CN114506054A - Process technology for producing colored and permanent anti-sticking sheet by continuous polyester polymerization - Google Patents
Process technology for producing colored and permanent anti-sticking sheet by continuous polyester polymerization Download PDFInfo
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- CN114506054A CN114506054A CN202210157915.8A CN202210157915A CN114506054A CN 114506054 A CN114506054 A CN 114506054A CN 202210157915 A CN202210157915 A CN 202210157915A CN 114506054 A CN114506054 A CN 114506054A
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- 229920000728 polyester Polymers 0.000 title claims abstract description 122
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 30
- 230000008569 process Effects 0.000 title claims abstract description 25
- 238000005516 engineering process Methods 0.000 title claims abstract description 6
- 239000000049 pigment Substances 0.000 claims abstract description 66
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- 239000000155 melt Substances 0.000 claims abstract description 37
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 16
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000009826 distribution Methods 0.000 claims abstract description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 239000011574 phosphorus Substances 0.000 claims abstract description 4
- 239000003381 stabilizer Substances 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 239000010936 titanium Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 38
- 239000002131 composite material Substances 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 238000005886 esterification reaction Methods 0.000 claims description 15
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 238000005096 rolling process Methods 0.000 claims description 10
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000007906 compression Methods 0.000 claims description 3
- 230000006835 compression Effects 0.000 claims description 3
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000010092 rubber production Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 33
- 230000006872 improvement Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000004595 color masterbatch Substances 0.000 description 6
- 239000003086 colorant Substances 0.000 description 5
- 238000011049 filling Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000010413 mother solution Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- -1 Polyethylene terephthalate Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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
- B29C48/03—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
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- 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
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
-
- 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
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/17—Articles comprising two or more components, e.g. co-extruded layers the components having different colours
-
- 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
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
Abstract
The invention discloses a process technology for producing colored and permanent anti-sticking sheets by continuous polyester polymerization, which belongs to the field of rubber production and comprises the following five steps: a polyester continuous polymerization direct tackifying step, a melt distribution step, a pigment adding step, an anti-sticking agent adding step and a sheet processing step; polyester continuous polymerization direct tackifying step: adding 65-80 parts of terephthalic acid and 20-30 parts of ethylene glycol which are used as raw materials in parts by weight into a feeding system, adding 0.1-15 parts of isophthalic acid, 0.01-0.4 part of diethylene glycol, 0.001-0.03 part of titanium catalyst and 0.001-0.04 part of phosphorus stabilizer, mixing the raw materials in proportion, and feeding the mixed raw materials into a slurry tank with a stirrer.
Description
Technical Field
The invention relates to a production process of polyethylene glycol terephthalate, in particular to a process for producing colored and permanently anti-sticking sheets by continuous polyester polymerization, belonging to the field of rubber material manufacture.
Background
Polyethylene terephthalate (PET), which is a milky white or pale yellow highly crystalline polymer, has smooth and glossy surface, good creep resistance, fatigue resistance, abrasion resistance and dimensional stability, small abrasion and high hardness, and has the maximum toughness of thermoplastic plastics; the electric insulation performance is good, and the influence of temperature is small; the composite material has the advantages of no toxicity, good weather resistance, good chemical resistance stability, low water absorption, weak acid and organic solvent resistance, good chemical reagent resistance and oil resistance, and no loss of physical and mechanical properties in a wider temperature range, and the excellent comprehensive properties enable the composite material to be widely applied in the packaging industry, and are particularly used for producing food packaging materials, beverage bottles, oil bottles and the like.
Due to the change of epidemic situation and consumption habit, the polyester sheet is rapidly developed as a packaging material of fast-moving products, is single in material, is easy to recycle, is environment-friendly, cheap and good, can partially replace a PVC sheet in the future, and has a large market application space; at present, most of the domestic sheet industry is a family workshop type processing device, polyester sheets are produced by a slicing method, the scale is small, the power consumption is large, the labor cost is high, and in addition, the comprehensive manufacturing cost is higher due to the expense of plant leasing, packaging, transportation, management and the like.
