CN102321319A - A kind of preparation method with supercritical co secondary process PVDC resin - Google Patents
A kind of preparation method with supercritical co secondary process PVDC resin Download PDFInfo
- Publication number
- CN102321319A CN102321319A CN201110175587A CN201110175587A CN102321319A CN 102321319 A CN102321319 A CN 102321319A CN 201110175587 A CN201110175587 A CN 201110175587A CN 201110175587 A CN201110175587 A CN 201110175587A CN 102321319 A CN102321319 A CN 102321319A
- Authority
- CN
- China
- Prior art keywords
- heating zone
- pvdc
- supercritical
- resin
- secondary process
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
-
- 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
- B29C2948/92514—Pressure
-
- 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
-
- 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
Abstract
The invention discloses a kind of preparation method with supercritical co secondary process PVDC resin; Adopt extrusion by melting; The PVDC powder is through first heating zone and the second heating zone partial melting in the twin screw extruder, when melt pressure rises to 10MPa when above, is that 40 ℃～70 ℃, pressure are the supercritical co of 10MPa～15MPa at the 3rd heating zone input temp; And regulate the 3rd and after the Heating temperature of each heating zone be 140 ℃～160 ℃; Then the PVDC powder of partial melting in the 3rd heating zone with the supercritical co melt blending, again through the 4th and after the heating zone extrude, the low temperature green of realization PVDC resin is extruded processing.Preparing method of the present invention can reduce the processing temperature of PVDC resin, and the reduction amplitude reaches 20 ℃～30 ℃, thereby has solved PVDC resin treatment window narrows, the labile problem of resin, is a kind of low cost, environmental protection, green non-poisonous preparation method.
Description
Technical field
The present invention relates to PVDC resin technology field, be specifically related to a kind of method for preparing the PVDC resin with the supercritical co secondary process.
Background technology
Polyvinylidene dichloride (PVDC) resin is that a kind of barrier is high, toughness is strong, heat-shrinkable and chemicalstability are excellent, and the perfect package material with good printing and heat sealability.Based on the performance characteristics of PVDC resin can satisfy fully the oxygen barrier of various products anticorrosion, at a distance from flavor protect fragrant, water proof is moistureproof, oil removal permeation-proof etc. intercepts requirements, the time limit of service that prolongs product greatly.And PVDC is not influenced by ambient moisture to the high obstructing performance of oxygen, compares with EVOH, PA, PVA to have remarkable advantages.In the U.S., the PVDC goods belong to the plastic material of non-toxic and safe, have been widely used in food product pack; In Germany, these wrapping material have green mark; In Japan, confirm to burn the amount not influence of PVDC to producing Dioxins.
But; The melt temperature of PVDC resin and decomposition temperature only differ about 20 ℃, so wherein better mobile temperature and decomposition temperature are very approaching, in extrusion; 2 ℃～3 ℃ of temperature fluctuations; Incomplete, mobile smooth or generation decomposition just might take place to plastify, so PVDC resin treatment difficulty is bigger, and higher to the requirement for anticorrosion of equipment.
For the difficult problem of PVDC resin treatment, business circles and academia generally adopt additives such as some softening agent, thermo-stabilizer and inhibitor, in the fusion plastification process, increase its flowability, and guarantee not decompose not oxidation.But along with the raising of the reach of science and people's living standard, food safety and sanitary requirement are more and more stricter, and the various additives in the product have been proposed acid test.External zooscopy result shows, softening agent can cause the animal dis motility rate to reduce, lose weight, hepatic and renal function descends, erythropenia in the blood, has mutagenicity and carinogenicity.The experimentation on animals that the researchist carries out shows that softening agent also can influence human body hormone system, and the teenager in particularly growing up is very unfavorable to boy's testis g and D.In addition, softening agent dissolving or migration can cause product to become fragile mechanical properties decrease.Therefore, seek and a kind ofly can play plastification to PVDC, the processing aid of asepsis environment-protecting is a urgent problem in the present PVDC resin treatment technology again.
