CN109957095A - The preparation method of polyalkylene terephthalates - Google Patents
The preparation method of polyalkylene terephthalates Download PDFInfo
- Publication number
- CN109957095A CN109957095A CN201811187492.4A CN201811187492A CN109957095A CN 109957095 A CN109957095 A CN 109957095A CN 201811187492 A CN201811187492 A CN 201811187492A CN 109957095 A CN109957095 A CN 109957095A
- Authority
- CN
- China
- Prior art keywords
- polyalkylene terephthalates
- preparation
- reaction
- alcohol
- terephthalates according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
- C08G63/02—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
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
-
- 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
- C08G63/82—Preparation processes characterised by the catalyst used
-
- 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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to the preparation methods of polyalkylene terephthalates, the method for being related to that the polyalkylene terephthalates resin with high viscosity and excellent color can be prepared within a short period of time in more detail.In the preparation method of polyalkylene terephthalates of the invention, it can be by using to being used in the resin that ethylene glycol is added in the polyethylene terephthalate (PET) of existing fiber, bottle, film etc., to prepare, intrinsic viscosity is very high and high functional plastics with color transparent such as glass.And, the monomer reaction product of half or so is transferred to polymer reactor by preparation method of the invention, and reactant slurry is added into surplus to carry out monomer reaction, so as to have the effect of preparing the polyalkylene terephthalates resin with high viscosity and excellent color in a short time.
Description
Technical field
The present invention relates to the preparation method of polyalkylene terephthalates, it is related in a short time may be used in more detail
Prepare the method with the polyalkylene terephthalates resin of high viscosity and excellent color.
Background technique
Polyalkylene terephthalates (Polyalkylene terephthalate) resinoid refers to as polyesters
By terephthalic acid (TPA) (terephthalic acid；) or dimethyl terephthalate (DMT) (dimethyl terephthalate TPA；
DMT) it is used as acid starting material, uses alkylen glycol compound as alcohol component, and pass through esterification under certain catalyst
And the high-molecular compound that polymer polymerizing reaction generates.
Until the 1980s because quality problems as the acid starting material have mainly used dimethyl terephthalate (DMT), but
Recently other than the special dimension generated due to output control problem, terephthalic acid (TPA) is used in worldwide.
This polyalkylene terephthalates resinoid can be divided into poly- terephthaldehyde according to the type of alcohol component (glycol)
Sour glycol ester (polyethylene terephthalate；PET) resin, polypropylene terephthalate
(polytrimethylene terephthalate；PTT) resin, polybutylene terephthalate (PBT) (polybutylene
terephthalate；PBT) resin, polycyclohexylene's dimethyl ester (polycyclohexylenedimethylene
terephthalate；PCT) resin etc..
Pet resin uses ethylene glycol (ethylene glycol) as alcohol component (glycol),
Polytrimethylene terephthalate uses 1,3-PD (1,3-propanediol) as alcohol component (glycol), and poly- pair
Butylene terephthalate resin uses 1,4-butanediol (Isosorbide-5-Nitrae-butanediol) as alcohol component (glycol), and poly- to benzene
Dioctyl phthalate cyclohexane dicarboxylates resin uses 1,4-CHDM (Isosorbide-5-Nitrae-cyclohexane as alcohol component (glycol)
dimethanol；CHDM).
Compared with the macromolecule resins such as polypropylene (PP), polyethylene (PE), these poly terephthalic acid alkylenes
Base ester resinoid has the outstanding features of all physical property such as heat resistance, the transparency, intensity, processability, therefore is widely used in day
Often in life, such as fiber, film, bottle.
Polyalkylene terephthalates resinoid usually has the homopolymer being made of single alcohol component
(homopolymer) form, but according to alcohol component, the fusing point of macromolecule resin, crystallinity, heat resistance, intensity, etc. it is all
Physical property has differences, according to required physical property, additionally it is possible to by using three kinds or more of glycol as raw polyol polyester copolymer or
Form that three kinds or more of homopolymer is mutually mixed produces.
As the most widely used polyethylene terephthalate of polyalkylene terephthalates resinoid because having
Outstanding physical property is widely used in the multiple fields such as fiber, bottle, film, still, for being used as highstrenghtpiston or Gao Gongneng
Plastics physical property is slightly worse, therefore there is a problem of being easily broken or the service life is not grown.Therefore, in the requirement such as beverage bottle, castor
Physical property compares in the stronger application of polyethylene terephthalate and has used sheet glass, but there are the following problems for vial, that is,
It not only is difficult to transport because of weight weight, but also is crushed during transportation because often colliding, and in transport or management process
In, due to generating sightless glass powder, thus it is very high to enter a possibility that internal.
Developing in order to solve these problems is polyethylene terephthalate (polyethylene
terephthalate glycol；PETG) resin.Pet resin is in polyethylene terephthalate
Ethylene glycol is added in ester non-crystalline resin is made, such as glass transparent and there is high-intensitive physical property, therefore be expected to become
It can replace high intensity, the high functionality plastics of polyethylene terephthalate and glass.So far, poly terephthalic acid second
Terephthalate resin is mainly used for food containers, soundproof wall, beverage bottle etc., but recently, is used as in South Korea and China etc.
