preferred embodiment of first aspect of the present invention, wherein, in described the first component, also comprise auxiliary agent, described auxiliary agent can be the conventional various auxiliary agents in this area, for example oxidation inhibitor and dispersion agent.
Wherein, described oxidation inhibitor can be any one or a few in aromatic amine oxidation inhibitor, Hinered phenols antioxidant, organic sulfide oxidation inhibitor, phosphite ester kind antioxidant, is preferably phosphite ester kind antioxidant.
It can be alkyl phosphorous acid ester that described phosphite ester kind antioxidant is preferably, aromatic yl phosphite, or its combination, concrete example comprises: three (2, 4-di-tert-butyl-phenyl) phosphorous acid ester, two [2-methyl-4, 6-bis-(1, 1 '-dimethyl ethyl) phenol] phosphoric acid ethyl ester, four (2, 4-di-t-butyl eight alkoxyl group-4, 4-xenyl) phosphoric acid ester, two (2, 4-di-tert-butyl-phenyl pentaerythritol diphosphites, (2, 4, 6-tri-tert phenyl-2-butyl-2-ethyl)-1, ammediol phosphorous acid ester, : two (2, 4-bis-p-isopropyl phenyl) pentaerythritol bis-phosphite, : 2, 2 '-ethylenebis (4, 6-di-tert-butyl-phenyl) fluorophosphite, : four (2, 4-di-tert-butyl-phenyl-4, 4-xenyl) biphosphonate, two (2, 4-dicumylphenyl) pentaerythritol diphosphites, distearyl pentaerythritol diphosphite, three (nonyl phenyl) phosphorous acid ester, three (2, 4-di-tert-butyl-phenyl) one or more in phosphorous acid ester, and be preferably two (2, 4-dicumylphenyl) pentaerythritol diphosphites, distearyl pentaerythritol diphosphite, three (nonyl phenyl) phosphorous acid ester, three (2, 4-di-tert-butyl-phenyl) one or more in phosphorous acid ester.
Wherein, described dispersion agent can be high-grade aliphatic ester, senior aliphatic amide, higher fatty acid salt, paraffin and synthetic low-molecular-weight wax or its arbitrary combination, concrete example comprises: the combination of any one or a few in whiteruss, Zinic stearas, barium stearate, Magnesium Stearate, copper stearate, glyceryl monostearate, Tristearoylglycerol, polyethylene wax, Poly Propylene Wax, polyethylene wax, the more preferably combination of any one or a few in whiteruss, Zinic stearas, Poly Propylene Wax, polyethylene wax.
In a kind of preferred embodiment aspect first of the present invention, described graft reaction raw material comprises the component of following weight proportion:
Fluoropolymer resin 100 weight parts;
Polar monomer 0.5-20 weight part;
Oxidation inhibitor 0.1-0.5 weight part;
Graft-promoting additive 0.1-0.3 weight part;
Dispersion agent 0.05-0.25 weight part.
Second aspect of the present invention is to provide a kind of method of producing percentage of grafting polymkeric substance, and described method comprises the steps:
Fluoropolymer resin 100 weight parts;
Polar monomer 0.5-20 weight part;
Oxidation inhibitor 0.1-0.5 weight part;
Graft-promoting additive 0.1-0.3 weight part;
Dispersion agent 0.05-0.25 weight part;
Parallel dual-screw extruding machine is provided, and described parallel dual-screw extruding machine is provided with 9 heating zone; Counter rotation twin screw extruder is provided, and the screw rod of described counter rotation twin screw extruder is divided into 5-7 heating zone;
Second component can be in the 1st heating zone or the 2nd heating zone adds, and is preferably in the 2nd heating zone heating;
Wherein, the fusing point of described fluoropolymer resin is preferably within the scope of 70-100 ℃, and melting index (2.16kg load) is preferably within the scope of 0.5-30g/10min.
Described fluoropolymer resin is one or more in the copolymer of alpha-olefin; Described alpha-olefin is selected from: one or more in ethene, propylene, butylene, hexene, octene.