At present, color master batches are extruded and added through a screw extruder to be mixed with a polyester melt which is heated and melted to produce the domestic colored sheet, the color master batches need to be heated and melted in the process, the cost is high, the mixing is not uniform, the color master batches are easy to decolor, especially the color master batches are easy to decolor due to the change of external environments such as temperature, humidity and illumination, the color master batches are easy to decolor, the sheet of the conventional process is placed for a long time, the surface of the sheet can be adhered, and the application value is lost.
The invention mainly aims to accurately add pigment color paste into a polyester melt pipeline, uniformly mix the pigment color paste and the polyester melt pipeline, has high control precision, achieves fine control, and finally obtains the colored polyester sheet which is not decolored and can be stored for a long time.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a process for producing colored and permanently anti-sticking sheets by continuous polyester polymerization, wherein in the process of directly casting a melt formed by polymerization of polyester, food-grade liquid color paste is added to the middle layer of the sheets, an anti-sticking agent is added to the surface layer of the sheets to form the colored composite anti-sticking sheets with an ABA three-layer structure, the color paste is added to the layer B, and the anti-sticking agent is added to the layer A, so that the color master batch manufacturing link and the heating and melting process are omitted, and the processing cost can be obviously reduced.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a process for the production of coloured and permanently release sheets by continuous polyester polymerization, characterized in that: the method comprises the following five steps: a polyester continuous polymerization direct tackifying step, a melt distribution step, a pigment adding step, an anti-sticking agent adding step and a sheet processing step;
polyester continuous polymerization direct tackifying step: adding 65-80 parts of terephthalic acid and 20-30 parts of ethylene glycol which are used as raw materials in parts by weight into a feeding system, adding 0.1-15 parts of isophthalic acid, 0.01-0.4 part of diethylene glycol, 0.001-0.03 part of titanium catalyst and 0.001-0.04 part of phosphorus stabilizer, mixing the raw materials in proportion, and feeding the mixed raw materials into a slurry tank with a stirrer.
The following is a further improvement of the above technical solution:
the raw materials are evenly stirred and then are sent into an esterification reaction kettle of a polymerization system by a slurry pump, esterification reaction is carried out at the temperature of 250-280 ℃ under 50-200KPa to generate an oligomer of the ethylene terephthalate BHET, and water generated in the esterification reaction is evaporated together with excessive ethylene glycol.
The following is a further improvement of the above technical solution:
the esterification reaction is carried out in an esterification reaction kettle at the reaction temperature of 255 ℃ and 280 ℃ and under the reaction pressure of 50-200KPa to generate an oligomer of the ethylene terephthalate BHET.
The following is a further improvement of the above technical solution:
the oligomer of the ethylene glycol terephthalate BHET in the step enters a polymerization kettle, the polymerization reaction is carried out at the vacuum degree of less than 100Pa and the reaction temperature of 275-; the obtained polymerized product is polyester melt with the viscosity of 0.72-0.85 dl/g.
The following is a further improvement of the above technical solution:
a melt distribution step: polyester melt with viscosity of 0.72-0.85dl/g is discharged from the polymerizer through a melt pump, and after passing through a melt filter, the melt is distributed to each sheet production line die through a melt distribution valve.
The following is a further improvement of the above technical solution:
pigment adding and mixing steps: adding 0.1-0.45 part of liquid pigment color paste into a color paste tank, uniformly stirring by a stirrer, pumping the mixture into a buffer tank by a color paste pump, metering by a metering pump, pressurizing by a booster pump, filtering by a filter, and mixing the mixture according to the mass ratio of the pigment color paste to the polyester melt of 0.1-1: a ratio of 100 was added to the main melt B stream of the melt pipe via the injection head.
The following is a further improvement of the above technical solution:
and an anti-sticking agent adding step, namely heating the high-concentration anti-sticking master batch to a molten state through a bin by an extruder, mixing the high-concentration anti-sticking master batch with the polyester melt according to the mass ratio of 1-10 ppm, and mixing the mixture with the polyester melt A material containing the anti-sticking agent through a mixer.