Cosmetics containers, application range become extensively, and then the attention rate of consumer is higher and higher.
Remember altogether in Korean Patent Publication No. 10-0838321, publication bulletin the 10-2013-0076733rd
The preparation method for having carried polyethylene terephthalate, in the document, due to illustrating poly- terephthaldehyde on same line
The preparation method of sour glycol ester resin and conventional polyester resinoid, therefore be not suitable for production and common poly terephthalic acid second two
Alcohol ester resin is compared, it is desirable that more highly viscous pet resin.For example, in polyethylene terephthalate
In the case where ester, if the intrinsic viscosity (Intrinsic Viscosity) and viscosity of raising definite part no longer improve, it can make
With highly viscous method is proposed by solid phase, still, polyethylene terephthalate is difficult to carry out solid phase, because
This, although starting to develop a long time ago, in preparation and use aspect, there are many limitations.
In this case, the inventors found that in a short time preparing transparent with simple process and reacting
The method for the high viscosity pet resin that property is improved, and complete the present invention.
Summary of the invention
It is an object of the present invention to solve problem as described above, provide using simple method and process conditions in short-term
The interior method for preparing the transparent and reactive high viscosity pet resin being improved.
In order to solve the technical problem, the present invention provides polyalkylene terephthalates (polyalkylene
Terephthalate glycol) preparation method, comprising: will include the slurry of dicarboxylic acids, alcohol, catalyst and stabilizer be added
The step of to monomer reaction device and by heating to carry out monomer reaction；And the product of the monomer reaction is transferred to polymerization
Come the step of carrying out polymerization reaction in object reactor, which is characterized in that will be described in 35 weight percent to 65 weight percent
Monomer reaction product is transferred to polymer reactor, and adds the slurry into surplus to carry out monomer reaction.
In the present invention, the polyalkylene terephthalates can be polyethylene terephthalate.
In the present invention, the dicarboxylic acids and alcohol of the molar ratio of 1:1.05 to 1:2.5 can be added.
In the present invention, the dicarboxylic acids can be selected from dimethyl terephthalate (DMT), terephthalic acid (TPA), M-phthalic acid
(isophthalic acid), naphthalene dicarboxylic acids (naphthalene dicarboxylic acid；) and their derivative NDA.
In the present invention, the alcohol can be for selected from by ethylene glycol (ethylene glycol；EG), 1,4-butanediol, new
Pentanediol (neopentyl glycol), 1,4-CHDM, 1,6- hexylene glycol (1,6-hexanediol) and three hydroxyl first
Base propane (trimethylol propane；TMP) the two or more polyalcohols in the group formed, it is preferable that may include 50 rubbing
Your percentage to 90 molar percentages ethylene glycol and 10 molar percentages to 50 molar percentages selected from by 1,4-butanediol,
One or more of the group of neopentyl glycol, 1,4-CHDM, 1,6- hexylene glycol and trimethylolpropane composition it is polynary
Alcohol.
In the present invention, the alcohol may include the three hydroxyl first that 0.1 molar percentage to 1.5 molar percentages is accounted in total alcohol
Base propane.
In the present invention, the catalyst can be for selected from by zinc acetate, calcium acetate, cobalt acetate, manganese acetate, dibutyl oxygen
Change tin, butyl isopropyl titanate esters, tetra isopropyl titanate, tetra-n-butyl titanate esters, tetra isopropyl titanate, four n-propyl titaniums
Acid esters, titanium oxide, one or more of the group of four fourth titanate esters and titanium chelate composition.
In the present invention, on the basis of the total weight of reactant, the catalyst of 20ppm to 800ppm can be added.
In the present invention, the stabilizer can be for selected from by trimethyl phosphate (trimethylphosphate), phosphoric acid
Triethyl (triethylphosphate), new penta 2 aryloxy group triguaiacyl phosphate (neopentyl diaryloxy
Triphosphate), triphenyl phosphate (triphenylphosphate), triethyl phosphonium mesitoyl acetate
(triethylphosphonoacetate), phosphoric acid (Phosphoric acid) and phosphorous acid (Phosphorous acid) group
At one or more of group.
In the present invention, on the basis of the total weight of reactant, the stabilizer of 30ppm to 600ppm can be added.
In the present invention, 220 DEG C of end reaction temperature can be made to 7 DEG C reaction temperature to heat up per minute 5 DEG C
The monomer reaction is carried out to 250 DEG C of modes.
In the present invention, the polymerization reaction can 250 DEG C to 280 DEG C at a temperature of carry out, can be through 30 minutes to 40 points
Clock vacuum carries out.
Preparation method of the invention can carry out under anaerobic state.
The present invention also provides the polyalkylene terephthalates prepared according to the method.
In the present invention, it is preferred to which the polyalkylene terephthalates are polyethylene terephthalate.
