CN106674497A - Modified polyethylene glycol terephthalate and preparation method thereof - Google Patents
Modified polyethylene glycol terephthalate and preparation method thereof Download PDFInfo
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Abstract
The invention discloses modified polyethylene glycol terephthalate and a preparation method thereof. The preparation method comprises the following steps of (1) under the condition of existence of an esterification catalyst, enabling ethylene glycol, terephthalic acid and a crystallizing accelerant to react, so as to obtain a reaction product; (2) removing unreacted ethylene glycol out of the reaction product, and condensing under the condition of condensation reaction, wherein the crystallizing accelerant is an irregular copolymer with structure units shown in formula (I) and formula (2) (shown in the description); R1 in the formula (1) is C2-C15 alkyl; the content of the structure unit shown in formula (I) is 1-10mol% in the crystallizing accelerant. The preparation method has the advantage that the crystallizing degree, crystallizing temperature and intrinsic viscosity of polyethylene glycol terephthalate can be comprehensive improved.
Description
Technical field
The present invention relates to a kind of preparation method of modified polyethylene terephthalate, and by the method
The modified polyethylene terephthalate for preparing.
Background technology
Polyethylene terephthalate (PET) is one of currently the most important ones synthetic material, mainly should
For producing fiber, film and beverage bottle etc..PET is cheap, with excellent wearability, heat-resisting
The characteristic such as property, chemical proofing, electrical insulating property and mechanical strength height, therefore, the sixties in 20th century
Just the application and development as engineering plastics has been started.At present PET engineering plastics be applied to automobile, motor,
The industries such as electronics, household electrical appliance and machinery.
When PET is used as engineering plastics, it has the disadvantage under conventional processing mould temperature (70-110 DEG C)
Crystallization rate is excessively slow, impact property poor and water imbibition is big etc., therefore limits its extensive application.From upper
Since century 70, people attempt by all means being modified PET.
With other crystalline polymers compared with PE, PP, PBT, the crystalline rate of PET is very low.According to
The maximum spherocrystal rate of rise of report PE is 5000 μm/min, and PET is only 10 μm/min.Therefore,
The crystallization kinetics of research PET, finds effective nucleator, improves crystalline rate, improves crystal property
It is an emphasis of PET study on the modification.
The nucleator species that can be used to improve PET crystalline rates is a lot, generally can be divided into homogeneous nucleation agent
With heterogeneous nucleation agent.Heterogeneous nucleation agent mainly includes that non-ionic macromolecule compound and low molecule are inorganization
Compound；Homogeneous nucleation agent mainly has low molecule organic carboxylate and the big class of macromolecular carboxylic acid's salt two.At present
PET the most frequently used heterogeneous nucleation agent is talcum powder, has been industrialized, and many scholars are also constantly studying it
Its new varieties.Although above-mentioned heterogeneous nucleation agent can significantly improve the crystalline rate of PET, there is also it and lack
Point.Because these additional particles are likely to become stress concentration point causes crackle, cause PET impact strengths
Reduce.In order to the PET for overcoming this shortcoming, outer Added Nucleating Agents will be strengthened with glass or other materials.
And homogeneous nucleation agent is just without this shortcoming, therefore the people for studying is also more and more.In organic nucleator,
Preferably, especially carboxylic acid sodium salt and carboxylic acid potassium salt's effect becomes apparent from the nucleating effect of metal carboxylate.But
Some metal carboxylates have seondary effect, and such as PET has degradation reaction, generates with Sodium Benzoate in extrusion
PET-Na, so that molecular weight is reduced.
Therefore, efficient homogeneous crystallization nucleating agent or accelerator are developed, the crystal property of PET is being guaranteed
On the premise of improving (crystalline rate and degree of crystallinity are improved), the performance of material is not reduced, be very necessary
's.
The content of the invention
The invention aims to solve how to improve polyethylene terephthalate degree of crystallinity and
Crystallization rate, does not reduce the problem of the viscosity of polyethylene terephthalate, there is provided one kind is modified
Polyethylene terephthalate and preparation method thereof.
To achieve these goals, the present invention provides a kind of preparation of modified polyethylene terephthalate
Method, including：(1) in the presence of esterification catalyst, ethylene glycol, terephthalic acid (TPA) and crystallization are promoted
Agent is reacted, and obtains product；2) product is removed into unreacted ethylene glycol, so
Carry out polycondensation under the conditions of polycondensation reaction afterwards；The crystallization promoter is containing structure list shown in formula (1)
Unit and the random copolymer of construction unit shown in formula (2),
Wherein, the R in formula (1)1For C2-C15Alkylidene, construction unit is in institute shown in formula (1)
It is 1-10mol% to state the content in crystallization promoter.
