CN101704942A - Preparation method of copolymerizing multi-branching PET material - Google Patents
Preparation method of copolymerizing multi-branching PET material Download PDFInfo
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- CN101704942A CN101704942A CN200910185363A CN200910185363A CN101704942A CN 101704942 A CN101704942 A CN 101704942A CN 200910185363 A CN200910185363 A CN 200910185363A CN 200910185363 A CN200910185363 A CN 200910185363A CN 101704942 A CN101704942 A CN 101704942A
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Abstract
The invention relates to a preparation method of a copolymerizing multi-branching PET material, which comprises the following technical processes of: stirring phthalic acid and glycol in a slurry mixing tank, pumping to a slurry feeding tank, placing the slurry feeding tank to an esterification kettle through a slurry injection nozzle, uniformly mixing and reacting the slurry through the cycle principle of a thermosiphon or the effect of a blender; injecting an esterified oligomer and additives on a pipeline through a gear pump to a prepolymerization kettle, flowing to a final polycondensation kettle when the materials reach the upside of the prepolymerization kettle, filtering a finally polymerized product through a melt filter, and pulling to a dicing cutter to prepare a polyester slice. The additives in the polycondensation process comprise a branching agent containing eight epoxy groups, antimony catalysts, polyphosphoric acid stabilizers and a cage type silsesquioxane dispersing agent. The branching agent adopted in the invention comprises eight functional groups capable of reacting with terminal hydroxyl group or terminal carboxyl of polyester, shows better blow molding and film-forming performance compared with the performance of copolymer PET using three or four functional groups, and can be used in the fields of packing materials and high-grade industrial silk for textile.
Description
(1) technical field
The present invention relates to a kind of polyfunctional group branching agent and PET monomer copolymerization and as a kind of preparation method of polyester material.Be mainly used in wrapping material and weaving and use advanced industrial silk field.
(2) background technology
Polyethylene terephthalate (PET) goods have good mechanical property, wear resistance, thermotolerance, chemical proofing and electrical insulating property, are widely used as fiber, film, beverage bottle and engineering plastics.Industrial production bottle level PET polyester slice is synthetic by two-step approach usually: melt phase polycondensation and solid phase polycondensation (SSP).After melt polymerization, the molecular weight of polyester can be in solid-state further raising.Solid phase polycondensation (SSP) has solved the problem that in the melt phase polycondensation viscous melt is stirred, and required temperature of reaction is low, has reduced degraded and side reaction.But the speed of response of solid phase polycondensation is slow, and technical process is long, adds the equipment investment cost height, so the third method of PET molecular weight occurred improving: chain extension/branching reaction method.The reaction principle of this kind production method is to contain the small molecular weight chainextender of reactive group or the end group generation chemical reaction of branching agent and PET, thereby effectively improves molecular weight.Use chainextender and can access a series of products from the monomer matrix resin to various range of viscosities, and reaction is very fast, handiness is big, without any need for extra investment.
From production technique, preparation long-chain branch branched polymer has direct polymerization method and reaction extrusion molding usually.The direct polymerization method is directly to add branching agent and polymer monomer to react in polycondensation vessel, and the molecular weight of synthetic product can meet or exceed the polymericular weight that forms through melt phase polycondensation.Its advantage is: compare with traditional melt phase polycondensation, shortened the reaction times, reduced energy consumption, reached energy conservation and environment protection.
From the molecular chain structure with a kind of polymkeric substance, for molecular weight identical linear polymer and branched polymer, the stretch behavior that they show under the stretching flow field is different.The melt viscosity of linear polymer is low, and the refractory property of hanging down is poor, when being subjected to stretching always from structure the weakest or the hottest place begin distortion, cause product performance to descend, have in addition can not moulding.The principal element of impact polymer melt strength is its molecular structure.General relative molecular mass is big more, and relative molecular mass distributes wide more, and its melt strength is big more, and the existence of branched structure can significantly improve the melt strength of polymkeric substance.Under the stretching flow field, strain rate is constant, the extensional viscosity of branched polymer begins to present gradually and increases, the exponentially level increases then, cash out tangible strain hardening behavior, this behavior can guarantee material when moulding stretches, and keeps homogeneous deformation, improves its spinning, foaming and film forming properties; On the other hand, introduce branched structure at main polymer chain, destroyed the regularity of molecular chain, material is amorphous state, adds the refinement nucleus effect of side chain, and the transparency is better.