Described polar monomer is selected from: one or more in maleic anhydride, vinylbenzene, methyl acrylate, glycidyl methacrylate.
Described graft-promoting additive is peroxidation and isopropyl benzene, tertiary octyl group peroxy esters, benzoyl peroxide formic acid, 2,5-dimethyl-2, one or more in 5-di-t-butyl peroxide hexane.
Described oxidation inhibitor is selected from: two (2,4-dicumylphenyl) pentaerythritol diphosphites, distearyl pentaerythritol diphosphite, one or more in three (nonyl phenyl) phosphorous acid ester, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester.
Described dispersion agent is one or more in whiteruss, Zinic stearas, polyethylene wax, Poly Propylene Wax.
In a kind of preferred embodiment aspect second of the present invention, in described parallel dual-screw extruding machine and/or counter rotation twin screw extruder, control temperature within the scope of 50-100 ℃, more preferably be controlled within the scope of 80-80 ℃, more preferably be controlled within the scope of 82-88 ℃, as 84 ℃, 85 ℃, 86 ℃, 87 ℃ etc.
Third aspect of the present invention is to provide a kind of device for the production of above-mentioned high percentage of grafting polymkeric substance, described device comprises parallel dual-screw extruding machine and counter rotation twin screw extruder, and the extrusion of described parallel dual-screw extruding machine is connected to the opening for feed of counter rotation twin screw extruder.
Wherein, parallel dual-screw extruding machine is provided with 9 heating zone, wherein, is provided with fluoropolymer resin opening for feed in the 1st heating zone; Position after resin feeding mouth is provided with liquid charging opening, and described liquid charging opening can be to be positioned at the 1st heating zone or the 2nd heating zone, and is preferably and is positioned at the 2nd heating zone.
Wherein, counter rotation twin screw extruder is provided with 5-7 heating zone, and wherein, the opening for feed of described counter rotation twin screw extruder is positioned at the 1st heating zone; Be provided with supercutical fluid charging opening in the 2nd heating zone.
Wherein, parallel dual-screw extruding machine screw slenderness ratio L/D scope is preferably (36-52): in 1 scope.
Wherein, counter rotation twin screw extruder screw slenderness ratio L/D is preferably (20-40): in 1 scope.
According to the first preferred embodiment of third aspect of the present invention, wherein, counter rotation twin screw extruder is also provided with vacuum pumping opening, and vacuum pumping opening is positioned at the extruding end of counter rotation twin screw extruder.For example, can be arranged on 3-the 5th heating zone (arranging in the situation of 5 heating zone) or 4-the 7th heating zone (arranging in the situation of 7 heating zone) of counter rotation twin screw extruder, be preferably and be arranged on 4-the 5th heating zone (arranging in the situation of 5 heating zone) or 6-the 7th heating zone (arranging in the situation of 7 heating zone), more preferably last heating zone.
For this reason, in the first preferred embodiment of third aspect of the present invention, also comprise vacuum pump, described vacuum pump connects vacuum pumping opening, more preferably, between described vacuum pump and vacuum pumping opening, is provided with snubber assembly.
According to the second preferred embodiment of third aspect of the present invention, wherein, parallel dual-screw extruding machine is also provided with venting port, described venting port is arranged on parallel dual-screw extruding machine end, be preferably and be arranged on 7-the 9th heating zone, be preferably and be arranged on 8-the 9th heating zone, be more preferably arranged on the 9th heating zone.
According to the third preferred embodiment of the 3rd aspect of the present invention, wherein, also comprise supercutical fluid generating apparatus, described supercutical fluid generating apparatus comprises storage vessel, volume pump, filtration equipment for clarifying, constant temperature pressure stabilizing device, supercritical fluid delivery pipeline one end connects storage vessel, after filtration equipment for clarifying, enter and be communicated with constant temperature pressure stabilizing device, then connect the supercutical fluid opening for feed of counter rotation twin screw extruder.
Wherein, volume pump can be mounted in the optional position between storage vessel and supercutical fluid opening for feed, is preferably the optional position between storage vessel and constant temperature pressure stabilizing device.