In the present invention, the intrinsic viscosity of the polyalkylene terephthalates can be for 0.5dl/g extremely
1.2dl/g, chromaticity coordinates L*Value can be 65 or more, b*Value can be 6 or less.
It, can be existing to being used in by utilizing in the preparation method of polyalkylene terephthalates of the invention
Fiber, bottle, film etc. polyethylene terephthalate in the resin of ethylene glycol is added, to prepare intrinsic viscosity very
High functional plastics high and with color transparent such as glass.
Also, the monomer reaction product of half or so is transferred to polymer reactor by preparation method of the invention, and to
Reactant slurry is added in surplus and carries out monomer reaction, so as to in a short time preparing with high viscosity and excellent
Color polyalkylene terephthalates resin effect.
Detailed description of the invention
Fig. 1 is the chemical structure for showing polyethylene terephthalate prepared in accordance with the present invention.
Fig. 2 is the schematic diagram of the inner section of Ubbelodhe (Ubbelodhe) viscosity tube.
Specific embodiment
Hereinafter, example of the invention is described in detail referring to attached drawing.Following the description is only used for understanding reality of the invention
Example, and do not limit protection scope.
The present invention relates to can be prepared transparent in a short time with simple procedures and have the highly viscous poly- to benzene of high intensity
The method of dicarboxylate resin.
In preferred example of the invention, it is preferable that the polyalkylene terephthalates are poly- to benzene two
Formic acid glycol ester.The chemical structure of the polyethylene terephthalate is as shown in Figure 1.
The polyethylene terephthalate can be by the way that second two be added into existing polyethylene terephthalate
Non-crystalline resin is made to prepare transparent and high-intensitive resin in alcohol, it is made not generate dimmed degree (haze).
Specifically, high functionality polyalkylene terephthalates resin of the invention can be prepared by the following method:
The preparation method of polyalkylene terephthalates resin, comprising: will comprising dicarboxylic acids, alcohol, catalyst and
The slurry of stabilizer is added to monomer reaction device and the step of by heating to carry out monomer reaction；And by the monomer reaction
Product the step of being transferred in polymer reactor to carry out polymerization reaction.
Hereinafter, this is described in detail by taking the pet resin as preferred example of the invention as an example
The preparation method of invention.
Dicarboxylic acids and alcohol
Preferably, the dicarboxylic acids uses aromatic dicarboxylic acid, such as dimethyl terephthalate (DMT), terephthalic acid (TPA), isophthalic
Dioctyl phthalate, naphthalene dicarboxylic acids and its derivative most preferably, use to prepare high functionality polyethylene terephthalate
One or more of dimethyl terephthalate (DMT) and terephthalic acid (TPA) most preferably use in terms of viscosity and color to benzene two
Formic acid.
Preferably, two or more ethylene glycol, 1,4-butanediol, neopentyl glycol, Isosorbide-5-Nitrae-hexamethylene is applied in combination in the alcohol
The polyalcohols such as dimethanol, 1,6- hexylene glycol, trimethylolpropane.
In the present invention, the more outstanding resin of reactivity in order to obtain, it is preferable that the alcohol component includes 50 mole hundred
Point than to 90 molar percentages ethylene glycol and 10 molar percentages to 50 molar percentages be selected from by 1,4-butanediol, new by penta
More than one the polyalcohol in group that glycol, 1,4-CHDM, 1,6- hexylene glycol and trimethylolpropane form.
It is that alicyclic diol can be used in cricoid recurring unit to form main chain, especially as preferred polyalcohol, it is preferred to use
1,4-CHDM.
Also, in order to improve reactivity and obtain high viscosity, it is important that introducing can prepare transparent resin without pressing down
Make functional polyalcohol.As this polyalcohol, it is preferable that addition accounts for 0.1 molar percentage to 1.5 mole hundred in total alcohol
Divide the trimethylolpropane of ratio.
Preferably, using the dicarboxylic acids and alcohol of the molar ratio of 1:1.05 to 1:2.5.If the molar ratio is 1:1.05
Hereinafter, the content for the alcohol being then excessively used is very little, it is difficult to Polymer Synthesizing is carried out, if 1:2.5 or more, due to commercial cost
Influence it is very big, therefore production prices are at burden.
Catalyst and stabilizer
Also, in order to obtain transparent and highly viscous resin, selecting for catalyst and stabilizer is critically important.
Preferably, in the present invention workable catalyst has zinc acetate, calcium acetate, cobalt acetate, manganese acetate, dibutyl oxygen
Change tin, butyl isopropyl titanate esters, tetra isopropyl titanate, tetra-n-butyl titanate esters, tetra isopropyl titanate, four n-propyl titaniums
Acid esters, titanium oxide, four fourth titanate esters, titanium chelate etc. are urged it is highly preferred that can be used in mixed way two kinds with the molar ratio of 9:1 to 8:2
Agent.
For stable high molecular polymerization, it is preferable that on the basis of the total weight of reactant, 20ppm to 800ppm is added
The catalyst.If catalyst input amount be 20ppm hereinafter, if since effect is unobvious, can not carry out polymerizeing well anti-
It answers, therefore, it is difficult to become macromolecule, if 800ppm or more, there are the changes of the color of prepared polyethylene terephthalate
The hidden danger of difference.
