CN105085874A - Polyester composition, and preparation method and use thereof - Google Patents
Polyester composition, and preparation method and use thereof Download PDFInfo
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- CN105085874A CN105085874A CN201410298034.3A CN201410298034A CN105085874A CN 105085874 A CN105085874 A CN 105085874A CN 201410298034 A CN201410298034 A CN 201410298034A CN 105085874 A CN105085874 A CN 105085874A
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Abstract
The invention discloses a polyester composition with low content of annular trimer, and a preparation method thereof. The polyester composition contains 1-100ppm of sulfur element and 1-100ppm of antimony element. The content of the annular trimer in the obtained polyester composition is 0.2-0.8wt%, the regeneration speed of the annular trimer in the polyester composition is very low, and the generation speed of the annular trimer in the process of melting at 300DEG C in nitrogen atmosphere is 0.001-0.015wt%/min, so the polyester composition can be used to films and other polyester products.
Description
Technical field
The present invention relates to a kind of polymer blend and manufacture method thereof and purposes, more specifically, relate to a kind of polymer blend of low cyclic trimer content.
Background technology
Polyester, particularly polyethylene terephthalate (PET), polytrimethylene terephthalate (PPT), polybutylene terephthalate (PBT), because of its excellent mechanical characteristics, chemical property, dimensional stability and the transparency, applied widely in fields such as fiber, film, resins.
Usually, in the polymerization process of polyester, inevitably produce co-product oligomeric thing, its amount generally accounts for about the 2wt% of polyester total amount.Said oligopolymer mainly refers to polymerization single polymerization monomer, dimer, cyclic trimer etc., wherein accounts for the overwhelming majority with cyclic trimer again, accounts for about the 1wt% of polyester total amount.Oligopolymer can pollute some assemblies on equipment such as mould, venting port, spinning jet in the process of masking or spinning, can cause the frequency gets higher of equipment cleaning, replacing like this, reduces production efficiency.
In addition, by product cyclic trimer also can separate out formation white foreign matter in polyester product such as the surfaces such as film, thin plate, bottle after shaping, causes the problems such as products formed is defective, Quality Down.When these polyester products are used for packaging material for food, cyclic trimer can enter the food in packaging, pollutes food.
Due to the existence of the problems referred to above, current those skilled in the art propose the method that some reduce cyclic trimer content in polyester.One of method, as Chinese patent CN101747531 discloses composition and the polymer blend of a kind of minimizing/suppression polyester oligomer content, this patent application removes a part of cyclic trimer by polyester and sequestrant, boron salt, amino-complex are carried out mixing method.But the polyester obtained by the method sequestrant, boron salt etc. in later stage high temperature process treating processes are easily separated out, and the Regeneration DeGrain to specific oligopolymer cyclic trimer.Method two, by the polyester that obtains through solid state polymerization or thermal treatment thus reduce the content of cyclic trimer in polyester under an inert gas, but this method can only reduce the content of initial cyclic trimer in polyester, can not solve the problem that it regenerates in follow-up high temperature process environment.The method also had such as Chinese patent CN102421820A discloses poly-(propylene glycol ester terephthalate) pellet of a kind of oligopolymer minimizing, its preparation method with an organic solvent extracts from polyester and removes cyclic trimer, this method follow-up needs reclaims a large amount of organic solvent, cost is higher, troublesome poeration, is industrially difficult to perform.
Summary of the invention
The object of the present invention is to provide a kind of cyclic trimer content low, and the good polymer blend of cyclic trimer melting Regeneration effect and manufacture method thereof.
There is reversible reaction between linear high polymer and cyclic trimer, for PET, cyclic trimer is wherein formed by two kinds of monomers (diprotic acid/diester and dibasic alcohol) of polyester raw material.
At a certain temperature, in polyester, the content of cyclic trimer can reach a balance saturation value, after reaching balance saturation value, can not increase.And temperature is higher, this balance saturation value is larger, and also namely the content of cyclic trimer is larger.
Although the content of cyclic trimer declines a bit in the polyester after the method for cyclic trimer can make initial treatment in general reduction polyester, but as discussed above, the reaction generating cyclic trimer is thermo-negative reaction, temperature when the follow-up use of polyester is as made fiber, film etc. will inevitably higher than the fusing point of polyester, reaction now can be carried out, until reach balance towards the direction generating cyclic trimer.Polymer blend of the present invention under nitrogen atmosphere 300 DEG C of meltings time cyclic trimer formation speed be 0.001 ~ 0.015wt%/min, by controlling the manufacture method of polymer blend, better, this formation speed can be controlled within the scope of 0.002 ~ 0.01wt%/min.Also namely, the present invention is to provide a kind of polymer blend solving cyclic trimer regeneration issues in subsequent high temperature processing environment.
Usually a certain amount of catalyzer can be added in the polymerization if antimony catalyst is to meet the reactive behavior needed for polyreaction, but existing catalyzer all exists a not enough place, namely the membership that adds of a large amount of catalyzer causes the reproduction speed of cyclic trimer in polyester very high.Therefore technical program of the present invention lies in, in order to ensure the catalytic activity providing polyreaction enough while the existing catalyst levels of reduction, adding sulfonic acid catalyst.Sulfonic acid catalyst add the reproduction speed that not only can not increase cyclic trimer, simultaneously and antimony catalyst and use, the activity of antimony can be reduced to a certain extent, the reproduction speed of reduction cyclic trimer.