The apparatus and method of the high percentage of grafting fluoropolymer resin of production provided by the invention, monomer reaction rate is high, there will not be crosslinked or degraded, can produce and obtain high percentage of grafting fluoropolymer resin, the percentage of grafting of the high percentage of grafting fluoropolymer resin of producing, up to 3.5%-5%, can be used as functional materials.
Accompanying drawing explanation
Fig. 1 is in the embodiment of the present invention, produces the device schematic diagram of high percentage of grafting polymkeric substance.
Embodiment
As shown in Figure 1, in the present embodiment, production equipment used comprises parallel dual-screw extruding machine 1, counter rotation twin screw extruder 2, and parallel dual-screw extruding machine 1 is extruded mixture send in counter rotation twin screw extruder 2.At the extruding end of counter rotation twin screw extruder 2, be provided with vacuum pump 23, vacuum pump 23 connects the vacuum pumping opening 22 of counter rotation twin screw extruder 2.Generally, between vacuum pump 23 and vacuum pumping opening 22, snubber assembly 24 is also set, as surge tank, to prevent that in vacuum, appearance is unexpected.
The method of producing high percentage of grafting polymkeric substance in the present embodiment is as follows:
Take raw material according to following ratio:
Wherein, propene/but-1-ene copolymer melt temperature is 83 ℃, and melting index is 10g/10min.
Propene/but-1-ene copolymer and Poly Propylene Wax, two (2,4-dicumylphenyl) pentaerythritol diphosphites are mixed, evenly, after add in the 1st heating zone of parallel dual-screw extruding machine 1 by fluoropolymer resin charging opening 11; Maleic anhydride, dicumyl peroxide are mixed, and at liquid charging opening, 12 places add, mixing in parallel dual-screw extruding machine.
The 9th heating zone of parallel dual-screw extruding machine 1 is provided with venting port 5, and to discharge the volatile gases generating in and process of grafting mixing at parallel dual-screw extruding machine 1, expellant gas is sent in alkali liquor container 51 and absorbed.
Parallel dual-screw extruding machine 1 temperature is controlled at 80-88 ℃, then, the mixture after mixing is sent into counter rotation twin screw extruder 2.
Counter rotation twin screw extruder 2 is divided into 7 heating zone, opening for feed 21 is in the 1st heating zone, parallel dual-screw extruding machine 1 is sent into the mixture after mixing in counter rotation twin screw extruder 2 by charging opening 21, in counter rotation twin screw extruder 2, carry out mixingly, the temperature of counter rotation twin screw extruder 2 is controlled at 82-88 ℃.
In the 3rd heating zone of counter rotation twin screw extruder 2, be provided with supercutical fluid charging opening 3, carbonic acid gas is extracted out from the measured pump 32 of storage vessel 30, after purifying by filtration equipment for clarifying 31, send into constant temperature pressure stabilizing device 33 and carry out preheating, generate supercutical fluid, be sent in counter rotation twin screw extruder 1, supercutical fluid add-on is 1ml/min.
By the granulation of gained extrudate.Products obtained therefrom percentage of grafting is detected, and percentage of grafting is 3.8%.
The method of producing high percentage of grafting polymkeric substance in the present embodiment is as follows:
Take raw material according to following ratio:
Wherein, ethylene/propene copolymer melt temperature is 75 ℃, and melting index is 4g/10min.
With reference to the method for embodiment 1, ethylene/propene copolymer and Poly Propylene Wax, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester are mixed, evenly, after add in the 1st heating zone of parallel dual-screw extruding machine 1 by fluoropolymer resin charging opening 11; Methyl acrylate, benzoyl peroxide formic acid are mixed, and at liquid charging opening, 12 places add, mixing in parallel dual-screw extruding machine.
Parallel dual-screw extruding machine 1 temperature is controlled at 75-85 ℃, then, the mixture after mixing is sent into counter rotation twin screw extruder 2, carries out mixingly in counter rotation twin screw extruder 2, and the temperature of counter rotation twin screw extruder 2 is controlled at 70-80 ℃.
