CN106279647A - A kind of polymer blend and its production and use - Google Patents
A kind of polymer blend and its production and use Download PDFInfo
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- CN106279647A CN106279647A CN201510303977.5A CN201510303977A CN106279647A CN 106279647 A CN106279647 A CN 106279647A CN 201510303977 A CN201510303977 A CN 201510303977A CN 106279647 A CN106279647 A CN 106279647A
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Abstract
The invention discloses a kind of polymer blend and preparation method thereof, mainly reacted by aromatic acid or its carboxylate and aliphatic dihydroxy alcohol and prepare, and containing pentavalent phosphate ester in this polymer blend, its content in terms of P elements relative to 500 ~ 1500ppm of polymer blend.This polymer blend is possibly together with relative to the magnesium elements that polymer blend total amount is 10 ~ 200ppm or manganese element.This polymer blend under the nitrogen oxygen mixed gas that oxygen concentration is 1% gel fraction after 300 DEG C of heat treatments at below 5wt%.This polymer blend can be used for the fields such as thin film.
Description
Technical field
The present invention relates to a kind of polymer blend of low gel fraction and the preparation method of this polymer blend and purposes.
Background technology
Polyester, particularly polyethylene terephthalate, PTT, polybutylene terephthalate (PBT) etc., due to have excellence machinery, physics, chemical property and be widely used in the production of fiber, thin film and other layered products.But, most polyester the most all can occur thermal-oxidative degradation and thermal decomposition, in thermal-oxidative degradation reacts, oxygen-derived free radicals attacks polyester benzene ring hydrogen, generates peroxidating functional group, and this peroxidating functional group instability can decompose again generation free radical, product after the free radical generated thermally decomposes as bridging point and polyester generates bridging structure, i.e. crosslink reaction, form infusibility jelly, the most also referred to as gel.In masking engineering, the generation of gel may cause melt filtration net frequently to be changed, and causes the rising of wastage of material and cost.It addition, occur on thin film that the fault of gel causes membrane quality to decline, purposes is limited.
Improving membrane quality to enable polyester to be preferably applied to masking domain variability, people have carried out much research to the shortcoming solving polyester gel.The method of research mainly has the polymerization stage at polyester to add some metal promoters with reduction effect at present, to obtaining relatively low polyester gel rate.Such as, Japanese Patent Laid-Open 2005-314643 and JP 2006-225621 are recorded by adding titanium compound in the oligomerization operations such as ester exchange, gelation can be suppressed to a certain extent, but the heat resistance of polyester own declines, and thermal cracking can occur thus can not fully suppress the generation of gel in long-term masking.The method that another kind can reduce polyester gel rate is also disclosed in Chinese patent CN98108099.5, add the copolyesters of a kind of main chain Shang You intermediary group the most in the polyester, and it is separated to make both be formed, then the dispersion farmland shape by controlling aforementioned copolyesters can obtain the polyester that gel fraction is relatively low, but the method process conditions are relative complex, and the stability of gel suppression is the highest.
Summary of the invention
It is an object of the invention to provide extremely low polymer blend of a kind of gel fraction and preparation method thereof.
The technical solution of the present invention is:
A kind of polymer blend, mainly reacted, by aromatic acid or its carboxylate and aliphatic dihydroxy alcohol, the constitutional repeating unit formed to constitute, containing pentavalent phosphate ester as shown in Equation 1 in this polymer blend, its content is 500 ~ 1500ppm relative to polymer blend total amount in terms of P elements；Possibly together with relative to the magnesium elements that polymer blend total amount is 10 ~ 200ppm or manganese element in this polymer blend, this polymer blend under the nitrogen oxygen mixed gas that oxygen concentration is 1% gel fraction after 300 DEG C of heat treatments at below 5wt%,
Formula 1,
In formula 1, X is Direct Bonding, or is CH2Or C(CH3)2。
The content of the above-mentioned phosphate ester of pentavalent as shown in Equation 1 is 700 ~ 1000ppm preferably with respect to polymer blend total amount in terms of P elements, the preferred Direct Bonding of X in formula 1.
In described polymer blend, the content of magnesium elements or manganese element is 50 ~ 150ppm preferably with respect to polymer blend total amount.