The following is a further improvement of the above technical solution:
extruding an ABA three-layer melt from a polyester melt A material and a main melt B material through a composite die head, wherein the layer A contains an anti-sticking agent and does not contain pigment, the layer B is a conventional polyester melt containing pigment and does not contain the anti-sticking agent, cooling the conventional polyester melt through a chill roll, tabletting the melt, and rolling to obtain the finished ABA three-layer colored composite anti-sticking sheet.
The following is a further improvement of the above technical solution:
the anti-sticking polyester melt A material and the main melt B material containing pigment respectively pass through a filter and then enter a die head of a sheet processing production line together.
The following is a further improvement of the above technical solution:
and a sheet processing step, wherein the polyester melt A and the polyester melt B respectively pass through a metering pump and then are extruded through a coat-hanger type die head together, the polyester melt A and the polyester melt B are cooled through a chill roll, the width of the sheet is mainly determined by the width of the die head, and the colored polyester sheet with the permanent anti-sticking effect of 150-1600 mu m is obtained through extrusion of a compression roll and stretching of traction rolls with different speeds and finally slitting and rolling.
The ABA colored composite anti-sticking sheet produced by the technology has diversified colors, can customize various colors such as red, green, blue, yellow, brown, milk white and the like according to different requirements of customers, has a permanent anti-sticking effect, and can be stored for a long time.
The process of the invention adds liquid pigment color paste into a color paste tank, the color paste is pumped into a buffer tank by a color paste pump after being stirred uniformly by a stirrer, the pigment added into a main melt B material of a melt pipeline through an injection head after being metered by a metering pump, pressurized by a booster pump and filtered by a filter can be adjusted according to the requirements of customers, and the uniform colored polyester melt is obtained after being mixed by a special melt pipeline mixer.
1-10 ppm of high-concentration anti-sticking master batch is heated to a molten state through a bin by an extruder, and is mixed with part of high-viscosity polyester melt in proportion through a special mixer to form an anti-sticking polyester melt A material which is uniformly mixed.
Extruding the material A and the material B through a composite die head to obtain an ABA three-layer melt, wherein the layer A contains an anti-sticking agent and does not contain pigment, the layer B is a conventional polyester melt containing pigment and does not contain the anti-sticking agent, cooling the conventional polyester melt through a chill roll, tabletting the conventional polyester melt, and rolling the conventional polyester melt into a finished ABA three-layer colored composite anti-sticking sheet.
Compared with the traditional process, the polyester colored sheet produced by adopting the process saves the heating and melting of pigment master batches, is easy to operate on line, has stronger flexibility, good mixing uniformity and low energy consumption, can obviously reduce the manufacturing cost of the colored sheet, is suitable for large-scale industrialization, can be stored for a long time without influencing the product quality and the use effect, and has wider market application prospect.
The invention mainly aims to accurately add pigment color paste into a polyester melt pipeline, uniformly mix the pigment color paste and the polyester melt pipeline, achieve fine control and achieve the purposes that the finally obtained colored polyester sheet is not decolorized and can be stored for a long time; in the melt czochralski sheet processing system, liquid pigment color paste liquid is added into a color paste tank, the color paste is pumped into a buffer tank by a color paste pump after being uniformly stirred by a stirrer, and the pigment is added into a main melt B material of a melt pipeline through an injection head after being metered by a metering pump, pressurized by a booster pump and filtered by a filter and can be adjusted according to the requirements of customers.
1-10 ppm of high-concentration anti-sticking master batch is heated to a molten state through a bin by an extruder, and is mixed with part of high-viscosity polyester melt in proportion by a mixer to form an anti-sticking polyester melt A material which is uniformly mixed.
Extruding the material A and the material B through a composite die head to obtain an ABA three-layer melt, wherein the layer A contains an anti-sticking agent and does not contain pigment, the layer B is a conventional polyester melt containing pigment and does not contain the anti-sticking agent, cooling the conventional polyester melt through a chill roll, tabletting the conventional polyester melt, and rolling the conventional polyester melt into a finished ABA three-layer colored composite anti-sticking sheet.