Technical scheme of the present invention:
A kind of polymer blend, containing relative to polymer blend total amount in this polymer blend is the element sulphur of 1 ~ 100ppm, and is the antimony element of 1 ~ 100ppm relative to the total amount of polymer blend; In this polymer blend, the content of cyclic trimer is 0.2 ~ 0.8wt%, and the content of preferred cyclic trimer is 0.2 ~ 0.6wt%, and during 300 DEG C of meltings, in polymer blend, the formation speed of cyclic trimer is 0.001 ~ 0.015wt%/min under a nitrogen.
Above-mentioned element sulphur comes from catalyzer sulfoacid compound.Having no particular limits catalyzer sulfoacid compound in the present invention, can be containing one or more sulfonic acid group (-SO in molecule
3a) unitary or polyhydric aliphatic race or aromatic azochlorosulfonate acid compound.Because in sulfoacid compound, the number of sulfonic acid group is more, larger on the impact of the polymer blend thermotolerance generated, therefore preferably contain aliphatic sulfonic compound or the aromatic azochlorosulfonate acid compound of unitary or dibasic sulfoacid group in the present invention.
The molecular formula of described unitary sulfoacid compound is R
1-SO
3a, R in formula
1for the aromatic alkyl of the alkylidene group of carbonatoms 1 ~ 20, the cycloalkyl of carbonatoms 3 ~ 20 or carbonatoms 6 ~ 20, segment R
1in can contain cycloalkyl, amino, hydroxyl, alkoxyl group, carboxyl, ester group, acyl group, aldehyde radical, amide group, itrile group, nitro or halogen group; In formula, A is protium or alkali metal, and alkali metal can be lithium, sodium, potassium etc.
The molecular formula of described dibasic sulfoacid compound is AO
3s-R
2-SO
3a, R in formula
2for the aromatic alkyl of the alkylidene group of carbonatoms 3 ~ 20, the cycloalkyl of carbonatoms 3 ~ 20 or carbonatoms 6 ~ 20; In formula, A is protium or alkali metal, and alkali metal can be lithium, sodium, potassium etc.
What the aliphatic sulfonic compound of unitary of the present invention and dibasic sulfoacid group or aromatics can be enumerated has methylsulfonic acid, ethyl sulfonic acid, propanesulfonic acid, fourth sulfonic acid, penta sulfonic acid, heptan sulfonic acid, pungent sulfonic acid, the ninth of the ten Heavenly Stems sulfonic acid, certain herbaceous plants with big flowers sulfonic acid, undecane sulfonic acid, dodecane sulfonic acid, toluene sulfonic acide, ethyl phenenyl azochlorosulfonate acid, propyl benzenesulfonic acid, naphthene sulfonic acid, Witco 1298 Soft Acid, cyclamic acid, cyclohexyl-ethyl sulfonic acid, methylene-sulfonic acid, ethionic acid, third disulfonic acid, fourth disulfonic acid, penta disulfonic acid, heptan disulfonic acid, pungent disulfonic acid, the ninth of the ten Heavenly Stems disulfonic acid, certain herbaceous plants with big flowers disulfonic acid, 1, 11-undecane disulfonic acid, 1, 12-dodecane disulfonic acid, 1, 20-eicosane disulfonic acid, dodecyl diphenyl oxide disulfonic acid, cyclohexyl ethionic acid, cyclohexyl fourth disulfonic acid, benzene disulfonic acid, naphthalene disulfonic acid, between benzene disulfonic acid, methanesulfonic sodium, benzene methanesulfonic acid potassium, sodium 1,3-benzenedisulfate.
In the above-mentioned sulfoacid compound enumerated, because the reactive behavior of methylsulfonic acid, benzene methanesulfonic acid, dodecylbenzene sulphur, a benzene disulfonic acid, methanesulfonic sodium, benzene methanesulfonic acid potassium, sodium 1,3-benzenedisulfate is high, catalytic effect is better, one or more therefore in the present invention more preferably in them.
Relative polymer blend total amount, wherein sulfur content is 1 ~ 100ppm, when sulfur content very little time, polymerization activity is inadequate; When sulfur content is too large, the impact of the acidity produced due to sulfonic acid group can cause the DEG of polymkeric substance to rise, and the hydrolytic resistance of polymer blend reduces.Usual DEG content can affect the thermotolerance of polymer blend and polyester article, the thermotolerance of the content of DEG more superpolyester goods is poorer, the thermotolerance of the content of DEG more oligomer ester goods is better, in order to make polyester film goods have excellent thermotolerance, the DEG content of general polymer blend controls at below 2wt%.When sulfur content is greater than 100ppm formula, the DEG content of polymer blend is greater than 2wt%, and polymer heat-resistant is poor.In order to obtain cyclic trimer content lower and under a nitrogen 300 DEG C of meltings time polymer blend in the lower polymer blend of the formation speed of cyclic trimer, in preferred polyester composition, the content of element sulphur is 2 ~ 50ppm.