The invention also discloses the preparation method of a kind of polymer blend, first aromatic acid or its carboxylate and aliphatic dihydroxy alcohol are obtained oligomer by esterification or ester exchange reaction, then oligomer is carried out polycondensation prepare polymer blend；The preparation process of polymer blend is added relative to the magnesium compound that polymer blend total amount is 12 ~ 210ppm or manganese compound in terms of magnesium elements or manganese element, add in the polycondensation reaction stage in terms of P elements, be equivalent to the pentavalent phosphate ester as shown in Equation 1 that polymer blend total amount is 550 ~ 1650ppm.
The addition of the pentavalent phosphate ester shown in described formula 1 in terms of P elements relative to polymer blend total amount preferably 775 ~ 1100ppm.
The addition of described magnesium compound or manganese compound in terms of magnesium elements or manganese element relative to polymer blend total amount preferably 55 ~ 155ppm；Described magnesium compound is magnesium acetate, magnesium nitrate, magnesium sulfate or magnesium carbonate, and described manganese compound is manganese acetate, manganese nitrate, manganese sulfate or manganese carbonate.
Simply, easily operate, the gel fraction of gained polymer blend is low, can be applicable to film applications for the manufacturing process of the polymer blend of the present invention.
Detailed description of the invention
Thermal-oxidative degradation and the thermal decomposition of the generation of gel and polyester self have a very large relationship.In thermal-oxidative degradation reacts, oxygen-derived free radicals attacks polyester benzene ring hydrogen, generating peroxidating functional group, this peroxidating functional group instability can decompose again generation free radical, and the product after the free radical generated can thermally decompose with polyester again crosslinks reaction formation gel.
The present invention reduces polymer blend generation of gel in the case of being heated by adding pentavalent phosphate ester as shown in Equation 1 and the compound containing magnesium elements or manganese element during preparing polyester slice.Pentavalent phosphate ester and magnesium elements, manganese element all can catch oxygen-derived free radicals, avoid polyester benzene ring hydrogen the most to a certain extent and are hacked, i.e. inhibit the generation of thermal-oxidative degradation, thus prevent the generation of cross-linking reaction.
The structural formula of described pentavalent phosphate ester as shown in Equation 1,
Formula 1
In formula 1, X is Direct Bonding, or is CH2Or C(CH3)2, preferably X is Direct Bonding, i.e. pentavalent phosphate ester as shown in formula A,
Formula A.
In theory, in polymer blend, the content of pentavalent phosphate ester the biggest gel inhibition is the best, but the pentavalent phosphate ester of excess can cause response time during polycondensation significantly to extend, and even cannot be polymerized.And if the content of pentavalent phosphate ester very little, less than 500ppm in terms of P elements, then can not catch oxygen-derived free radicals due to the content deficiency of pentavalent phosphate ester effectively in polymer blend, can not get the polymer blend with low gel fraction.Therefore in the polymer blend of the present invention, the content of pentavalent phosphate ester is 500 ~ 1500ppm, preferably 700 ~ 1000ppm relative to polymer blend total amount in terms of P elements.
Simultaneously possibly together with magnesium elements or manganese element in polymer blend, pentavalent phosphate ester can be coordinated to catch oxygen-derived free radicals, to improve the gel inhibition of polymer blend further.Described magnesium elements comes from the magnesium-containing compound added when preparing polymer blend, such as magnesium acetate, magnesium nitrate, magnesium sulfate, magnesium carbonate etc.；Described manganese element come from when preparing polymer blend add containing manganese compound, such as manganese acetate, manganese nitrate, manganese sulfate, manganese carbonate etc..In polymer blend, the content of magnesium elements or manganese element is 10 ~ 200ppm relative to polymer blend total amount.If in polymer blend, the content of magnesium elements or manganese element is less than 10ppm, then not enough due to the content of magnesium elements or manganese element, it is impossible to well coordinating pentavalent phosphate ester to catch oxygen-derived free radicals, polymer blend masking performance also can be deteriorated simultaneously；And if the content of magnesium elements or manganese element is more than 200ppm in polymer blend, then too much the heat resistance of polymer blend can be caused to be deteriorated due to the content of magnesium elements or manganese element.In the present invention, in preferred polymer blend, the content of magnesium elements or manganese element is 50 ~ 150ppm.
