CN107118339A - A kind of continuous method for preparing modified poly ester - Google Patents
A kind of continuous method for preparing modified poly ester Download PDFInfo
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- CN107118339A CN107118339A CN201610104196.8A CN201610104196A CN107118339A CN 107118339 A CN107118339 A CN 107118339A CN 201610104196 A CN201610104196 A CN 201610104196A CN 107118339 A CN107118339 A CN 107118339A
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- 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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
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- 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
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- 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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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- 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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6926—Dicarboxylic acids and dihydroxy compounds
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
A kind of method of continuous production modified poly ester, methods described is mainly included the following steps that：By terephthalic acid (TPA), dihydric alcohol and catalyst preparation into slurry；Gained slurry is added continuously in esterification system carry out esterification, obtains terephthalic acid (TPA) binary alcohol esters oligomer；The oligomer of gained is well mixed into homogeneous system with the modifying agent added online after adjusting temperature through heat exchanger and carries out equal qualitative response, obtains homogeneous thing；Gained homogeneous thing enters polycondensation system and carries out polycondensation reaction, obtains modified poly ester pre-polymer melt；Gained pre-polymer melt enters crystallization pelletizing system and carries out pelletizing shaping and crystallization, obtains pre-crystallized modified poly ester prepolymer chips；The pre-crystallized prepolymer chips of gained enter solid-phase tack producing system and carry out solid state polycondensation, obtain Modified polyester chips.Method using the present invention can effectively suppress the generation of side reaction in modified poly ester polymerization production process, make the modified poly ester form and aspect of production excellent.
Description
Technical field
The present invention relates to a kind of method for producing modified poly ester, specifically, it is related to a kind of continuous production modified poly ester
Method.
Background technology
Polyester has good mechanical property, wearability, creep resistance, low water absorbable, dimensional stability, electric insulation
Property and moulding processability, are widely used in terms of fiber, Packaging Bottle, film, engineering plastics,
Turn into one of most important chemical industry synthesis material in the world.By high speed development for many years, global PET industry is obtained
Significant growth, but caused structural superfluous outstanding problem is developed at a too fast speed there is also product homogeneity,
The sustainable development of the permanent industry of polyester is had a strong impact on.Adjust the product mix, exploitation new product, new technology develop difference
Change product, the multi-level demand to meet market, improve the market competitiveness and realize current PET industry transition and upgrade
The task of top priority.
The technological approaches of polyester new product development is mainly changes polyester by the method for physical modification or chemical modification
Molecular structure or composition, introduce functional component so that assign polyester cationic dyeing, it is fire-retardant, hydrophilic, can
The characteristics such as biodegradation.But being due to there is the problem of heat endurance is poor polyester functional modification component, in high temperature more
The side reactions such as thermal degradation easily occur under heating condition, causes the form and aspect deterioration of prepared modified poly ester, changes so as to limit
The application of property polyester.
Chinese patent ZL200910312459.4 discloses right in a kind of continuous method for preparing modified poly ester, this method
The ethylene glycol solution of PET oligomer melt and three monomers or many monomers and additive is in the duct
It is well mixed, while carrying out the reaction in esterification later stage, modified poly ester is obtained subsequently into polymerisation is carried out in polycondensation vessel.
Because the residence time of the monomer of function ingredients three or many monomers under the high temperature conditions is longer, prepared modified poly ester is because of work(
Xanthochromia easily occurs for the side reactions such as the thermal degradation that energy component occurs in polymerization process, and form and aspect b values are higher.
In order to overcome defect of the prior art, spy proposes the present invention.
The content of the invention
On the one hand, the invention provides a kind of method of continuous production modified poly ester, this method shortens polycondensation phase
Reaction time, and the modified poly ester even structure of production, form and aspect are excellent.
On the other hand, the invention provides a kind of method of continuous production modified poly ester, this method accelerates modified poly-
The crystallization rate of ester prepolymer, and crystallinity is high.
A kind of method of continuous production modified poly ester of the present invention, comprises the following steps：
(1) raw material terephthalic acid (TPA), dihydric alcohol carry out esterification, obtain terephthalic acid (TPA) binary alcohol esters oligomer；
(2) oligomer prepared in step (1) is mixed with modifying agent, is carried out equal qualitative response, is obtained homogeneous thing
(3) homogeneous thing is prepared in step (2) and carries out melt polycondensation reaction, modified poly ester pre-polymer melt is obtained；
(4) pre-polymer melt is prepared in step (3) and carries out pelletizing shaping and crystallization, pre-crystallized modification is obtained and gathers
Ester prepolymer chips；
(5) pre-crystallized modified poly ester prepolymer chips are prepared in step (4) and carry out solid state polycondensation, are obtained
Modified polyester chips.
The method of the continuous production modified poly ester of the present invention, shortens the reaction time of polycondensation phase, and production changes
Property polyester construction it is uniform, form and aspect are excellent；On the other hand, the crystallization rate of modified poly ester prepolymer, and crystallization are accelerated
Degree is high.
Brief description of the drawings
Fig. 1 is the continuous process flow diagram for producing modified poly ester of the present invention.
Embodiment
The method to a kind of continuous production modified poly ester of the present invention is described in further detail below.Do not limit this hair
Bright protection domain, its protection domain is defined with claims.Some disclosed details are disclosed real to each
Apply scheme and comprehensive understanding is provided.However, those skilled in the relevant art know, do not use one or more of these specific
Details, and use the situation of other materials etc. also to realize embodiment.
Unless the context otherwise requires, in specification and claims, term " comprising ", "comprising" should be managed
Solve for it is open including implication, as " include, but are not limited to ".
Mentioned " embodiment ", " embodiment ", " another embodiment " or " some realities in the description
Apply scheme " etc. refer to it is related to the embodiment described by specifically related to feature, structure or characteristic be included in
In at least one embodiment.Therefore, " embodiment ", " embodiment ", " another embodiment " or " certain
A little embodiments " are It is not necessary to refer both to identical embodiment.And, specific feature, structure or characteristic can be
It is combined in any manner in one or more embodiments.Each feature disclosed in specification, can with appoint
What can provide the alternative characteristics substitution of identical, impartial or similar purpose.Therefore removing has special instruction, disclosed spy
Levy the general example of only impartial or similar features.