The invention mainly solves the technical problems that under the conditions of not influencing the performance of polyester products and not increasing the production cost, pigment color paste and an anti-sticking agent are added, and the pigment color paste and the inorganic anti-sticking agent are uniformly mixed in a high-viscosity polyester melt, so that the problems of color and long-term storage in the production of polyester sheets are finally solved, and the color fastness is high.
The beneficial effects of the invention are as follows: in a continuous polymerization and melt straight-pull sheet processing system, the pigment is added in line, and pigment color paste is added to the middle layer to produce colored polyester sheets with different color requirements, so that the procedures of granulation, packaging, transportation, heating and melting and the like of pigment master batches are saved, and the method belongs to domestic initiatives.
The anti-sticking agent is internally added, so that the anti-sticking agent has a permanent anti-sticking effect, and the product has long-term storage performance, is suitable for mass production and long-distance transportation and storage, and has a good market prospect; the technical problem of uniformly mixing the pigment color paste and the high-concentration master batch with the common polyester melt at a high viscosity in proportion is solved, the pigment and the high-concentration anti-sticking agent master batch are added on a large production line for continuously polymerizing direct casting sheets, and the production cost is reduced.
Detailed Description
Example, a process for the continuous polymerization of polyester to produce a colored and permanent release sheet comprising five steps: a polyester continuous polymerization direct tackifying step, a melt distribution step, a pigment adding step, an anti-sticking agent adding step and a sheet processing step; polyester continuous polymerization direct tackifying step: adding 65-80 parts of terephthalic acid and 20-30 parts of ethylene glycol which are used as raw materials in parts by weight into a feeding system, adding 0.1-15 parts of isophthalic acid, 0.01-0.4 part of diethylene glycol, 0.001-0.03 part of titanium catalyst and 0.001-0.04 part of phosphorus stabilizer, mixing the raw materials in proportion, and feeding the mixed raw materials into a slurry tank with a stirrer.
The raw materials are evenly stirred and then are sent into an esterification reaction kettle of a polymerization system by a slurry pump, the esterification reaction is carried out at the temperature of 250-280 ℃ under 50-200KPa to generate an oligomer of the ethylene terephthalate BHET, and water generated in the esterification reaction is evaporated together with excessive glycol.
The esterification reaction is carried out in an esterification reaction kettle at the reaction temperature of 255 ℃ and 280 ℃ and under the reaction pressure of 50-200KPa to generate an oligomer of the ethylene terephthalate BHET.
The oligomer of the ethylene glycol terephthalate BHET in the step enters a polymerization kettle, the polymerization reaction is carried out at the vacuum degree of less than 100Pa and the reaction temperature of 275-295 ℃, and the ethylene glycol is recovered through a recovery tower and is recycled as a raw material; the obtained polymerized product is polyester melt with the viscosity of 0.72-0.85 dl/g.
A melt distribution step: polyester melt with viscosity of 0.72-0.85dl/g is discharged from the polymerizer through a melt pump, and after passing through a melt filter, the melt is distributed to each sheet production line die through a melt distribution valve.
Pigment adding and mixing steps: adding 0.1-0.45 part of liquid pigment color paste into a color paste tank, uniformly stirring by a stirrer, pumping the mixture into a buffer tank by a color paste pump, metering by a metering pump, pressurizing by a booster pump, filtering by a filter, and mixing the mixture according to the mass ratio of the pigment color paste to the polyester melt of 0.1-1: a ratio of 100 was added to the main melt B stream of the melt pipe via the injection head.
And an anti-sticking agent adding step, namely heating the high-concentration anti-sticking master batch to a molten state through a bin by an extruder, mixing the high-concentration anti-sticking master batch with the polyester melt according to the mass ratio of 1-10 ppm, and mixing the mixture with the polyester melt A material containing the anti-sticking agent through a mixer.
Extruding an ABA three-layer melt from a polyester melt A material and a main melt B material through a composite die head, wherein the layer A contains an anti-sticking agent and does not contain pigment, the layer B is a conventional polyester melt containing pigment and does not contain the anti-sticking agent, cooling the conventional polyester melt through a chill roll, tabletting the melt, and rolling to obtain the finished ABA three-layer colored composite anti-sticking sheet.
