CN103524723A - Fluorine polyester and preparation method thereof - Google Patents
Fluorine polyester and preparation method thereof Download PDFInfo
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- CN103524723A CN103524723A CN201310445993.9A CN201310445993A CN103524723A CN 103524723 A CN103524723 A CN 103524723A CN 201310445993 A CN201310445993 A CN 201310445993A CN 103524723 A CN103524723 A CN 103524723A
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Abstract
The invention relates to fluorine polyester and a preparation method thereof. The fluorine polyester relates to polyethylene glycol terephthalate with hydrogen on a benzene ring substituted by fluorine; terephthalic acid containing fluorine and ethylene glycol are adopted as raw materials, an inhibitor is added, and the mixture is subjected to an esterification reaction in a nitrogen condition at certain temperature and under certain pressure to obtain an esterified product; and then, a catalyst and a stabilizer are added into the esterified product, a condensation polymerization reaction is performed at certain temperature and under certain pressure, and the fluorine polyester is prepared after the low vacuum stage and the high vacuum stage of the condensation polymerization reaction. The obtained fluorine polyester has good heat stability and machinability and can be directly used for spinning, film forming and the like; and with the introduction of fluorine atoms, the performance of a polyester material in the aspects of superhydrophobicity, hydrophobicity, oleophobicity and pollution prevention is improved, and the fluorine polyester has a huge prospect in manufacture of waterproof clothes, dirty-resistant work clothes and work clothes of some special industries.
Description
Technical field
The present invention relates to a kind of fluorine polyester and preparation method thereof, particularly relate to fluorine polyester that a kind of benzene ring hydrogen replaced by fluorine and preparation method thereof.
Background technology
Polyester (PET) is one of the most widely used synthetic high polymer of the current mankind; as far back as twentieth century, just synthesized PET the forties; and find that it has excellent performance, and be widely used in the fields such as weaving, packing, health care, automobile, electronic apparatus, safety precaution, environment protection.
Along with social progress, the raising of living standards of the people, needs more and more higher to differential, the functionalization of trevira.Therefore also become particularly important of the modification of polyester, polyester modification object, except conventional polyester performance is optimized, is mainly to give new polyester differential functional characteristic by modified method.Such as: antistatic, fire-retardant, moisture absorbing and sweat releasing, antifouling deodorization etc.At present, the main new variety of polyester have: antistatic polyester, high-strength wearable polyester, imitative cotton ultra-soft polyester, super-hydrophobicity polyester, anti-soil polyester etc.
At present, by introduce fluorine atom in polymkeric substance, thereby improve the surface property of material, as hydro-oleophobicity and didirtresistance etc., and give polyester material various functions.Because fluoropolymer has low surface energy, low-friction coefficient and non-adhesivity conventionally, dust dirt such as is difficult to adhere at the characteristic, so the anti-soil wear resistance of fluoropolymer is good.And current fluoropolymer be take fluoroolefins base polymer as main (such as tetrafluoroethylene, polyvinylidene difluoride (PVDF), fluorinated ethylene propylene copolymer, ethylene-tetrafluoroethylene copolymer etc.); The research of fluorochemical urethane, fluorochemical polyether, fluorine-containing polyester etc. relatively lags behind.
Many scholars are studied fluorochemicals modified poly ester, and have obtained certain achievement.The mode of fluorochemicals modified poly ester is mainly by adding fluorine-containing end-capping reagent at present, or adds the fluorochemicalss such as Fluorinated dihydric alcohol, fluorine-containing diprotic acid to carry out modified poly ester as the 3rd monomer.In Chinese patent CN101139434A, adopt adding of fluorine-containing end-capping reagent, dimethyl isophthalate and butyleneglycol adopt ester-interchange method, add fluorine-containing end-capping reagent N-hydroxyethyl perfluor decoylamide, have prepared the low and polyester material that stain resistant performance is good of fluorine content.Hu Juan (Hu Juan. the molecular designing of fluorine-containing polyester and photoresist material waveguide material and performance study [D]. Master's thesis, Jilin: Jilin University, 2007.) utilize the principle of molecular designing, by adding the mode of Fluorinated dihydric alcohol copolymerization, p-phthaloyl chloride, hexafluoro bisphenol-a and fluorine-containing ethohexadiol terpolymer have been synthesized to the polyester of novel high fluorine content.This polyester has excellent performance and is applied to optical waveguide material.