Definition：
Equal qualitative response：Refer to exchange reaction in the present invention, exchange reaction includes ester exchange reaction, acid amides exchange reaction
And ester-amide exchange reaction, wherein ester exchange reaction refers to that ester and alcohol/acid/ester (different esters) reaction generation one are new
The reaction of ester and a new alcohol/acid/ester；Acid amides exchange reaction refers to that acid amides reacts from ammonia/acid/acid amides (different acid amides)
Generate the reaction of a new acid amides and a new ammonia/acid/acid amides；Ester-amide exchange reaction refers to that ester group reacts with acid amides and given birth to
Into a new ester and a new acid amides.
Homogeneous thing：Homogeneous thing refers to the product modification polyester oligomer of exchange reaction.Polyester improver is usually with many
Functional compounds such as polyacid, polyalcohol, polyamine, polyester or polyamide, the reaction that polyester improver has
Property functional group's such as hydroxyl, carboxyl, amino, ester group or amide groups is with terephthalic acid (TPA) binary alcohol esters oligomer by exchanging
Reaction generation modified poly ester oligomer, can be achieved material system from the blend of polyester improver and oligomer to homogeneous
The transformation of modified poly ester oligomer.
Term " modifying agent "：The material all including polyester property can be improved；The including but not limited to dye of positive ion
Dyeability modifier, flame-proof modifier, hydrophilic modifier, biodegradable modifying agent etc..
Term " oligomer " refers to the polymer being made up of less repeat unit, and its relative molecular mass is between small point
Between son and macromolecule.Term " prepolymer " is the material that monomer is progressively polymerized, for the present invention, in advance
A kind of relatively low polymer of molecular weight of the polymer of polymers between oligomer and final polymer, is often referred to prepare
The polymer of final polymer previous stage.
Term " crystallization pelletizing " is a kind of means to polymer morphology processing.In field of polymer technology, macromolecule passes through
Processing can be crystallized, i.e. polymer crystallization (Crystallization of polymers), be macromolecular chain component arrangement
Process, in the process, macromolecular chain is folded up, and forms orderly region, and such region turns into platelet,
Platelet can be piled into bigger spherical structure, referred to as spherocrystal.Macromolecule can be crystallized from melt cooling, can also pass through machinery
Stretching or solvent evaporative crystallization.
Term " solid phase polycondensation " (solid state polycondensation, abbreviation SSP) refers to reactant feed solid
Condensation reaction under body state.Field is synthesized in high polymer, solid phase polycondensation is particularly suitable for crystallizable high polymer.Will
Monomer or the relatively low performed polymer of molecular weight are heated to more than glass transition temperature, and the process of polymerisation is carried out below fusing point.
Term " inherent viscosity " refers to the reduced viscosity when Polymer Solution concentration goes to zero.Represent individual molecule
Contribution to solution viscosity, is the viscosity for reflecting polymer characteristicses, and its value does not become with concentration.Inherent viscosity and high score
The relative molecular mass of son has quantitative relation, commonly uses the numerical value of inherent viscosity [η] to ask for relative molecular mass,
Or measuring as high polymer relative molecular weight.
Embodiment：
On the one hand, a kind of method of continuous production modified poly ester, comprises the following steps：
(1) raw material terephthalic acid (TPA), dihydric alcohol carry out esterification, obtain terephthalic acid (TPA) binary alcohol esters oligomer；
(2) oligomer prepared in step (1) is mixed with modifying agent, is carried out equal qualitative response, is obtained homogeneous thing
(3) homogeneous thing is prepared in step (2) and carries out melt polycondensation reaction, modified poly ester pre-polymer melt is obtained；
(4) pre-polymer melt is prepared in step (3) and carries out pelletizing shaping and crystallization, pre-crystallized modification is obtained and gathers
Ester prepolymer chips；
(5) pre-crystallized modified poly ester prepolymer chips are prepared in step (4) and carry out solid state polycondensation, are obtained
Modified polyester chips.
Described dihydric alcohol refers to the molecule containing two hydroxyls on alkyl, and general two hydroxyls are respectively at two of alkyl
On different carbon atoms.In the present invention, described dihydric alcohol includes aliphatic dihydroxy alcohol, aromatic diol；It is preferred that,
Described dihydric alcohol includes straight-chain aliphatic dihydric alcohol, it is further preferred that described dihydric alcohol includes the straight-chain aliphatic of saturation
Dihydric alcohol.
In one embodiment, described dihydric alcohol includes ethylene glycol, propane diols and/or butanediol.
In some embodiments, the mol ratio of raw material terephthalic acid (TPA) and dihydric alcohol is 1:1.05~1:2.
Esterification in step (1) is carried out at one or successively in two esterifying kettles.
In some embodiments, esterification is progress in an esterifying kettle, esterification reaction temperature is 220~275 DEG C,
Esterification reaction pressure is 100~400kPa.
In some embodiments, esterification is successively carried out in two esterifying kettles, and the reaction temperature of the first esterifying kettle is
220~275 DEG C, reaction pressure be 100~400kPa, the reaction temperature of second esterification kettle is 220~275 DEG C, reaction pressure
Power is 100~200kPa.
The parameters such as the proportionate relationship in step (1) between the temperature of pet reaction, pressure, reactant and urge
Species and consumption of agent etc. can also use other conventional process of this area.As long as the oligomeric of certain degree of polymerization can be obtained
Thing.
In some embodiments, the terephthalic acid (TPA) binary alcohol esters oligomer that step (1) esterification is prepared
The degree of polymerization is 1~8.
In order to obtain the polyester fiber of excellent combination property, or the polyester fiber with property, generally preparing
Chemical modification is carried out when polyester, outside basic monomer, increases Third monomer, or the 3rd, the 4th monomer etc.