The anti-sticking polyester melt A material and the main melt B material containing pigment respectively pass through a filter and then enter a die head of a sheet processing production line together.
And a sheet processing step, wherein the polyester melt A and the polyester melt B respectively pass through a metering pump and then are extruded through a coat-hanger type die head together, the polyester melt A and the polyester melt B are cooled through a chill roll, the width of the sheet is mainly determined by the width of the die head, and the colored polyester sheet with the permanent anti-sticking effect of 150-1600 mu m is obtained through extrusion of a compression roll and stretching of traction rolls with different speeds and finally slitting and rolling.
The ABA colored composite anti-sticking sheet produced by the technology has diversified colors, can customize various colors such as red, green, blue, yellow, brown, milk white and the like according to different requirements of customers, has a permanent anti-sticking effect, and can be stored for a long time.
The process of the invention adds liquid pigment color paste into a color paste tank, the color paste is pumped into a buffer tank by a color paste pump after being stirred uniformly by a stirrer, the pigment added into a main melt B material of a melt pipeline through an injection head after being metered by a metering pump, pressurized by a booster pump and filtered by a filter can be adjusted according to the requirements of customers, and the uniform colored polyester melt is obtained after being mixed by a special melt pipeline mixer.
1-10 ppm of high-concentration anti-sticking master batch is heated to a molten state through a bin by an extruder, and is mixed with part of high-viscosity polyester melt in proportion through a special mixer to form an anti-sticking polyester melt A material which is uniformly mixed.
Extruding the material A and the material B through a composite die head to obtain an ABA three-layer melt, wherein the layer A contains an anti-sticking agent and does not contain pigment, the layer B is a conventional polyester melt containing pigment and does not contain the anti-sticking agent, cooling the conventional polyester melt through a chill roll, tabletting the conventional polyester melt, and rolling the conventional polyester melt into a finished ABA three-layer colored composite anti-sticking sheet.
Compared with the traditional process, the polyester colored sheet produced by adopting the process saves the heating and melting of pigment master batches, is easy to operate on line, has stronger flexibility, good mixing uniformity and low energy consumption, can obviously reduce the manufacturing cost of the colored sheet, is suitable for large-scale industrialization, can be stored for a long time without influencing the product quality and the use effect, and has wider market application prospect.
The invention mainly aims to accurately add pigment color paste into a polyester melt pipeline, uniformly mix the pigment color paste, have small filling amount and high control precision, achieve fine control, and finally obtain the colored polyester sheet which is not decolored and can be stored for a long time.
After the liquid pigment color paste liquid is uniformly stirred by the stirrer, the liquid pigment color paste liquid is pumped into a buffer tank, is metered by a metering pump, pressurized by a booster pump and filtered by a filter, and is proportionally added into the main melt B material of the melt pipeline through an injection head, so that the pigment can be adjusted according to the requirements of customers.
1-10 ppm of high-concentration anti-sticking master batch is heated to a molten state through a bin by an extruder, and is mixed with part of high-viscosity polyester melt in proportion by a mixer to form an anti-sticking polyester melt A material which is uniformly mixed.
Extruding the material A and the material B through a composite die head to obtain an ABA three-layer melt, wherein the layer A contains an anti-sticking agent and does not contain pigment, the layer B is a conventional polyester melt containing pigment and does not contain the anti-sticking agent, cooling the conventional polyester melt through a chill roll, tabletting the conventional polyester melt, and rolling the conventional polyester melt into a finished ABA three-layer colored composite anti-sticking sheet.
The invention mainly solves the technical problems that how to add pigment color paste and anti-sticking agent on line under the conditions of not influencing the performance of polyester products and not increasing the production cost, and ensures that the pigment color paste and the inorganic anti-sticking agent are uniformly mixed in the high-viscosity polyester melt, and finally solves the problems of colored production of polyester sheets, long-term storage and high color fastness.
On the basis of a conventional continuous polymerization process, in a melt czochralski sheet processing system, food grade pigment color paste is added in line and an anti-sticking agent is added on the surface of the melt czochralski sheet, so that the permanent anti-sticking composite colored polyester sheet with the ABA three-layer structure and high viscosity and added value is produced, and the permanent anti-sticking composite colored polyester sheet can be used for colored food grade packaging materials with different color requirements, is safe and safe to use and safe to store for a long time and does not influence the using effect.