The polyethylene terephthalate present invention also offers one kind is modified by obtained in the inventive method.
In the method that the present invention is provided, by the course of reaction that ethylene glycol and terephthalic acid (TPA) are carried out,
Will containing construction unit shown in formula (1) and construction unit shown in formula (2) random copolymer as crystallization
Accelerator adds, so that the final modified polyethylene terephthalate for preparing can obtain raising
Degree of crystallinity and crystallization temperature, and polymer molecular weight do not reduce.Further, the esterification that the method is used
The compound containing thulium is further comprises in catalyst, the modified of preparation is further improved
The crystallization temperature of polyethylene terephthalate.Wherein, modified polyethylene terephthalate is determined
Melting enthalpy to characterize degree of crystallinity, enthalpy is higher shows that degree of crystallinity is higher for melting, determines modified poly- to benzene two
To characterize crystalline rate, crystallization temperature is higher to show crystalline rate more to the crystallization temperature of formic acid glycol ester
Hurry up, determine modified inherent viscosity of the polyethylene terephthalate at 25 DEG C to characterize molecular weight, it is special
Property viscosity shows that more greatly molecular weight is bigger.In embodiment 1-6, the modified poly terephthalic acid second two of preparation
The melting enthalpy of alcohol ester can be more than 45J/g, specially 45.2-52.3J/g；Crystallization temperature be 176 DEG C with
On, specially 176.5-182.3 DEG C；Inherent viscosity at 25 DEG C is more than 0.72dL/g, specially
0.72-0.825dL/g.And do not add crystallization promoter to be also not used in comparative example 1 and contain thulium
Compound as esterification catalyst, therefore the polyethylene terephthalate for obtaining melting enthalpy, knot
The numerical value of the inherent viscosity at brilliant temperature and 25 DEG C is below the product of embodiment 1-6.Change in comparative example 2
Enter to employ the compound containing thulium as esterification catalyst, thus obtain it is poly- to benzene two
The crystallization temperature of formic acid glycol ester is compared comparative example 1 and is improve, but the characteristic at melting enthalpy and 25 DEG C
The numerical value of viscosity still is below the product of embodiment 1-6.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The present invention provides a kind of preparation method of modified polyethylene terephthalate, including：(1) exist
In the presence of esterification catalyst, ethylene glycol, terephthalic acid (TPA) and crystallization promoter are reacted, obtained anti-
Answer product；2) product is removed into unreacted ethylene glycol, then under the conditions of polycondensation reaction
Carry out polycondensation；The crystallization promoter is containing construction unit shown in formula (1) and structure shown in formula (2)
The random copolymer of unit,
Wherein, the R in formula (1)1For C2-C15Alkylidene, construction unit is in institute shown in formula (1)
It is 1-10mol% to state the content in crystallization promoter.
The present inventor has found under study for action, in the esterification of polyethylene terephthalate
Will containing construction unit shown in formula (1) and construction unit shown in formula (2) random copolymer as crystallization
Accelerator adds fashionable, and it is anti-that the crystallization promoter can utilize the oh group that contains in its structure to participate in esterification
Should be that final modified polyethylene terephthalate introduces link of drawing money on credit with follow-up polycondensation reaction
Structure, and the ordered arrangement of this long-chain branch, can be effectively facilitated the crystal of polyethylene terephthalate
Generation, the crystal property for improving polyethylene terephthalate and the molecular weight for not affecting polymer.By
This proposes the present invention.
, according to the invention it is preferred in the case of, in formula (1), R1For C3-C8Alkylidene, preferably
R1For C8Straight-chain alkyl-sub.
According to the present invention, the addition of the crystallization promoter can improve the obtained poly- terephthaldehyde that is modified
The crystal property of sour glycol ester, under preferable case, the crystallization promoter and terephthalic acid (TPA)
Weight ratio is 1：(100-5000), preferably 1：(250-2000).
, according to the invention it is preferred in the case of, terephthalic acid (TPA) is 1 with the mol ratio of ethylene glycol:(1-1.5).
, according to the invention it is preferred in the case of, the crystallization promoter is prepared by following methods：In nitrogen and
In the presence of transition metal catalyst system, 4-methyl-1-pentene monomer is carried out with monomer shown in formula (3)
Copolyreaction,
Wherein, R1For C2-C15Alkylidene, preferred R1For C3-C8Alkylidene, more preferably formula (3)
Shown monomer is 9- decen-1-ols；The consumption of monomer is the crystallization promoter shown in formula (3)
1-10mol%.