Polymer blend of the present invention under the nitrogen oxygen mixed gas that oxygen concentration is 1% gel fraction after 300 DEG C of heat treatments at below 5wt%.
The invention also discloses the preparation method of a kind of polymer blend, first aromatic acid or its carboxylate and aliphatic dihydroxy alcohol are obtained oligomer by esterification or ester exchange reaction, then oligomer is carried out polycondensation prepare polymer blend；The preparation process of polymer blend is added relative to the magnesium compound that polymer blend total amount is 12 ~ 210ppm or manganese compound in terms of magnesium elements or manganese element, add in the polycondensation reaction stage in terms of P elements, be equivalent to the pentavalent phosphate ester as shown in Equation 1 that polymer blend total amount is 550 ~ 1650ppm.
It is 775 ~ 1100ppm that the addition of above-mentioned pentavalent phosphate ester as shown in Equation 1 is preferably equivalent to polymer blend total amount in terms of P elements.
Described aromatic acid or its carboxylate can be p-phthalic acid or its carboxylate, M-phthalic acid or its carboxylate etc., wherein preferred p-phthalic acid.Described aliphatic dihydroxy alcohol can be ethylene glycol, propylene glycol, butanediol, dimethyl propylene glycol or methyl isophthalic acid, ammediol, wherein preferred ethylene glycol.
In addition to principal monomer, the catalyst of routine also can be used in the preparation process of polymer blend, as inorganic antimony compounds can be added as catalyst in esterification or polycondensation phase, the preferred antimony oxide of described inorganic antimony compounds, antimony pentoxide, most preferably antimony oxide.The addition of inorganic antimony compounds is 50～200ppm relative to polymer blend total amount in terms of antimony element, preferably 60～100ppm.So, preferable catalytic effect can either be realized, will not cause polymer generates substantial amounts of foreign body because of too much antimony element again, affect the quality of polymer.
When polymer blend is to be obtained oligomer by aromatic acid and aliphatic dihydroxy alcohol by esterification, then oligomer carrying out polycondensation when preparing, magnesium compound or manganese compound can add in polycondensation reaction；When polymer blend is to be obtained oligomer by aromatic acid carboxylate and aliphatic dihydroxy alcohol by ester exchange reaction, oligomer is carried out polycondensation again when preparing, magnesium compound or manganese compound can add in ester exchange reaction, the most both make use of the catalysis of magnesium compound or manganese compound, it has the effect reducing gel again, and the polycondensation reaction stage later can no longer add magnesium compound or manganese compound.
The addition of described magnesium compound or manganese compound is 12～210ppm relative to polymer blend total amount in terms of magnesium elements or manganese element, preferably 55 ~ 155ppm.Magnesium compound or how many pairs of reaction rates of manganese compound content and the final heat resistance of gained polyester, gel fraction and masking all have a certain impact.When addition is too high, then the thermostability of gained polymer blend is deteriorated；When addition is too low, then reaction rate reduces, and the gel fraction of gained polymer blend is on the rise, and masking is deteriorated.
The preferred magnesium acetate of described magnesium compound, magnesium nitrate, magnesium sulfate or magnesium carbonate, more preferably magnesium acetate；The preferred manganese acetate of described manganese compound, manganese nitrate, manganese sulfate or manganese carbonate, more preferably manganese acetate.
In order to prevent the generation of foreign body in the reaction prepare polymer blend from causing the pressure oscillation of follow-up masking engineering, preferably add stabilizer phosphorus compound in the polycondensation reaction stage, its addition is be equivalent to polymer blend total amount in terms of P elements 5～100ppm, preferably 20～80ppm.Stabilizer phosphorus compound in the present invention is the various phosphorus-containing compounds of trivalent or pentavalent, can be phosphoric acid, trimethyl phosphate, phosphine acyl acetic acid three ethyl；Can also be diethyl phosphite, phenyl-phosphite；Can also is that double (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites or double (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites etc., preferred stabilizer phosphorus compound is trimethyl phosphate.
