CN106977884A - Atactic polyester composition and preparation method thereof and flame retardant polyester composition and preparation method thereof - Google Patents
Atactic polyester composition and preparation method thereof and flame retardant polyester composition and preparation method thereof Download PDFInfo
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- CN106977884A CN106977884A CN201610030759.3A CN201610030759A CN106977884A CN 106977884 A CN106977884 A CN 106977884A CN 201610030759 A CN201610030759 A CN 201610030759A CN 106977884 A CN106977884 A CN 106977884A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from 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
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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
- C08G63/78—Preparation processes
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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
- C08G63/78—Preparation processes
- C08G63/80—Solid-state polycondensation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/10—Applications used for bottles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/12—Applications used for fibers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a kind of atactic polyester composition and preparation method thereof and flame retardant polyester composition and preparation method thereof.Composition includes：(1) polyester A, contains repeat unitWith repeat unit-R-OCH2CH2CH2O-, R are the construction unit from phosphor-containing flame-proof monomer；(2) polyester B, contains structure-S-R1- S-and/or structure-S-R2—R1—R2- S-, R1For the construction unit from chain extender, R2For the construction unit from anhydrides compound, S represents polyester A；Construction unitMol ratio with R is 70：30~99：1；R1And R2Content be respectively construction unit
Description
Technical field
The present invention relates to a kind of atactic polyester composition and preparation method thereof, and including the atactic polyester composition
Flame retardant polyester composition and preparation method thereof.
Background technology
PTT (PTT) because its have high intensity, high-modulus, high resiliency, conformality, heat resistance and
The advantages of spinnability, it is widely used in usually as fiber, film, Packaging Bottle, automobile and electronic device engineering plastics etc.
In industry and daily life.
However, PTT belongs to combustible material, in burning, HRR is big, calorific value is high, flame propagation speed, once
Cause fire, harmfulness greatly, huge threat is brought to people's life and property safety, this greatly limits its application.
In order to further expand PTT application, it is necessary to carry out flame-retarded processing to it.Generally carried out using by fire retardant and PTT
The method of blending or copolymerization carries out flame-retarded processing to it, wherein the blending method of addition fire retardant, because addition is big, often
PTT physical and mechanical properties is caused significantly to decline；Although and copolymerization method consumption is small, it is possible to assign its permanent fire retardant,
It is difficult the flame retardant polyester for obtaining HMW to be, it is difficult to meet the application fields such as high-intensity fiber, engineering plastics to high-molecular-weight poly
The flame-retardancy requirements of ester, this greatly limits the application of flame retardant polyester.
The flame retardant polyester of higher intrinsic viscosity can be obtained by extending the melt polycondensation time, but this method is due in height
Carried out under warm condition of high voltage, energy consumption is big and requires high to production equipment, is unfavorable for industrial production.Solid phase is a kind of preferable
The method for improving molecular weight of polyesters, its technique is simple, running cost is low and side reaction is few, but solid phase polymerization method occurs poly-
Below ester particle fusing point, reaction rate is slow, generally requires the reaction time grown very much, this also constrains its application industrially.
Chemical chain extension method is connected two or more pieces polyester molecule chain by adding chain extender, plays a part of increasing molecular weight,
This method reaction speed is fast, effect is good, cost is low, has the disadvantage that the crystal property of products obtained therefrom is deteriorated.
The content of the invention
The defect prepared the invention aims to the poor and existing copolyesters of the resistance to molten drop for solving copolyesters there is provided
A kind of atactic polyester composition and preparation method thereof and flame retardant polyester composition and preparation method thereof.
To achieve these goals, the invention provides a kind of atactic polyester composition, the atactic polyester composition
Including：(1) polyester A, the polyester A contains repeat unitWith repeat unit-R-
OCH2CH2CH2O-, wherein, R is the construction unit from phosphor-containing flame-proof monomer；(2) polyester B, the polyester B contain structure-
S—R1- S-and/or structure-S-R2—R1—R2- S-, wherein, R1For the construction unit from chain extender, R2For from
The construction unit of anhydrides compound, S represents the polyester A；Construction unit in the atactic polyester compositionMol ratio with R is 70：30~99：1；R1Content be construction unitAnd knot
0.1~3mol% of the summation of structure unit R；R2Content be construction unitWith construction unit R summation
0.5~5mol%；The intrinsic viscosity of the atactic polyester is 1.5dL/g~2.9dL/g.
Present invention also offers a kind of method for preparing the atactic polyester composition that the present invention is provided, this method includes：
(1a) carries out terephthalic acid (TPA), propane diols and phosphor-containing flame-proof monomer to be esterified instead in the presence of nitrogen protection and esterification catalyst
Should；Or (1b) is in the presence of ester exchange catalyst, dimethyl terephthalate (DMT), propane diols and phosphor-containing flame-proof monomer are subjected to ester
Exchange reaction；(2) ester exchange offspring that the esterification products or step (1b) obtained step (1a) are obtained, first carries out precondensation
Reaction, then carries out polycondensation reaction, obtained copolyester prepolymer；(3) copolyester prepolymer is first carried out crystallizing pre- place
Reason, then carry out solid state polycondensation；(4) enter after the product heats melting obtained step (3) with chain extender, anhydrides compound
Row chain extending reaction, obtains fire-retardant atactic polyester.
Present invention also offers a kind of flame retardant polyester composition, on the basis of the gross weight of said composition, said composition bag
Include 98~99.96 weight % atactic polyester, 0.02~1 weight % antioxidant, 0.02~1 weight % stabilizer；Its
In, the atactic polyester composition that the atactic polyester provides for the present invention.
Present invention also offers a kind of method for preparing the flame retardant polyester composition that the present invention is provided, this method includes will
The atactic polyester of 100 parts by weight, the antioxidant of 0.02~1 parts by weight, the stabilizer of 0.02~1 parts by weight are mixed and squeezed
Go out granulation, obtain the flame retardant polyester composition.