, according to the invention it is preferred in the case of, the weight average molecular weight of the crystallization promoter is 10,000-20 ten thousand,
Preferably 2.8 ten thousand -14.7 ten thousand；Molecular weight distribution is 1.5-4, preferably 2.1-3.1.
According to the present invention, in the method for preparing the crystallization promoter, under preferable case, the transition
Metal catalyst system includes metallocene compound and co-catalyst.
Preferably, the metallocene compound is the metallocene of the subgroup of racemic bridging the 4th, more preferably
The metallocene compound is dimethyl silicon bridge two (2- methyl-indenyls) zirconium dichloride.
Preferably, the co-catalyst is MAO (MAO).
, according to the invention it is preferred in the case of, with 4-methyl-1-pentene monomer, monomer shown in formula (3) and
On the basis of the consumption total amount of the transition metal catalyst system, the concentration of the metallocene compound is
10-6Mol/L to 10-2mol/L。
, according to the invention it is preferred in the case of, the mol ratio of the co-catalyst and the metallocene compound
For (100-10000):1.
In the present invention, the metallocene compound can add copolyreaction in the form of toluene solution, molten
The concentration of the contained metallocene compound can be the conventional selection in this area in liquid, repeat no more.Institute
Stating co-catalyst can add copolyreaction in the form of toluene solution, the contained co-catalyst in solution
Concentration can be the conventional selection in this area, repeat no more.
According to the present invention, in the method for preparing the crystallization promoter, under preferable case, the copolymerization
The temperature of reaction is 40-60 DEG C, and the gauge of the copolyreaction is 0.05-0.15MPa, described common
The time of poly- reaction is 4-8h.
In the present invention, in the method for preparing the crystallization promoter, the copolyreaction can be in toluene
Carry out in solution.
In the present invention, in preparing the method for the crystallization promoter, after copolyreaction, can also include
The product of copolyreaction is added into acidic ethanol, polymer is filtrated to get, then by polymer under vacuo
It is dried, obtains final crystallization promoter product standby.
According to the present invention, in step (1), under preferable case, the esterification catalyst includes component a
And/or component b；Component a is 1 with the mol ratio of component b:(0-2), preferably 1：(0-1),
More preferably 1：(0.2-1).
, according to the invention it is preferred in the case of, component a is at least one by chemical formula RE (R2)3Represent
Compound, wherein, RE is thulium, R2It is selected from halogen, alkoxyl, aryloxy group, second
Acyl acetonyl, R3At least one in COO- groups and their hydrate, R3For C1-C30's
Alkyl；Preferred ingredient a is Lanthanum Stearate, stearic acid neodymium, lanthanum acetylacetone, acetylacetone,2,4-pentanedione neodymium, chlorination
At least one in lanthanum and isopropoxy neodymium.
, according to the invention it is preferred in the case of, component b is selected from chemical formula M (OR4)x1、M2Ox2With
M(-OOCR5)x3At least one in the compound of expression, wherein, M is titanium or zinc, x1, x2 and
X3 is each independently 2,3 or 4, R4For C1-C10Alkyl, R5For C1-C30Alkyl；It is preferred that
Component b is at least one in butyl titanate, titanium dioxide and zinc acetate.
, according to the invention it is preferred in the case of, in step (1), component a in the esterification catalyst
It is 1 with the weight ratio of terephthalic acid (TPA)：(500-5000).
, according to the invention it is preferred in the case of, in step (1), the temperature of the reaction is 220-260
DEG C, preferred 220-250 DEG C；The gauge of the reaction is 0.1-0.4MPa, preferably 0.2-0.4MPa；
The time of the reaction is 0.5-4h.
In the present invention, in step (2), the product for obtaining is processed, first produced reaction
Thing removes unreacted ethylene glycol, can be vacuum form, and gauge is 500-600Pa, and the time is
0.5-1h；Then the product of removing ethylene glycol is carried out into polycondensation reaction.
, according to the invention it is preferred in the case of, the temperature of the polycondensation reaction is 270-300 DEG C, preferably
270-290℃；The gauge of the polycondensation reaction is 0-300Pa, preferably 20-200Pa.
In the present invention, the time of the polycondensation reaction is the product that the polycondensation reaction proceeds in polymeric kettle
When reaching desired viscosity, stop reaction；It is preferred that the time of the polycondensation reaction is 60-100min.