Modifying agent so that macromolecular structure changes, has reached some physics of improvement, the purpose of chemical property.For example change
Dyeability, fire resistance, spinning property of kind polyester etc..Described modifying agent includes that polyester property institute can be improved
Some materials；Including but not limited to cationic dyeing modifying agent, flame-proof modifier, hydrophilic modifier, can be biological
Degradation modification agent etc..
Described cationic dyeing modifying agent includes：M-phthalic acid binaryglycol ester -5- sodium sulfonates etc..
In some embodiments, the addition of M-phthalic acid binaryglycol ester -5- sodium sulfonates is terephthalic acid (TPA) total moles
0.5 several~10mol%, preferably 1.2~3mol.
Described flame-proof modifier includes：Carboxyethyl phenyl hypophosphorous acid binaryglycol ester etc..
In some embodiments, the addition of carboxyethyl phenyl hypophosphorous acid binaryglycol ester is terephthalic acid (TPA) total mole number
3~15mol%, preferably 5~10mol%.
Described hydrophilic modifier includes：Polyethylene glycol etc..
In some embodiments, the addition of polyethylene glycol is 3~20wt% of modified poly ester gross mass, preferably
5~10wt%.
Described biodegradable modifying agent includes：Poly butylene succinate etc..
The addition of polyethylene glycol is the 10~50wt%, preferably 20~40wt% of modified poly ester gross mass.
In some embodiments, in step (2), addition is mixed modifying agent with oligomer online.Mixing can be
Dynamic mixer and/or static mixer are mixed.Wherein, dynamic mixer preferably high-shear homogenizing pump；Static state is mixed
The preferential tubular static mixer of clutch.Can certainly be using other hybrid modes or mixing arrangement, as long as will change
Property agent is well mixed with oligomer.
In step (2), before oligomer is mixed with modifier, oligomer is 180~240 through heat exchanger regulation temperature
℃。
In step (2), described equal qualitative response is carried out in homogeneous system.
In some embodiments, homogeneous reaction system includes booster pump, homogeneous reactor and the outlet pressure being sequentially connected
Regulating valve.
It is preferred that, the homogeneous reactor is that the choked flow allocation unit in vertical tubular reactor, homogeneous reactor is preferred
Wire packing；Homogeneous reactor content enters outgoing direction for bottom in and top out, is coordinated by booster pump and outlet pressure regulating valve
Regulate and control reaction pressure in homogenizer.
In some embodiments, in step (2), the temperature of described equal qualitative response is 180~250 DEG C.
In some embodiments, in step (2), the Stress control of equal qualitative response is in 200~1000kPa.
In some embodiments, in step (2), the time that equal qualitative response is carried out is 5~30min.
The polyester improver added online is uniform by blender physical mixed with terephthalic acid (TPA) binary alcohol esters oligomer
Enter homogeneous reaction system afterwards, in homogeneous reaction system, polyester improver passes through ester with terephthalic acid (TPA) binary alcohol esters
The exchange reactions such as exchange reaction, acid amides exchange reaction or ester-amide exchange reaction generate modified poly ester oligomer, can be real
Existing material system from polyester improver and oligomer transformation from blend to homogeneous modified poly ester oligomer, so as to have
Effect ensure that the homogeneity of subsequent melt polycondensation reaction.In addition, reaction pressure, reaction temperature by regulating and controlling equal qualitative response
Degree and reaction time can be between Effective Regulation oligomer and modifying agent ester exchange reaction, acid amides exchange reaction or ester-
The degree of the qualitative response such as acid amides exchange reaction, the macromolecular structure of Effective Regulation modified poly ester.
In some embodiments, the melt polycondensation reaction of step (3) is carried out in vertical falling-film reactor.Material from
Be allocated at the top of reactor, using self gravitation in reactor falling liquid film cell surface homogeneous film formation.Falling liquid film is anti-
It is 3~30 layers, preferably 5~20 layers to answer falling-film tower disc layer number in kettle.
In some embodiments, in step (3), the temperature of melt polycondensation reaction is 150~260 DEG C；Melt polycondensation
The pressure of reaction is 300~5000Pa.
In some embodiments, in step (3), the residence time of melt polycondensation reaction is 30~90min.
In some embodiments, the inherent viscosity for the modified poly ester pre-polymer melt that step (3) is prepared is
0.1~0.5dL/g.
In some embodiments, in step (4), the side of pelletizing shaping and crystallization treatment is carried out to pre-polymer melt
Method includes, and pre-polymer melt is cut into drop and is cooled and shaped and crystallizes in temperature is 50~98 DEG C of water, preferably water
Temperature be 60~95 DEG C.
The pelletizing shaping of pre-polymer melt is blended with crystallization in the present invention, by regulate and control the temperature of pelletizing process water with
Energy of the polyester molecule chain in order needed for regular arrangement crystallization is provided, while the process water for being impregnated into polyester molecule interchain can
To play a part of plasticizer to improve the mobility of polyester molecule chain, promote the generation of crystallization process.
The present invention is before solid state polycondensation, and pre-polymer melt will carry out crystallization granulation, to reach certain crystallinity,
Prevent particle from bonding.The crystallization pelletizing process of the present invention, pre-polymer melt is cut into after liquid under higher water temperature
It is cooled and shaped and crystallizes, prepolymer molecule chain is easier to occur regular arrangement form crystal in order under this condition, so that
The softening temperature of section is raised as crystallinity is improved, can effectively prevent section in solid phase polycondensation process
By blocking under warming, be conducive to the progress of follow-up solid-phase polymerization.
It is anti-into solid-phase tack producing system progress solid-phase tack producing that described solid state polycondensation includes pre-crystallized prepolymer chips
Should, obtain Modified polyester chips.There is crystalline region and amorphous area, the repetition list of macromolecular in the reaction particles of solid phase polycondensation
First and nonactive reactive group will be frozen in crystalline region, and terminated radical, small molecule, and catalytic component then by
Repel amorphous area so that the valid density of reactive group is greatly increased, the mutual collision frequency between group is strengthened,
So as to accelerate the speed of polymerisation, the small molecule by-product of generation is then reacted by vacuum or inert gas outflow
System, promotes reaction constantly to be carried out to product direction, improves constantly molecular weight of product.In this way can be effective
Suppress the generation of side reaction in modified poly ester polymerization production process, make the modified poly ester form and aspect of production excellent.