Construction unit containing phosphor-containing flame-proof monomer, chain extender in the structure for the atactic polyester composition that the present invention is provided
And the construction unit with anhydrides compound associated with chain extender, the atactic polyester composition can be provided and containing the nothing
The flame retardant polyester composition of polyester composition is advised with better flame resistance, more preferable resistance to melt-dropping property.And with vertical
Direct combustion burns the more preferable resistance to melt-dropping property that reignition molten drop number is less represented in test result.The sample obtained such as embodiment
A-1~A-9 and B-1~B-2, carries out vertical burn test (according to UL-94 standards), and as a result reignition molten drop number is less than 8
Drop, and sample D-1~D-2 that comparative example is obtained is that molten drop is violent.
The preparation method of the atactic polyester composition of the present invention is provided, by using solid phase and melting after polycondensation
Mode associated with chain extension, first passes through solid phase polymerization method within a short period of time by the intrinsic viscosity of the copolyester prepolymer of polycondensation reaction
Improve to a certain extent, then carry out after melting chain extending reaction, and then improve the molecular weight of product.Nothing is improved with prior art
The method for advising the molecular weight of copolyesters is compared, due to solid polycondensation of the prior art only with solid phase polymerization method, rather than the present invention
Close and mode associated with chain extension, obtaining producing with the molecular weight identical of the fire-retardant atactic polyester of HMW of the present invention
During product, prior art, which needs to react, continues the longer time, it is seen that the present invention can realize the reduction for preparing energy consumption.In addition, should
Method is simple and convenient, it is easy to control and realize industrialized production.
Atactic polyester composition and flame retardant polyester composition that the present invention is provided, available for fiber, film, polyester bottles,
The fields such as engineering plastics.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides a kind of atactic polyester composition, the atactic polyester composition includes：(1) polyester A, it is described
Polyester A contains repeat unitWith repeat unit-R-OCH2CH2CH2O-, wherein, R is
Construction unit from phosphor-containing flame-proof monomer；(2) polyester B, the polyester B contains structure-S-R1- S-and/or structure-
S—R2—R1—R2- S-, wherein, R1For the construction unit from chain extender, R2For the structure list from anhydrides compound
Member, S represents the polyester A；Construction unit in the atactic polyester compositionMol ratio with R is 70：
30~99：1；R1Content be construction unitWith 0.1~3mol% of construction unit R summation；R2's
Content is construction unitWith 0.5~5mol% of construction unit R summation；The spy of the atactic polyester
Property glutinous number be 1.5dL/g~2.9dL/g.
Preferably, the intrinsic viscosity of the atactic polyester is 1.7dL/g~2.6dL/g.
In the present invention, the method that the atactic polyester composition can be tested by proton nmr spectra determines what is contained
Structure and each structural unit content.Specific method is as follows：5mg is weighed through dissolving the sample that precipitation process is crossed, deuterated reagent is added
CF3COOD0.6ml wiring solution-formings are tested.Internal standard compound is tetramethylsilane (TMS).
In the present invention, S represents that the polyester A refers to that S is derived from the polyester A, and specifically, S is the end group of the polyester A
Reacted the structure to be formed with the chain extender.
According to the present invention, R is that the construction unit from phosphor-containing flame-proof monomer refers to phosphor-containing flame-proof monomer with propane diols through contracting
It is poly- to react structure obtaining, being present in the atactic polyester composition.The phosphor-containing flame-proof monomer can be 9,10- bis-
At least one in the miscellaneous phenanthrene-succinic acid of hydrogen -9- oxa- -10- phosphinylidynes, 2- carboxyethyl methylphosphinates and 2- carboxyethyl phenyl phosphinic acids
Kind.Under preferable case, R structure isIn
It is at least one；It is preferred that R structure is
According to the present invention, R1The end carboxyl for referring to chain extender and the polyester A for the construction unit from chain extender rolls into a ball reaction
Structure obtaining, being present in the atactic polyester composition.The chain extender can for 2,2 '-bis- (2- oxazolines), 2,2 '-
At least one of (1,4- phenylenes) double (2- oxazolines) and 2,2 '-(1,3- phenylenes) double (2- oxazolines).Under preferable case, R1
Structure beWithAt least one of.
According to the present invention, R2Refer to anhydrides compound and the polyester A for the construction unit from anhydrides compound
The new end carboxyl of terminal hydroxy group group reaction generation, then the new end carboxyl obtained again with chain extender reaction, be present in it is described
Structure in atactic polyester composition.The anhydrides compound phthalic anhydride and/or pyromellitic acid anhydride.It is preferred that
In the case of, R2Structure beAnd/or
According to the present invention, the limited oxygen index of the atactic polyester is 28.0~36.5；According to nothing described in UL-94 standards
The vertical combustion grade of rule copolyesters reaches V-0 grades, shows as just putting out from fire after lighting for the second time, molten drop number is not more than 6 drops.
Present invention also offers a kind of method for preparing the atactic polyester composition that the present invention is provided, this method includes：
(1a) carries out terephthalic acid (TPA), propane diols and phosphor-containing flame-proof monomer to be esterified instead in the presence of nitrogen protection and esterification catalyst
Should；Or (1b) is in the presence of ester exchange catalyst, dimethyl terephthalate (DMT), propane diols and phosphor-containing flame-proof monomer are subjected to ester
Exchange reaction；(2) ester exchange offspring that the esterification products or step (1b) obtained step (1a) are obtained, first carries out precondensation
Reaction, then carries out polycondensation reaction, obtained copolyester prepolymer；(3) copolyester prepolymer is first carried out crystallizing pre- place
Reason, then carry out solid state polycondensation；(4) enter after the product heats melting obtained step (3) with chain extender, anhydrides compound
Row chain extending reaction, obtains fire-retardant atactic polyester.
According to the present invention, the pressure of esterification described in step (1a) is 0.2~0.4MPa, the temperature of the esterification
Spend for 200~280 DEG C, the time of the esterification is 0.5~4h.
Preferably, the mol ratio of the summation and propane diols of terephthalic acid (TPA) and the phosphor-containing flame-proof monomer is 1:1.2~1:
2。
Preferably, the mol ratio of terephthalic acid (TPA) and the phosphor-containing flame-proof monomer is 70：30~99：1.