The polyethylene terephthalate present invention also offers one kind is modified by obtained in the inventive method.
, according to the invention it is preferred in the case of, the crystallization temperature of the modified polyethylene terephthalate
For more than 176 DEG C, the melting enthalpy of the modified polyethylene terephthalate is more than 45J/g, institute
Inherent viscosity of the modified polyethylene terephthalate at 25 DEG C is stated for more than 0.72dL/g.
Preferably, the melting enthalpy of the modified polyethylene terephthalate can be 45.2-52.3J/g；Knot
Brilliant temperature is 176.5-182.3 DEG C；Inherent viscosity at 25 DEG C is 0.72-0.825dL/g.
Hereinafter will be described the present invention by embodiment.
In following examples and comparative example, the physico-chemical parameter being related to is tested by the following method：
Inherent viscosity：Determined according to GB/T14190-2008, solvent made with phenol tetrachloroethane mixed liquor,
Determination of ubbelohde viscometer is used at 25 DEG C.
DSC methods：On the analyzers of Perkin Elmer Pyris 1, by modified polyethylene terephthalate
Ester sample is heated to 300 DEG C with the speed of 10 DEG C/min from 50 DEG C, through heat scan twice, once
Cooling scanning, the melting enthalpy and crystallization temperature of determination sample.
GPC method：The molecular weight and molecular weight distribution of crystallization promoter are determined, instrument is Waters
Alliance GPCV2000, use 1,2,4- trichloro-benzenes for mobile phase, the measure at 150 DEG C.
13C NMR：The content of construction unit shown in crystallization promoter Chinese style (1) is adopted13C NMR are surveyed
Fixed, instrument is Bruker AVANCE III-400, using d4- o-dichlorohenzene is solvent, at 125 DEG C
Determine, the relaxation time is 10s.
Raw material used in following examples and comparative example is commercially available.
Preparation example 1
The synthesis of crystallization promoter poly- (4-methyl-1-pentene-co-9- decen-1-ols)
By dry 100ml polymerization bottles, flushed three times repeatedly with nitrogen after vacuumizing.At 25 DEG C,
Stirring is opened, the 4-methyl-1-pentene of 3.0ml is sequentially added in polymerization bottle, the 9- decylene-1s of 0.5ml-
Alcohol, the methylaluminoxane toluene solution of 12.0ml (contains aluminium methyl in per ml methylaluminoxane toluene solution
Oxygen alkane is 1.67mmol), 1.0ml contains 50 μm of ol dimethyl silicon bridge two (2- methyl-indenyls) zirconium dichlorides
The toluene solution of (being purchased from STREM companies), it is 50 DEG C, gauge then to start timing in temperature
To carry out copolyreaction 6h under 0.1MPa.Stop stirring, reactant liquor is carefully poured into beaker, add acid
Change ethanol, stir more than 6 hours, be filtrated to get polymer.Polymer is vacuum dried at 60 DEG C
24 hours, obtain product.
The copolymer is designated as into J-1, carry out GPC and13C NMR are determined, and weight average molecular weight is 7.6 ten thousand,
Molecular weight distribution is 2.5, is 3.5mol% from the content of the construction unit of 9- decen-1-ol monomers.
Preparation example 2
The synthesis of crystallization promoter poly- (4-methyl-1-pentene-co-9- decen-1-ols)
By dry 100ml polymerization bottles, flushed three times repeatedly with nitrogen after vacuumizing.At 25 DEG C,
Stirring is opened, the 4-methyl-1-pentene of 3.0ml is sequentially added in polymerization bottle, the 9- decylene-1s of 0.1ml-
Alcohol, the methylaluminoxane toluene solution of 12.0ml (contains aluminium methyl in per ml methylaluminoxane toluene solution
Oxygen alkane is 1.67mmol), 1.0ml contains 50 μm of ol dimethyl silicon bridge two (2- methyl-indenyls) zirconium dichlorides
Toluene solution, then start timing temperature be 40 DEG C, gauge be 0.15MPa under carry out altogether
Poly- reaction 4h.Stop stirring, reactant liquor is carefully poured into beaker, add acidic ethanol, stir 6 hours
More than, it is filtrated to get polymer.Polymer is vacuum dried 24 hours at 60 DEG C, product is obtained.
The copolymer is designated as into J-2, carry out GPC and13C NMR are determined, and weight average molecular weight is 14.7
Ten thousand, molecular weight distribution is 3.1, is 1mol% from the content of the construction unit of 9- decen-1-ol monomers.