Yet the polyester that these are contained to fluorine element is applied to there is certain limitation in weaving and wrapping material, subject matter is that the molecular weight of polyesters that contains fluorine element of prior art is low, can not meet the requirement of spinning and film forming; Prior art is mainly to give its water proof anti-soil function by the fluorine-containing rear Collator Mode of fabric at present, and the problem such as that the shortcoming of this class methods maximum is to be difficult to solve is ageing, weather resistance and wear resistance, and waste time and energy.
Therefore, develop fluorine-containing polyester for weave and super-hydrophobic, the hydrophobic and oil repellent of wrapping material, the modification of antifouling property will have important theory significance and using value.
Summary of the invention
The object of this invention is to provide a kind of fluorine polyester and preparation method thereof, particularly relate to fluorine polyester that a kind of benzene ring hydrogen replaced by fluorine and preparation method thereof.Fluorine-containing polyester of the present invention has been introduced fluorine atom on the main chain of polymkeric substance, and the fluorine-containing polyester slice of preparing can be directly used in spinning, masking etc.Fluorine-containing polyester described in the present invention is terephthalic acid and the ethylene glycol by contain fluorine atoms on phenyl ring, the fluorine-containing polyester obtaining through over-churning and polycondensation, and this fluorine-containing polyester slice can direct fabrics, film forming etc.And by copolymerization method, polyester is carried out to hydrophobic antifouling modification, and can fundamentally solve the problems such as ageing, the weather resistance of hydrophobic antifouling polyester and wear resistance, also can well solve this class problem that wastes time and energy.
The invention provides a kind of preparation method of fluorine polyester, be divided into esterification and polycondensation two steps; Concrete steps are:
Described esterification:
Adopt fluorine-containing terephthalic acid and ethylene glycol as raw material, add inhibitor, carry out esterification after being made into uniform sizing material; Esterification is pressurizeed in nitrogen atmosphere, and pressure-controlling is at normal pressure～0.4MPa, and temperature is at 230～250 ℃, and what esterification water quantity of distillate reached theoretical value more than 90% is esterification terminal;
Described fluorine-containing terephthalic acid is tetrafluoro terephthalic acid or 2,5-difluoro terephthalic acid;
Described inhibitor is a kind of in magnesium oxide, silicon oxide, calcium oxide, zinc oxide and manganese oxide; On phenyl ring due to di-carboxylic acid used, there is fluorine atom, the electronegativity of fluorine atom is large, conjugative effect at esterification stage fluorine atom strengthens the acidity of di-carboxylic acid, cause the activity of carboxyl in di-carboxylic acid to increase simultaneously, speed of response is accelerated, and speed of response increase easily makes side reaction produce, these side reaction products have larger impact to follow-up polycondensation, the end-blocking product that particularly generates alkene and aldehyde, has restricted the increase of molecular weight of product; From experimental result, if do not add inhibitor, synthetic molecular weight of polyesters is on the low side, can not meet the demand of spinning and film forming; Adding for controlling the speed in esterification stage of inhibitor, has reduced side reaction, has improved the molecular weight of product, makes fluorine polyester meet spinning requirement.
Conventionally, in polyester esterification process, be that the hydrogen ion that ionizes out by di-carboxylic acid used is as the catalyzer of esterification, carry out self-catalyzed reaction, by regulating the temperature, pressure of esterification and micromolecularly ejecting the speed of controlling its esterification, yet the prerequisite of carrying out esterification is under certain temperature of reaction and pressure, just can carry out esterification.In the situation that temperature is too low or pressure is inadequate, esterification can not carry out or speed extremely slow, thereby affect follow-up technique.If the small molecules in esterification is failed timely discharge and is easily caused unnecessary side reaction.In the building-up process of fluorine polyester, conjugative effect due to fluorine, at esterification stage fluorine atom, the acidity of di-carboxylic acid is strengthened, cause the activity of carboxyl in di-carboxylic acid to increase simultaneously, speed of response is accelerated, side reaction increases, be difficult to control, and then affect the growth of molecular weight of product, thus add inhibitor, by selecting metal oxide used to regulate.Described metal oxide can dissociate by following two kinds of modes:
Here M is metal ion, if the electronegativity of M is quite large, the electron pair of oxonium ion is had to stronger magnetism, so just can make O-H key weaken, and is conducive to react dissociation; On the contrary, if the electronegativity of M is little, so just will generate alkali center.M-O-H is similar with amphoteric substance, and when having alkaline matter to exist, reaction will be undertaken by the mode of acid dissociation; And when acidic substance exist, by the mode of alkali formula ionization, undertaken.The M-O of reversed reaction from acid dissociation mode and alkali formula ionization mode
-and M
+visible, M
+as acid sites, its intensity only has direct relation with the electronegativity of metal ion, and M-O
-in O ion relevant with the negative charge density on oxygen as the intensity at alkali center, negative charge density is larger, intensity is also larger.Negative charge density on visible oxonium ion and metal ion electronegativity have close relationship, and metal ion electronegativity is less, and negative charge density is just larger.So, the acid and alkalescence of metal oxide has just all connected with the electronegativity of metal ion, and the large oxide compound of electronegativity of metal ion is mainly acid, and what electronegativity was little is alkalescence.