Preferably, the addition of the esterification catalyst is the total amount of feeding of terephthalic acid (TPA) and the phosphor-containing flame-proof monomer
0.01~0.1mol%.
Preferably, the phosphor-containing flame-proof monomer is 2- carboxyethyl methylphosphinates, 2- carboxyethyl phenyl phosphinic acids and 9,10-
At least one of miscellaneous phenanthrene-succinic acid of the miscellaneous -10- phosphinylidynes of dihydro-9-oxy, preferably 2- carboxyethyl phenyl phosphinic acids.
Preferably, the catalyst for realizing above-mentioned esterification that the esterification catalyst can use for this area, it is more excellent
Elect the esterification catalyst containing Sb as, the particularly preferred esterification catalyst is Sb2O3。
Specifically, esterification can be described in step (1a)：By terephthalic acid (TPA), propane diols, phosphor-containing flame-proof monomer
Added with catalyst in reaction unit, stir, then vacuumize successively, esterification is forced into after logical nitrogen displacement four times
Pressure, carry out esterification at a temperature of being warming up to esterification.Pressure is maintained in 0.3~0.4MPa, when esterification generation
Water close to theoretical amount and system pressure no longer change substantially when, be slowly depressurized to normal pressure discharging.
According to the present invention, the temperature of ester exchange reaction described in step (1b) is 160~220 DEG C, the ester exchange reaction
Time be 0.5~6h.
Preferably, the mol ratio of the summation and propane diols of dimethyl terephthalate (DMT) and the phosphor-containing flame-proof monomer is 1:
1.2~1:2.
Preferably, the mol ratio of dimethyl terephthalate (DMT) and the phosphor-containing flame-proof monomer is 70：30~99：1.
Preferably, the addition of the ester exchange catalyst is dimethyl terephthalate (DMT), propane diols and the phosphorous resistance
Fire 0.01~0.1mol% of the total amount of feeding of monomer.
Preferably, the phosphor-containing flame-proof monomer is 2- carboxyethyl methylphosphinates, 2- carboxyethyl phenyl phosphinic acids and 9,10-
At least one of miscellaneous phenanthrene-succinic acid of the miscellaneous -10- phosphinylidynes of dihydro-9-oxy, preferably 2- carboxyethyl phenyl phosphinic acids.
Preferably, the catalyst for realizing above-mentioned ester exchange reaction that the ester exchange catalyst can use for this area,
The more preferably ester exchange catalyst containing Sb, the particularly preferred ester exchange catalyst is Sb2O3。
Specifically, ester exchange reaction can be described in step (1b)：By dimethyl terephthalate (DMT), propane diols, phosphorous
Flame-retardant monomer and catalyst are added in reaction unit, stir, ester is then carried out under the temperature and time of ester exchange reaction
Exchange reaction.
According to the present invention, in step (2), the pressure of the prepolymerization reaction is 100~600Pa, the prepolymerization reaction
Temperature be 220~280 DEG C, time of the prepolymerization reaction is 1~3h.
Preferably, the pressure of the polycondensation reaction is 10~200Pa, and the temperature of the polycondensation reaction is 260~300 DEG C,
The time of the polycondensation reaction is 0.5~5h.
Preferably, the intrinsic viscosity of the copolyester prepolymer is 0.3dL/g~0.8dL/g.
According to the present invention, the copolyester prepolymer is granulated before crystallization pretreatment described in step (3), obtained
The size of particle is 10~10000/g.
Preferably, the pressure of the crystallization pretreatment is 10~200Pa, and the temperature of the crystallization pretreatment is 100~160
DEG C, the time of the crystallization pretreatment is 0.5~4h.
Preferably, the pressure of the solid state polycondensation is 10~200Pa, and the temperature of the solid state polycondensation is 160
~225 DEG C, the time of the solid state polycondensation is 4~20h.
According to the present invention, heating melting described in step (4) is to be heated to 190~270 DEG C under nitrogen protection.
Preferably, the addition of the chain extender is terephthalic acid (TPA) or dimethyl terephthalate (DMT) and the phosphor-containing flame-proof
0.1~3mol% of the summation of monomer.
Preferably, the addition of the anhydrides compound is terephthalic acid (TPA) or dimethyl terephthalate (DMT) and described contained
0.5~5mol% of the summation of phosphorus flame-retardant monomer.
Preferably, the pressure of the chain extending reaction is 10~200Pa, and the temperature of the chain extending reaction is 260~300 DEG C,
The time of the chain extending reaction is 5~60min.
Preferably, the chain extender is 2,2 '-bis- (2- oxazoline) and 2, and 2 '-(Isosorbide-5-Nitrae-phenylene) is double (2- oxazolines)
At least one of with 2,2 '-(1,3- phenylenes) double (2- oxazolines).
Preferably, the anhydrides compound is phthalic anhydride and/or pyromellitic acid anhydride.
Specifically, chain extending reaction is described in step (4)：Under nitrogen protection, product heats step (3) obtained are extremely
190~270 DEG C, after after sample completely melting, while chain extender and anhydrides compound are added, then in the pressure of chain extending reaction
Under power, temperature and time, stirring carries out chain extending reaction.
Present invention also offers a kind of flame retardant polyester composition, on the basis of the gross weight of said composition, said composition bag
Include 100 weight % atactic polyester, 0.02~1 weight % antioxidant, 0.02~1 weight % stabilizer；Wherein, it is described
The atactic polyester composition that atactic polyester provides for the present invention.
The flame retardant polyester composition can also include other processing aids, such as delustering agent.Antioxidant, stabilizer, delustering agent
It is the common knowledge of this area Deng processing aid, for example antioxidant can be triphenyl phosphite, and stabilizer can be poly- carbon
Diimine delustering agent can be titanium dioxide, and other auxiliary agents are no longer repeated one by one.
Present invention also offers a kind of method for preparing the flame retardant polyester composition that the present invention is provided, this method includes will
The atactic polyester of 100 parts by weight, the antioxidant of 0.02~1 parts by weight, the stabilizer of 0.02~1 parts by weight are mixed and squeezed
Go out granulation, obtain the flame retardant polyester composition.