Supercritical co secondary process technology; Be to use the widest secondary process technology at present, major cause is that carbonic acid gas is nontoxic, the low and low price of critical temperature; And its can swelling or dissolve nearly all polymkeric substance, comprises the macromolecular material that is considered to anti-solvent usually.Supercritical co has very strong plastification to polymkeric substance; Can reduce the second-order transition temperature of polymkeric substance; For example, massfraction is that 8%～10% carbonic acid gas can be reduced to the second-order transition temperature of simple glass attitude polymkeric substance below the room temperature from 80 ℃～100 ℃.
Application facet for super critical CO 2 technology; Publication number be CN1247125A Chinese patent " the adding method of supercritical co; and through using this addition method to produce the method for foamed thermoplastic resin's product " in, mainly be as whipping agent production foamed thermoplastic resin product with supercritical co.Publication number is during the one Chinese patent application of CN101125947A " contains high melt strength, propylene of long branched chain structure and preparation method thereof "; The high melt strength, propylene that contains long branched chain structure with the supercritical co secondary process; Wherein supercritical co is used to suppress polyacrylic degraded; Strengthen the diffusion of molecule simultaneously, promote the generation of reaction.
Summary of the invention
Technical purpose of the present invention provides a kind of preparation method with supercritical co secondary process PVDC resin, and this method can reduce the processing temperature of PVDC resin to fusing point, thereby solves PVDC resin treatment window narrows, the labile problem of resin.Utilize this method, can realize the preparation of unmanageable PVDC fiber and foam material product, widen the Application Areas of PVDC resin.
The present invention realizes that the technical scheme that above-mentioned technical purpose adopts is: a kind of preparation method with supercritical co secondary process PVDC resin; Adopt extrusion by melting; The PVDC powder is melt extruded moulding through twin screw extruder, and it is characterized in that: described twin screw extruder is processed by corrosion resistant Hastelloy C-276 material; Described twin screw extruder is divided into three heating zone at least, and the PVDC powder gets into the 3rd heating zone after through first heating zone and the second heating zone partial melting; When the pressure of PVDC melt in the twin screw extruder rises to 10MPa when above; At the 3rd heating zone input temp is that 40 ℃～70 ℃, pressure are the supercritical co of 10MPa～15MPa, and the Heating temperature of regulating each later heating zone of the 3rd heating zone and the 3rd heating zone is 140 ℃～160 ℃; Each heating zone melt extruded with supercritical co after the PVDC powder of partial melting reached through the 3rd, realized that the low temperature green of PVDC resin is extruded processing.
In order to improve the mixture homogeneity of PVDC powder and supercritical co; Preferably twin screw extruder is divided into four heating zone at least; The Heating temperature of each heating zone that described the 3rd heating zone and the 3rd heating zone are later is 140 ℃～160 ℃; PVDC powder and supercritical co be at the 3rd heating zone melt blending, again through the 4th and after the heating zone extrude.Preferred as further, described twin screw extruder is divided into 4～12 heating zone.
The Heating temperature of described first heating zone is preferably 138 ℃～167 ℃, and the Heating temperature of second heating zone is preferably 141 ℃～166 ℃.
The Heating temperature of described the 3rd heating zone is 140 ℃～150 ℃.
The preferred input temp of described supercritical co is 40 ℃～50 ℃.
The pressure of described supercritical co is high relatively more, easyly more in the PVDC melt, spread, but pressure is too high, and equipment is had certain damage, and preferred pressure is 12MPa～15MPa.
When the pressure of PVDC melt preferably rises to 12MPa～15MPa in the described twin screw extruder, the input supercritical co in the 3rd heating zone.
Described PVDC powder preferably carries out feeding with 5 kilograms/hour～20 kilograms/hour rate of feeding; The input flow velocity of described supercritical co is preferably 1 ml/min～5 ml/min so that the input of supercritical co just with screw rod in the PVDC melt material flux matched.
Described PVDC resin is a kind of by in vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-methylmethacrylate copolymer or the vinylidene chloride-acrylonitrile copolymer, and wherein the quality of vinylidene chloride accounts for 60%～95%.
The feeding precision of described PVDC powder preferably is not less than 0.01 gram/minute.
Utilizing method of the present invention, can be monofilament, porous-film and dense film with PVDC resin low temperature green processing.