The stabilizer for common polyester reaction can be used in workable stabilizer in the present invention, but more excellent
Trimethyl phosphate, triethyl phosphate, new penta 2 aryloxy group triguaiacyl phosphate, triphenyl phosphate, three second is used alone or as a mixture in selection of land
Base phosphinylidyne acetic acid ester, phosphoric acid (Phosphoric acid), the stabilizers such as phosphorous acid.
Preferably, relative to total reactant, the stabilizer of 30ppm to 600ppm is added.If stabiliser content is
Hereinafter, then there is the hidden danger of the color variation of polyethylene terephthalate, if 600ppm or more, when because of reaction in 30ppm
Between it is elongated and there are productivity decline hidden danger be difficult to obtain the polymer of high molecular weight if stabilizer is more than catalyst.
Reaction process
The preparation method of polyethylene terephthalate of the invention includes: first step, by mixed dicarboxylic acid, alcohol,
Catalyst, stabilizer slurry be added to monomer reaction device and carry out esterification；And second step, complete esterification
Product is transferred to polymer reactor to carry out polymerization reaction.
It heats up 5 DEG C to 7 DEG C carry out per minute upon start preferably as the monomer reaction of the first reaction.Reactor
Interior temperature starts by-product occur between 160 DEG C to 180 DEG C.By-product is mainly methanol or water, and destilling tower temperature is risen
And the first drop by-product referred to as initial point (initial point) when falling down.If the initial point time is 20 after reaction starts
Minute within, then due to temperature steeply rises and there are the hidden danger that monomer disperses, if more than 50 minutes, then due to the reaction time become
Color that is long and there are problems that resin is deteriorated and productivity also declines.
Preferably, it is persistently reacted after initial point, so that end reaction temperature is 220 DEG C to 250 DEG C.It is preferred that
Ground, monomer reaction time are 120 minutes to 240 minutes.Preferably, by monomer reaction generate product have 100 to 800 it
Between COOH acid value (acid value).
As described above, pet reaction uses dimethyl terephthalate (DMT) or terephthalic acid (TPA), it is preferred to use terephthaldehyde
Acid, but be the shortcomings that terephthalic acid (TPA), it is not easy to be melted in alcohol, such as ethylene glycol, therefore react slack-off, when as a result leading to reaction
Between it is elongated.
In the present invention, for this purpose, by the reactant increase as the monomer reaction (ester reaction) of the first reaction come for twice into
Row reaction, and the reaction product of 25 weight percent to 75 weight percent is transferred to polymer reactor, resultant product is logical
It crosses and adds the reactant slurry for being equivalent to transfer amount (dicarboxylic acids, alcohol, catalyst, stabilizer etc.) Lai Jinhang monomer reaction.More
Preferably, the amount of the reaction product of Xiang Suoshu polymer reactor transfer is 35 weight percent to 65 weight percents of gross product
Than most preferably 45 to 55 weight percent.
In general, monomer reaction starts to knot if monomeric products disposably to be put into polymer reactor to react
Beam needs about 6 hours to 8 hours or so.On the contrary, only the monomeric products of 35 weight percent to 65 weight percent are shifted
To polymer reactor, and residue and reactant slurry are mixed in the case where carrying out monomer reaction again, there is integral inverted
3 hours to 4 hours or so effects are greatly decreased between seasonable.The reduction in this reaction time is easy the color management of resin,
And it is attributable to improve productivity and reduces production cost.
Polymerization reaction is carried out by making the reactant (monomer) for being transferred to polymer reactor heat up again.Preferably,
Polymerization reaction DEG C is started to warm up from 240 DEG C to 260,250 DEG C to 280 DEG C at a temperature of carry out polymerization reaction.
Preferably, once stablizing to a certain extent, reactor to be gone from reactor as early as possible through vacuum convenient for producing high-molecular
Except by-product.At this time, it is preferable that vacuum is slowly applicable in 30 minutes to 40 minutes.If vacuum be applicable in it is too fast, there are monomer or
Oligomer is distributed to the case where condenser.In the case, if vacuum line blocks, vacuum degree declines, and is difficult to carry out macromolecule
Change, and dispersing due to unreacting substance, the molar ratio of dicarboxylic acids and alcohol mismatches, so that the poly- of required physical property can not be obtained
Close object.For example, so that pressure is dropped to 10mmHg from 760mmHg in 30 minutes to 40 minutes by input program, thus, it can
Dispersing for monomer or oligomer is prevented by being accurately applicable in vacuum.Preferably, to prevent from dispersing as much as possible, pressure reduction is arrived
After 10mmgHg, pressure is set to drop to 0.1mmHg from 10mmHg in 15 minutes.