According to the present invention, the extruding pelletization is carried out in double screw extruder, and temperature is 240~280 DEG C, screw speed
For 50~70r/min, pressure is 0.05~0.15MPa.
The pressure being related in the present invention is gauge pressure.
The present invention will be described in detail by way of examples below.
In following examples and comparative example,
The composition of atactic polyester composition passes through the determination that feeds intake of raw material, and wherein propane diols is excessive, it is believed that to benzene
Dioctyl phthalate or dimethyl terephthalate (DMT), reaction has been involved in phosphor-containing flame-proof monomer；
The intrinsic viscosity [η] of prepolymer and atactic polyester composition is with phenol/1,1,2,2- tetrachloroethanes (volumes
Than=1:1) it is solvent, is configured to the solution that concentration is 0.5g/dL, is measured with dark type viscometer at 25 DEG C；
The tensile property of atactic polyester composition and flame retardant polyester composition is measured according to ASTM D638-03 standards；
Impact strength is measured according to ASTM D256-05 standards；
Limited oxygen index by atactic polyester composition and flame retardant polyester composition by being made 120 × 6.5 × 3.2mm3
Standard oxygen exponential spline, determined according to ASTM D2863-97 standards on HC-2C oxygen index instruments；
Vertical combustion by atactic polyester composition and flame retardant polyester composition by being made 125 × 12.7 × 3.2mm3's
Standard batten, is determined according to UL-94 standards using CZF-2 types Vertical combustion instrument.
Embodiment 1
This example demonstrates that the preparation method of the atactic polyester composition of the present invention.
(1) esterification：Terephthalic acid (TPA) 817g, propane diols 481g, 2- contracting ethylphenyl time phosphine are added into reactor
Acid (CEPP) 55g, 0.350g catalyst Sb2O3, stir, then vacuumize successively, lead to nitrogen displacement gas reactor four times
After be forced into 0.1MPa, be to slowly warm up at 260 DEG C carry out esterification, while pressure maintains 0.2MPa, esterification generation
Water is separated by still, when the water of generation no longer changes substantially close to theoretical amount and system pressure, is slowly depressurized to normal pressure
And take the remaining water of system out of；
(2) copolyester prepolymer processed：By the product of esterification, the first prepolymerization reaction at pressure 200Pa and 260 DEG C
1h；Polycondensation 5h discharges at 20Pa and 280 DEG C again, and the intrinsic viscosity of gained copolyester prepolymer body is 0.78dL/g；
(3) solid state polycondensation：The copolyester prepolymer of gained is a granulated into the particle of 10000/g sizes, Ran Houqu
500g particle crystallization pretreatment 2h under 100 DEG C and vacuum (10Pa), then carry out solid state polycondensation under 220 DEG C and 20Pa
20h；
(4) chain extending reaction：The product that step (3) is obtained is heated to 270 DEG C under nitrogen protection, treats sample all thawings
Afterwards, while adding the 3.0mol% of terephthalic acid (TPA) and CEPP summation 2,2 '-bis- (2- oxazolines), terephthalic acid (TPA) and
The 1.5mol% of CEPP summation phthalic anhydride, chain extending reaction 10min is carried out under 270 DEG C, pressure 20Pa, nothing is obtained
Advise polyester composition A-1.
A-1 composition the results are shown in Table 1, and wherein R comes from CEPP, R1Come from 2,2 '-bis- (2- oxazolines), R2Come from
Phthalic anhydride.
A-1 is subjected to performance test, test result is shown in Table 2.
Embodiment 2
This example demonstrates that the preparation method of the atactic polyester composition of the present invention.
(1) ester exchange reaction：Add into reactor dimethyl terephthalate (DMT) 953g, propane diols 496g, 110g
CEPP, 0.361g Sb2O3, stir, ester exchange reaction 4h then carried out at 220 DEG C；
(2) copolyester prepolymer processed：By the product of ester exchange reaction, the first prepolymerization reaction at pressure 200Pa and 230 DEG C
1h；Polycondensation 4h discharges at 20Pa and 280 DEG C again, and the intrinsic viscosity of gained copolyester prepolymer body is 0.65dL/g；
(3) solid state polycondensation：The copolyester prepolymer of gained is a granulated into the particle of 8000/g sizes, Ran Houqu
500g particle crystallization pretreatment 2h under 100 DEG C and vacuum (10Pa), then carry out solid state polycondensation under 225 DEG C and 20Pa
15h；
(4) chain extending reaction：The product that step (3) is obtained is heated to 225 DEG C under nitrogen protection, treats sample all thawings
Afterwards, at the same add the 1.5mol% of dimethyl terephthalate (DMT) and CEPP summation 2,2 '-bis- (2- oxazolines), terephthaldehyde
(mass ratio is 1 to the 2.5mol% of dimethyl phthalate and CEPP summation phthalic anhydride and pyromellitic acid anhydride mixture:
1) chain extending reaction 15min, is carried out under 260 DEG C, pressure 20Pa, atactic polyester composition A-2 is obtained.
A-2 composition the results are shown in Table 1, and wherein R comes from CEPP, R1Come from 2,2 '-bis- (2- oxazolines), R2Come from
Phthalic anhydride and pyromellitic acid anhydride.
A-2 is subjected to performance test, test result is shown in Table 2.
Embodiment 3
This example demonstrates that the preparation method of the atactic polyester composition of the present invention.
(1) ester exchange reaction：Add into reactor dimethyl terephthalate (DMT) 953g, propane diols 512g, 165g
CEPP, 0.372g Sb2O3, stir, ester exchange reaction 2h then carried out at 200 DEG C；
(2) copolyester prepolymer processed：By the product of ester exchange reaction, the first prepolymerization reaction at pressure 200Pa and 260 DEG C
1h；Polycondensation 6h discharges at 20Pa and 280 DEG C again, and the intrinsic viscosity of gained copolyester prepolymer body is 0.69dL/g；
(3) solid state polycondensation：The copolyester prepolymer of gained is a granulated into the particle of 7500/g sizes, Ran Houqu
500g particle crystallization pretreatment 2h under 100 DEG C and vacuum (100Pa), then progress solid phase polycondensation is anti-under 190 DEG C and 20Pa
Answer 8h；
(4) chain extending reaction：The product that step (3) is obtained is heated to 250 DEG C under nitrogen protection, treats sample all thawings
Afterwards, at the same add the 0.3mol% of dimethyl terephthalate (DMT) and CEPP summation 2,2 '-bis- (2- oxazolines), terephthaldehyde
The 3.5mol% of dimethyl phthalate and CEPP summation pyromellitic acid anhydride, chain extending reaction is carried out under 300 DEG C, pressure 20Pa
20min, obtains atactic polyester composition A-3.