In order to prevent the ethylene glycol in the reaction system preparing polyester slice from generating diethylene glycol from polycondensation under slant acidity environment, cause the decline of polymer blend heat resistance, present invention preferably uses some meta-alkalescence metallic compounds regulator as the acid or alkali environment of reaction system, thus suppress the excess generation of diethylene glycol, its addition is to be equivalent to the 0.5～20ppm of polyester total amount, preferably 3～10ppm with elemental metal therein.The preferred sodium acetate of regulator alkaline metal cpds, potassium acetate, lithium acetate, sodium hydroxide, potassium hydroxide or Lithium hydrate, the most more preferably lithium acetate in the present invention.
Any method commonly known in the art can be used when polymer blend of the present invention is used for preparing thin film, illustrate the most as an example:
Join after prepared polymer blend is vacuum dried 7 hours at 130 DEG C in double screw extruder and carry out fusion plastification；Melt after fusion plastification is sent into formed cast strand mould, and uses the electrostatic print addition non-stretched PTFE film after the cold cydariform of surface temperature 20～30 DEG C becomes cooling and solidifying；Non-stretched PTFE film is first preheated at temperature 70～90 DEG C, then at temperature 70～90 DEG C, carry out 2～5 times of longitudinal stretchings obtain longitudinal stretching film, again the longitudinal stretching film obtained is preheated at 70～90 DEG C, at temperature 80～100 DEG C, carry out 3～6 times of cross directional stretchs；The biaxial stretching film obtained, under annealing device, 200～250 DEG C of heat treatments 10 seconds, then carry out relaxation processes at 200～250 DEG C under 4% transverse direction；Finally carry out homogeneous cooling, curling, obtain biaxially oriented polyester film.
The present invention catches the characteristic of oxygen-derived free radicals by utilizing pentavalent phosphate ester as shown in Equation 1 and magnesium compound or manganese compound, adding them into the polymer blend obtaining having excellent gel inhibition in the course of reaction of polymer blend, gel fraction is at below 5wt%.And obtained polymer blend can effectively suppress the generation of jello when thin film fabrication, thus greatly reducing the replacement frequency of the drainage screen in thin film fabrication engineering, production cost is also minimized.Meanwhile, the surface of obtained thin film does not haves yet and produces flaw point because of jello.
Method of testing involved in the present invention is described as follows:
(1) phosphorus element content of pentavalent phosphate ester
Hydrogen spectrum according to nuclear magnetic resonance, NMR can record the content in the polyester of the meta-xylene functional group being connected with P elements in pentavalent phosphate ester of the present invention, and the structural formula further according to this pentavalent phosphate ester extrapolates phosphorus content.
(2) phosphorus element content of stabilizer phosphorus compound
After 5g polymer blend is melted in thermal station, it is pressed into tabular with hydraulic press, then testing with fluorescent X-ray elemental analyser, measured phosphorus element content cuts the phosphorus element content of pentavalent phosphate ester more i.e. can calculate the phosphorus element content of stabilizer phosphorus compound.
(3) magnesium elements or manganese element content
Precise 2g polyester, after using concentrated nitric acid/hydrogen peroxide to clear up in 100 DEG C～160 DEG C, is diluted quantitatively according to required concentration.Then test with ICP-MS analyser, with reference to the calibration curve using standard sample to make in advance, measure the content of various element.Experiment test precision 0.5ppm.
(4) gel fraction
Polymer blend is ground into the powder of below particle diameter 300 μm, takes this powder 0.5000 ~ 0.5999g as sample, and be dried more than 2 hours under the vacuum condition of 50 DEG C.It is passed through, through dried sample, nitrogen oxygen mixed gas that oxygen concentration is 1% and carries out heat treatment by the temperature of 300 DEG C, taking out after 6 hours and let cool to room temperature.Sample after heat treatment 20ml hexafluoroisopropanol (HFIP) dissolves 1 hour at normal temperatures.Then filter with 400 ~ 800 mesh metal screens, then wash with dichloromethane, finally HFIP insoluble matter is dried, weighs.The computing formula of gel fraction is as follows:
Gel fraction (wt%)=(HFIP insoluble matter weight/example weight) × 100%.