Be in producing high-molecular with the progress of polymerization reaction, performance number increases according to the load of viscosity, if but performance number not
It is further added by and shakes, then carry out pole-changing (Pole Change) rapidly to reduce mixing speed, so that induced-viscosity increases again
Add.Because viscosity is not further added by if polymer is wrapped in blender, depolymerization occurs instead, therefore viscosity reduces.Like this,
Reaction can be terminated, by improving viscosity to the maximum extent so as to prepare the resin with required viscosity.
In the present invention, to keep the color of pet resin more transparent, various reactions are considered as
Condition such as catalyst, stabilizer, reaction temperature, stirring, reactor, but most importantly blocks oxygen in process.
Preferably, oxygen blocking carries out in entire step, including in the reactor adds reactant to monomer reaction device
When, when monomer reaction, after monomer reaction to polymer reactor shift when, when polymerization reaction and discharge product when.From this angle
Degree apparently, in order to which it is preferable to use nitrogen for vacuum breaking and discharge pressure.In entire process, reactant is prevented by blocking oxygen
Oxidation, and the fire as caused by generable gas in the reaction can be prevented.
In the present invention, it is substantially based on batch polymerization method (Batch Polymerization) and illustrates reaction process,
But in the case where being suitable for large-scale serial production equipment, pass through continuous polymerization (Continuous
Polymerization it) produces more advantageous.Probably, polymerization is used advantageously in the case where annual 200 tons of production or more,
But batch polymerization may be more advantageous in the case where producing 200 tons of situations below.
The physical property of resin
Intrinsic viscosity (the Intrinsic of pet resin prepared by the method for the present invention
It Viscosity) is 0.4dl/g to 1.2dl/g, preferably 0.65dl/g to 0.90dl/g.With intrinsic viscosity be 0.6dl/g extremely
The common pet resin of 0.65dl/g or so is compared, and level is significantly high, only ensure it is this
In the case where intrinsic viscosity, it is likely to obtain such as glass transparent and the high resin of intensity.
And, it is preferable that pet resin of the invention has the L of chromaticity coordinates*Value is 65 or more,
b*Value is 6 the following values, it is highly preferred that L*Value is 70 or more, b*Value is 5 or less.
Purposes
Since pet resin of the invention is such as glass transparent and intensity is very high, it is suitble to be applicable in
In food containers, kraut refrigerator, pickles bucket, cosmetics containers, 3D printer resin, tooth associated resin etc..
In particular, currently, be used in the use of most of resin of 3D printer from cereal extract made of be understood to mean environment-friendly type
The polylactic acid (PLA) of resin, polylactic acid has the shortcomings that frangibility.In order to solve this disadvantage, acrylonitrile butadiene benzene is proposed
Ethylene (ABS) resin, still, acrylonitrile butadiene styrene resin generates pernicious gas because of thawing in 3D printing, therefore,
In view of most 3D printing operation carries out in narrow space, thus in the presence of hurting the hidden of human body when working long hours
Suffer from.
Since pet resin of the invention is transparent, viscosity is high and will not be discharged and to be harmful to the human body
Gas can be usefully used in 3D printer, also by replacing the polylactic acid or acrylonitrile butadiene styrene resin
The polylactic resin and polyethylene terephthalate as ep-type material can be used in mixed way.
Also, since pet resin of the invention is transparent and high-intensitive, it may also be used for plantation
Tooth is used or the purposes such as fixing teeth facing.
Embodiment
Hereinafter, present invention will be further described in detail through examples.For those skilled in the art, these
Embodiment is only used for illustrating the present invention, and it is obvious for being not construed as limiting the scope.
Intrinsic viscosity measuring method
The pet resin of Examples and Comparative Examples is dissolved in adjacent chlorobenzene with the concentration of 1.2g/dl
After phenol (chlorophenol), intrinsic viscosity is determined by using Ubbelodhe viscosity tube.
The internal temperature of viscosity tube is maintained at 35 DEG C, as shown in Fig. 2, solution (Solution) is passed through inside viscosity tube
Time between the a-b of section is t, and solvent is t by required time (delivery time (Efflux time))0When, specific viscosity
(Specific Viscosity) and intrinsic viscosity are defined as.
* specific viscosity:
(wherein, t is that solvent passes through the time needed for viscosity agent internal rules section；t0Pass through same zone for measurement solution
Between time)
* intrinsic viscosity:
(wherein, A is Huggins (Huggins) constant, be 0.247, c is concentration value, is 1.2dl/g)
Embodiment 1
Weigh the dimethyl terephthalate (DMT) (DMT) of 291g (1.5gmol), the ethylene glycol of 97.65g (1.575gmol)
(EG), the 1,4-CHDM (CHDM) of 94g (0.653gmol), 3g (0.022gmol) trimethylolpropane (TMP),
Titanium dioxide (the TiO of the four fourth titanate esters (TBT) of 0.1g, 0.04g2), the phosphoric acid (PA) of 0.15g and the tripotassium phosphate of 0.04g
Ester (TM) is simultaneously ready to.