A-3 composition the results are shown in Table 1, and wherein R comes from CEPP, R1Come from 2,2 '-bis- (2- oxazolines), R2Come from
Pyromellitic acid anhydride.
A-3 is subjected to performance test, test result is shown in Table 2.
Embodiment 4
This example demonstrates that the preparation method of the atactic polyester composition of the present invention.
(1) ester exchange reaction：Add into reactor dimethyl terephthalate (DMT) 953g, propane diols 527g, 220g
CEPP, 0.383g Sb2O3, stir, ester exchange reaction 1h then carried out at 190 DEG C；
(2) copolyester prepolymer processed：By the product of ester exchange reaction, the first prepolymerization reaction at pressure 200Pa and 265 DEG C
1h；Polycondensation 8h discharges at 20Pa and 280 DEG C again, and the intrinsic viscosity of gained copolyester prepolymer body is 0.72dL/g；
(3) solid state polycondensation：The copolyester prepolymer of gained is a granulated into the particle of 2000/g sizes, Ran Houqu
500g particle crystallization pretreatment 2h under 100 DEG C and vacuum (50Pa), then carry out solid state polycondensation under 170 DEG C and 20Pa
10h；
(4) chain extending reaction：The product that step (3) is obtained is heated to 240 DEG C under nitrogen protection, treats sample all thawings
Afterwards, while adding dimethyl terephthalate (DMT) and the 2.3mol% of CEPP summation 2,2 '-(1,3- phenylene) double (2- oxazoles
Quinoline), the 1.5mol% of dimethyl terephthalate (DMT) and CEPP summation pyromellitic acid anhydride, under 270 DEG C, pressure 20Pa
Chain extending reaction 30min is carried out, atactic polyester composition A-4 is obtained.
A-4 composition the results are shown in Table 1, and wherein R comes from CEPP, R1Come from 2,2 '-(1,3- phenylenes) double (2- oxazoles
Quinoline), R2Come from pyromellitic acid anhydride.
A-4 is subjected to performance test, test result is shown in Table 2.
Embodiment 5
This example demonstrates that the preparation method of the atactic polyester composition of the present invention.
(1) ester exchange reaction：Add into reactor dimethyl terephthalate (DMT) 953g, propane diols 543g, 275g
CEPP, 0.394g Sb2O3, stir, ester exchange reaction 3.5h then carried out at 210 DEG C；
(2) copolyester prepolymer processed：By the product of ester exchange reaction, the first prepolymerization reaction at pressure 200Pa and 270 DEG C
1h；Polycondensation 7h discharges at 20Pa and 280 DEG C again, and the intrinsic viscosity of gained copolyester prepolymer body is 0.75dL/g；
(3) solid state polycondensation：The copolyester prepolymer of gained is a granulated into the particle of 2500/g sizes, Ran Houqu
500g particle crystallization pretreatment 2h under 100 DEG C and vacuum (30Pa), then carry out solid state polycondensation under 180 DEG C and 20Pa
12h；
(4) chain extending reaction：The product that step (3) is obtained is heated to 230 DEG C under nitrogen protection, treats sample all thawings
Afterwards, while adding dimethyl terephthalate (DMT) and the 1.5mol% of CEPP summation 2,2 '-(1,3- phenylene) double (2- oxazoles
Quinoline), the 1.5mol% of dimethyl terephthalate (DMT) and CEPP summation phthalic anhydride and pyromellitic acid anhydride and mixed
(mass ratio is 1 to compound:1) chain extending reaction 5min, is carried out under 270 DEG C, pressure 20Pa, atactic polyester composition A-5 is obtained.
A-5 composition the results are shown in Table 1, and wherein R comes from CEPP, R1Come from 2,2 '-(1,3- phenylenes) double (2- oxazoles
Quinoline), R2Come from phthalic anhydride and pyromellitic acid anhydride.
A-5 is subjected to performance test, test result is shown in Table 2.
Embodiment 6
This example demonstrates that the preparation method of the atactic polyester composition of the present invention.
(1) ester exchange reaction：Add into reactor dimethyl terephthalate (DMT) 953g, propane diols 558g, 330g
CEPP, 0.406g Sb2O3, stir, ester exchange reaction 3h then carried out at 215 DEG C；
(2) copolyester prepolymer processed：By the product of ester exchange reaction, the first prepolymerization reaction at pressure 200Pa and 230 DEG C
1h；Polycondensation 5h discharges at 20Pa and 280 DEG C again, and the intrinsic viscosity of gained copolyester prepolymer body is 0.81dL/g；
(3) solid state polycondensation：The copolyester prepolymer of gained is a granulated into the particle of 3000/g sizes, Ran Houqu
500g particle crystallization pretreatment 2h under 100 DEG C and vacuum (60Pa), then carry out solid state polycondensation under 160 DEG C and 20Pa
7h；
(4) chain extending reaction：The product that step (3) is obtained is heated to 190 DEG C under nitrogen protection, treats sample all thawings
Afterwards, while adding dimethyl terephthalate (DMT) and the 2.0mol% of CEPP summation 2,2 '-bis- (2- oxazolines) and 2,2 '-
(mass ratio is 1 to the mixture of (1,4- phenylenes) double (2- oxazolines):1), dimethyl terephthalate (DMT) and CEPP summation
3.5mol% phthalic anhydride, carries out chain extending reaction 25min under 270 DEG C, pressure 20Pa, obtains atactic polyester combination
Thing A-6.