Documents more both domestic and external and patent have been reported some and have been adopted the method that directly prepares branching PET at polymerization stage, have caused many-sided concern.Hudson (Hudson) is at Macromolecules (macromole), disclosing on the 33:9255-6261 (2000) with bishydroxyethyl terephthalate is that basic polymerization single polymerization monomer, tetramethylolmethane are that branching unit, phenol are as end-capping reagent, adopt antimonous oxide as catalyzer, by changing the ratio of end-capping reagent and branched monomer, synthesized the different PET of degree of branching.
There are three problems in the copolymerization branching PET of above-mentioned formation: the first, and used branching agent is confined to three, the four-functional group branching agent, contains more the branching agent of polyfunctional group number and is not used effectively; The second, the synthetic product lays particular emphasis on theoretical investigation, gets in touch not closely with actual production, does not more consider energy conservation and environment protection; The 3rd, though the processing characteristics of branched product is improved, the performance of product when solid-state and bad can only be used as additive, thereby limited its application at the polyester other field.
(3) summary of the invention
The objective of the invention is to overcome above-mentioned deficiency, a kind of have good stretching and blown film performance are provided, can be applied to wrapping material and weaving preparation method with the copolymerizing multi-branching PET material in advanced industrial silk field.
The object of the present invention is achieved like this: a kind of preparation method of copolymerizing multi-branching PET material, and described method comprises following technological process:
(1) esterification: terephthalic acid and ethylene glycol stir by density of setting or mol ratio in slurry mix tank, be pumped into the slurry feeding tank, the slurry feeding tank enters esterifying kettle through the slurry injection nozzle, in circulation theory or the agitator effect by thermosiphon, and the slurry reaction that is uniformly mixed;
(2) polycondensation: the oligopolymer after toothed gear pump is with esterification injects prepolymerization kettle together with each additive on the pipeline, prepolymerization kettle is a upflowing big gun cover tower, temperature of reaction is at 280～290 ℃, pressure 16～25mmHg, flow to terminal polymerization kettle after material arrives the prepolymerization kettle top, the temperature of reaction of terminal polymerization kettle is 285～295 ℃, pressure≤1mmHg, product after eventually poly-draws to dicing machine and makes polyester slice after fondant filter filters;
In the described esterification technique terephthalic acid and ethylene glycol feed intake density than or mol ratio be: terephthalic acid: ethylene glycol=1: 1～2.2;
Additive comprises in the described polycondensating process branching agent, antimony-based catalyst, polyphosphoric acid stablizer and the cage-type silsesquioxane dispersion agent that contains eight epoxide groups, add-on is as the criterion with the content in polyester slice, the weight percent 0.005～0.02% of branching agent, antimony-based catalyst is 200～300ppm, polyphosphoric acid is 1～30ppm, and cage-type silsesquioxane is 1～50ppm;
The described branching agent that contains eight epoxide groups is Epon SU-8 (epoxy bisphenol A-type glycidyl ether, a Britain shell chemical company).
Described antimony-based catalyst and cage-type silsesquioxane addition manner are: earlier antimony-based catalyst and cage-type silsesquioxane are dissolved in respectively in the ethylene glycol, are heated to 50～70 ℃ and stirred 2～3 hours, inject by the additive nozzle.
The branched structure that contains in the topological framework of polymkeric substance is many more, and the strain hardening phenomenon that material shows under the stretching flow field is obvious more, thereby more helps the stretching and the blown film of melt.From polymerization reaction mechanism, reactive group is many more, and reflecting point increases, and the possibility that forms side chain is also many more, from this point, adopts that the epoxy branching agent that contains eight functional groups is better than three, Fourth Ring oxygen branching agent.But functional group is many more, also can bring some problems: the first, and copolyreaction when taking place with PET in branching agent, and the possibility that is formed network structure by crosslinking reaction also increases greatly, thereby influences the final performance of product; The second, in reaction, exist product viscosity and improve rapidly and cause that regional area is overheated to cause degraded.First problem mainly according to the stoichiometric of branching reaction, solve by the concentration of control branching agent.The generation of branched structure is epoxide group open loop on the branching agent and end carboxyl or the terminal hydroxy group generation chemical reaction of PET in essence, because epoxy-terminated and lateral hydroxyl group all may become further crosslinked group, therefore the branching agent content that adds can directly influence the final structure of product; Second problem suppressed by add thermo-stabilizer (phosphoric acid class material) and cage-type silsesquioxane dispersion agent in reaction.The stablizer of polyphosphoric acid reacts with the metal catalyst that promotes thermal destruction, generates the metal tripolyphosphate ester compound, has reduced the catalyst metal activity, thereby has improved the thermal stability of PET.The cage-type silsesquioxane dispersion agent has played good dispersiveness with the structure of the similar cage shape of its uniqueness, guarantees material polymeric homogeneity.