After esterifier is added in dimethyl terephthalate (DMT), by the ethylene glycol of half of weighing or so amount, Isosorbide-5-Nitrae-ring
Hexane dimethanol and trimethylolpropane are put into reactor.Then, catalyst (four fourth titanate esters and titanium dioxide are successively put into
Titanium) and stabilizer (phosphoric acid, trimethyl phosphate), and put into the other half alcohol, just as cleaning be stained on input port and blender acid,
Catalyst, stabilizer etc..After putting into raw material, after flowing through nitrogen slightly, reactor cap is covered, then flows nitrogen slightly again
It crosses.
After carrying out 1 minute nitrogen purging, start to react by heating.The temperature of reactor is set to heat up per minute 5~7 DEG C,
To the esterification of induced reaction object.Initial point is adjusted to 30~40 minutes, and maximum temperature is adjusted to 240 DEG C.
In order to which the half of monomer is transferred to polymer reactor, in the reactor by siphon (siphon) pipe from ceiling
It is inserted into 2/3 down and is transferred to polymer reactor by applying nitrogen pressure come the monomer being located on siphon pipe
(polymerization autoclave；PA).
After the half of transfer product, the slurry comprising the reactant is filled up in esterifier, carries out monomer again
Reaction.Maximum temperature is adjusted to 240 DEG C, checks the reaction time until by-product all comes out, as a result confirmation monomer reaction carries out
220 minutes.
Reaction temperature is warming up to 250 DEG C to make the monomer shifted to polymer reactor carry out polymerization reaction.Vacuum degree
It is adjusted to 0.01tor, after vacuum reaction carries out 140 minutes or so, pet resin is prepared for by discharge.
The physical property of reaction condition and the polyethylene terephthalate of preparation is as described in Table 1.
Embodiment 2 is to embodiment 5
It is same as Example 1 other than the composition and reaction temperature of dicarboxylic acids and alcohol is documented contents in table 1
Process is prepared for pet resin.
Comparative example 1 is to comparative example 5
Polyethylene terephthalate is prepared with reaction condition with documented form in following table 1, in monomer reaction
Afterwards, the product of whole amount is transferred to polymer reactor to carry out polymerization reaction, to prepare polyethylene terephthalate
Ester resin.
Table 1
Such as the table 1, can confirm, with used as dicarboxylic acids the embodiment 1 of dimethyl terephthalate (DMT) to 3 phase of embodiment
Than completing the monomer reaction time faster using the embodiment 4 of terephthalic acid (TPA) and the process of embodiment 5.
Also, it can confirm compared with the process of the comparative example of the monomeric products to polymer reactor transfer whole amount, to
Polymer reactor shifts the 1/2 of monomeric products and reactant slurry is added to be had come the process for carrying out the embodiment of monomer reaction
Faster monomer reaction speed, can also prepare the poly terephthalic acid with similar or higher levels of intrinsic viscosity and color
Glycol ester resin.
Claims (19)
1. a kind of preparation method of polyalkylene terephthalates, comprising: dicarboxylic acids, alcohol, catalyst and steady will be included
The slurry for determining agent is added to monomer reaction device and the step of by heating to carry out monomer reaction；And
The step of product of the monomer reaction is transferred in polymer reactor to carry out polymerization reaction, which is characterized in that
The monomer reaction product of 35 weight percent to 65 weight percent is transferred to polymer reactor, and to residue
The slurry is added in amount to carry out monomer reaction.
2. the preparation method of polyalkylene terephthalates according to claim 1, which is characterized in that described poly-
Terephthalic acid (TPA) alkylidene diol ester is polyethylene terephthalate.
3. the preparation method of polyalkylene terephthalates according to claim 1, which is characterized in that be added 1:
The dicarboxylic acids and alcohol of 1.05 to 1:2.5 molar ratio.
4. the preparation method of polyalkylene terephthalates according to claim 1, which is characterized in that described two
Carboxylic acid is selected from dimethyl terephthalate (DMT), terephthalic acid (TPA), M-phthalic acid, naphthalene dicarboxylic acids and their derivative.
5. the preparation method of polyalkylene terephthalates according to claim 1, which is characterized in that the alcohol
For selected from by ethylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-CHDM, 1,6- hexylene glycol and trimethylolpropane
Two or more polyalcohols in the group of composition.
6. the preparation method of polyalkylene terephthalates according to claim 5, which is characterized in that the alcohol
Including 50 molar percentages to the ethylene glycol of 90 molar percentages and selected from by 1,4-butanediol, neopentyl glycol, Isosorbide-5-Nitrae-hexamethylene
10 molar percentages to 50 Mole percents of one or more of the group of dimethanol, 1,6- hexylene glycol and trimethylolpropane composition
The polyalcohol of ratio.
7. the preparation method of polyalkylene terephthalates according to claim 5, which is characterized in that the alcohol
It include the trimethylolpropane that 0.1 molar percentage to 1.5 molar percentages is accounted in total alcohol.
8. the preparation method of polyalkylene terephthalates according to claim 1, which is characterized in that described to urge
Agent is selected from by zinc acetate, calcium acetate, cobalt acetate, manganese acetate, Dibutyltin oxide, butyl isopropyl titanate esters, four isopropyls
Base titanate esters, tetra-n-butyl titanate esters, tetra isopropyl titanate, four n-propyl titanate esters, titanium oxide, four fourth titanate esters and titanium chela
Close one or more of the group of object composition.