In the 3rd heating zone of counter rotation twin screw extruder 2, be provided with supercutical fluid charging opening 3, carbonic acid gas is extracted out from the measured pump 32 of storage vessel 30, after purifying by filtration equipment for clarifying 31, send into constant temperature pressure stabilizing device 33 and carry out preheating, generate supercutical fluid, be sent in counter rotation twin screw extruder 1, supercutical fluid add-on is 3ml/min.
Counter rotation twin screw extruder 2 is by the material extruding pelletization after mixing.Products obtained therefrom percentage of grafting is detected, and percentage of grafting is 4.3%.
The method of producing high percentage of grafting polymkeric substance in the present embodiment is as follows:
Take raw material according to following ratio:
Wherein, propylene/1-hexene copolymer melt temperature is 90 ℃, and melting index is 16g/10min.
With reference to the method for embodiment 1, propylene/1-hexene copolymer is mixed with Poly Propylene Wax, distearyl pentaerythritol diphosphite, evenly, after add in the 1st heating zone of parallel dual-screw extruding machine 1 by fluoropolymer resin charging opening 11; By vinylbenzene, 2,5-dimethyl-2,5-di-t-butyl peroxide hexane mixes, and at liquid charging opening, 12 places add.
Parallel dual-screw extruding machine 1 temperature is controlled at 85-100 ℃, then, the mixture after mixing is sent into counter rotation twin screw extruder 2, carries out mixingly in counter rotation twin screw extruder 2, and the temperature of counter rotation twin screw extruder 2 is controlled at 80-95 ℃.
In the 3rd heating zone of counter rotation twin screw extruder 2, be provided with supercutical fluid charging opening 3, carbonic acid gas is extracted out from the measured pump 32 of storage vessel 30, after purifying by filtration equipment for clarifying 31, send into constant temperature pressure stabilizing device 33 and carry out preheating, generate supercutical fluid, be sent in counter rotation twin screw extruder 1, supercutical fluid add-on is 4.5ml/min.
Counter rotation twin screw extruder 3 is extruded the material after mixing, sends into moulding in mould 4, makes product.
Products obtained therefrom percentage of grafting is detected, and percentage of grafting is 4.8%.
The method of producing high percentage of grafting polymkeric substance in the present embodiment is as follows:
Take raw material according to following ratio:
Wherein, propylene/1-octene copolymer melt temperature is 78 ℃, and melting index is 25g/10min.
With reference to the method for embodiment 1, propylene/1-octene copolymer is mixed with Poly Propylene Wax, three (nonyl phenyl) phosphorous acid ester, evenly, after add in the 1st heating zone of parallel dual-screw extruding machine 1 by fluoropolymer resin charging opening 11; By glycidyl methacrylate, 2,5-dimethyl-2,5-di-t-butyl peroxide hexane mixes, and at liquid charging opening, 12 places add.
Parallel dual-screw extruding machine 1 temperature is controlled at 80-90 ℃, then, the mixture after mixing is sent into counter rotation twin screw extruder 2, carries out mixingly in counter rotation twin screw extruder 2, and the temperature of counter rotation twin screw extruder 2 is controlled at 70-88 ℃.In the 3rd heating zone of counter rotation twin screw extruder 2, be provided with supercutical fluid charging opening 3, carbonic acid gas is extracted out from the measured pump 32 of storage vessel 30, after purifying by filtration equipment for clarifying 31, send into constant temperature pressure stabilizing device 33 and carry out preheating, generate supercutical fluid, be sent in counter rotation twin screw extruder 1, supercutical fluid add-on is 2.5ml/min.
Counter rotation twin screw extruder 3 is extruded the material after mixing, sends into moulding in mould 4, makes product.
Products obtained therefrom percentage of grafting is detected, and percentage of grafting is 4.1%.