Also containing the antimony element relative to polymer blend total amount 1 ~ 100ppm in polymer blend of the present invention, when antimony element content is lower than 1ppm, the activity of solid state polymerization is inadequate, and in polymer blend, the content of cyclic trimer can be higher, higher than more than 0.8wt%; When antimony element content is higher than 100ppm, can remain a large amount of metallic element in polymer blend, during 300 DEG C of meltings, in polymer blend, the formation speed of cyclic trimer can be very large under a nitrogen.Preferred polyester composition antimony element content is 2 ~ 60ppm.
Sulfoacid compound can be added as catalyzer in the polymerization process of polymer blend of the present invention, when the sulfoacid compound added is when in molecular formula, A is the compound of protium, this compound can cause whole polymer to be tied to form acidity, the DEG content in polymer blend can be caused to raise, thermotolerance is deteriorated, cause the terminal carboxyl(group) of polymer blend to increase, hydrolytic resistance also can be deteriorated to a certain extent simultaneously.Therefore, also preferably alkali metal is contained in polymer blend of the present invention.Alkali metal can regulate the pH value of whole system, reduces the end COOH content of polymer blend, improves the hydrolytic resistance of polymer blend further.But in polymer blend, the content of alkali metal is unsuitable excessive, otherwise the thermotolerance of polymer blend can be caused to be deteriorated.In the present invention, in preferred polyester composition, the content of alkali metal is 1 ~ 400ppm.Described alkali metal can be lithium, sodium, potassium, caesium etc., one or more wherein in preferred lithium, sodium or potassium, uses rear polymer blend thermotolerance better.
In preferred polyester composition, the mol ratio of element sulphur and alkali metal is 0.2 ~ 1.5.
Above-mentioned alkali metal comes from sulfoacid compound or alkali metal compound.Alkali metal compound of the present invention refer to except sulfoacid compound other contain the compound of alkali metal, as acetic acid an alkali metal salt, alkali metal citrates, oxalic acid an alkali metal salt, alkali metal persulfates etc.That specifically can enumerate has Lithium Acetate, sodium-acetate, Potassium ethanoate, cesium acetate, sodium oxalate, Tripotassium Citrate, sodium sulfate, potassium oxalate etc.
The invention also discloses a kind of manufacture method of polymer blend, mainly comprise the prepolymerization reaction that aromatic binary carboxylic acid or its esterified derivative and aliphatic dihydroxy alcohol are obtained by reacting molecular weight polymers, with the polycondensation being obtained polyester by molecular weight polymers polymerization, catalyzer sulfoacid compound and antimony compounds is added in the polycondensation stage, wherein the addition of sulfoacid compound accounts for 2 ~ 200ppm of polymer blend in element sulphur, preferably 4 ~ 100ppm, the addition of antimony compounds accounts for 1 ~ 100ppm of polymer blend, preferably 2 ~ 60ppm in antimony element; And polyester polycondensation obtained again carries out solid state polymerization obtains polymer blend.
In the present invention, catalyzer sulfoacid compound is had no particular limits, preferably contain aliphatic sulfonic compound or the aromatics of unitary and dibasic sulfoacid group.
The molecular formula of described unitary sulfoacid compound is R
1-SO
3a, R in formula
1for the aromatic alkyl of the alkylidene group of carbonatoms 1 ~ 20, the cycloalkyl of carbonatoms 3 ~ 20 or carbonatoms 6 ~ 20, segment R
1in can contain cycloalkyl, amino, hydroxyl, alkoxyl group, carboxyl, ester group, acyl group, aldehyde radical, amide group, itrile group, nitro or halogen group; In formula, A is protium or alkali metal, and alkali metal can be lithium, sodium, potassium etc.
The molecular formula of described dibasic sulfoacid compound is AO
3s-R
2-SO
3a, R in formula
2for the aromatic alkyl of the alkylidene group of carbonatoms 3 ~ 20, the cycloalkyl of carbonatoms 3 ~ 20 or carbonatoms 6 ~ 20; In formula, A is protium or alkali metal, and alkali metal can be lithium, sodium, potassium etc.
What the aliphatic sulfonic compound of unitary of the present invention and dibasic sulfoacid group or aromatics can be enumerated has methylsulfonic acid, ethyl sulfonic acid, propanesulfonic acid, fourth sulfonic acid, penta sulfonic acid, heptan sulfonic acid, pungent sulfonic acid, the ninth of the ten Heavenly Stems sulfonic acid, certain herbaceous plants with big flowers sulfonic acid, undecane sulfonic acid, dodecane sulfonic acid, toluene sulfonic acide, ethyl phenenyl azochlorosulfonate acid, propyl benzenesulfonic acid, naphthene sulfonic acid, Witco 1298 Soft Acid, cyclamic acid, cyclohexyl-ethyl sulfonic acid, methylene-sulfonic acid, ethionic acid, third disulfonic acid, fourth disulfonic acid, penta disulfonic acid, heptan disulfonic acid, pungent disulfonic acid, the ninth of the ten Heavenly Stems disulfonic acid, certain herbaceous plants with big flowers disulfonic acid, 1, 11-undecane disulfonic acid, 1, 12-dodecane disulfonic acid, 1, 20-eicosane disulfonic acid, dodecyl diphenyl oxide disulfonic acid, cyclohexyl ethionic acid, cyclohexyl fourth disulfonic acid, benzene disulfonic acid, naphthalene disulfonic acid, between benzene disulfonic acid, methanesulfonic sodium, benzene methanesulfonic acid potassium, sodium 1,3-benzenedisulfate etc.