The invention has the beneficial effects as follows:
Branching agent commonly used generally contains three to four energy and the terminal hydroxy group of polyester or the functional group of end carboxyl reaction, as glycerine, tetramethylolmethane etc. and the branching agent that the present invention adopts contains eight energy and the terminal hydroxy group of polyester or the functional group of end carboxyl reaction, contain more branched structure in the material structure, do not have gel component in the product, show than adopt three, four-functional group copolymerization PET has better blowing and film forming properties.
The melt phase polycondensation time of the copolymerization branching reaction time ratio routine that the present invention adopts has shortened 20～40min.So this project energy-saving effect is good, when enhancing productivity, reduced production cost.
The present invention can be used for wrapping material and advanced industrial silk field is used in weaving.
(4) embodiment
Embodiment 1:
1, terephthalic acid and ethylene glycol stir by density of setting or mol ratio (1: 1～2.2) in slurry mix tank, be pumped into the slurry feeding tank, the slurry feeding tank enters esterifying kettle through the slurry injection nozzle, in circulation theory or the agitator effect by thermosiphon, the slurry reaction that is uniformly mixed.Oligopolymer after toothed gear pump is with esterification is together with each additive on the pipeline: be dissolved in antimony-based catalyst, cage-type silsesquioxane in the ethylene glycol respectively earlier, be heated to 70 ℃ and stirred 3 hours, inject by the additive nozzle, add-on is as the criterion with the content in polyester, antimony-based catalyst is 300ppm, epoxy branching agent Epon SU-8 (weight percent) is 0.015%, and the cage-type silsesquioxane add-on is 50ppm; Polyphosphoric acid injects at another nozzle, and the content of add-on in polyester is 30ppm.
2, oligopolymer enters prepolymerization kettle.Prepolymerization kettle is a upflowing big gun cover tower, and temperature of reaction is at 280～290 ℃, and pressure 16～25mmHg flows to terminal polymerization kettle after material arrives the prepolymerization kettle top.The temperature of reaction of terminal polymerization kettle is 285～295 ℃, pressure≤1mmHg.
3, the product after eventually poly-through cooling, pelletizing, drying, can obtain limiting viscosity and be 0.50～0.70 polyester slice after fondant filter filters.
Claims (1)
1. the preparation method of a copolymerizing multi-branching PET material is characterized in that described method comprises following technological process:
(1) esterification: terephthalic acid and ethylene glycol stir by density of setting or mol ratio in slurry mix tank, be pumped into the slurry feeding tank, the slurry feeding tank enters esterifying kettle through the slurry injection nozzle, in circulation theory or the agitator effect by thermosiphon, and the slurry reaction that is uniformly mixed;
(2) polycondensation: the oligopolymer after toothed gear pump is with esterification injects prepolymerization kettle together with each additive on the pipeline, prepolymerization kettle is a upflowing big gun cover tower, temperature of reaction is at 280～290 ℃, pressure 16～25mmHg, flow to terminal polymerization kettle after material arrives the prepolymerization kettle top, the temperature of reaction of terminal polymerization kettle is 285～295 ℃, pressure≤1mmHg, product after eventually poly-draws to dicing machine and makes polyester slice after fondant filter filters;
In the described esterification technique terephthalic acid and ethylene glycol feed intake density than or mol ratio be: terephthalic acid: ethylene glycol=1: 1～2.2;
Additive comprises in the described polycondensating process branching agent, antimony-based catalyst, polyphosphoric acid stablizer and the cage-type silsesquioxane dispersion agent that contains eight epoxide groups, add-on is as the criterion with the content in polyester slice, the weight percent 0.005～0.02% that contains the branching agent of eight epoxide groups, antimony-based catalyst is 200～300ppm, polyphosphoric acid is 1～30ppm, and cage-type silsesquioxane is 1～50ppm;
The described branching agent that contains eight epoxide groups is Epon SU-8, is produced by Britain shell chemical company;
Described antimony-based catalyst and cage-type silsesquioxane addition manner are: earlier antimony-based catalyst and cage-type silsesquioxane are dissolved in respectively in the ethylene glycol, are heated to 50～70 ℃ and stirred 2～3 hours, inject by the additive nozzle.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10094050B2 (en) | 2015-11-04 | 2018-10-09 | Industrial Technology Research Institute | Fiber and method of manufacturing the same |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10094050B2 (en) | 2015-11-04 | 2018-10-09 | Industrial Technology Research Institute | Fiber and method of manufacturing the same |
| US10100440B2 (en) | 2015-11-04 | 2018-10-16 | Industrial Technology Research Instittute | Polyester and method of manufacturing the same |
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