Preparation example 3
The synthesis of crystallization promoter poly- (4-methyl-1-pentene-co-9- decen-1-ols)
By dry 100ml polymerization bottles, flushed three times repeatedly with nitrogen after vacuumizing.At 25 DEG C,
Stirring is opened, the 4-methyl-1-pentene of 3.0ml is sequentially added in polymerization bottle, the 9- decylene-1s of 1ml-
Alcohol, the methylaluminoxane toluene solution of 12.0ml (contains aluminium methyl in per ml methylaluminoxane toluene solution
Oxygen alkane is 1.67mmol), 1.0ml contains 50 μm of ol dimethyl silicon bridge two (2- methyl-indenyls) zirconium dichlorides
Toluene solution, then start timing temperature be 60 DEG C, gauge be 0.05MPa under carry out altogether
Poly- reaction 8h.Stop stirring, reactant liquor is carefully poured into beaker, add acidic ethanol, stir 6 hours
More than, it is filtrated to get polymer.Polymer is vacuum dried 24 hours at 60 DEG C, product is obtained.
The copolymer is designated as into J-3, carry out GPC and13C NMR are determined, and weight average molecular weight is 2.8 ten thousand,
Molecular weight distribution is 2.1, is 10mol% from the content of the construction unit of 9- decen-1-ol monomers.
Embodiment 1
This example demonstrates that the preparation method of the modified polyethylene terephthalate of the present invention.
(1) react：By the terephthalic acid (TPA) (PTA) of 500g, the ethylene glycol (EG) of 250g,
The J-1 of the Lanthanum Stearate of 0.62g, the zinc acetate of 0.23g and 2g is added in 2.5L polymeric kettles to be carried out instead
Should.The temperature of reaction is 240 DEG C, and gauge is 0.2MPa, and the time is 150min.By rectifying
Device discharges the water that reaction is generated.Polymeric kettle pressure is down to normal pressure by reaction after terminating；
(2) polycondensation reaction：It is 600Pa to discharge unreacted ethylene glycol that polymeric kettle is vacuumized, when
Between be 80min；Continue to be decompressed to 200Pa, while polymeric kettle is risen into high-temperature extremely being contracted to 270 DEG C
Poly- reaction, the time of polycondensation reaction is 80min, and the product in polymeric kettle reaches desired viscosity, is stopped anti-
Should, discharge product.
Inherent viscosity, melting enthalpy and the crystallization temperature of product are determined, 1 is the results are shown in Table.
Embodiment 2
This example demonstrates that the preparation method of the modified polyethylene terephthalate of the present invention.
(1) react：By the terephthalic acid (TPA) (PTA) of 500g, the ethylene glycol (EG) of 187g,
The J-2 of the lanthanum chloride of 0.62g, the butyl titanate of 0.42g and 0.25g is added in 2.5L polymeric kettles
Row reaction.The temperature of reaction is 220 DEG C, and gauge is 0.4MPa, and the time is 30min.By essence
Distillation unit discharges the water that reaction is generated.Polymeric kettle pressure is down to normal pressure by reaction after terminating；
(2) polycondensation reaction：It is 500Pa to discharge unreacted ethylene glycol that polymeric kettle is vacuumized, when
Between be 60min；Continue to be decompressed to 100Pa, while polymeric kettle is risen into high-temperature extremely being contracted to 290 DEG C
Poly- reaction, the time of polycondensation reaction is 60min, and the product in polymeric kettle reaches desired viscosity, is stopped anti-
Should, discharge product.
Inherent viscosity, melting enthalpy and the crystallization temperature of product are determined, 1 is the results are shown in Table.
Embodiment 3
This example demonstrates that the preparation method of the modified polyethylene terephthalate of the present invention.
(1) react：By the terephthalic acid (TPA) (PTA) of 500g, the ethylene glycol (EG) of 280g,
The acetylacetone,2,4-pentanedione neodymium of 0.62g, the titanium dioxide of 0.12g and the J-3 of 0.45g are added in 2.5L polymeric kettles
Reacted.The temperature of reaction is 250 DEG C, and gauge is 0.3MPa, and the time is 240min.It is logical
Cross rectifier unit and discharge the water that reaction is generated.Polymeric kettle pressure is down to normal pressure by reaction after terminating；
(2) polycondensation reaction：It is 550Pa to discharge unreacted ethylene glycol that polymeric kettle is vacuumized, when
Between be 45min；Continue to be decompressed to 20Pa, while polymeric kettle is risen into high-temperature extremely carries out polycondensation to 300 DEG C
Reaction, the time of polycondensation reaction is 100min, and the product in polymeric kettle reaches desired viscosity, is stopped anti-
Should, discharge product.