In the above-mentioned sulfoacid compound enumerated, because the reactive behavior of methylsulfonic acid, benzene methanesulfonic acid, Witco 1298 Soft Acid, a benzene disulfonic acid, methanesulfonic sodium, benzene methanesulfonic acid potassium and sodium 1,3-benzenedisulfate is high, catalytic effect is better, one or more therefore in the present invention more preferably in them.
The manufacture method of polymer blend disclosed in the invention described above, preferably adds alkali metal compound in the polycondensation stage, makes the content of alkali metal in polymer blend be 1 ~ 400ppm.
Described alkali metal compound can be acetic acid an alkali metal salt, alkali metal citrates, oxalic acid an alkali metal salt, alkali metal persulfates etc.So concrete that can be Lithium Acetate, lithium oxalate, Lithium Citrate de, Lithium Sulphate, Potassium ethanoate, potassium oxalate, Tripotassium Citrate, potassium sulfate, sodium-acetate, sodium oxalate, Trisodium Citrate, sodium sulfate etc., wherein preferred Lithium Acetate, Potassium ethanoate, sodium-acetate.
Catalyzer antimony compounds of the present invention is not particularly limited, can be inorganic antimony compounds or organo-antimony compound, preferred antimonous oxide, antimony peroxide etc., wherein most preferably antimonous oxide.Carry out can also adding stablizer phosphorus compound in polymerization process at molecular weight polymers, can be trivalent or phosphoric organic or inorganic compound, that simply enumerates has phosphoric acid, trimethyl phosphite 99, triphenylphosphate etc.
Solid state polymerization of the present invention be polyester slice under the dry condition, at the temperature of 100 ~ 180 DEG C heat 0.5 ~ 8 hour preparation crystallization after; Again the temperature of 190 ~ 235 DEG C, under nitrogen circulation or under reduced pressure, solid state polymerization 1 ~ 50 hour.
Cyclic trimer content in polymer blend of the present invention is low, during 300 DEG C of meltings, the Regeneration of cyclic trimer is effective under nitrogen atmosphere, and the manufacture method industry of this polymer blend is simple, easy to operate, processing cost is low, gained polymer blend excellent heat resistance, can be used for film preparation.
The following describes measuring method and the evaluation method of indices of the present invention.
(1) mensuration of cyclic trimer
Adopt liquid chromatography marker method, accurate weighing polymer blend 0.1000g, adding ortho chloro phenol dissolves completely at 150 DEG C to polymer blend, then cool, add the inner mark solution of p-terphenyl/methylene dichloride, adding methanol solution again makes polyester separate out, and gets the mensuration that solution carries out oligopolymer after centrifugation.
(2) carboxyl-content (COOH)
Adopt optics titration measuring, polyester slice is dissolved in the mixed solution of ortho-methyl phenol and chloroform (weight ratio 70:30), adds bromthymol blue indicator, then carry out titration with in the ethanolic soln of the potassium hydroxide of 0.05N.
(3) limiting viscosity (IV)
Polyester slice 0.8g is dissolved in 10ml ortho-chloro phenol solution, tests with the automatic viscosity test set (VTS-032UC) of clutch society under 25 degree.
(4) formation speed of cyclic trimer
Getting appropriate polymer blend, to test its cyclic trimer content be C
3(0) (wt%), the content then this polymer blend being tested at 300 DEG C of temperature its cyclic trimer after thermal treatment 30min is C
3(30) (wt%), reproduction speed (wt%/min)=[C of cyclic trimer
3(30)-C
3(0)]/30.
(5) Sb element, phosphoric, alkali metal (lithium, sodium, potassium) measure
5g polymer blend after melting, is pressed into tabular with hydropress in thermal station, is then tested with fluorescent X-ray elemental analyser.
(6) element sulphur measures
Through AQF-100(Mitsubishi chemistry system) combustion method pre-treatment, by IC(ICS-2000, Dionex) quantitative assay.
(7) glycol ether (DEG) assay
Using monoethanolamine as solvent, dissolve with 1,6-Yi bis-Chun ∕ methanol mixed post-heating, then add methyl alcohol ultrasonic cleaner and clean 10 minutes.Then add acid and carry out neutralizing treatment, after filtration, use gas chromatograph (Shimadzu Corp GC-14A) to measure filtrate.
(8) hydrolytic resistance (COOH)
The polymer blend weighing 3.2g is cut into slices in small test tube, puts into hydrolysis instrument, takes out the COOH of test section under 150 DEG C of water vapour after processing 4h
hydrolyzable,
COOH=COOH
hydrolyzable.-COOH
before hydrolyzable .
Embodiment
By from the embodiment enumerated and comparative example, advantage of the present invention is described in detail below.The present invention has more than and is limited to following embodiment.
Part of compounds involved in embodiment is as follows:
(1) terephthalic acid (PTA): grade is high purity, raises sub-petrochemical industry;
(2) ethylene glycol (EG): BASF AG;
(3) antimonous oxide (AO): this Jing of Mining Co., Ltd.;
(4) antimony glycol (AG): Yangzhou Yang Tai Chemical Co., Ltd.