9. the preparation method of polyalkylene terephthalates according to claim 1, which is characterized in that with reaction
On the basis of the total weight of object, the catalyst of 20ppm to 800ppm is added.
10. the preparation method of polyalkylene terephthalates according to claim 1, which is characterized in that described
Stabilizer is selected from by trimethyl phosphate, triethyl phosphate, new penta 2 aryloxy group triguaiacyl phosphate, triphenyl phosphate, triethyl phosphine
One or more of ethyl sodio acetoacetic ester, phosphoric acid and group of phosphorous acid composition.
11. the preparation method of polyalkylene terephthalates according to claim 1, which is characterized in that with anti-
On the basis of the total weight for answering object, the stabilizer of 30ppm to 600ppm is added.
12. the preparation method of polyalkylene terephthalates according to claim 1, which is characterized in that with logical
Cross reaction temperature to heat up per minute 5 DEG C makes 220 DEG C to 250 DEG C of end reaction temperature of mode carry out the list to 7 DEG C
Precursor reactant.
13. the preparation method of polyalkylene terephthalates according to claim 1, which is characterized in that described
Polymerization reaction 250 DEG C to 280 DEG C at a temperature of carry out.
14. the preparation method of polyalkylene terephthalates according to claim 1, which is characterized in that described
Polymerization reaction is carried out by being applicable in through 30 minutes to 40 minutes vacuum.
15. the preparation method of polyalkylene terephthalates according to claim 1, which is characterized in that in nothing
It is carried out under oxygen condition.
16. a kind of polyalkylene terephthalates, which is characterized in that according to claim 1 to described in any one of 15
Method preparation.
17. polyalkylene terephthalates according to claim 16, which is characterized in that the poly- terephthaldehyde
Sour alkylidene diol ester is polyethylene terephthalate.
18. polyalkylene terephthalates according to claim 16, which is characterized in that there is 0.5dl/g extremely
The intrinsic viscosity of 1.2dl/g.
19. polyalkylene terephthalates according to claim 16, which is characterized in that chromaticity coordinates L*Value is 65
More than, b*Value is 6 or less.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020170178677A KR20190076681A (en) | 2017-12-22 | 2017-12-22 | Method for Preparing Polyalkylene Terephthalate glycol |
| KR10-2017-0178677 | 2017-12-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109957095A true CN109957095A (en) | 2019-07-02 |
Family
ID=67023212
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811187492.4A Pending CN109957095A (en) | 2017-12-22 | 2018-10-12 | The preparation method of polyalkylene terephthalates |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR20190076681A (en) |
| CN (1) | CN109957095A (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1383437A (en) * | 2000-03-24 | 2002-12-04 | 钟纺株式会社 | Modified polyester and process for continuously producing same |
| US6559272B1 (en) * | 2001-10-12 | 2003-05-06 | Sk Chemicals Co. Ltd. | Method for preparing copolyester resins using titanium dioxide/silicon dioxide coprecipitate catalyst in the form of suspension in glycol |
| CN1422885A (en) * | 2001-02-27 | 2003-06-11 | 天津石油化工公司化纤厂 | New-type polyester continuous polymerization catalytic-stabilizing method |
| CN1487964A (en) * | 2001-01-22 | 2004-04-07 | �Ϻ���ͨ��ѧ | Process for manufacture of polyesters based on 1,4-cyclohexanedimethanol and isophthalicacid |
| CN1800236A (en) * | 2004-12-31 | 2006-07-12 | 中国石化仪征化纤股份有限公司 | Highly transparent copolyester preparation method |
| KR20080052932A (en) * | 2006-12-08 | 2008-06-12 | 에스케이케미칼주식회사 | Flame retardant copolyester resin composition including 1,4-cyclohexanedimethanol and preparation method thereof |
| CN102443149A (en) * | 2011-10-28 | 2012-05-09 | 金发科技股份有限公司 | Continuous production method for biodegradable aliphatic-aromatic copolyester |
| CN102558515A (en) * | 2011-12-06 | 2012-07-11 | 上海聚友化工有限公司 | Method for continuously preparing biodegradable plastic |
| CN102585191A (en) * | 2012-01-13 | 2012-07-18 | 华东理工大学 | Novel tower reactor and application of novel tower reactor in continuously producing polyester polyol |
| CN102993419A (en) * | 2011-09-14 | 2013-03-27 | 中国石油化工股份有限公司 | Continuous production method of high-molecular-weight polyester |
| CN104854162A (en) * | 2012-10-29 | 2015-08-19 | 伍德-伊文达-菲瑟股份有限公司 | Process for producing a high-molecular-weight polyester or copolyester, and also polymer blends containing such |
-
2017
- 2017-12-22 KR KR1020170178677A patent/KR20190076681A/en not_active Application Discontinuation
-
2018
- 2018-10-12 CN CN201811187492.4A patent/CN109957095A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1383437A (en) * | 2000-03-24 | 2002-12-04 | 钟纺株式会社 | Modified polyester and process for continuously producing same |