Pass through above-described embodiment, can find out, the method and apparatus of the high percentage of grafting fluoropolymer resin of production provided by the present invention can obtain the fluoropolymer resin of the percentage of grafting of 3.5%-5%, has higher percentage of grafting (if patent US5650468 products obtained therefrom percentage of grafting is only for 0.4-1.7%, CN101143946A products obtained therefrom percentage of grafting are only 0.3-1.2%) than traditional fusion-grafting method or reaction extrusion method products obtained therefrom.
Above specific embodiments of the invention be have been described in detail, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and alternative also all among category of the present invention.Therefore, equalization conversion and the modification done without departing from the spirit and scope of the invention, all should contain within the scope of the invention.
Claims (16)
1. a method of producing high percentage of grafting polymkeric substance, is characterized in that, described method comprises the steps:
Step 1, provides graft reaction raw material, comprises fluoropolymer resin, graft copolymerization monomer and graft-promoting additive; Parallel dual-screw extruding machine is provided, and described parallel dual-screw extruding machine is provided with 9 heating zone; Counter rotation twin screw extruder is provided, and described counter rotation twin screw extruder is provided with 5-7 heating zone;
Step 2, the first component including fluoropolymer resin is added in the 1st heating zone of parallel dual-screw extruding machine, the position of second component including the liquid of polar monomer and graft-promoting additive after fluoropolymer resin opening for feed adds, mixing plasticizing in parallel dual-screw extruding machine;
Step 3, parallel dual-screw extruding machine is sent into described counter rotation twin screw extruder by the mixture after mixing in the 1st heating zone of counter rotation twin screw extruder; And, add supercutical fluid in the 2nd heating zone of counter rotation twin screw extruder;
Step 4, counter rotation twin screw extruder is extruded material, granulation, or send into mould making articles.
2. method according to claim 1, is characterized in that, described polyolefine melt temperature is within the scope of 70-100 ℃, and melting index is preferably within the scope of 0.5-30g/10min.
3. method according to claim 1 and 2, is characterized in that, described fluoropolymer resin is alpha-olefin copolymer.
4. method according to claim 3, is characterized in that, α-aliphatics alkene that alpha-olefin is C1-C10.
5. method according to claim 1 and 2, is characterized in that, in described parallel dual-screw extruding machine and/or counter rotation twin screw extruder, temperature is controlled within the scope of 50-100 ℃.
6. method according to claim 1, is characterized in that, in described parallel dual-screw extruding machine, screw slenderness ratio L/D is at (36-52): in 1 scope; Screw slenderness ratio L/D is at (20-40): in 1 scope.
7. according to the method described in claim 1 or 6, it is characterized in that, in described parallel dual-screw extruding machine, screw speed is 300-600r/min; In described counter rotation twin screw extruder, screw speed is 300-600r/min.
8. method according to claim 1, is characterized in that, described supercutical fluid is selected from supercritical co, overcritical nitrogen, supercritical water or its arbitrary combination.
9. according to the method described in claim 1 or 8, it is characterized in that, described supercutical fluid add-on is 0.2-1ml/min.
10. method according to claim 1, it is characterized in that, described graft copolymerization monomer is for containing the two bond polarity monomers of C=C, and certainly contains the comonomer polar monomer of hydroxyl, alkoxyl group, carbonyl, carboxyl, ether, ester group, aromatic base or its combination.
11. methods according to claim 1, is characterized in that, described graft-promoting additive is organo-peroxide.
12. methods according to claim 1, is characterized in that, in described the first component, also comprise oxidation inhibitor and dispersion agent.
13. methods of stating according to claim 12, is characterized in that, described oxidation inhibitor is phosphite ester kind antioxidant.
14. methods of stating according to claim 12, is characterized in that, described dispersion agent is any one or a few the combination in whiteruss, Zinic stearas, Poly Propylene Wax, polyethylene wax.