(5) phosphoric acid (PA): Shanghai Hao Hua Chemical Co., Ltd.;
(6) methylsulfonic acid: Aladdin reagent;
(7) Phenylsulfonic acid: Aladdin reagent;
(8) benzene disulfonic acid between: Aladdin reagent;
(9) fourth disulfonic acid: Aladdin reagent;
(10) dodecyl diphenyl oxide disulfonic acid: Aladdin reagent;
(11) 1,3,5-naphthalene trisulfonic acids: Aladdin reagent;
(12) Lithium Acetate: Aladdin reagent;
(13) Potassium ethanoate: Aladdin reagent;
(14) methanesulfonic sodium: Aladdin reagent;
(15) benzene methanesulfonic acid potassium: Aladdin reagent;
(16) sodium 1,3-benzenedisulfate: Aladdin reagent;
(17) cesium acetate: Aladdin reagent.
Embodiment 1
At the temperature of 250 DEG C, by the PTA of 166 weight parts, the EG of 71.3 weight parts adds reaction kettle of the esterification, carries out esterification at ambient pressure, and upon completion of the ester reaction, esterification temperature in the kettle is 250 DEG C, and fractionation water outlet obtains molecular weight polymers.
The catalyst methanesulfonic acid being equivalent to polymer blend 10ppm in element sulphur is added in gained molecular weight polymers, antimony element meter is equivalent to the catalyst A O of polymer blend weight 50ppm, the Potassium ethanoate of polymer blend weight 16ppm is equivalent in basic metal potassium element, the stablizer PA of polymer blend weight 20ppm is equivalent in phosphoric, start decompression after 5min, heat up, pressure was decompressed to about 300Pa through 1 hour, and temperature rose to 290 DEG C after 1.5 hours; At the end of polycondensation, reacting kettle inner pressure is about 200Pa.By the polymkeric substance obtained again at 220 DEG C solid state polymerization within 18 hours, obtain polymer blend.By polymer blend melting at 300 DEG C, calculate the reproduction speed of cyclic trimer according to the cyclic trimer gauge before and after melting.Concrete physical property sees attached list.
Embodiment 2
At the temperature of 250 DEG C, by the PTA of 166 weight parts, the EG of 71.3 weight parts adds reaction kettle of the esterification, carries out esterification at ambient pressure, and upon completion of the ester reaction, esterification temperature in the kettle is 250 DEG C, and fractionation water outlet obtains molecular weight polymers.
The catalyst methanesulfonic acid sodium being equivalent to polymer blend 20ppm in element sulphur is added in gained molecular weight polymers, antimony element meter is equivalent to the catalyst A O of polymer blend weight 2ppm, the stablizer PA of polymer blend weight 10ppm is equivalent in phosphoric, start decompression after 5min, heat up, pressure was decompressed to about 300Pa through 1 hour, and temperature rose to 290 DEG C after 1.5 hours; At the end of polycondensation, reacting kettle inner pressure is about 200Pa.By the polymkeric substance obtained again at 230 DEG C solid state polymerization within 14 hours, obtain polymer blend.By polymer blend melting under 300 degree, calculate the reproduction speed of cyclic trimer according to the cyclic trimer gauge before and after melting.Concrete physical property sees attached list.
Embodiment 3
At the temperature of 250 DEG C, by the PTA of 166 weight parts, the EG of 71.3 weight parts adds reaction kettle of the esterification, carries out esterification at ambient pressure, and upon completion of the ester reaction, esterification temperature in the kettle is 250 DEG C, and fractionation water outlet obtains molecular weight polymers.
The catalyzer benzene methanesulfonic acid potassium being equivalent to polymer blend 40ppm in element sulphur is added in gained molecular weight polymers, antimony element meter is equivalent to the catalyst A O of polymer blend weight 50ppm, the stablizer PA of polymer blend weight 20ppm is equivalent in phosphoric, start decompression after 5min, heat up, pressure was decompressed to about 300Pa through 1 hour, and temperature rose to 290 DEG C after 1.5 hours; At the end of polycondensation, reacting kettle inner pressure is about 200Pa.By the polymkeric substance obtained again at 210 DEG C solid state polymerization within 24 hours, obtain polymer blend.By polymer blend melting under 300 degree, calculate the reproduction speed of cyclic trimer according to the cyclic trimer gauge before and after melting.Concrete physical property sees attached list.
Embodiment 4
At the temperature of 250 DEG C, by the PTA of 166 weight parts, the EG of 71.3 weight parts adds reaction kettle of the esterification, carries out esterification at ambient pressure, and upon completion of the ester reaction, esterification temperature in the kettle is 250 DEG C, and fractionation water outlet obtains molecular weight polymers.
The catalyzer benzene methanesulfonic acid being equivalent to polymer blend 50ppm in element sulphur is added in gained molecular weight polymers, antimony element meter is equivalent to the catalyst A O of polymer blend weight 3ppm, the sodium-acetate of polymer blend weight 40ppm is equivalent in alkali metallic sodium element, the stabilizer T EPA of polymer blend weight 10ppm is equivalent in phosphoric, start decompression after 5min, heat up, pressure was decompressed to about 300Pa through 1 hour, and temperature rose to 290 DEG C after 1.5 hours; At the end of polycondensation, reacting kettle inner pressure is about 200Pa.By the polymkeric substance obtained again at 230 DEG C solid state polymerization within 14 hours, obtain polymer blend.By polymer blend melting under 300 degree, calculate the reproduction speed of cyclic trimer according to the cyclic trimer gauge before and after melting.Concrete physical property sees attached list.