Inherent viscosity, melting enthalpy and the crystallization temperature of product are determined, 1 is the results are shown in Table.
Embodiment 4
This example demonstrates that the preparation method of the modified polyethylene terephthalate of the present invention.
(1) react：By the terephthalic acid (TPA) (PTA) of 500g, the ethylene glycol (EG) of 250g,
The Lanthanum Stearate of 0.62g and the J-1 of 2g are added in 2.5L polymeric kettles and are reacted.The temperature of reaction is
240 DEG C, gauge is 0.2MPa, and the time is 150min.Discharge what reaction was generated by rectifier unit
Water.Polymeric kettle pressure is down to normal pressure by reaction after terminating；
(2) polycondensation reaction：It is 600Pa to discharge unreacted ethylene glycol that polymeric kettle is vacuumized, when
Between be 80min；Continue to be decompressed to 200Pa, while polymeric kettle is risen into high-temperature extremely being contracted to 270 DEG C
Poly- reaction, the time of polycondensation reaction is 80min, and the product in polymeric kettle reaches desired viscosity, is stopped anti-
Should, discharge product.
Inherent viscosity, melting enthalpy and the crystallization temperature of product are determined, 1 is the results are shown in Table.
Embodiment 5
This example demonstrates that the preparation method of the modified polyethylene terephthalate of the present invention.
(1) react：By the terephthalic acid (TPA) (PTA) of 500g, the ethylene glycol (EG) of 250g,
The lanthanum chloride of 0.62g and the J-2 of 0.25g are added in 2.5L polymeric kettles and are reacted.The temperature of reaction
For 220 DEG C, gauge is 0.4MPa, and the time is 30min.Reaction is discharged by rectifier unit to generate
Water.Polymeric kettle pressure is down to normal pressure by reaction after terminating；
(2) polycondensation reaction：It is 500Pa to discharge unreacted ethylene glycol that polymeric kettle is vacuumized, when
Between be 60min；Continue to be decompressed to 100Pa, while polymeric kettle is risen into high-temperature extremely being contracted to 290 DEG C
Poly- reaction, the time of polycondensation reaction is 60min, and the product in polymeric kettle reaches desired viscosity, is stopped anti-
Should, discharge product.
Inherent viscosity, melting enthalpy and the crystallization temperature of product are determined, 1 is the results are shown in Table.
Embodiment 6
This example demonstrates that the preparation method of the modified polyethylene terephthalate of the present invention.
(1) react：By the terephthalic acid (TPA) (PTA) of 500g, the ethylene glycol (EG) of 250g,
The acetylacetone,2,4-pentanedione neodymium of 0.62g and the J-3 of 0.45g are added in 2.5L polymeric kettles and are reacted.Reaction
Temperature is 250 DEG C, and gauge is 0.3MPa, and the time is 240min.Discharged by rectifier unit anti-
The water that should be generated.Polymeric kettle pressure is down to normal pressure by reaction after terminating；
(2) polycondensation reaction：It is 550Pa to discharge unreacted ethylene glycol that polymeric kettle is vacuumized, when
Between be 45min；Continue to be decompressed to 20Pa, while polymeric kettle is risen into high-temperature extremely carries out polycondensation to 300 DEG C
Reaction, the time of polycondensation reaction is 100min, and the product in polymeric kettle reaches desired viscosity, is stopped anti-
Should, discharge product.
Inherent viscosity, melting enthalpy and the crystallization temperature of product are determined, 1 is the results are shown in Table.
Comparative example 1
(1) esterification：By the terephthalic acid (TPA) (PTA) of 500g, the ethylene glycol (EG) of 250g
And the antimony acetate of 0.24g is added in 2.5L polymeric kettles and carries out esterification.The temperature of esterification is
240 DEG C, gauge is 0.2MPa, and the time is 150min.Discharge what reaction was generated by rectifier unit
Water.Polymeric kettle pressure is down to normal pressure by esterification after terminating；
(2) polycondensation reaction：It is 600Pa to discharge unreacted ethylene glycol that polymeric kettle is vacuumized, when
Between be 80min；Continue to be decompressed to 200Pa, while polymeric kettle is risen into high-temperature extremely being contracted to 270 DEG C
Poly- reaction, the time of polycondensation reaction is 80min, and the product in polymeric kettle reaches desired viscosity, is stopped anti-
Should, discharge product.