(5) tone (b value)
Use Japan to produce SM-T45 type colour difference meter to test.B value is sample outward appearance in blue or the index of yellow degree, and codomain scope is typically-120 to+120.When b value the highest explanation sample outward appearance tends to yellow；When b value the lowest explanation sample outward appearance tends to blueness.In time without particular/special requirement, it is optimal that b value tends to when 0.
(6) masking
Masking is to be judged with the stickiness drawing cold drum after polymer discharge in film-forming process by observation.When polymer is fitted with cold drum and occurs without peeling, masking is good, represents by "○"；When after polymer with cold drum laminating, peeling off occurs in occasional, but when not affecting masking, masking is preferable, represents with " △ "；When polymer and cold drum are peeled off and more even can not be fitted, it is impossible to during masking, masking is poor, represents by "×".
The part of compounds related in the embodiment listed in the present invention is as follows:
1. p-phthalic acid (being abbreviated as TPA)；
2. M-phthalic acid (being abbreviated as IPA)
3. dimethyl terephthalate (DMT) (being abbreviated as DMT)；
4. ethylene glycol (being abbreviated as EG)；
5. butanediol (being abbreviated as BDO)
6. p-phthalic acid diethyl diester (being abbreviated as BHT)
7. antimony oxide (being abbreviated as AO)；
8. trimethyl phosphate (being abbreviated as TMPA)；
9. lithium acetate (being abbreviated as LAH)；
10. pentavalent phosphate ester is as shown in following formula A ~ C；
Formula A,
Formula B,
Formula C.
Present disclosure is described by the following examples, but the invention is not limited in content listed by embodiment.
Embodiment 1
At 250 DEG C, the p-phthalic acid (TPA) of 166 weight portions and the ethylene glycol (EG) (i.e. the mol ratio of EG Yu TPA is 1.15 1) of 72 weight portions are carried out esterification, by the volume of production of water byproduct, response rate to be esterified reaches more than 97%, is transferred in polymeric kettle by prepared new p-phthalic acid diethyl diester (BHT) oligomer.The stabilizer trimethyl phosphate (TMPA) being equivalent to polymer blend total amount 45ppm in terms of P elements is added successively in polymeric kettle, the regulator lithium acetate (LAH) being equivalent to polymer blend total amount 7ppm in terms of elemental lithium is added after 5 minutes, the pentavalent phosphate ester (formula A) being equivalent to polymer blend total amount as 550ppm is counted with P elements, the magnesium acetate of polymer blend total amount 12ppm is equivalent in terms of magnesium elements, the catalytic antimony trioxide (AO) being equivalent to polymer blend total amount 70ppm in terms of antimony element is added after 20 minutes, add and terminate within latter 5 minutes, to start decompression, heat up, whole course of reaction is 3.5 hours, spue after reaching required polymer viscosity, cooling and dicing, prepare polymer blend section.Concrete physical property sees attached list.
Masking step: join after prepared polymer blend is vacuum dried 7 hours at 130 DEG C in double screw extruder and carry out fusion plastification；Melt after fusion plastification is sent into formed cast strand mould, and uses the electrostatic print addition non-stretched PTFE film after the cold cydariform of surface temperature 25 DEG C becomes cooling and solidifying；Non-stretched PTFE film is first preheated at temperature 80 DEG C, at temperature 85 DEG C, then carries out 3.5 times of longitudinal stretchings obtain longitudinal stretching film, then the longitudinal stretching film obtained is preheated at 80 DEG C, at temperature 90 DEG C, carry out 5 times of cross directional stretchs；The biaxial stretching film obtained, under annealing device, 230 DEG C of heat treatments 10 seconds, then carry out relaxation processes at 230 DEG C under 4% transverse direction；Finally carry out homogeneous cooling, curling, obtain biaxially oriented polyester film.During masking, after polymer is fitted with cold drum, peeling off occurs in occasional, but does not affect masking, and masking is preferable.
Embodiment 2
The pentavalent phosphate ester (formula A) being equivalent to polymer blend total amount as 1650ppm is counted in polycondensation phase interpolation with P elements, is equivalent to the manganese acetate of polymer blend total amount 210ppm in terms of manganese element.Other steps are with embodiment 1.
During masking, polymer is fitted with cold drum and occurs without peeling, and masking is good.