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig;
The described polycondensation rough vacuum stage, in esterification products, add catalyzer and stablizer, under the condition of negative pressure, start polycondensation, this staged pressure is steadily evacuated to below absolute pressure 1KPa by normal pressure, temperature is controlled at 250～270 ℃, and the reaction times is 40～60 minutes;
Described polycondensation high vacuum stage of Fig, after the described polycondensation rough vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and temperature of reaction is controlled at 270～285 ℃, 1～2 hour reaction times.Polycondensation is with reactor agitator motor power or the in-line viscometer reading judgement reaction end that is as the criterion.
A kind of fluorine polyester that the inventive method makes, refers to the polyethylene terephthalate that benzene ring hydrogen is replaced by fluorine, and its general structure is
Or
N=80～200 wherein.
As preferred technical scheme:
The preparation method of a kind of fluorine polyester as above, described ethylene glycol and the mol ratio of fluorine-containing terephthalic acid are 1.2～2.0: 1.
The preparation method of a kind of fluorine polyester as above, described catalyzer is selected from a kind of in antimonous oxide, antimony glycol and antimony acetate, and catalyst levels is 0.01%～0.05% of described fluorine-containing terephthalic acid weight.
The preparation method of a kind of fluorine polyester as above, described stablizer is selected from a kind of in triphenylphosphate, trimethyl phosphite 99 and trimethyl phosphite, and stabilizing agent dosage is 0.01%～0.05% of described fluorine-containing terephthalic acid weight.
The preparation method of a kind of fluorine polyester as above, the add-on of described inhibitor is 0.01%～0.05% of described fluorine-containing terephthalic acid weight.
Esterification of the present invention is in the stage, reaction end actual water quantity of distillate producing in esterification reach theoretical value 90% with on grasp.Theoretical value is the quantity of distillate of gained water while pressing chemical equation complete reaction.Due to esterification this as reversible reaction, moreover raw material has residually in transport pipe, and along with the carrying out of reaction, the viscosity of system increases, and can cause shipwreck that esterification produces therefrom to discharge.
In polycondensation high vacuum stage of Fig of the present invention, the numerical value that reaction end reaches setting by reactor beater motor power and in-line viscometer calculation value is grasped.The setting numerical value of its reactor beater motor power of different devices and in-line viscometer calculation value is not necessarily identical, and setting determining of numerical value can obtain by the analysis to polyester slice.
The fluorine-containing copolyesters of gained of the present invention is due to the introducing of fluorine atom, improved super-hydrophobic, hydrophobic and oil repellent, the antifouling aspect performance of polyester material, at waterproof garment, in the working suit manufacture of the working suit bearing dirty and some special industry, has huge prospect.
Beneficial effect:
1, the copolyesters contain fluorine atoms making; strong electronegativity due to fluorine; high C-F bond energy and the copolyesters that the shielding protection effect of carbochain makes to synthesize is also had except the performance of the traditional polyester of further lifting well heat-resisting, ageing-resistant, resistance to chemical attack and low electric capacity; low combustible; the performances such as low-refraction also have some special electric property, as low-k simultaneously; the advantages such as high-insulativity, have expanded range of application.
2, in polyester esterification process, by inhibiting, can control the speed of esterification, reduce the generation of side reaction.
3, the fluorine-containing copolyester section of gained can direct fabrics, film forming.
4, the fluorine-containing copolyesters of gained has good thermostability and workability.