In some embodiments, solid phase polycondensation process is carried out in solid-phase tack producing system, described solid-phase tack producing system bag
Crystallization and two technological processes of solid phase polycondensation are included, temperature during crystallization is 110~200 DEG C, the temperature of solid state polycondensation
For 120~230 DEG C.
It is preferred that, temperature during crystallization is 130~190 DEG C.
It is preferred that, the temperature of solid state polycondensation is 160~220 DEG C.
In the present invention, the species of catalyst and the consumption of catalyst that each step chemically reacts used are ability
Domain conventional material and consumption.Even adding different modifying agent, those skilled in the art are according to modifying agent with gathering
The reactive group of ester can select to use appropriate catalyst and consumption.
Compared with prior art, on the one hand, the present invention uses the poly- solid phase polycondensation process route of homogeneous-preshrunk, reduces
The generation of side reaction in polymerization process, makes the modified poly ester even structure of production, and form and aspect are excellent.
On the other hand, by the optimum organization of the optimization design and the technological process of production of reactor structure, not only make
The approximate laminar flow reaction of polymerisation of modified poly ester, and the reaction time in melt polycondensation stage significantly shortened, taken off
Wave efficiency to greatly improve, so as to effectively inhibit the generation of side reaction in modified poly ester polymerization production process, make production
Modified poly ester even structure, form and aspect are excellent.
On the other hand, the present invention is modified polyester pelletizing shaping using crystallization pelletizing system, in system high temperature technique
The crystallization of modified poly ester pelletizing can be effectively induced in the presence of water, so as to solve because of molecular structure regularity reduction institute band
The problem of modified poly ester crystallization rate come slows down.
Another further aspect, the present invention is adjusted using tubular reactor as homogeneous reactor and booster pump and pressure export
Valve group into homogeneous reaction system, by regulate and control equal qualitative response reaction pressure and reaction temperature can Effective Regulation oligomer with
The degree of the qualitative response such as alcoholysis, acidolysis or ester exchange between modifying agent, the macromolecular of Effective Regulation modified poly ester
Structure.
Instantiation：
Embodiments of the invention are modified the production of polyester according to the flow shown in accompanying drawing 1, further oligomer with
After the blended device of modifying agent that line is added is well mixed, equal qualitative response is carried out into homogeneous reaction system.The homogeneous
Reaction system includes booster pump, homogeneous reactor and the outlet pressure regulating valve being sequentially connected；The homogeneous reactor is
The preferred wire packing of choked flow allocation unit in vertical tubular reactor, homogeneous reactor.Oligomer is mixed with modifying agent
Thing is conveyed from homogeneous reactor bottom by booster pump enters homogeneous reactor.Material is being flowed over into homogeneous reactor
The choked flow allocation unit that Cheng Zhonghui is filled in reactor persistently splits, shears, re-mix make material realize it is high
The mode of laminar flow is kept to flow while effect mixing.On the one hand booster pump supplements homogeneous reactor choked flow allocation unit institute
The crushing of generation, on the other hand coordinates the pressure of the equal qualitative response of regulation and control with homogeneous reactor outlet pressure-regulating valve.Pass through
Regulate and control the reaction pressure and reaction temperature of equal qualitative response can realize alcoholysis between oligomer and modifying agent, acidolysis or
The degree of the qualitative response such as ester exchange, the macromolecular structure of Effective Regulation modified poly ester.
Embodiment 1
The mol ratio of acid and alcohol is in the slurry that terephthalic acid (TPA), ethylene glycol and antimony-based catalyst are deployed into, slurry
1:1.34；
Being transported in the esterification system being made up of vertical esterifying kettle for gained slurry continuous uniform carries out esterification, wherein
Esterifying kettle reaction temperature is 270 DEG C, reaction pressure is 170kPa.When the degree of polymerization of ethylene glycol terephthalate reaches
When 3, oligomer is continuously and stably produced by oligomer pump from esterifying kettle；
M-phthalic acid diethylene glycol after obtained oligomer is adjusted the temperature into 230 DEG C through heat exchanger with adding online
Ester -5- sodium sulfonates (SIPE) solution is changed enters homogeneous after the tubular static mixer being arranged on pipeline is well mixed
Reaction system carries out equal qualitative response, obtains homogeneous thing；Wherein, oligomer and SIPE flow-rate ratio are 88:12, homogeneous
The reaction temperature of reaction is 230 DEG C, reaction pressure be 400kPa, residence time be 10min；
Homogeneous thing is delivered to polycondensation vessel and carries out melt polycondensation reaction, and obtained inherent viscosity melts for 0.1dL/g prepolymer
The reaction temperature of body, wherein melt polycondensation reaction is 260 DEG C, reaction pressure be 3000Pa, residence time be 30min；
Pre-polymer melt is delivered to crystallization pelletizing system and carries out pelletizing shaping and crystallization, wherein crystallization pelletizing system work
The temperature of skill water is 98 DEG C.
Pre-crystallized prepolymer chips are delivered to the temperature that solid-phase tack producing system carries out solid state polycondensation, wherein crystallizer
For 200 DEG C, the temperature of solid state polycondensation device is 230 DEG C.When the inherent viscosity of Modified polyester chips reaches 0.55dL/g,
Will section extraction cooling packing from solid state polycondensation device.The modified poly ester is PET-SIPE copolymers, SIPE chains
The introducing of section imparts modified poly ester cationic dye capable of dyeing performance, and the form and aspect b values of section are 4.