A-6 composition the results are shown in Table 1, and wherein R comes from CEPP, R1Come from 2,2 '-bis- (2- oxazolines) and 2,2 '-
(Isosorbide-5-Nitrae-phenylene) is double (2- oxazolines), R2Come from phthalic anhydride.
A-6 is subjected to performance test, test result is shown in Table 2.
Embodiment 7
This example demonstrates that the preparation method of the atactic polyester composition of the present invention.
(1) esterification：Terephthalic acid (TPA) 817g, propane diols 481g, 55g CEPP, 0.350g are added into reactor
Catalyst Sb2O3, stir, then vacuumize successively, be forced into 0.1MPa after logical nitrogen displacement gas reactor four times, delay
Slow be warming up at 260 DEG C carries out esterification, while pressure maintains 0.34MPa, the water of esterification generation is separated by still,
When the water of generation no longer changes substantially close to theoretical amount and system pressure, normal pressure is slowly depressurized to and by the remaining water band of system
Go out；
(2) copolyester prepolymer processed：By the product of esterification, the first prepolymerization reaction at pressure 200Pa and 275 DEG C
1h；Polycondensation 3h discharges at 20Pa and 280 DEG C again, and the intrinsic viscosity of gained copolyester prepolymer body is 0.63dL/g；
(3) solid state polycondensation：The copolyester prepolymer of gained is a granulated into the particle of 1500/g sizes, Ran Houqu
500g particle crystallization pretreatment 2h under 100 DEG C and vacuum (80Pa), then carry out solid state polycondensation under 170 DEG C and 20Pa
8h；
(4) chain extending reaction：The product that step (3) is obtained is heated to 245 DEG C under nitrogen protection, treats sample all thawings
Afterwards, while adding terephthalic acid (TPA) and the 1.2mol% of CEPP summation 2,2 '-bis- (2- oxazolines) and 2,2 '-(1,3- is sub-
Phenyl) (mass ratio is 1 for the mixture of double (2- oxazolines):1), the 4.0mol% of terephthalic acid (TPA) and CEPP summation adjacent benzene
Dicarboxylic acid anhydride, chain extending reaction 10min is carried out under 270 DEG C, pressure 20Pa, atactic polyester composition A-7 is obtained.
A-7 composition the results are shown in Table 1, and wherein R comes from CEPP, R1Come from 2,2 '-bis- (2- oxazolines) and 2,2 '-
(1,3- phenylene) is double (2- oxazolines), R2Come from phthalic anhydride.
A-7 is subjected to performance test, test result is shown in Table 2.
Embodiment 8
This example demonstrates that the preparation method of the atactic polyester composition of the present invention.
(1) esterification：Terephthalic acid (TPA) 817g, propane diols 496g, 110g CEPP, 0.361g are added into reactor
Catalyst Sb2O3, stir, then vacuumize successively, be forced into 0.1MPa after logical nitrogen displacement gas reactor four times, delay
Slow be warming up at 260 DEG C carries out esterification, while pressure maintains 0.32MPa, the water of esterification generation is separated by still,
When the water of generation no longer changes substantially close to theoretical amount and system pressure, normal pressure is slowly depressurized to and by the remaining water band of system
Go out；
(2) copolyester prepolymer processed：By the product of esterification, the first prepolymerization reaction at pressure 200Pa and 280 DEG C
1h；Polycondensation 9h discharges at 20Pa and 280 DEG C again, and the intrinsic viscosity of gained copolyester prepolymer body is 0.85dL/g；
(3) solid state polycondensation：The copolyester prepolymer of gained is a granulated into the particle of 1000/g sizes, Ran Houqu
500g particle crystallization pretreatment 2h under 100 DEG C and vacuum (20Pa), then carry out solid state polycondensation under 200 DEG C and 20Pa
4h；
(4) chain extending reaction：The product that step (3) is obtained is heated to 265 DEG C under nitrogen protection, treats sample all thawings
Afterwards, at the same add the 1.0mol% of terephthalic acid (TPA) and CEPP summation 2,2 '-(1,3- phenylene) double (2- oxazolines) and
(mass ratio is 1 to the mixture of 2,2 '-(1,4- phenylenes) double (2- oxazolines):1), terephthalic acid (TPA) and CEPP summation
(mass ratio is 1 for 2.0mol% phthalic anhydride and the mixture of pyromellitic acid anhydride:1), in 270 DEG C, pressure 20Pa
Lower progress chain extending reaction 15min, obtains atactic polyester composition A-8.
A-8 composition the results are shown in Table 1, and wherein R comes from CEPP, R1Come from 2,2 '-(1,3- phenylenes) double (2- oxazoles
Quinoline) and 2,2 '-(Isosorbide-5-Nitrae-phenylene) is double (2- oxazolines), R2Come from phthalic anhydride and pyromellitic acid anhydride.
A-8 is subjected to performance test, test result is shown in Table 2.
Embodiment 9
This example demonstrates that the preparation method of the atactic polyester composition of the present invention.
(1) ester exchange reaction：Add into reactor dimethyl terephthalate (DMT) 953g, propane diols 512g, 165g
CEPP, 0.372g Sb2O3, stir, ester exchange reaction 0.5h then carried out at 165 DEG C；
(2) copolyester prepolymer processed：By the product of ester exchange reaction, the first prepolymerization reaction at pressure 200Pa and 260 DEG C
1h；Polycondensation 6h discharges at 20Pa and 280 DEG C again, and the intrinsic viscosity of gained copolyester prepolymer body is 0.76dL/g；
(3) solid state polycondensation：The copolyester prepolymer of gained is a granulated into the particle of 2500/g sizes, Ran Houqu
500g particle crystallization pretreatment 2h under 100 DEG C and vacuum (50Pa), then carry out solid state polycondensation under 180 DEG C and 20Pa
6h；
(4) chain extending reaction：The product that step (3) is obtained is heated to 265 DEG C under nitrogen protection, treats sample all thawings
Afterwards, while adding dimethyl terephthalate (DMT) and the 0.5mol% of CEPP summation 2,2 '-bis- (2- oxazolines) and 2,2 '-
(mass ratio is 1 to the mixture of (1,3- phenylenes) double (2- oxazolines):1), dimethyl terephthalate (DMT) and CEPP summation
5.0mol% pyromellitic acid anhydride, chain extending reaction 5min is carried out under 270 DEG C, pressure 20Pa, atactic polyester group is obtained
Compound A-9.