Embodiment
Below in conjunction with embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
A kind of fluorine polyester of the present invention, refers to the polyethylene terephthalate that benzene ring hydrogen is replaced by fluorine, and its general structure is
N=80～200 wherein.
Embodiment 1
A preparation method for fluorine polyester, is divided into esterification and polycondensation two steps.Concrete steps are:
Described esterification:
Adopt ethylene glycol that mol ratio is 1.2: 1 and tetrafluoro terephthalic acid as raw material, add 0.01% magnesium oxide of tetrafluoro terephthalic acid weight simultaneously, carry out esterification after being made into uniform sizing material; Esterification is in nitrogen atmosphere, and pressure-controlling is at 0.4MPa, and temperature is controlled at 250 ℃, and it is esterification terminal that esterification water quantity of distillate reaches 90% of theoretical value.
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The described polycondensation rough vacuum stage, 0.01% the stablizer triphenylphosphate that adds 0.01% the catalytic antimony trioxide of tetrafluoro terephthalic acid weight and tetrafluoro terephthalic acid weight in esterification products, under the condition of negative pressure, start polycondensation, this staged pressure is steadily evacuated to absolute pressure by normal pressure and is less than 1KPa, temperature is controlled at 255 ℃, and the reaction times is 60 minutes.
Described polycondensation high vacuum stage of Fig, after the described polycondensation rough vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and temperature of reaction is controlled at 270 ℃, 2 hours reaction times.Polycondensation is with reactor agitator motor power or the in-line viscometer reading judgement reaction end that is as the criterion.Discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, obtains fluorine-containing polyester slice.
Embodiment 2
A preparation method for fluorine polyester, is divided into esterification and polycondensation two steps.Concrete steps are:
Described esterification:
Adopt ethylene glycol that mol ratio is 1.4: 1 and 2,5-difluoro terephthalic acid as raw material, add 0.03% silicon oxide of 2,5-difluoro terephthalic acid weight simultaneously, carry out esterification after being made into uniform sizing material; Esterification is pressurizeed in nitrogen atmosphere, and pressure-controlling is at 0.3MPa, and temperature is controlled at 245 ℃, and it is esterification terminal that esterification water quantity of distillate reaches 90% of theoretical value.
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The described polycondensation rough vacuum stage, in esterification products, add 2,0.02% catalyst glycol antimony and 2 of 5-difluoro terephthalic acid weight, 0.02% stablizer trimethyl phosphite 99 of 5-difluoro terephthalic acid weight, under the condition of negative pressure, start polycondensation, this staged pressure is steadily evacuated to absolute pressure by normal pressure and is less than 800Pa, and temperature is controlled at 250 ℃, and the reaction times is 50 minutes.
Described polycondensation high vacuum stage of Fig, after the described polycondensation rough vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 80Pa, and temperature of reaction is controlled at 275 ℃, 2 hours reaction times.Polycondensation is with reactor agitator motor power or the in-line viscometer reading judgement reaction end that is as the criterion.Discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, obtains fluorine-containing polyester slice.
Embodiment 3
A preparation method for fluorine polyester, is divided into esterification and polycondensation two steps.Concrete steps are:
Described esterification:
Adopt ethylene glycol that mol ratio is 1.6: 1 and tetrafluoro terephthalic acid as raw material, add 0.05% calcium oxide of tetrafluoro terephthalic acid weight simultaneously, carry out esterification after being made into uniform sizing material; Esterification is pressurizeed in nitrogen atmosphere, and pressure-controlling is at 0.2MPa, and temperature is controlled at 240 ℃, and it is esterification terminal that esterification water quantity of distillate reaches 90% of theoretical value.
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The described polycondensation rough vacuum stage, 0.03% the stablizer trimethyl phosphite that adds 0.03% catalyst acetic acid antimony of tetrafluoro terephthalic acid weight and tetrafluoro terephthalic acid weight in esterification products, under the condition of negative pressure, start polycondensation, this staged pressure is steadily evacuated to absolute pressure by normal pressure and is less than 600Pa, temperature is controlled at 260 ℃, and the reaction times is 50 minutes.
Described polycondensation high vacuum stage of Fig, after the described polycondensation rough vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 60Pa, and temperature of reaction is controlled at 280 ℃, 1.5 hours reaction times.Polycondensation is with reactor agitator motor power or the in-line viscometer reading judgement reaction end that is as the criterion.Discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, obtains fluorine-containing polyester slice.