Embodiment 2
The mol ratio of acid and alcohol is in the slurry that terephthalic acid (TPA), ethylene glycol and antimony-based catalyst are deployed into, slurry
1:2；
Gained slurry continuous uniform is transported to the esterification system being made up of vertical first esterifying kettle and vertical second esterification kettle
Carry out esterification in system, the first esterifying kettle reaction temperature is 220 DEG C, reaction pressure is 100kPa, second esterification kettle
220 DEG C of reaction temperature, reaction pressure are 100kPa., will when the degree of polymerization of ethylene glycol terephthalate reaches 1
Oligomer is continuously and stably produced by oligomer pump from esterifying kettle；
Carboxyethyl phenyl hypophosphorous acid diethylene glycol after oligomer is adjusted the temperature into 210 DEG C through heat exchanger with adding online
Ester (CEPPE) solution is changed enters homogeneous reaction system after the tubular static mixer being arranged on pipeline is well mixed
Equal qualitative response is carried out, homogeneous thing is obtained；Wherein, the flow-rate ratio of oligomer and CEPPE solution is 80:20, homogeneous is anti-
The reaction temperature answered is 210 DEG C, reaction pressure be 800kPa, residence time be 15min；
Homogeneous thing is delivered to polycondensation vessel and carries out melt polycondensation reaction, obtained inherent viscosity is 0.25dL/g prepolymer
The reaction temperature of melt, wherein melt polycondensation reaction is 245 DEG C, reaction pressure be 1000Pa, residence time be 60min；
Pre-polymer melt is delivered to crystallization pelletizing system and carries out pelletizing shaping and crystallization, wherein crystallization pelletizing system work
The temperature of skill water is 98 DEG C；
Pre-crystallized prepolymer chips are delivered to the temperature that solid-phase tack producing system carries out solid state polycondensation, wherein crystallizer
For 160 DEG C, the temperature of solid state polycondensation device is 210 DEG C.When the inherent viscosity of Modified polyester chips reaches 0.76dL/g,
Will section extraction cooling packing from solid state polycondensation device.The modified poly ester is PET-CEPPE copolymers, CEPPE
The introducing of segment imparts modified poly ester fire resistance, and the form and aspect b values of section are 3.
Embodiment 3
The mol ratio of acid and alcohol is in the slurry that terephthalic acid (TPA), ethylene glycol and antimony-based catalyst are deployed into, slurry
1:1.15；
Gained slurry continuous uniform is transported to the esterification system being made up of vertical first esterifying kettle and vertical second esterification kettle
Carry out esterification in system, the first esterifying kettle reaction temperature is 265 DEG C, reaction pressure is 200kPa, second esterification kettle
270 DEG C of reaction temperature, reaction pressure are 120kPa., will when the degree of polymerization of ethylene glycol terephthalate reaches 5
Oligomer is continuously and stably produced by oligomer pump from esterifying kettle；
Cetomacrogol 1000 (PEG1000) after oligomer is adjusted the temperature into 235 DEG C through heat exchanger with adding online
Enter homogeneous reaction system after the high-shear homogenizing pump being arranged on pipeline is well mixed and carry out equal qualitative response, obtain
Homogeneous thing；Wherein, oligomer and PEG1000 flow-rate ratio are 90:10, the reaction temperature of equal qualitative response is 235 DEG C,
Reaction pressure be 300kPa, residence time be 15min；
Homogeneous thing is delivered to polycondensation vessel and carries out melt polycondensation reaction, obtained inherent viscosity is 0.22dL/g prepolymer
The reaction temperature of melt, wherein melt polycondensation reaction is 260 DEG C, reaction pressure be 1000Pa, residence time be 60min；
Pre-polymer melt is delivered to crystallization pelletizing system and carries out pelletizing shaping and crystallization, wherein crystallization pelletizing system work
The temperature of skill water is 70 DEG C；
Pre-crystallized prepolymer chips are delivered to the temperature that solid-phase tack producing system carries out solid state polycondensation, wherein crystallizer
For 140 DEG C, the temperature of solid state polycondensation device is 230 DEG C.When the inherent viscosity of Modified polyester chips reaches 0.70dL/g,
Will section extraction cooling packing from solid state polycondensation device.The modified poly ester is PET-PEG copolymers, PEG chains
The introducing of section imparts the excellent moisture pick-up properties of modified poly ester, and the form and aspect b values of section are 5.
Embodiment 4
The mol ratio of acid and alcohol is in the slurry that terephthalic acid (TPA), ethylene glycol and antimony-based catalyst are deployed into, slurry
1:1.05；
Gained slurry continuous uniform is transported to the esterification system being made up of vertical first esterifying kettle and horizontal second esterification kettle
Carry out esterification in system, the first esterifying kettle reaction temperature is 275 DEG C, reaction pressure is 400kPa, second esterification kettle
275 DEG C of reaction temperature, reaction pressure are 200kPa., will when the degree of polymerization of ethylene glycol terephthalate reaches 8
Oligomer is continuously and stably produced by oligomer pump from esterifying kettle；
The polyamide (PA) added after oligomer is adjusted the temperature into 250 DEG C through heat exchanger and online is by being arranged on pipe
High-shear homogenizing pump on road enters homogeneous reaction system after being well mixed and carries out equal qualitative response, obtains homogeneous thing；Wherein,
Oligomer and PA flow-rate ratio are 80:20, the reaction temperature of equal qualitative response is 250 DEG C, reaction pressure be 600kPa,
Residence time is 10min；
Homogeneous thing is delivered to polycondensation vessel and carries out melt polycondensation reaction, obtained inherent viscosity is 0.15dL/g prepolymer
The reaction temperature of melt, wherein melt polycondensation reaction is 230 DEG C, reaction pressure be 1000Pa, residence time be 45min；
Pre-polymer melt is delivered to crystallization pelletizing system and carries out pelletizing shaping and crystallization, wherein crystallization pelletizing system technique
The temperature of water is 80 DEG C；
Obtained pre-crystallized prepolymer chips are delivered to solid-phase tack producing system and carry out solid state polycondensation, wherein crystallizer
Temperature be 130 DEG C, the temperature of solid state polycondensation device is 200 DEG C.When the inherent viscosity of Modified polyester chips reaches
0.85dL/g, the extraction cooling packing from solid state polycondensation device by section.The modified poly ester is PET-PA copolymers,
The introducing of PA segments imparts the excellent moisture pick-up properties of modified poly ester, and the form and aspect b values of section are 6.