Embodiment 5
At the temperature of 250 DEG C, by the PTA of 166 weight parts, the EG of 71.3 weight parts adds reaction kettle of the esterification, carries out esterification at ambient pressure, and upon completion of the ester reaction, esterification temperature in the kettle is 250 DEG C, and fractionation water outlet obtains molecular weight polymers.
The catalyzer sodium 1,3-benzenedisulfate being equivalent to polymer blend 25ppm in element sulphur is added in gained molecular weight polymers, antimony element meter is equivalent to the catalyst A O of polymer blend weight 50ppm, the stabilizer T EPA of polymer blend weight 30ppm is equivalent in phosphoric, start decompression after 5min, heat up, pressure was decompressed to about 300Pa through 1 hour, and temperature rose to 290 DEG C after 1.5 hours; At the end of polycondensation, reacting kettle inner pressure is about 200Pa.By the polymkeric substance obtained again at 230 DEG C solid state polymerization within 14 hours, obtain polymer blend.By polymer blend melting under 300 degree, calculate the reproduction speed of cyclic trimer according to the cyclic trimer gauge before and after melting.Concrete physical property sees attached list.
Embodiment 6
At the temperature of 250 DEG C, by the PTA of 166 weight parts, the EG of 71.3 weight parts adds reaction kettle of the esterification, carries out esterification at ambient pressure, and upon completion of the ester reaction, esterification temperature in the kettle is 250 DEG C, and fractionation water outlet obtains molecular weight polymers.
Add in gained molecular weight polymers be equivalent to polymer blend 10ppm in element sulphur catalyzer between benzene disulfonic acid, antimony element meter is equivalent to the catalyst A G of polymer blend weight 50ppm, the Lithium Acetate of polymer blend weight 4ppm is equivalent in alkali metal lithium element, the stabilizer T EPA of polymer blend weight 25ppm is equivalent in phosphoric, start decompression after 5min, heat up, pressure was decompressed to about 300Pa through 1 hour, and temperature rose to 290 DEG C after 1.5 hours; At the end of polycondensation, reacting kettle inner pressure is about 200Pa.By the polymkeric substance obtained again at 230 DEG C solid state polymerization within 14 hours, obtain polymer blend.By polymer blend melting under 300 degree, calculate the reproduction speed of cyclic trimer according to the cyclic trimer gauge before and after melting.Concrete physical property sees attached list.
Embodiment 7
At the temperature of 250 DEG C, by the PTA of 166 weight parts, the EG of 71.3 weight parts adds reaction kettle of the esterification, carries out esterification at ambient pressure, and upon completion of the ester reaction, esterification temperature in the kettle is 250 DEG C, and fractionation water outlet obtains molecular weight polymers.
The catalyst methanesulfonic acid being equivalent to polymer blend 40ppm in element sulphur is added in gained molecular weight polymers, antimony element meter is equivalent to the catalyst A G of polymer blend weight 40ppm, the cesium acetate of polymer blend weight 300ppm is equivalent in basic metal cesium element, the stabilizer TMP A of polymer blend weight 35ppm is equivalent in phosphoric, start decompression after 5min, heat up, pressure was decompressed to about 300Pa through 1 hour, and temperature rose to 290 DEG C after 1.5 hours; At the end of polycondensation, reacting kettle inner pressure is about 200Pa.By the polymkeric substance obtained again at 210 DEG C solid state polymerization within 14 hours, obtain polymer blend.By polymer blend melting under 300 degree, calculate the reproduction speed of cyclic trimer according to the cyclic trimer gauge before and after melting.Concrete physical property sees attached list.
Embodiment 8
At the temperature of 250 DEG C, by the PTA of 166 weight parts, the EG of 71.3 weight parts adds reaction kettle of the esterification, carries out esterification at ambient pressure, and upon completion of the ester reaction, esterification temperature in the kettle is 250 DEG C, and fractionation water outlet obtains molecular weight polymers.
The catalyst methanesulfonic acid being equivalent to polymer blend 30ppm in element sulphur is added in gained molecular weight polymers, antimony element meter is equivalent to the catalyst A G of polymer blend weight 40ppm, the stabilizer TMP A of polymer blend weight 50ppm is equivalent in phosphoric, start decompression after 5min, heat up, pressure was decompressed to about 300Pa through 1 hour, and temperature rose to 290 DEG C after 1.5 hours; At the end of polycondensation, reacting kettle inner pressure is about 200Pa.By the polymkeric substance obtained again at 230 DEG C solid state polymerization within 14 hours, obtain polymer blend.By polymer blend melting under 300 degree, calculate the reproduction speed of cyclic trimer according to the cyclic trimer gauge before and after melting.Concrete physical property sees attached list.
Embodiment 9
At the temperature of 250 DEG C, by the PTA of 166 weight parts, the EG of 71.3 weight parts adds reaction kettle of the esterification, carries out esterification at ambient pressure, and upon completion of the ester reaction, esterification temperature in the kettle is 250 DEG C, and fractionation water outlet obtains molecular weight polymers.