The melt from the die head is rolled into a finished product ABA three-layer colored composite anti-sticking polyester sheet after tabletting and slitting, and the specific parameters of the polyester sheet are as follows: thickness range: 150um to 1600um and the intrinsic viscosity is 0.75 to 0.85 dl/g.
No air bubbles with the inner diameter of 900 square centimeters larger than 1 millimeter appear, and less than 3 air bubbles with the diameter of less than or equal to 1 millimeter appear.
The number of the different points is not more than 10 within 900 square centimeters, the particle size of the superior product is not more than 0.5-1 millimeter, and the different points are uniformly distributed.
Physical properties, wherein the tensile strength is more than or equal to 35Mpa in the longitudinal direction and the transverse direction; elongation at break%, elongation at break in both the transverse and machine directions was greater than 3%.
The transparent sheet has light transmittance of 90% or more, haze of less than 3%, and wetting tension of more than 30 mu/m.
Performance parameters of PET sheets: density 1.33g/cm 3; oxygen permeability of 4-4.5 cm x mm/(m x 24h x 0.1 MPa); tensile strength: longitudinal direction 53MPa, transverse direction 53 MPa; moisture permeability 3G × mm/(M × 24 h); elongation at break: longitudinal 250% and transverse 250%;
(ii) a Dimensional change by heating: longitudinal direction is less than or equal to 5 percent, and transverse direction is less than or equal to 5 percent.
Melt mixer, pressure, 50-160 bar; the temperature is 275-300 ℃; the revolution is 60-300 rpm; the mixing uniformity is more than or equal to 99 percent; the rotor and the stator are distributed in a star shape and mixed; the special melt mixer is driven by a motor, a motor bearing is connected with a rotor to rotate, the polyester master batch of the high-concentration anti-sticking agent and the polyester melt are injected from opposite directions, the rotor and the stator are distributed in a star-shaped high mixing mode, and the mixing uniformity reaches more than 99%.
The pigment filling system is food-grade pigment color paste, the added pigment is liquid, the pigment is uniformly stirred in a color paste tank and then is conveyed into a buffer tank by a color paste pump, the pigment is metered by a metering pump, and the pigment is pressurized by a booster pump and is added into the material B in the melt pipeline through an injection head.
The pigment can adjust the colors of red, green, blue, yellow, brown, milk white and the like according to the requirements of customers, the maximum pressure of a pigment filling facility is 20Mpa, the filling amount range is 4.2-60000g/h, and the precision is +/-2%; the viscosity of the pigment paste is 5000-12000, the density is generally 1-1.2g/cm3, and the fineness is generally 20-70 μm.
In the step of adding the anti-sticking agent, in a conventional continuous polymerization melt straight-pull sheet processing system, 1-10 ten thousand ppm of high-concentration anti-sticking master batch is heated to a molten state through a bin by a screw extruder, is metered by a melt pump and is mixed with part of polyester melt by a mixer according to a certain concentration to form an anti-sticking mother solution A material, the anti-sticking mother solution A material is added into a die head of the sheet processing system according to 300-2000ppm of the anti-sticking mother solution A material, the material A is divided into two parts in the die head through a distribution plate, the melt from the die head forms an ABA three-layer composite structure A layer containing the anti-sticking agent, and the thickness of the sheet can be controlled by adjusting the flow of the metering pump and the opening of the die lip.
Claims (10)
1. A process technology for producing colored and permanent anti-sticking sheets by continuous polyester polymerization is characterized in that:
the method comprises the following five steps: a polyester continuous polymerization direct tackifying step, a melt distribution step, a pigment adding step, an anti-sticking agent adding step and a sheet processing step;
polyester continuous polymerization direct tackifying step: adding 65-80 parts of terephthalic acid and 20-30 parts of ethylene glycol which are used as raw materials in parts by weight into a feeding system, adding 0.1-15 parts of isophthalic acid, 0.01-0.4 part of diethylene glycol, 0.001-0.03 part of titanium catalyst and 0.001-0.04 part of phosphorus stabilizer, mixing the raw materials in proportion, and feeding the mixed raw materials into a slurry tank with a stirrer.