Compared with prior art, the present invention adopts following technical measures:
(1) adopt supercritical carbon dioxide fluid to replace the softening agent secondary process PVDC resin that often uses in the prior art, supercritical co has played the effect of softening agent, false solvent in this process, thereby has increased fusion PVDC resin flow property;
(2) simultaneously, optimize the input position of supercritical co: be chosen in the 3rd heating zone, promptly after the PVDC powder is through first heating zone and the second heating zone partial melting, import supercritical co, thereby avoided following problem:
A, when too early input supercritical co because the also not fusion of PVDC powder, feed supercritical co and may cause carbonic acid gas to spray from charging opening this moment, do not have due effect;
B, when having served as late input supercritical co, because the fully fusion of PVDC powder, and shear down sharply decomposition, feed supercritical co more at this moment, also do not have effect at all at twin screw;
(3) and then, optimize input opportunity, input pressure and the input temp of supercritical co: the pressure that is chosen in the PVDC melt rises to 10MPa when above, input temp is that 40 ℃～70 ℃, pressure are the supercritical co of 10MPa～15MPa;
After adopting above technical measures; Melt extrude at PVDC and to add supercritical co in the process; And supercritical co rapidly, evenly, stably is penetrated among the fused PVDC, has brought into play plasticising, the viscosity reduction effect of supercritical co most effectively.The experiment proof; Adopt these technical measures can when guaranteeing abundant fusion PVDC resin, reduce the processing temperature of PVDC resin greatly; The reduction amplitude reaches 20 ℃～30 ℃; Thereby solved PVDC resin treatment window narrows, the labile problem of resin, can realize the preparation of unmanageable PVDC fiber and foam material product, widened the Application Areas of PVDC resin.In addition, supercritical co is a kind of non-toxic supercritical fluid of environmental protection, thereby has avoided softening agent harmful to human and the healthy problem of other biological commonly used.Therefore, the present invention is the preparation method of a kind of low temperature, green with the preparation method of supercritical co secondary process PVDC resin.
Embodiment
Below in conjunction with specific embodiment the present invention is described in further detail.
Embodiment 1:
Take by weighing a certain amount of PVDC powder that forms by vinylidene chloride-chloroethylene copolymer, join in the barrel, guarantee the PVDC powder between the minimum feed supplement lower limit and the highest feed supplement upper limit, and the setting rate of feeding is 8 kilograms/hour.The twin screw extruder that startup is processed by corrosion resistant Hastelloy C-276 material, the main frame speed governing is 86.5 rev/mins, the Melt Pump rotating speed is 5.1 rev/mins.Twin screw extruder is divided into 10 heating zone, and wherein the Heating temperature of first and second heating zone is respectively 139 ℃ and 161 ℃.The PVDC powder gets into the 3rd heating zone through the later half plasticizing in first, second heating zone.When the pressure of PVDC melt in the twin screw extruder rises to 12.5MPa; At the 3rd heating zone input temp is that 40 ℃, pressure are that 13MPa, flow velocity are the supercritical co of 3 ml/min; And the Heating temperature of regulating the 3rd heating zone to last heating zone is respectively 146 ℃, 150 ℃, 150 ℃, 145 ℃, 145 ℃, 145 ℃, 145 ℃, 155 ℃; The abundant fusion plastification of PVDC, moment of torsion per-cent is 30%, the course of processing is steady.The PVDC extruded stock is transparent, smooth surface, and color and luster is good, and does not take place obviously to decompose.Utilize this method, but low temperature green production PVDC monofilament, dense film or porous-film.
The comparative example 1:
In order to compare with embodiment 1, the preparation condition of present embodiment is basic and embodiment 1 is similar, and different is not add supercritical co; Concrete outcome is: PVDC fails to plastify; Screw torque overload through the 3rd to the 4th heating zone the time, auto can't be processed.