The catalyzer benzene methanesulfonic acid being equivalent to polymer blend 50ppm in element sulphur is added in gained molecular weight polymers, antimony element meter is equivalent to the catalyst A G of polymer blend weight 100ppm, the stabilizer TMP A of polymer blend weight 10ppm is equivalent in phosphoric, start decompression after 5min, heat up, pressure was decompressed to about 300Pa through 1 hour, and temperature rose to 290 DEG C after 1.5 hours; At the end of polycondensation, reacting kettle inner pressure is about 200Pa.By the polymkeric substance obtained again at 220 DEG C solid state polymerization within 16 hours, obtain polymer blend.By polymer blend melting under 300 degree, calculate the reproduction speed of cyclic trimer according to the cyclic trimer gauge before and after melting.Concrete physical property sees attached list.
Embodiment 10
At the temperature of 250 DEG C, by the PTA of 166 weight parts, the EG of 71.3 weight parts adds reaction kettle of the esterification, carries out esterification at ambient pressure, and upon completion of the ester reaction, esterification temperature in the kettle is 250 DEG C, and fractionation water outlet obtains molecular weight polymers.
The catalyzer benzene methanesulfonic acid being equivalent to polymer blend 120ppm in element sulphur is added in gained molecular weight polymers, antimony element meter is equivalent to the catalyst A G of polymer blend weight 40ppm, the stabilizer T EPA of polymer blend weight 10ppm is equivalent in phosphoric, start decompression after 5min, heat up, pressure was decompressed to about 300Pa through 1 hour, and temperature rose to 290 DEG C after 1.5 hours; At the end of polycondensation, reacting kettle inner pressure is about 200Pa.By the polymkeric substance obtained again at 230 DEG C solid state polymerization within 14 hours, obtain polymer blend.By polymer blend melting under 300 degree, calculate the reproduction speed of cyclic trimer according to the cyclic trimer gauge before and after melting.Concrete physical property sees attached list.
Embodiment 11
At the temperature of 250 DEG C, by the PTA of 166 weight parts, the EG of 71.3 weight parts adds reaction kettle of the esterification, carries out esterification at ambient pressure, and upon completion of the ester reaction, esterification temperature in the kettle is 250 DEG C, and fractionation water outlet obtains molecular weight polymers.
The catalyzer dodecyl diphenyl oxide disulfonic acid being equivalent to polymer blend 50ppm in element sulphur is added in gained molecular weight polymers, antimony element meter is equivalent to the catalyst A G of polymer blend weight 40ppm, the stabilizer T EPA of polymer blend weight 10ppm is equivalent in phosphoric, start decompression after 5min, heat up, pressure was decompressed to about 300Pa through 1 hour, and temperature rose to 290 DEG C after 1.5 hours; At the end of polycondensation, reacting kettle inner pressure is about 200Pa.By the polymkeric substance obtained again at 230 DEG C solid state polymerization within 14 hours, obtain polymer blend.By polymer blend melting under 300 degree, calculate the reproduction speed of cyclic trimer according to the cyclic trimer gauge before and after melting.Concrete physical property sees attached list.
Embodiment 12
At the temperature of 250 DEG C, by the PTA of 166 weight parts, the EG of 71.3 weight parts adds reaction kettle of the esterification, carries out esterification at ambient pressure, and upon completion of the ester reaction, esterification temperature in the kettle is 250 DEG C, and fractionation water outlet obtains molecular weight polymers.
The catalyzer 1 being equivalent to polymer blend 50ppm in element sulphur is added in gained molecular weight polymers, 3,5-naphthalene trisulfonic acid, antimony element meter is equivalent to the catalyst A G of polymer blend weight 40ppm, the stabilizer T EPA of polymer blend weight 10ppm is equivalent in phosphoric, start decompression after 5min, heat up, pressure was decompressed to about 300Pa through 1 hour, and temperature rose to 290 DEG C after 1.5 hours; At the end of polycondensation, reacting kettle inner pressure is about 200Pa.By the polymkeric substance obtained again at 230 DEG C solid state polymerization within 14 hours, obtain polymer blend.By polymer blend melting under 300 degree, calculate the reproduction speed of cyclic trimer according to the cyclic trimer gauge before and after melting.Concrete physical property sees attached list.
Comparative example 1
At the temperature of 250 DEG C, by the PTA of 166 weight parts, the EG of 71.3 weight parts adds reaction kettle of the esterification, carries out esterification at ambient pressure, and upon completion of the ester reaction, esterification temperature in the kettle is 250 DEG C, and fractionation water outlet obtains molecular weight polymers.
In gained molecular weight polymers, add the catalyst methanesulfonic acid being equivalent to polymer blend 200ppm in element sulphur, start decompression after 5min, heat up, pressure was decompressed to about 300Pa through 1 hour, and temperature rose to 290 DEG C after 1.5 hours; At the end of polycondensation, reacting kettle inner pressure is about 200Pa.By the polymkeric substance obtained again at 230 DEG C solid state polymerization within 14 hours, obtain polymer blend.By polymer blend melting under 300 degree, calculate the reproduction speed of cyclic trimer according to the cyclic trimer gauge before and after melting.Concrete physical property sees attached list.
Comparative example 2
At the temperature of 250 DEG C, by the PTA of 166 weight parts, the EG of 71.3 weight parts adds reaction kettle of the esterification, carries out esterification at ambient pressure, and upon completion of the ester reaction, esterification temperature in the kettle is 250 DEG C, and fractionation water outlet obtains molecular weight polymers.