Embodiment 3
The pentavalent phosphate ester (formula A) being equivalent to polymer blend total amount as 775ppm is counted in polycondensation phase interpolation with P elements, is equivalent to the magnesium nitrate of polymer blend total amount 80ppm in terms of magnesium elements.Other steps are with embodiment 1.
During masking, polymer is fitted with cold drum and occurs without peeling, and masking is good.
Embodiment 4
The pentavalent phosphate ester being equivalent to polymer blend total amount as 1100ppm is counted in polycondensation phase interpolation with P elements, is equivalent to the manganese nitrate of polymer blend total amount 180ppm in terms of manganese element.Other steps are with embodiment 1.
During masking, polymer is fitted with cold drum and occurs without peeling, and masking is good.
Embodiment 5
The pentavalent phosphate ester (formula B) being equivalent to polymer blend total amount as 950ppm is counted in polycondensation phase interpolation with P elements, is equivalent to the magnesium carbonate of polymer blend total amount 55ppm in terms of magnesium elements.Other steps are with embodiment 1.
During masking, polymer is fitted with cold drum and occurs without peeling, and masking is good.
Embodiment 6
At 250 DEG C, the p-phthalic acid (TPA) of 166 weight portions and the butanediol (BDO) (i.e. the mol ratio of BDO Yu TPA is 1.15 1) of 104 weight portions are carried out esterification, the pentavalent phosphate ester (formula C) being equivalent to polymer blend total amount as 1350ppm is counted in polycondensation phase interpolation with P elements, is equivalent to the manganese sulfate of polymer blend total amount 155ppm in terms of manganese element.Other steps are with embodiment 1.
During masking, polymer is fitted with cold drum and occurs without peeling, and masking is good.
Embodiment 7
At 250 DEG C, the M-phthalic acid (IPA) of 166 weight portions and the ethylene glycol (EG) (i.e. the mol ratio of EG Yu IPA is 1.15 1) of 72 weight portions are carried out esterification, the pentavalent phosphate ester (formula A) being equivalent to polymer blend total amount as 650ppm is counted in polycondensation phase interpolation with P elements, is equivalent to the magnesium acetate of polymer blend total amount 30ppm in terms of magnesium elements.Other steps are with embodiment 1.
During masking, polymer is fitted with cold drum and occurs without peeling, and masking is good.
Embodiment 8
Dimethyl terephthalate (DMT) (DMT) and ethylene glycol (EG) are placed in the polymerization flask being furnished with rectifying column with the mol ratio of 1 1.8, at a temperature of 140 DEG C, carry out ester exchange reaction.In ester-exchange reaction, interpolation is equivalent to the manganese acetate of polymer blend total amount 40ppm in terms of manganese element and mixes, and reacts at ambient pressure.After reaction terminates, prepared p-phthalic acid diethyl diester (BHT) oligomer is transferred to carry out in polymeric kettle polycondensation reaction.The stabilizer trimethyl phosphate (TMPA) being equivalent to polyester total amount 45ppm in terms of P elements is added successively in polymeric kettle, the regulator lithium acetate (LAH) being equivalent to polymer blend total amount 7ppm in terms of elemental lithium is added after 5 minutes, the pentavalent phosphate ester (formula A) being equivalent to polymer blend total amount as 1000ppm is counted with P elements, the catalytic antimony trioxide (AO) being equivalent to polymer blend total amount 70ppm in terms of antimony element is added after 20 minutes, add and terminate within latter 5 minutes, to start decompression, heat up, whole course of reaction is 2.5 hours, spue after reaching required polymer viscosity, cooling and dicing, prepare polyester slice.Concrete physical property sees attached list.
Masking step is with embodiment 1. during masking, and polymer is fitted with cold drum and occurs without peeling, and masking is good.
Comparative example 1
Polycondensation phase adds the magnesium acetate being equivalent to polymer blend total amount 62ppm in terms of magnesium elements, without pentavalent phosphate ester of the present invention.Other steps are with embodiment 1.
During masking, polymer is fitted with cold drum and occurs without peeling, and masking is good.
Comparative example 2
The pentavalent phosphate ester (formula A) being equivalent to polymer blend total amount as 100ppm is counted in polycondensation phase interpolation with P elements, is equivalent to the magnesium acetate of polymer blend total amount 62ppm in terms of magnesium elements.Other steps are with embodiment 1.