Produce the method for high percentage of grafting polymkeric substance for 15. 1 kinds, it is characterized in that, described method comprises the steps:
Step 1, provides graft reaction raw material, and described graft reaction raw material comprises the component of following weight proportion:
Fluoropolymer resin 100 weight parts;
Polar monomer 0.5-20 weight part;
Oxidation inhibitor 0.1-0.5 weight part;
Graft-promoting additive 0.1-0.3 weight part;
Dispersion agent 0.05-0.25 weight part;
Parallel dual-screw extruding machine is provided, and described parallel dual-screw extruding machine is provided with 9 heating zone; Counter rotation twin screw extruder is provided, and the screw rod of described counter rotation twin screw extruder is divided into 5-7 heating zone;
Step 2, the first component including fluoropolymer resin, oxidation inhibitor, dispersion agent is added in the 1st heating zone of parallel dual-screw extruding machine, the position of second component including the liquid of polar monomer and graft-promoting additive after the first component charging opening adds, mixing plasticizing in parallel dual-screw extruding machine;
Step 3, parallel dual-screw extruding machine is sent into described counter rotation twin screw extruder by the mixture after mixing in the 1st heating zone of incongruous double screw; And in the 2nd heating zone of counter rotation twin screw extruder, add supercutical fluid;
Step 4, counter rotation twin screw extruder is extruded material, and gained extrudate is carried out to film forming through curtain coating, calendering, carries out shaping by cooling, traction, finally obtains glued membrane by winding process.
16. 1 kinds of devices for the production of above-mentioned high percentage of grafting polymkeric substance, is characterized in that, described device comprises parallel dual-screw extruding machine and counter rotation twin screw extruder, and the extrusion of described parallel dual-screw extruding machine is connected to the opening for feed of counter rotation twin screw extruder; Wherein:
Parallel dual-screw extruding machine is provided with 9 heating zone, wherein, is provided with fluoropolymer resin opening for feed in the 1st heating zone; Position after fluoropolymer resin opening for feed is provided with liquid charging opening;
Counter rotation twin screw extruder is provided with 5-7 heating zone, and wherein, the opening for feed of described counter rotation twin screw extruder is positioned at the 1st heating zone; Be provided with supercutical fluid charging opening in the 2nd heating zone.
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| CN201310072578.3A CN103772613A (en) | 2013-03-07 | 2013-03-07 | Method and device for producing polymer with high grafting rate |
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| CN201310072578.3A CN103772613A (en) | 2013-03-07 | 2013-03-07 | Method and device for producing polymer with high grafting rate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104057595A (en) * | 2014-06-04 | 2014-09-24 | 浙江太湖远大新材料有限公司 | Mixing device of dual-order extruder |
| CN104479078A (en) * | 2014-12-31 | 2015-04-01 | 广州鹿山新材料股份有限公司 | Grafting reaction device and molten grafting reaction method |
| CN108357136A (en) * | 2018-02-02 | 2018-08-03 | 杨高品 | Medicine preparation double screw extruder |
| WO2019200839A1 (en) * | 2018-04-17 | 2019-10-24 | 佳易容相容剂江苏有限公司 | Toughening agent for high-performance polyester and alloy thereof, and preparation method therefor |
| TWI794753B (en) * | 2021-02-26 | 2023-03-01 | 田文森 | Supercritical fluid material injection molding machine and method thereof |
-
2013
- 2013-03-07 CN CN201310072578.3A patent/CN103772613A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104057595A (en) * | 2014-06-04 | 2014-09-24 | 浙江太湖远大新材料有限公司 | Mixing device of dual-order extruder |
| CN104479078A (en) * | 2014-12-31 | 2015-04-01 | 广州鹿山新材料股份有限公司 | Grafting reaction device and molten grafting reaction method |
| CN104479078B (en) * | 2014-12-31 | 2017-01-04 | 广州鹿山新材料股份有限公司 | A kind of graft reaction device and melting graft reaction method |
| CN108357136A (en) * | 2018-02-02 | 2018-08-03 | 杨高品 | Medicine preparation double screw extruder |
| WO2019200839A1 (en) * | 2018-04-17 | 2019-10-24 | 佳易容相容剂江苏有限公司 | Toughening agent for high-performance polyester and alloy thereof, and preparation method therefor |
| TWI794753B (en) * | 2021-02-26 | 2023-03-01 | 田文森 | Supercritical fluid material injection molding machine and method thereof |
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Application publication date: 20140507 |