The catalyst A O being equivalent to weight polyester 110ppm in antimony element is added in gained molecular weight polymers, the stabilizer TMP A of weight polyester 35ppm is equivalent in phosphoric, start decompression after 5min, heat up, pressure was decompressed to about 300Pa through 1 hour, and temperature rose to 290 DEG C after 1.5 hours; At the end of polycondensation, reacting kettle inner pressure is about 200Pa.By the polymkeric substance obtained again at 230 DEG C solid state polymerization within 14 hours, obtain polymer blend.By polymer blend melting under 300 degree, calculate the reproduction speed of cyclic trimer according to the cyclic trimer gauge before and after melting.Concrete physical property sees attached list.
Subordinate list:
In subordinate list, M represents alkali metal.
Claims (13)
1. a polymer blend, is characterized in that: containing relative to polymer blend total amount in this polymer blend is the element sulphur of 1 ~ 100ppm, and is the antimony element of 1 ~ 100ppm relative to the total amount of polymer blend; In this polymer blend, the content of cyclic trimer is 0.2 ~ 0.8wt%, and during 300 DEG C of meltings, in polymer blend, the formation speed of cyclic trimer is 0.001 ~ 0.015wt%/min under a nitrogen.
2. polymer blend according to claim 1, is characterized in that: described element sulphur comes from catalyzer sulfoacid compound.
3. polymer blend according to claim 2, is characterized in that: described sulfoacid compound is aliphatic sulfonic compound containing unitary or dibasic sulfoacid group or aromatic azochlorosulfonate acid compound.
4. the polymer blend according to Claims 2 or 3, is characterized in that: the carbonatoms of described sulfoacid compound is 1 ~ 20.
5. polymer blend according to claim 1 and 2, is characterized in that: described sulfur content is 2 ~ 50ppm relative to the content of polymer blend.
6. polymer blend according to claim 1, is characterized in that: the content of described antimony element is 2 ~ 60ppm relative to the content of polymer blend.
7. polymer blend according to claim 1, is characterized in that: also containing relative to the total amount of polymer blend in this polymer blend is the alkali metal of 1 ~ 400ppm.
8. the polymer blend according to claim 1 or 7, is characterized in that: described basic metal is lithium, sodium or potassium.
9. the polymer blend according to claim 1 or 7, is characterized in that: described element sulphur and the mol ratio of alkali metal are 0.2 ~ 1.5.
10. the manufacture method of a polymer blend as claimed in claim 1, mainly comprise the prepolymerization reaction that aromatic binary carboxylic acid or its esterified derivative and aliphatic dihydroxy alcohol are obtained by reacting molecular weight polymers, with the polycondensation being obtained polyester by molecular weight polymers polymerization, it is characterized in that: add catalyzer sulfoacid compound and antimony compounds in the polycondensation stage, wherein the addition of sulfoacid compound is equivalent to 2 ~ 200ppm of polymer blend in element sulphur, and the addition of antimony compounds is equivalent to 1 ~ 100ppm of polymer blend in antimony element; And polyester polycondensation obtained again carries out solid state polymerization obtains polymer blend.
The manufacture method of 11. polymer blends according to claim 10, is characterized in that: add alkali metal compound in the polycondensation stage, make the content of alkali metal in polymer blend be 1 ~ 400ppm.
12., according to the manufacture method of polymer blend described in claim 11, is characterized in that: described alkali metal compound is Lithium Acetate, sodium-acetate or Potassium ethanoate.
13. 1 kinds of polymer blend application in the film as claimed in claim 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109563646A (en) * | 2018-09-04 | 2019-04-02 | 晓星高新材料株式会社 | Tufted carpet comprising polyethylene terephthalate bulked continuous filament |
| CN110092897A (en) * | 2019-03-28 | 2019-08-06 | 北京化工大学 | The method that binary composite catalyst catalyzes and synthesizes polyether ester |
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| JPH1036495A (en) * | 1996-07-25 | 1998-02-10 | Nippon Ester Co Ltd | Continuous production of polyester having excellent transparency |
| CN1578801A (en) * | 2001-12-21 | 2005-02-09 | 纳幕尔杜邦公司 | Method for increasing solid state polymerization rate of polyester polymers |
| CN1942504A (en) * | 2004-04-12 | 2007-04-04 | 东洋纺织株式会社 | Polyester resin, molded articles thereof, and process for production of the articles |
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| CN1137538A (en) * | 1995-06-01 | 1996-12-11 | 恩尼彻姆公司 | High activity catalytic system for synthesis of poly(ethylene terephthalate) |
| JPH1036495A (en) * | 1996-07-25 | 1998-02-10 | Nippon Ester Co Ltd | Continuous production of polyester having excellent transparency |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109563646A (en) * | 2018-09-04 | 2019-04-02 | 晓星高新材料株式会社 | Tufted carpet comprising polyethylene terephthalate bulked continuous filament |
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| CN110092897A (en) * | 2019-03-28 | 2019-08-06 | 北京化工大学 | The method that binary composite catalyst catalyzes and synthesizes polyether ester |
| CN110092897B (en) * | 2019-03-28 | 2021-03-26 | 北京化工大学 | Method for synthesizing polyether ester by catalysis of binary composite catalyst |
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