The comparative example 2:
In order to do further contrast with comparative example 1, the preparation condition of present embodiment is basic and comparative example 1 is similar, and different is to have reset the 3rd heating zone to the ten Heating Zone Temperature.Concrete preparation method is following:
Take by weighing a certain amount of PVDC powder, join in the barrel, guarantee the PVDC powder between the minimum feed supplement lower limit and the highest feed supplement upper limit, and the setting rate of feeding is 8 kilograms/hour.The twin screw extruder that startup is processed by corrosion resistant Hastelloy C-276 material, the main frame speed governing is 86.5 rev/mins, the Melt Pump rotating speed is 5.1 rev/mins.Twin screw extruder is divided into 10 heating zone, and wherein the Heating temperature of first and second heating zone is respectively 139 ℃ and 161 ℃.The PVDC powder gets into the 3rd heating zone through the later half plasticizing in first, second heating zone.When the pressure of PVDC melt in the twin screw extruder rises to 12.5MPa; At the 3rd heating zone input temp is that 40 ℃, pressure are that 13MPa, flow velocity are the supercritical co of 3 ml/min; And the Heating temperature of regulating the 3rd to the tenth heating zone is respectively 166 ℃, 170 ℃, 170 ℃, 165 ℃, 165 ℃, 165 ℃, 165 ℃, 165 ℃, and PVDC excessively plastifies, and discharges a large amount of HCl gases; Moment of torsion per-cent is 60%, and doubtful generation is crosslinked.The PVDC extruded stock is dark brown, surface irregularity, and the color and luster obfuscation takes place obviously to decompose.
In conjunction with embodiment 1 and comparative example 1,2, the result finds: 1) in fusing point accessory temperature scope, the common screw melt-processed causes the decomposition of PVDC resin, crosslinked even carbonization easily; 2) adding of supercritical co can reduce the processing temperature of PVDC resin when guaranteeing abundant fusion plastification PVDC resin, the reduction amplitude reaches 25 ℃.
Embodiment 2:
Take by weighing a certain amount of PVDC powder that forms by vinylidene chloride-methyl methacrylate copolymer, join in the barrel, guarantee the PVDC powder between the minimum feed supplement lower limit and the highest feed supplement upper limit, and the setting rate of feeding is 12 kilograms/hour.The twin screw extruder that startup is processed by corrosion resistant Hastelloy C-276 material, the main frame speed governing is 86 rev/mins, the Melt Pump rotating speed is 6.7 rev/mins.Twin screw extruder is divided into 10 heating zone, and wherein the Heating temperature of first and second heating zone is respectively 167 ℃ and 165 ℃.The PVDC powder becomes molten state after through the heating of first heating zone and second heating zone and gets into the 3rd heating zone.When the pressure of PVDC melt in the twin screw extruder rises to 13.5MPa; At the 3rd heating zone input temp is that 45 ℃, pressure are that 15MPa, flow velocity are the supercritical co of 4 ml/min; And the Heating temperature of regulating the 3rd heating zone to last heating zone is respectively 143 ℃, 147 ℃, 147 ℃, 142 ℃, 142 ℃, 142 ℃, 142 ℃, 152 ℃; The abundant fusion plastification of PVDC, moment of torsion per-cent is 35%, the course of processing is steady.The PVDC extruded stock is transparent, smooth surface, and color and luster is good, and does not take place obviously to decompose.Utilize this method, but low temperature green production PVDC monofilament, dense film or porous-film.
The comparative example 3:
In order to compare with embodiment 2, the preparation condition of present embodiment is basic and embodiment 2 is similar, and different is the adding difference on opportunity of supercritical co.Specific as follows:
Take by weighing a certain amount of PVDC powder, join in the barrel, guarantee the PVDC powder between the minimum feed supplement lower limit and the highest feed supplement upper limit, and the setting rate of feeding is 12 kilograms/hour.The twin screw extruder that startup is processed by corrosion resistant Hastelloy C-276 material, the main frame speed governing is 86 rev/mins, the Melt Pump rotating speed is 6.7 rev/mins.Twin screw extruder is divided into 10 heating zone, and wherein the Heating temperature of first and second heating zone is respectively 167 ℃ and 165 ℃.The PVDC powder gets into the 3rd heating zone through becoming half plasticizing behind first, second heating zone.When the pressure of PVDC melt in the twin screw extruder is 3.5MPa; At the 3rd heating zone input temp is that 45 ℃, pressure are that 15MPa, flow velocity are the supercritical co of 4 ml/min; And the Heating temperature of regulating the 3rd heating zone to last heating zone is respectively 143 ℃, 147 ℃, 147 ℃, 142 ℃, 142 ℃, 142 ℃, 142 ℃, 152 ℃, and the abundant fusion plastification of result: PVDC, moment of torsion per-cent are 37%; Mouth mould generation melt fracture, and with aeration sound.The PVDC extruded stock turns white, and the surface is the snakeskin shape, shade deviation, but do not take place obviously to decompose.