| CN1487964A (en) * | 2001-01-22 | 2004-04-07 | �Ϻ���ͨ��ѧ | Process for manufacture of polyesters based on 1,4-cyclohexanedimethanol and isophthalicacid |
| CN1422885A (en) * | 2001-02-27 | 2003-06-11 | 天津石油化工公司化纤厂 | New-type polyester continuous polymerization catalytic-stabilizing method |
| US6559272B1 (en) * | 2001-10-12 | 2003-05-06 | Sk Chemicals Co. Ltd. | Method for preparing copolyester resins using titanium dioxide/silicon dioxide coprecipitate catalyst in the form of suspension in glycol |
| CN1800236A (en) * | 2004-12-31 | 2006-07-12 | 中国石化仪征化纤股份有限公司 | Highly transparent copolyester preparation method |
| KR20080052932A (en) * | 2006-12-08 | 2008-06-12 | 에스케이케미칼주식회사 | Flame retardant copolyester resin composition including 1,4-cyclohexanedimethanol and preparation method thereof |
| CN102993419A (en) * | 2011-09-14 | 2013-03-27 | 中国石油化工股份有限公司 | Continuous production method of high-molecular-weight polyester |
| CN102443149A (en) * | 2011-10-28 | 2012-05-09 | 金发科技股份有限公司 | Continuous production method for biodegradable aliphatic-aromatic copolyester |
| CN102558515A (en) * | 2011-12-06 | 2012-07-11 | 上海聚友化工有限公司 | Method for continuously preparing biodegradable plastic |
| CN102585191A (en) * | 2012-01-13 | 2012-07-18 | 华东理工大学 | Novel tower reactor and application of novel tower reactor in continuously producing polyester polyol |
| CN104854162A (en) * | 2012-10-29 | 2015-08-19 | 伍德-伊文达-菲瑟股份有限公司 | Process for producing a high-molecular-weight polyester or copolyester, and also polymer blends containing such |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20190076681A (en) | 2019-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3260482B1 (en) | A process for producing a polyester by reacting furandicarboxylic acid or an ester thereof, cyclohexanedimethanol and ethylene glycol | |
| TWI353994B (en) | ||
| CN101679619B (en) | Process for the preparation of copolyesters based on 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexandimethanol | |
| CN102336896B (en) | Preparation method of lightly-crosslinked aliphatic-aromatic copolyester | |
| CN106604948B (en) | For generating the technique of poly- (terephthalic acid (TPA) propylene diester) comprising low-level by-product | |
| US9416224B2 (en) | Method for continuous production of biodegradable aliphatic/aromatic polyester copolymer | |
| AU2014374626A2 (en) | Composition for producing biodegradable polyester resin, and production method for biodegradable polyester resin | |
| CN104640905A (en) | Method for producing polycyclohexylenedimethylene terephthalate resin having excellent coloring property and polycyclohexylenedimethylene terephthalate resin produced thereby | |
| US10072118B2 (en) | Polycyclohexylenedimethylene terephthalate resin having enhanced crystallization speed and method for preparing same | |
| KR20080024161A (en) | Alicyclic polyester, process for producing the same, and resin composition | |
| KR20140076356A (en) | Method for continuous production of biodegradable aliphatic/aromatic polyester copolymer | |
| CN109957095A (en) | The preparation method of polyalkylene terephthalates | |
| KR102202138B1 (en) | Method for Preparing Polycyclohexylenedimethylene Terephthalate Glycol | |
| KR20200062615A (en) | A preparation method of High molecular weight aliphatic carbonate and aromatic ester copolymer resin | |
| KR101691700B1 (en) | Preparation method of aliphatic copolyester resin | |
| KR101911385B1 (en) | A method for manufacturing polycyclohexylene dimethylene terephthalate resin with an enhanced flexibility | |
| CN114524923B (en) | Biodegradable polyester based on dodecanedioic acid and ethylene glycol, and preparation method and application thereof | |
| TW201333068A (en) | Catalyst for synthesizing polyester resin and method of manufacturing polyester resin using the same | |
| JP5732153B2 (en) | Method for producing copolyester | |
| US3438944A (en) | Antimony oxalate as a polycondensation catalyst | |
| CN114957625B (en) | Biodegradable polyester based on dodecanedioic acid and butanediol, and preparation method and application thereof | |
| CN103113563B (en) | A kind of cladodification aliphatic polyester and synthetic method thereof | |
| KR102589193B1 (en) | Biodegradable polyester copolymer comprising anhydrosugar alcohol and anhydrosugar alcohol based polycarbonate diol and preparation method thereof, and molded article comprising the same | |
| KR101716004B1 (en) | Preparation method of aliphatic copolyester resin | |
| US3489720A (en) | Use of metal stannate polycondensation catalysts in preparing polyethylene terephthalate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190702 |
|
| WD01 | Invention patent application deemed withdrawn after publication |