Inherent viscosity, melting enthalpy and the crystallization temperature of product are determined, 1 is the results are shown in Table.
Comparative example 2
(1) esterification：By the terephthalic acid (TPA) (PTA) of 500g, the ethylene glycol (EG) of 250g
And the Lanthanum Stearate of 0.62g is added in 2.5L polymeric kettles and carries out esterification.The temperature of esterification
240 DEG C, gauge is 0.2MPa, and the time is 150min.Discharge what reaction was generated by rectifier unit
Water.Polymeric kettle pressure is down to normal pressure by esterification after terminating；
(2) polycondensation reaction：It is 600Pa to discharge unreacted ethylene glycol that polymeric kettle is vacuumized, when
Between be 80min；Continue to be decompressed to 200Pa, while polymeric kettle is risen into high-temperature extremely being contracted to 270 DEG C
Poly- reaction, the time of polycondensation reaction is 80min, and the product in polymeric kettle reaches desired viscosity, is stopped anti-
Should, discharge product.
Inherent viscosity, melting enthalpy and the crystallization temperature of product are determined, 1 is the results are shown in Table.
Table 1
| Sample | Inherent viscosity (dL/g) | Melting enthalpy △ H (J/g) | Crystallization temperature Tc (DEG C) |
| Comparative example 1 | 0.670 | 32.1 | 170.9 |
| Comparative example 2 | 0.682 | 36.2 | 179.4 |
| Embodiment 1 | 0.780 | 48.5 | 180.2 |
| Embodiment 2 | 0.750 | 45.2 | 177.5 |
| Embodiment 3 | 0.825 | 52.3 | 182.3 |
| Embodiment 4 | 0.765 | 47.8 | 182.1 |
| Embodiment 5 | 0.720 | 46.3 | 176.5 |
| Embodiment 6 | 0.783 | 50.4 | 178.9 |
Can be seen that using containing structure shown in formula (1) from the data of embodiment, comparative example and table 1
The random copolymer of unit and construction unit shown in formula (2) is used as crystallization promoter, wherein formula (1) institute
Show that construction unit comes from 9- decen-1-ol monomers, formula (2) construction unit come from 4- methyl isophthalic acids-
Amylene monomer, participates in the course of reaction of ethylene glycol and terephthalic acid (TPA), while adding containing rare earth metal unit
Component a of element as esterification catalyst, obtained modified polyethylene terephthalate in this approach,
The inherent viscosity that can be significantly increased, illustrating the molecular weight of product does not reduce, it is possible to thus judge
There is long-chain branch to generate in product modification polyethylene terephthalate, and being modified for obtaining is poly- to benzene two
Formic acid glycol ester has melting enthalpy and the crystallization temperature for improving simultaneously, illustrates modified poly terephthalic acid second
The degree of crystallinity of diol ester is improved, and crystalline rate is improved.
Although in addition, component a containing thulium is also added in comparative example 2 as esterification
Catalyst, the crystallization temperature of product is compared comparative example 1 and is had been improved, but can not improve the spy of product
Property viscosity and melting enthalpy.By the result of embodiment 1-6 can be seen that the method for the present invention obtains it is modified
Polyethylene terephthalate can simultaneously have crystallization temperature, inherent viscosity and the melting enthalpy for improving.
Illustrate that the method for the present invention there can be the performance of more preferable synthesis improvement polyethylene terephthalate
Effect.
Claims (10)
1. a kind of preparation method of modified polyethylene terephthalate, including：
(1) in the presence of esterification catalyst, ethylene glycol, terephthalic acid (TPA) and crystallization promoter are carried out
Reaction, obtains product；
(2) product is removed into unreacted ethylene glycol, is then entered under the conditions of polycondensation reaction
Row polycondensation；
The crystallization promoter is containing construction unit shown in formula (1) and construction unit shown in formula (2)
Random copolymer,
Wherein, the R in formula (1)1For C2-C15Alkylidene, construction unit is in institute shown in formula (1)
It is 1-10mol% to state the content in crystallization promoter.