Embodiment 3:
Take by weighing a certain amount of PVDC powder that forms by vinylidene chloride-acrylonitrile compolymer, join in the barrel, guarantee the PVDC powder between the minimum feed supplement lower limit and the highest feed supplement upper limit, and the setting rate of feeding is 5 kilograms/hour.The twin screw extruder that startup is processed by corrosion resistant Hastelloy C-276 material, the main frame speed governing is 80 rev/mins, the Melt Pump rotating speed is 5.8 gram/minute.Twin screw extruder is divided into 10 heating zone, and wherein the Heating temperature of first and second heating zone is respectively 162 ℃ and 166 ℃.The PVDC powder gets into the 3rd heating zone through the later half plasticizing in first, second heating zone.When the pressure of PVDC melt in the twin screw extruder rises to 15MPa; At the 3rd heating zone input temp is that 55 ℃, pressure are that 15MPa, flow velocity are the supercritical co of 2.5 ml/min; And the temperature of regulating the 3rd to the tenth heating zone is respectively 146 ℃, 150 ℃, 150 ℃, 145 ℃, 145 ℃, 145 ℃, 145 ℃, 155 ℃; The abundant fusion plastification of result: PVDC, moment of torsion per-cent is 28%, the course of processing is steady.The PVDC extruded stock is transparent, smooth surface, and color and luster is good, and does not take place obviously to decompose.Utilize this method, but low temperature green production PVDC monofilament, dense film or porous-film.
Embodiment 4:
Take by weighing a certain amount of PVDC powder that forms by vinylidene chloride-methyl methacrylate copolymer, join in the barrel, guarantee the PVDC powder between the minimum feed supplement lower limit and the highest feed supplement upper limit, and the setting rate of feeding is 18 kilograms/hour.The twin screw extruder that startup is processed by corrosion resistant Hastelloy C-276 material, the main frame speed governing is 95 rev/mins, the Melt Pump rotating speed is 7.6 rev/mins.Twin screw extruder is divided into 10 heating zone, and wherein the Heating temperature of first and second heating zone is respectively 139 ℃ and 141 ℃.The PVDC powder becomes molten state after through the heating of first heating zone and second heating zone and gets into the 3rd heating zone.When the pressure of PVDC melt in the twin screw extruder rises to 13.5MPa; At the 3rd heating zone input temp is that 47 ℃, pressure are that 14MPa, flow velocity are the supercritical co of 4.5 ml/min; And the Heating temperature of regulating the 3rd heating zone to last heating zone is respectively 143 ℃, 148 ℃, 149 ℃, 144 ℃, 144 ℃, 144 ℃, 143 ℃, 155 ℃; The abundant fusion plastification of PVDC, moment of torsion per-cent is 37%, the course of processing is steady.The PVDC extruded stock is transparent, smooth surface, and color and luster is good, and does not take place obviously to decompose.Utilize this method, but low temperature green production PVDC monofilament, dense film or porous-film.
Claims (11)
1. preparation method with supercritical co secondary process PVDC resin; Adopt extrusion by melting; The PVDC powder is melt extruded moulding through twin screw extruder, and it is characterized in that: described twin screw extruder is processed by corrosion resistant Hastelloy C-276 material; Described twin screw extruder is divided into three heating zone at least, and the PVDC powder gets into the 3rd heating zone after through first heating zone and the second heating zone partial melting; When the pressure of PVDC melt in the twin screw extruder rises to 10MPa when above; At the 3rd heating zone input temp is that 40 ℃～70 ℃, pressure are the supercritical co of 10MPa～15MPa, and the Heating temperature of regulating each later heating zone of the 3rd heating zone and the 3rd heating zone is 140 ℃～160 ℃; Each heating zone melt extruded with supercritical co after the PVDC powder of partial melting reached through the 3rd, realized that the low temperature green of PVDC resin is extruded processing.
2. a kind of preparation method according to claim 1 with supercritical co secondary process PVDC resin; It is characterized in that: described twin screw extruder is divided into four heating zone at least; The Heating temperature of each heating zone that described the 3rd heating zone and the 3rd heating zone are later is 140 ℃～160 ℃; PVDC powder and supercritical co be at the 3rd heating zone melt blending, again through the 4th and after the heating zone extrude.