During masking, polymer is fitted with cold drum and occurs without peeling, and masking is good.
Comparative example 3
Polycondensation phase interpolation counts the pentavalent phosphate ester (formula A) being equivalent to polymer blend total amount as 800ppm, without magnesium of the present invention or the compound of manganese with P elements.Other steps are with embodiment 1.
During masking, polymer and cold drum are peeled off and more even can not be fitted, it is impossible to masking.
Comparative example 4
The pentavalent phosphate ester (formula A) being equivalent to polymer blend total amount as 5000ppm is counted in polycondensation phase interpolation with P elements, is equivalent to the magnesium acetate of polymer blend total amount 62ppm in terms of magnesium elements.Other steps are with embodiment 1.During polycondensation due to phosphorus compound addition too much, catalysqt deactivation is caused to be polymerized.
Subordinate list 1
Claims (9)
1. a polymer blend, mainly contain and reacted, by aromatic acid or its carboxylate and aliphatic dihydroxy alcohol, the constitutional repeating unit formed, it is characterized in that: containing pentavalent phosphate ester as shown in Equation 1 in this polymer blend, its content is 500 ~ 1500ppm relative to polymer blend total amount in terms of P elements；Possibly together with relative to the magnesium elements that polymer blend total amount is 10 ~ 200ppm or manganese element in this polymer blend, this polymer blend under the nitrogen oxygen mixed gas that oxygen concentration is 1% gel fraction after 300 DEG C of heat treatments at below 5wt%,
Formula 1,
In formula 1, X is Direct Bonding, or is CH2Or C(CH3)2。
Polymer blend the most according to claim 1, is characterized in that: the content of described pentavalent phosphate ester as shown in Equation 1 is 700 ~ 1000ppm relative to polymer blend total amount in terms of P elements.
Polymer blend the most according to claim 1, is characterized in that: described X is Direct Bonding.
Polymer blend the most according to claim 1, is characterized in that: containing relative to the magnesium elements that polymer blend total amount is 50 ~ 150ppm or manganese element in this polymer blend.
5. the preparation method of polymer blend described in a claim 1, first aromatic acid or its carboxylate and aliphatic dihydroxy alcohol are obtained oligomer by esterification or ester exchange reaction, again oligomer is carried out polycondensation and prepare polymer blend, it is characterized in that: add relative to the magnesium compound that polymer blend total amount is 12 ~ 210ppm or manganese compound in terms of magnesium elements or manganese element in the preparation process of polymer blend, add in the polycondensation reaction stage in terms of P elements, be equivalent to the pentavalent phosphate ester as shown in Equation 1 that polymer blend total amount is 550 ~ 1650ppm.
The most according to claim 5, the preparation method of polymer blend, is characterized in that: the addition of described pentavalent phosphate ester as shown in Equation 1 is 775 ~ 1100ppm relative to polymer blend total amount in terms of P elements.
The most according to claim 5, the preparation method of polymer blend, is characterized in that: the addition of described magnesium compound or manganese compound is 55 ~ 155ppm relative to polymer blend total amount in terms of magnesium elements or manganese element.
8. according to the preparation method of polymer blend described in claim 5 or 6, it is characterized in that: described magnesium compound is magnesium acetate, magnesium nitrate, magnesium sulfate or magnesium carbonate, described manganese compound is manganese acetate, manganese nitrate, manganese sulfate or manganese carbonate.
9. a polymer blend as claimed in claim 1 application in the film.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017149843A (en) * | 2016-02-24 | 2017-08-31 | 東レ株式会社 | Polyester resin composition for transparent optical film |
| TWI664186B (en) * | 2017-10-05 | 2019-07-01 | 遠東新世紀股份有限公司 | Phosphate ester material and preparation method thereof, polyester resin containing phosphate ester material and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017149843A (en) * | 2016-02-24 | 2017-08-31 | 東レ株式会社 | Polyester resin composition for transparent optical film |
| TWI664186B (en) * | 2017-10-05 | 2019-07-01 | 遠東新世紀股份有限公司 | Phosphate ester material and preparation method thereof, polyester resin containing phosphate ester material and preparation method thereof |
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