Embodiment 5
The mol ratio of acid and alcohol is in the slurry that terephthalic acid (TPA), propane diols and Titanium series catalyst are deployed into, slurry
1:1.4；
Gained slurry continuous uniform is transported to the esterification system being made up of vertical first esterifying kettle and horizontal second esterification kettle
Carry out esterification in system, the first esterifying kettle reaction temperature is 240 DEG C, reaction pressure is 250kPa, second esterification kettle
245 DEG C of reaction temperature, reaction pressure are 150kPa., will when the degree of polymerization of propylene glycol ester terephthalate reaches 4
Oligomer is continuously and stably produced by oligomer pump from esterifying kettle；
M-phthalic acid DPG ester -5- sulphurs after oligomer is adjusted the temperature into 230 DEG C through heat exchanger with adding online
Sour sodium (SIPT) solution is changed enters homogeneous reaction system after the tubular static mixer being arranged on pipeline is well mixed
Equal qualitative response is carried out, homogeneous thing is obtained；Wherein, oligomer and SIPT flow-rate ratio are 80:20, equal qualitative response it is anti-
To answer temperature be 230 DEG C, reaction pressure be 1000kPa, residence time be 5min；
Homogeneous thing is delivered to polycondensation vessel and carries out melt polycondensation reaction, obtained inherent viscosity is 0.34dL/g prepolymer
The reaction temperature of melt, wherein melt polycondensation reaction is 235 DEG C, reaction pressure be 500Pa, residence time be 30min.
Pre-polymer melt is delivered to crystallization pelletizing system and carries out pelletizing shaping and crystallization, wherein crystallization pelletizing system technique
The temperature of water is 90 DEG C；
Obtained pre-crystallized prepolymer chips are delivered to solid-phase tack producing system and carry out solid state polycondensation, wherein crystallizer
Temperature be 120 DEG C, the temperature of solid state polycondensation device is 190 DEG C.When the inherent viscosity of Modified polyester chips reaches
0.80dL/g, the extraction cooling packing from solid state polycondensation device by section.The modified poly ester is PTT-SIPT copolymers,
The introducing of SIPT segments imparts modified poly ester cationic dye capable of dyeing performance, and the form and aspect b values of section are 5.
Embodiment 6
The mol ratio of acid and alcohol is in the slurry that terephthalic acid (TPA), propane diols and Titanium series catalyst are deployed into, slurry
1:1.4；
Gained slurry continuous uniform is transported to the esterification system being made up of vertical first esterifying kettle and horizontal second esterification kettle
Carry out esterification in system, the first esterifying kettle reaction temperature is 240 DEG C, reaction pressure is 250kPa, second esterification kettle
245 DEG C of reaction temperature, reaction pressure are 150kPa., will when the degree of polymerization of propylene glycol ester terephthalate reaches 4
Oligomer is continuously and stably produced by oligomer pump from esterifying kettle；
M-phthalic acid DPG ester -5- sulphurs after oligomer is adjusted the temperature into 230 DEG C through heat exchanger with adding online
Sour sodium (SIPT) solution enters after the tubular static mixer being arranged on pipeline is well mixed into homogeneous reaction system
The equal qualitative response of row, obtains homogeneous thing；Wherein, oligomer and SIPT flow-rate ratio are 80:20, the reaction of equal qualitative response
Temperature is 230 DEG C, reaction pressure be 1000kPa, residence time be 5min.
Homogeneous thing is delivered to polycondensation vessel and carries out melt polycondensation reaction, obtained inherent viscosity is 0.34dL/g prepolymer
The reaction temperature of melt, wherein melt polycondensation reaction is 235 DEG C, reaction pressure be 500Pa, residence time be 30min.
Pre-polymer melt is delivered to crystallization pelletizing system and carries out pelletizing shaping and crystallization, wherein crystallization pelletizing system technique
The temperature of water is 90 DEG C；
Obtained pre-crystallized prepolymer chips are delivered to solid-phase tack producing system and carry out solid state polycondensation, wherein crystallizer
Temperature be 120 DEG C, the temperature of solid state polycondensation device is 190 DEG C.When the inherent viscosity of Modified polyester chips reaches
0.80dL/g, the extraction cooling packing from solid state polycondensation device by section.The modified poly ester is PTT-SIPT copolymers,
The introducing of SIPT segments imparts modified poly ester cationic dye capable of dyeing performance, and the form and aspect b values of section are 5.
Embodiment 7
The mol ratio of acid and alcohol is in the slurry that terephthalic acid (TPA), butanediol and Titanium series catalyst are deployed into, slurry
1:1.12；
Being transported in the esterification system being made up of vertical esterifying kettle for gained slurry continuous uniform carries out esterification, its
In, esterifying kettle reaction temperature is 240 DEG C, reaction pressure is 140kPa.When the degree of polymerization of mutual-phenenyl two acid bromide two alcohol ester
When reaching 3, oligomer is continuously and stably produced by oligomer pump from esterifying kettle；
Poly butylene succinate (PBS) warp after oligomer is adjusted the temperature into 200 DEG C through heat exchanger with adding online
Cross and enter the equal qualitative response of homogeneous reaction system progress after the high-shear homogenizing pump being arranged on pipeline is well mixed, obtain
Matter thing；Wherein, oligomer and PBS flow-rate ratio are 70:30, the reaction temperature of equal qualitative response is 200 DEG C, reacted
Pressure be 500kPa, residence time be 30min；
Homogeneous thing is delivered to polycondensation vessel and carries out melt polycondensation reaction, obtained inherent viscosity is 0.40dL/g prepolymer
The reaction temperature of melt, wherein melt polycondensation reaction is 200 DEG C, reaction pressure be 5000Pa, residence time be 90min.
Pre-polymer melt is delivered to crystallization pelletizing system and carries out pelletizing shaping and crystallization, wherein crystallization pelletizing system work
The temperature of skill water is 60 DEG C.