3. a kind of preparation method with supercritical co secondary process PVDC resin according to claim 2, it is characterized in that: described twin screw extruder is divided into 4～12 heating zone.
4. according to claim 1,2 or 3 described a kind of preparing methods with supercritical co secondary process PVDC resin; It is characterized in that: the Heating temperature of described first heating zone is 138 ℃～167 ℃, and the Heating temperature of second heating zone is 141 ℃～166 ℃.
5. according to claim 1,2 or 3 described a kind of preparing methods with supercritical co secondary process PVDC resin, it is characterized in that: the Heating temperature of described the 3rd heating zone is 140 ℃～150 ℃.
6. according to claim 1,2 or 3 described a kind of preparing methods with supercritical co secondary process PVDC resin, it is characterized in that: the input temp of described supercritical co is 40 ℃～50 ℃.
7. according to claim 1,2 or 3 described a kind of preparing methods with supercritical co secondary process PVDC resin, it is characterized in that: the pressure of described supercritical co is 12MPa～15MPa.
8. according to claim 1,2 or 3 described a kind of preparing methods with supercritical co secondary process PVDC resin; It is characterized in that: when the pressure of PVDC melt rises to 12MPa～15MPa in the described twin screw extruder, the input supercritical co in the 3rd heating zone.
9. according to claim 1,2 or 3 described a kind of preparing methods with supercritical co secondary process PVDC resin; It is characterized in that: the rate of feeding of described PVDC powder is 5 kilograms/hour～20 kilograms/hour, and the input flow velocity of supercritical co is 1 ml/min～5 ml/min.
10. according to claim 1,2 or 3 described a kind of preparing methods with supercritical co secondary process PVDC resin; It is characterized in that: described PVDC resin is a kind of by in vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-methylmethacrylate copolymer or the vinylidene chloride-acrylonitrile copolymer, and wherein the quality of vinylidene chloride accounts for 60%～95%.
11. according to claim 1,2 or 3 described a kind of preparing methods with supercritical co secondary process PVDC resin, it is characterized in that: described PVDC resin treatment is shaped to monofilament, porous-film or dense film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101755876A CN102321319B (en) | 2011-06-27 | 2011-06-27 | Supercritical carbon dioxide assisted preparation method of PVDC (polyvinyl dichloride) resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101755876A CN102321319B (en) | 2011-06-27 | 2011-06-27 | Supercritical carbon dioxide assisted preparation method of PVDC (polyvinyl dichloride) resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102321319A true CN102321319A (en) | 2012-01-18 |
| CN102321319B CN102321319B (en) | 2013-03-13 |
Family
ID=45449165
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011101755876A Expired - Fee Related CN102321319B (en) | 2011-06-27 | 2011-06-27 | Supercritical carbon dioxide assisted preparation method of PVDC (polyvinyl dichloride) resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102321319B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110625908A (en) * | 2019-09-27 | 2019-12-31 | 河南双汇投资发展股份有限公司 | Preparation method of PVDC preservative film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6790870B1 (en) * | 1999-09-20 | 2004-09-14 | North Carolina State University | Methods of making foamed materials of blended thermoplastic polymers using carbon dioxide |
| CN101003174A (en) * | 2006-12-28 | 2007-07-25 | 中北大学 | Forming machine for extruding assistant high molecular material in supercritical fluid |
-
2011
- 2011-06-27 CN CN2011101755876A patent/CN102321319B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6790870B1 (en) * | 1999-09-20 | 2004-09-14 | North Carolina State University | Methods of making foamed materials of blended thermoplastic polymers using carbon dioxide |
| CN101003174A (en) * | 2006-12-28 | 2007-07-25 | 中北大学 | Forming machine for extruding assistant high molecular material in supercritical fluid |
Non-Patent Citations (2)
| Title |
|---|
| SRINIVAS SIRIPURAPU ETAL: "Generation of microcellular foams of PVDF and its blends using supercritical carbon dioxide in a continuous process", 《POLYMER》, vol. 43, no. 20, 1 September 2002 (2002-09-01), pages 5511 - 5520, XP004374464, DOI: doi:10.1016/S0032-3861(02)00407-X * |