A-9 composition the results are shown in Table 1, and wherein R comes from CEPP, R1Come from 2,2 '-bis- (2- oxazolines) and 2,2 '-
(1,3- phenylene) is double (2- oxazolines), R2Come from pyromellitic acid anhydride.
A-9 is subjected to performance test, test result is shown in Table 2.
Embodiment 10
This example demonstrates that the preparation method of the flame retardant polyester composition of the present invention.
By the atactic polyester composition A-1 of 100 parts by weight, triphenyl phosphite (antioxidant), 1 weight of 0.02 parts by weight
The amount poly- carbodiimide of part (stabilizer) is mixed, then using double screw extruder as extrusion equipment, each section of temperature be 240 DEG C,
260 DEG C, 280 DEG C, 260 DEG C, 240 DEG C (head), screw speed 60r/min squeezed mixture under the conditions of pressure 0.1MPa
Go out granulation, obtain flame retardant polyester composition B-1.
B-1 is subjected to performance test, test result is shown in Table 1.
Embodiment 11
According to the method for embodiment 10, unlike, A-1 is substituted with A-2, flame retardant polyester composition B-2 is obtained.
B-2 is subjected to performance test, test result is shown in Table 1.
Comparative example 1
(1) ester exchange reaction：Added into reactor terephthalic acid (TPA) 817g, propane diols 496g, 110g CEPP,
0.361g, is stirred, and ester exchange reaction 3h is then carried out at 220 DEG C；
(2) copolyester prepolymer processed：By the product of ester exchange reaction, the first prepolymerization reaction at pressure 200Pa and 260 DEG C
1h；Polycondensation 4h discharges at 20Pa and 280 DEG C again, and the intrinsic viscosity of gained copolyester prepolymer body is 0.67dL/g.Obtain random
Polyester composition D-1.
D-1 structure composition measurement result is shown in Table 1, and wherein R comes from CEPP.
D-1 is subjected to performance test, test result is shown in Table 1.
Comparative example 2
According to the method for embodiment 10, unlike, A-1 is substituted with D-1, flame retardant polyester composition D-2 is obtained.
D-2 is subjected to performance test, test result is shown in Table 1.
Table 1
Table 2
The atactic polyester composition that the present invention is provided it can be seen from the data of above-described embodiment, comparative example and table 1 can
With less with reignition molten drop number in better flame resistance, especially vertical burn test result, copolyesters is improved
Resistance to molten drop.Obtain the atactic polyester composition and prepared by combining solid phase polycondensation with chemical chain extension method, gained macromolecule
Flame retardant polyester PTT is measured, its mechanical property obtains a certain degree of raising, on the basis of original fire resistance is kept, material
Resistance to melt-dropping property is greatly improved.
Claims (15)
1. a kind of atactic polyester composition, the atactic polyester composition includes：
(1) polyester A, the polyester A contains repeat unitWith repeat unit-R-
OCH2CH2CH2O-, wherein, R is the construction unit from phosphor-containing flame-proof monomer；
(2) polyester B, the polyester B contains structure-S-R1- S-and/or structure-S-R2—R1—R2- S-, wherein, R1
For the construction unit from chain extender, R2For the construction unit from anhydrides compound, S represents the polyester A；
Construction unit in the atactic polyester compositionMol ratio with R is 70：30~99：1；R1's
Content is construction unitWith 0.1~3mol% of construction unit R summation；R2Content be structure list
MemberWith 0.5~5mol% of construction unit R summation；
The intrinsic viscosity of the atactic polyester is 1.5dL/g~2.9dL/g.
2. atactic polyester composition according to claim 1, wherein, R structure isAt least one of；It is preferred that R structure is
3. atactic polyester composition according to claim 1, wherein, R1Structure be At least one of.
4. atactic polyester composition according to claim 1, wherein, R2Structure be
5. the atactic polyester composition according to any one in claim 1-4, wherein, the spy of the atactic polyester
Property glutinous number be 1.7dL/g~2.6dL/g.
6. the atactic polyester composition according to any one in claim 1-4, wherein, the oxygen of the atactic polyester
Index is 28.0~36.5；Vertical combustion grade according to atactic polyester described in UL-94 standards reaches at V-0 grades, second point
Show as just putting out from fire after combustion, molten drop number is not more than 6 drops.
7. a kind of method for preparing the atactic polyester composition in claim 1-6 described in any one, this method includes：
Terephthalic acid (TPA), propane diols and phosphor-containing flame-proof monomer are carried out ester by (1a) in the presence of nitrogen protection and esterification catalyst
Change reaction；Or
Dimethyl terephthalate (DMT), propane diols and phosphor-containing flame-proof monomer are carried out ester friendship by (1b) in the presence of ester exchange catalyst
Change reaction；
(2) ester exchange offspring that the esterification products or step (1b) obtained step (1a) are obtained, first carries out prepolymerization reaction,
Then polycondensation reaction is carried out, obtained copolyester prepolymer；
(3) copolyester prepolymer is first subjected to crystallization pretreatment, then carries out solid state polycondensation；
(4) chain extending reaction is carried out with chain extender, anhydrides compound after the product heats melting obtained step (3), is hindered
Fire atactic polyester.