Pre-crystallized prepolymer chips are delivered to the temperature that solid-phase tack producing system carries out solid state polycondensation, wherein crystallizer
For 120 DEG C, the temperature of solid state polycondensation device is 160 DEG C.When the inherent viscosity of Modified polyester chips reaches 1.00dL/g,
Will section extraction cooling packing from solid state polycondensation device.The modified poly ester is PBT-PBS copolymers, PBS chains
The introducing of section imparts the excellent biodegradable performance of modified poly ester, and the form and aspect b values of section are 5.
Embodiment 8
The mol ratio of acid and alcohol is in the slurry that terephthalic acid (TPA), butanediol and Titanium series catalyst are deployed into, slurry
1:2；
Being transported in the esterification system being made up of vertical esterifying kettle for gained slurry continuous uniform carries out esterification, its
In, esterifying kettle reaction temperature is 220 DEG C, reaction pressure is 100kPa.When the degree of polymerization of mutual-phenenyl two acid bromide two alcohol ester
When reaching 1, oligomer is continuously and stably produced by oligomer pump from esterifying kettle；
Poly adipate succinic acid ester (PBA) warp after oligomer is adjusted the temperature into 180 DEG C through heat exchanger with adding online
Cross and enter the equal qualitative response of homogeneous reaction system progress after the high-shear homogenizing pump being arranged on pipeline is well mixed, obtain
Matter thing；Wherein, oligomer and PBA flow-rate ratio are 60:40, the reaction temperature of equal qualitative response is 180 DEG C, reacted
Pressure be 500kPa, residence time be 30min；
Homogeneous thing is delivered to polycondensation vessel and carries out melt polycondensation reaction, obtained inherent viscosity is 0.50dL/g prepolymer
The reaction temperature of melt, wherein melt polycondensation reaction is 150 DEG C, reaction pressure be 300Pa, residence time be 90min.
Pre-polymer melt is delivered to crystallization pelletizing system and carries out pelletizing shaping and crystallization, wherein crystallization pelletizing system technique
The temperature of water is 50 DEG C；
Obtained pre-crystallized prepolymer chips are delivered to solid-phase tack producing system and carry out solid state polycondensation, wherein crystallizer
Temperature be 110 DEG C, the temperature of solid state polycondensation device is 120 DEG C.When the inherent viscosity of Modified polyester chips reaches
1.20dL/g, the extraction cooling packing from solid state polycondensation device by section.The modified poly ester is PBT-PBA copolymers,
The introducing of PBA segments imparts the excellent biodegradable performance of modified poly ester, and the form and aspect b values of section are 5.5.
Comparative example 1
The mol ratio of acid and alcohol is in the slurry that terephthalic acid (TPA), ethylene glycol and antimony-based catalyst are deployed into, slurry
1:1.34；
Being transported in the esterification system being made up of vertical esterifying kettle for gained slurry continuous uniform carries out esterification, wherein
Esterifying kettle reaction temperature is 270 DEG C, reaction pressure is 170kPa.When the degree of polymerization of ethylene glycol terephthalate reaches
When 3, oligomer is continuously and stably produced by oligomer pump from esterifying kettle；
M-phthalic acid binaryglycol ester -5- sulphurs after oligomer is adjusted the temperature into 230 DEG C through heat exchanger with adding online
Sour sodium (SIPE) solution is changed enters homogeneous reaction system after the tubular static mixer being arranged on pipeline is well mixed
Equal qualitative response is carried out, homogeneous thing is obtained；Wherein, oligomer and SIPE flow-rate ratio are 88:12, equal qualitative response it is anti-
To answer temperature be 230 DEG C, reaction pressure be 400kPa, residence time be 10min.
Homogeneous thing is delivered to precondensation kettle and carries out prepolymerization reaction, obtained inherent viscosity is 0.1dL/g prepolymer
The reaction temperature of melt, wherein prepolymerization reaction is 260 DEG C, reaction pressure be 3000Pa, residence time be 30min；
Pre-polymer melt is delivered to whole batch condensation polymerization reactor and carries out whole polycondensation reaction, wherein, the poly- reaction temperature of final minification is 275
DEG C, reaction pressure be 100Pa, as whole polymer melt inherent viscosity 0.55dL/g, whole polymer melt is delivered to pelletizing
System carries out pelletizing and obtains Modified polyester chips.Modified poly ester is PET-SIPE copolymers, and the introducing of SIPE segments is assigned
Modified poly ester cationic dye capable of dyeing performance is given, the form and aspect b values of section are 7.
In order to further illustrate to the modification prepared by embodiment 1 and comparative example 1 below beneficial effects of the present invention
Polyester slice performance indications are tested, and test event is as follows：Fusing point (DEG C), method of testing：With reference to GB/T
14190-2008；Carboxyl-content (mol/t), method of testing：With reference to GB/T 14190-2008；Diethylene glycol content (%),
Method of testing：With reference to GB/T 14190-2008；Form and aspect b values, method of testing：With reference to GB/T 14190-2008.Survey
Test result is shown in Table 1.
Table 1
It can see from table 1, compared with the Modified polyester chips that comparative example 1 is produced, what embodiment 1 was produced
The carboxyl-contents of Modified polyester chips, diethylene glycol content and form and aspect b values are low, and fusing point is high, shows that embodiment 1 is produced
The quality of Modified polyester chips be better than the Modified polyester chips that are produced of comparative example 1.The performance indications carboxylic of polyester slice
Base content, diethylene glycol content, the height of form and aspect b values can be used as side reaction occurrence degree in sign polyester production process
Index.Side reaction degree is smaller in polyester production process, carboxyl-content, diethylene glycol content and the form and aspect b values of section
Lower, the regularity of molecular structure is better, and fusing point is higher.Embodiment 1 is using the poly- solid phase polycondensation production of homogeneous-preshrunk
Process route, compared with the normal polyester production process route that comparative example 1 is used, makes the reaction in melt polycondensation stage
Temperature is greatly reduced, the reaction time significantly shortens, and effectively inhibits the hair of side reaction in modified poly ester polymerization production process
Raw, the modified poly ester even structure produced, form and aspect are excellent.
It should be appreciated that the narration of the above is only example and illustrative for the present invention as set forth in the claims, and
It is non-that it is any limitation as.It should be noted that this specification and embodiment should only be looked at as example, reality of the invention
Scope and spirit should be determined by claim.