2. A process of producing colored and permanent release sheets by continuous polyester polymerization as claimed in claim 1 wherein:
the raw materials are evenly stirred and then are sent into an esterification reaction kettle of a polymerization system by a slurry pump, esterification reaction is carried out at the temperature of 250-280 ℃ under 50-200KPa to generate an oligomer of the ethylene terephthalate BHET, and water generated in the esterification reaction is evaporated together with excessive ethylene glycol.
3. A process of producing coloured and permanently release sheets by continuous polyester polymerisation according to claim 2, characterised in that: the esterification reaction is carried out in an esterification reaction kettle at the reaction temperature of 255 ℃ and 280 ℃ and under the reaction pressure of 50-200KPa to generate an oligomer of the ethylene terephthalate BHET.
4. A continuous polyester polymerization process for producing colored and permanent release sheets according to claim 3, wherein:
the oligomer of the ethylene glycol terephthalate BHET in the step enters a polymerization kettle, the polymerization reaction is carried out at the vacuum degree of less than 100Pa and the reaction temperature of 275-; the obtained polymerized product is polyester melt with the viscosity of 0.72-0.85 dl/g.
5. A process of producing colored and permanent release sheets by continuous polyester polymerization according to claim 4 wherein:
a melt distribution step: polyester melt with viscosity of 0.72-0.85dl/g is discharged from the polymerizer through a melt pump, and after passing through a melt filter, the melt is distributed to each sheet production line die through a melt distribution valve.
6. A process of producing colored and permanent release sheets by continuous polyester polymerization according to claim 5, wherein:
pigment adding and mixing steps: adding 0.1-0.45 part of liquid pigment color paste into a color paste tank, uniformly stirring by a stirrer, pumping the mixture into a buffer tank by a color paste pump, metering by a metering pump, pressurizing by a booster pump, filtering by a filter, and mixing the mixture according to the mass ratio of the pigment color paste to the polyester melt of 0.1-1: a ratio of 100 was added to the main melt B charge of the melt pipe via the injection head.
7. A process of producing colored and permanent release sheets by continuous polyester polymerization according to claim 6, wherein: and an anti-sticking agent adding step, namely heating the high-concentration anti-sticking master batch to a molten state through a bin by an extruder, mixing the high-concentration anti-sticking master batch with the polyester melt according to the mass ratio of 1-10 ppm, and mixing the mixture with the polyester melt A material containing the anti-sticking agent through a mixer.
8. A process of continuous polyester polymerization to produce colored and permanent release sheets according to claim 7 wherein: extruding an ABA three-layer melt from a polyester melt A material and a main melt B material through a composite die head, wherein the layer A contains an anti-sticking agent and does not contain pigment, the layer B is a conventional polyester melt containing pigment and does not contain the anti-sticking agent, cooling the conventional polyester melt through a chill roll, tabletting the melt, and rolling to obtain the finished ABA three-layer colored composite anti-sticking sheet.
9. A process of continuous polyester polymerization to produce colored and permanent release sheet according to claim 8 wherein: the anti-sticking polyester melt A material and the main melt B material containing pigment respectively pass through a filter and then enter a die head of a sheet processing production line together.
10. A process for the continuous polymerization of polyester to produce colored and permanent release sheets according to claim 9, wherein:
and a sheet processing step, wherein the polyester melt A and the polyester melt B respectively pass through a metering pump and then are extruded through a coat-hanger type die head together, the polyester melt A and the polyester melt B are cooled through a chill roll, the width of the sheet is mainly determined by the width of the die head, and the colored polyester sheet with the permanent anti-sticking effect of 150-1600 mu m is obtained through extrusion of a compression roll and stretching of traction rolls with different speeds and finally slitting and rolling.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115582927A (en) * | 2022-10-14 | 2023-01-10 | 富海(山东)包装材料有限公司 | Process technology and equipment for producing colored high-viscosity polyester bottle flakes |
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