8. method according to claim 7, wherein, the pressure of esterification described in step (1a) is 0.2~0.4MPa,
The temperature of the esterification is 200~280 DEG C, and the time of the esterification is 0.5~4h；Terephthalic acid (TPA) and described contain
The summation of phosphorus flame-retardant monomer and the mol ratio of propane diols are 1:1.2~1:2, terephthalic acid (TPA) rubs with the phosphor-containing flame-proof monomer
You are than being 70：30~99：1；The addition of the esterification catalyst is total throwing of terephthalic acid (TPA) and the phosphor-containing flame-proof monomer
0.01~0.1mol% of doses；The phosphor-containing flame-proof monomer is 2- carboxyethyl methylphosphinates, 2- carboxyethyl phenyl phosphinic acids
At least one of with the miscellaneous phenanthrene-succinic acid of the miscellaneous -10- phosphinylidynes of 9,10- dihydro-9-oxies, the esterification catalyst is Sb2O3。
9. method according to claim 7, wherein, the temperature of ester exchange reaction described in step (1b) is 160~220
DEG C, the time of the ester exchange reaction is 0.5~6h；The summation and third of dimethyl terephthalate (DMT) and the phosphor-containing flame-proof monomer
The mol ratio of glycol is 1:1.2~1:2, the mol ratio of dimethyl terephthalate (DMT) and the phosphor-containing flame-proof monomer is 70：30~
99：1；The addition of the ester exchange catalyst is the total amount of feeding of dimethyl terephthalate (DMT) and the phosphor-containing flame-proof monomer
0.01~0.1mol%；The phosphor-containing flame-proof monomer is 2- carboxyethyl methylphosphinates, 2- carboxyethyl phenyl phosphinic acids and 9,10-
At least one of miscellaneous phenanthrene-succinic acid of the miscellaneous -10- phosphinylidynes of dihydro-9-oxy, the ester exchange catalyst is Sb2O3。
10. method according to claim 7, wherein, in step (2), the pressure of the prepolymerization reaction for 100~
600Pa, the temperature of the prepolymerization reaction is 220~280 DEG C, and the time of the prepolymerization reaction is 1~3h；The polycondensation is anti-
The pressure answered is 10~200Pa, and the temperature of the polycondensation reaction is 260~300 DEG C, time of the polycondensation reaction for 0.5~
5h；The intrinsic viscosity of the copolyester prepolymer is 0.3dL/g~0.8dL/g.
11. method according to claim 7, wherein, by the copolyester prepolymer before crystallization pretreatment described in step (3)
Thing is granulated, and the size of obtained particle is 10~10000/g；The pressure of the crystallization pretreatment is 10~200Pa, institute
The temperature for stating crystallization pretreatment is 100~160 DEG C, and the time of the crystallization pretreatment is 0.5~4h；The solid state polycondensation
Pressure be 10~200Pa, the temperature of the solid state polycondensation is 160~225 DEG C, and the time of the solid state polycondensation is
4~36h.
12. the method described in 7 according to claim, wherein, heating melting described in step (4) is heats under nitrogen protection
To 190~270 DEG C；The addition of the chain extender is terephthalic acid (TPA) or dimethyl terephthalate (DMT) and the phosphor-containing flame-proof list
0.1~3mol% of the summation of body；The addition of the anhydrides compound is terephthalic acid (TPA) or dimethyl terephthalate (DMT)
With 0.5~5mol% of the summation of the phosphor-containing flame-proof monomer；The pressure of the chain extending reaction is 10~200Pa, the chain extension
The temperature of reaction is 260~300 DEG C, and the time of the chain extending reaction is 5~60min；The chain extender is 2,2 '-bis- (2- Evil
Oxazoline), at least one in 2,2 '-(1,4- phenylenes) double (2- oxazolines) and 2,2 '-(1,3- phenylenes) double (2- oxazolines)
Kind, the anhydrides compound is phthalic anhydride and/or pyromellitic acid anhydride.
13. a kind of flame retardant polyester composition, on the basis of the gross weight of said composition, said composition includes 98~99.96 weights
Measure % atactic polyester, 0.02~1 weight % antioxidant, 0.02~1 weight % stabilizers；Wherein, the random copolymerization
Ester is the atactic polyester composition described in any one in claim 1-6.
14. a kind of method of the flame retardant polyester composition prepared described in claim 13, this method is included the nothing of 100 parts by weight
Rule copolyesters, the antioxidant of 0.02~1 parts by weight, the stabilizer of 0.02~1 parts by weight mix and extruding pelletization, obtain institute
State flame retardant polyester composition.
15. method according to claim 14, wherein, the extruding pelletization is carried out in double screw extruder, and temperature is
240~280 DEG C, screw speed is 50~70r/min, and pressure is 0.05~0.15MPa.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020746A (en) * | 2007-03-19 | 2007-08-22 | 北京化工大学 | Prepn process of biodegradable polyamidoester |
| CN101434689A (en) * | 2007-11-13 | 2009-05-20 | 北京化工大学 | Method for preparing high molecular weight biodegradable polyester by combined chain extension |
| CN101974148A (en) * | 2010-09-17 | 2011-02-16 | 四川大学 | High-molecular weight phosphorous flame retardant random copolyester and preparation method thereof |
| CN102030894A (en) * | 2010-12-01 | 2011-04-27 | 四川大学 | Phosphoric terephthalic acid propylene glycol ester antiflaming block copolyester and preparation method thereof |
| CN103709679A (en) * | 2013-11-29 | 2014-04-09 | 金发科技股份有限公司 | Modified aliphatic-aromatic copolyester and its preparation method and use |
| CN104119538A (en) * | 2013-04-24 | 2014-10-29 | 东丽纤维研究所（中国）有限公司 | Flame retardant and preparation method thereof, and flame-retardant polyester and application thereof |
-
2016
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020746A (en) * | 2007-03-19 | 2007-08-22 | 北京化工大学 | Prepn process of biodegradable polyamidoester |
| CN101434689A (en) * | 2007-11-13 | 2009-05-20 | 北京化工大学 | Method for preparing high molecular weight biodegradable polyester by combined chain extension |
| CN101974148A (en) * | 2010-09-17 | 2011-02-16 | 四川大学 | High-molecular weight phosphorous flame retardant random copolyester and preparation method thereof |
| CN102030894A (en) * | 2010-12-01 | 2011-04-27 | 四川大学 | Phosphoric terephthalic acid propylene glycol ester antiflaming block copolyester and preparation method thereof |
| CN104119538A (en) * | 2013-04-24 | 2014-10-29 | 东丽纤维研究所（中国）有限公司 | Flame retardant and preparation method thereof, and flame-retardant polyester and application thereof |
| CN103709679A (en) * | 2013-11-29 | 2014-04-09 | 金发科技股份有限公司 | Modified aliphatic-aromatic copolyester and its preparation method and use |
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