Claims (10)
1. a kind of method of continuous production modified poly ester, comprises the following steps：
(1) raw material terephthalic acid (TPA), dihydric alcohol carry out esterification, obtain terephthalic acid (TPA) binary alcohol esters oligomer,
It is preferred that, described dihydric alcohol includes straight-chain aliphatic dihydric alcohol, it is further preferred that described dihydric alcohol includes the straight of saturation
Chain fatty race dihydric alcohol；Most preferably, described dihydric alcohol is ethylene glycol, propane diols and/or butanediol；
(2) oligomer prepared in step (1) is mixed with modifying agent, is carried out equal qualitative response, is obtained homogeneous
Thing
(3) homogeneous thing is prepared in step (2) and carries out melt polycondensation reaction, modified poly ester prepolymer is obtained and melts
Body；
(4) pre-polymer melt is prepared in step (3) and carries out pelletizing shaping and crystallization, pre-crystallized modification is obtained
Polyester prepolyer is cut into slices；
(5) pre-crystallized modified poly ester prepolymer chips are prepared in step (4) and carry out solid state polycondensation, are obtained
To Modified polyester chips；It is preferred that, the inherent viscosity of Modified polyester chips is 0.5~1.2dL/g.
2. according to the method described in claim 1, it is characterised in that in step (4), pre-polymer melt is entered
The method of row pelletizing shaping and crystallization treatment includes, and pre-polymer melt is cut into drop and is 50~98 DEG C of water in temperature
Middle cooling and shaping are simultaneously crystallized；It is preferred that 60~95 DEG C of the temperature of water.
3. method according to claim 1 or 2, it is characterised in that equal qualitative response is carried out in homogeneous system,
Homogeneous reaction system includes booster pump, homogeneous reactor and the outlet pressure regulating valve being sequentially connected；
It is preferred that, the homogeneous reactor is that the choked flow allocation unit in vertical tubular reactor, homogeneous reactor is excellent
Select wire packing；Homogeneous reactor content enters outgoing direction for bottom in and top out, passes through booster pump and outlet pressure regulating valve
Coordinate reaction pressure in regulation and control homogenizer.
4. method according to claim 1 or 2, it is characterised in that the temperature of equal qualitative response is 180~250
℃；The Stress control of equal qualitative response is in 200~1000kPa.
5. the method according to claim any one of 1-4, it is characterised in that in step (3), melting contracting
The temperature of poly- reaction is 150~260 DEG C；The pressure of melt polycondensation reaction is 300~5000Pa.
6. method according to claim 1 or 5, it is characterised in that the melt polycondensation reaction of step (3)
Carried out in vertical falling-film reactor, falling-film tower disc layer number is 3~30 layers, preferably 5~20 layers in falling liquid film reactor.
7. method according to claim 1 or 2, it is characterised in that the solid phase polycondensation process of step (5)
Carried out in solid-phase tack producing system, described solid-phase tack producing system includes crystallization and two technological processes of solid phase polycondensation；
It is preferred that, temperature during crystallization is 110~200 DEG C, it is further preferred that temperature during crystallization is 130~190 DEG C,
It is preferred that, the temperature of solid state polycondensation is 120~230 DEG C, it is further preferred that the temperature of solid state polycondensation is
160~220 DEG C.
8. according to the method described in claim 1, it is characterised in that the esterification of step (1) at one or
Carried out successively in two esterifying kettles；
It is preferred that, the esterification of step (1) is carried out in an esterifying kettle, and esterification reaction temperature is 220~275
DEG C, esterification reaction pressure be 100~400kPa；Or
Esterification is carried out in two esterifying kettles successively, and the reaction temperature of the first esterifying kettle is 220~275 DEG C, instead
It is 100~400kPa to answer pressure, and the reaction temperature of second esterification kettle is 220~275 DEG C, reaction pressure is
100~200kPa.
9. the method according to claim 1 or 8, it is characterised in that step (1) obtains terephthalic acid (TPA)
The degree of polymerization of binary alcohol esters oligomer is 1~8.
10. according to claim 1, the method described in any one of 8-9, it is characterised in that what step (3) was obtained changes
Property polyester prepolyer melt inherent viscosity be 0.1~0.5dL/g.
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| CN109503434A (en) * | 2018-11-16 | 2019-03-22 | 泰山医学院 | A kind of multicomponent process for catalytic synthesis of the modifying agent M-phthalic acid dipropylene glycol ester -5- sodium sulfonate of polyester PTT |
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| CN109503434A (en) * | 2018-11-16 | 2019-03-22 | 泰山医学院 | A kind of multicomponent process for catalytic synthesis of the modifying agent M-phthalic acid dipropylene glycol ester -5- sodium sulfonate of polyester PTT |
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| CN109705318B (en) * | 2018-12-29 | 2020-11-24 | 中国纺织科学研究院有限公司 | Method for continuously producing polyester color master batch and polyester color master batch |
| CN109705327A (en) * | 2018-12-29 | 2019-05-03 | 中国纺织科学研究院有限公司 | A kind of production method of functional polyester, production system and functional polyester fiber |
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| CN109705318A (en) * | 2018-12-29 | 2019-05-03 | 中国纺织科学研究院有限公司 | A kind of method and Polyester color master batch of continuous production of polyesters Masterbatch |
| TWI705085B (en) * | 2019-06-03 | 2020-09-21 | 遠東新世紀股份有限公司 | Polymer, producing method thereof, and method of producing fiber |
| CN112210076A (en) * | 2019-07-11 | 2021-01-12 | 中国石油化工股份有限公司 | Method and device for continuously producing polyether amide elastomer |
| CN112210076B (en) * | 2019-07-11 | 2023-08-15 | 中国石油化工股份有限公司 | Method and device for continuously producing polyether amide elastomer |
| CN111072944A (en) * | 2019-12-31 | 2020-04-28 | 绍兴惠群新材料科技有限公司 | PBT polyester titanium catalyst composite material system and preparation method thereof |
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