| 张艳君等: "超临界CO2在连续挤出微孔塑料中的应用", 《合成树脂及塑料》, vol. 23, no. 4, 25 July 2006 (2006-07-25), pages 72 - 75 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110625908A (en) * | 2019-09-27 | 2019-12-31 | 河南双汇投资发展股份有限公司 | Preparation method of PVDC preservative film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102321319B (en) | 2013-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104650506B (en) | A kind of degradable environmentally-friendly plastic | |
| US11926711B2 (en) | TPS/PLA/PBAT blend modified biodegradable resin prepared by using chain extender and preparation method thereof | |
| CN104497365B (en) | The Bentonite/Starch composite degradation material of melt intercalated method production and manufacture method | |
| CN103102632A (en) | Chlorinated polyvinyl chloride modified material and preparation method thereof | |
| CN108659421B (en) | Chlorinated polyvinyl chloride composition and pipe preparation method | |
| CN109294117B (en) | Plum blossom pipe and production process thereof | |
| CN108929527A (en) | A kind of PBAT/ modified starch full-biodegradable film and its preparation method and application having both high ductibility and high obstructing performance | |
| CN109535674A (en) | Using the PPC/PLA/PBAT blending and modifying Biodegradable resin and preparation method thereof of chain extender preparation | |
| CN105585759A (en) | Full-biomass composite plastic and preparing method thereof | |
| CN103897291A (en) | PVC-U pipe fitting | |
| CN104371219A (en) | Medical heat-resistant anti-aging composite plastic and preparation method thereof | |
| CN112500611B (en) | Biodegradable plastic bag and preparation method thereof | |
| CN102321319B (en) | Supercritical carbon dioxide assisted preparation method of PVDC (polyvinyl dichloride) resin | |
| CN103665662A (en) | Heat-shrinkable PVC film and making method thereof | |
| CN113512281B (en) | Modified PGA material, preparation method thereof and modified PGA film | |
| CN106554580A (en) | A kind of PVC packagings for foodstuff composition and preparation method thereof | |
| CN106519622A (en) | High molecular polycarbonate alloy material and preparation method thereof | |
| CN111087766A (en) | Thermoplastic blend material, blend thermoplastic film and preparation method thereof | |
| CN112552618B (en) | High-fluidity hard PVC material for injection molding and preparation method thereof | |
| CN108864493B (en) | Edible composite film and preparation method thereof | |
| CN107286612A (en) | A kind of plastic packaging bag | |
| CN113604010A (en) | Biological-based material PHBV and polyester modified antibacterial, deodorizing and antiviral master batch | |
| CN106947118A (en) | A kind of biodegradable thermoplastic's material and its processing method and application | |
| CN111349273A (en) | High-starch-filled HDPE (high-density polyethylene) film blowing special material and preparation method thereof | |
| CN110804291A (en) | Biodegradable composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: NINGBO JUHUA CHEMICAL INDUSTRY TECHNOLOGY CO., LTD Effective date: 20120515 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| C53 | Correction of patent of invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Xue Lixin Inventor after: Guo Zhiyi Inventor after: Wu Xiangfa Inventor after: Han Jinming Inventor after: Liu Fu Inventor after: Du Jili Inventor after: Wang Yi Inventor after: Chen Linyan Inventor before: Xue Lixin Inventor before: Wu Xiangfa Inventor before: Liu Fu Inventor before: Wang Yi |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: XUE LIXIN WU XIANGFA LIU FU WANG YI TO: XUE LIXIN GUO ZHIYI WU XIANGFA HAN JINMING LIU FU DU JILI WANG YI CHEN LINYAN |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20120515 Address after: No. 519 Road, 315201 Zhejiang Zhuang Zhenhai District of city of Ningbo Province Applicant after: Ningbo Institute of Material Technology and Engineering Chinese Academy of Scien Co-applicant after: Ningbo Juhua Chemical Industry Technology Co., Ltd. Address before: No. 519 Road, 315201 Zhejiang Zhuang Zhenhai District of city of Ningbo Province Applicant before: Ningbo Institute of Material Technology and Engineering Chinese Academy of Scien |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130313 Termination date: 20180627 |