2. method according to claim 1, wherein, in formula (1), R1For C3-C8Asia
Alkyl, preferred R1For C8Straight-chain alkyl-sub；The weight ratio of the crystallization promoter and terephthalic acid (TPA)
For 1：(100-5000), preferably 1：(250-2000)；Terephthalic acid (TPA) is with the mol ratio of ethylene glycol
1:(1-1.5)。
3. method according to claim 1 and 2, wherein, the crystallization promoter is by with lower section
It is prepared by method：In the presence of nitrogen and transition metal catalyst system, by 4-methyl-1-pentene monomer and formula (3)
Shown monomer carries out copolyreaction,
Wherein, R1For C2-C15Alkylidene, preferred R1For C3-C8Alkylidene, more preferably formula (3)
Shown monomer is 9- decen-1-ols；The consumption of monomer is the crystallization promoter shown in formula (3)
1-10mol%；The weight average molecular weight of the crystallization promoter is 10,000-20 ten thousand, and molecular weight distribution is 1.5-4.
4. method according to claim 3, wherein, the transition metal catalyst system includes
Metallocene compound and co-catalyst, the metallocene compound is the cyclopentadienyl of the subgroup of racemic bridging the 4th
Metal, the co-catalyst is MAO；It is preferred that the metallocene compound is dimethyl silicon bridge two
(2- methyl-indenyls) zirconium dichloride；With 4-methyl-1-pentene monomer, monomer and the mistake shown in formula (3)
On the basis of crossing the consumption total amount of metal catalyst system, the concentration of the metallocene compound is 10-6
Mol/L to 10-2mol/L；The co-catalyst is with the mol ratio of the metallocene compound
(100-10000):1。
5. the method according to claim 3 or 4, wherein, the temperature of the copolyreaction is 40-60
DEG C, the gauge of the copolyreaction is 0.05-0.15MPa, and the time of the copolyreaction is 4-8h.
6. the method according to any one in claim 1-5, wherein, the esterification catalyst
Including component a and/or component b；
Component a is at least one by chemical formula RE (R2)3The compound of expression, wherein, RE is rare earth gold
Category element, R2It is selected from halogen, alkoxyl, aryloxy group, levulinic ketone group, R3COO- groups and
At least one in their hydrate, R3For C1-C30Alkyl；Preferred ingredient a be Lanthanum Stearate,
At least one in stearic acid neodymium, lanthanum acetylacetone, acetylacetone,2,4-pentanedione neodymium, lanthanum chloride and isopropoxy neodymium；
Component b is selected from chemical formula M (OR4)x1、M2Ox2With M (- OOCR5)x3In the compound of expression
At least one, wherein, M is titanium or zinc, and x1, x2 and x3 are each independently 2,3 or 4,
R4For C1-C10Alkyl, R5For C1-C30Alkyl；Preferred ingredient b is butyl titanate, dioxy
Change titanium and at least one in zinc acetate；
Component a is 1 with the mol ratio of component b:(0-2), preferably 1：(0-1), more preferably 1：
(0.2-1)。
7. method according to claim 6, wherein, component a in the esterification catalyst with
The weight ratio of terephthalic acid (TPA) is 1：(500-5000).
8. the method according to any one in claim 1-7, wherein, in step (1),
The temperature of the reaction is 220-260 DEG C, and the gauge of the reaction is 0.1-0.4MPa, described anti-
The time answered is 0.5-4h.
9. the method according to any one in claim 1-8, wherein, the polycondensation reaction
Temperature is 270-300 DEG C, and the gauge of the polycondensation reaction is 0-300Pa, the polycondensation reaction when
Between be 60-100min.
10. be modified poly- terephthaldehyde obtained in a kind of method by described in any one in claim 1-9
Sour glycol ester.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001123054A (en) * | 1999-10-28 | 2001-05-08 | Teijin Ltd | Flame resistant resin composition and its molding |
| CN101153111A (en) * | 2006-09-27 | 2008-04-02 | 上海杰事杰新材料股份有限公司 | Polyethylene terephthalate composite material and method of producing the same |
| CN102453313A (en) * | 2011-09-20 | 2012-05-16 | 福建奥峰科技有限公司 | High-temperature-resistance flame-retardation enhanced polyethylene terephthalate (PET), preparation method thereof and purpose thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001123054A (en) * | 1999-10-28 | 2001-05-08 | Teijin Ltd | Flame resistant resin composition and its molding |
| CN101153111A (en) * | 2006-09-27 | 2008-04-02 | 上海杰事杰新材料股份有限公司 | Polyethylene terephthalate composite material and method of producing the same |
| CN102453313A (en) * | 2011-09-20 | 2012-05-16 | 福建奥峰科技有限公司 | High-temperature-resistance flame-retardation enhanced polyethylene terephthalate (PET), preparation method thereof and purpose thereof |
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