Embodiment 4
A preparation method for fluorine polyester, is divided into esterification and polycondensation two steps.Concrete steps are:
Described esterification:
Adopt ethylene glycol that mol ratio is 1.8: 1 and tetrafluoro terephthalic acid as raw material, add 0.03% zinc oxide of tetrafluoro terephthalic acid weight simultaneously, carry out esterification after being made into uniform sizing material; Esterification is pressurizeed in nitrogen atmosphere, and pressure-controlling is at 0.2MPa, and temperature is controlled at 235 ℃, and it is esterification terminal that esterification water quantity of distillate reaches 90% of theoretical value.
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The described polycondensation rough vacuum stage, 0.04% the stablizer trimethyl phosphite 99 that adds 0.04% the catalytic antimony trioxide of tetrafluoro terephthalic acid weight and tetrafluoro terephthalic acid weight in esterification products, under the condition of negative pressure, start polycondensation, this staged pressure is steadily evacuated to absolute pressure by normal pressure and is less than 500Pa, temperature is controlled at 265 ℃, and the reaction times is 50 minutes.
Described polycondensation high vacuum stage of Fig, after the described polycondensation rough vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 50Pa, and temperature of reaction is controlled at 280 ℃, 1 hour reaction times.Polycondensation is with reactor agitator motor power or the in-line viscometer reading judgement reaction end that is as the criterion.Discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, obtains fluorine-containing polyester slice.
Embodiment 5
A preparation method for fluorine polyester, is divided into esterification and polycondensation two steps.Concrete steps are:
Described esterification:
Adopt ethylene glycol that mol ratio is 2.0: 1 and 2,5-difluoro terephthalic acid as raw material, add 0.04% manganese oxide of 2,5-difluoro terephthalic acid weight simultaneously, carry out esterification after being made into uniform sizing material; Esterification is pressurizeed in nitrogen atmosphere, and pressure-controlling is at normal pressure, and temperature is controlled at 230 ℃, and it is esterification terminal that esterification water quantity of distillate reaches 90% of theoretical value.
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The described polycondensation rough vacuum stage, in esterification products, add 2,0.05% the catalytic antimony trioxide and 2 of 5-difluoro terephthalic acid weight, 0.05% stablizer triphenylphosphate of 5-difluoro terephthalic acid weight, under the condition of negative pressure, start polycondensation, this staged pressure is steadily evacuated to absolute pressure by normal pressure and is less than 400Pa, and temperature is controlled at 270 ℃, and the reaction times is 40 minutes.
Described polycondensation high vacuum stage of Fig, after the described polycondensation rough vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 50Pa, and temperature of reaction is controlled at 285 ℃, 1 hour reaction times.Polycondensation is with reactor agitator motor power or the in-line viscometer reading judgement reaction end that is as the criterion.Discharging when polymer viscosity reaches desirable value, through Cast Strip, cooling, pelletizing, obtains fluorine-containing polyester slice.
Claims (6)
1. a preparation method for fluorine polyester, is characterized in that: the preparation method of described fluorine polyester is divided into esterification and polycondensation two steps;
Concrete steps are:
Described esterification:
Adopt fluorine-containing terephthalic acid and ethylene glycol as raw material, add inhibitor, carry out esterification after being made into uniform sizing material, obtain esterification products; Esterification is pressurizeed in nitrogen atmosphere, and pressure-controlling is at normal pressure～0.4MPa, and temperature is at 230～250 ℃, and what esterification water quantity of distillate reached theoretical value more than 90% is esterification terminal;
Described fluorine-containing terephthalic acid is tetrafluoro terephthalic acid or 2,5-difluoro terephthalic acid;
Described inhibitor is a kind of in magnesium oxide, silicon oxide, calcium oxide, zinc oxide and manganese oxide;
Described polycondensation:
Comprise polycondensation rough vacuum stage and polycondensation high vacuum stage of Fig:
The described polycondensation rough vacuum stage, in described esterification products, add catalyzer and stablizer, under the condition of negative pressure, start polycondensation, this staged pressure is steadily evacuated to below absolute pressure 1KPa by normal pressure, temperature is controlled at 250～270 ℃, and the reaction times is 40～60 minutes;
Described polycondensation high vacuum stage of Fig, after the described polycondensation rough vacuum stage, continues to vacuumize, and makes reaction pressure be down to absolute pressure and is less than 100Pa, and temperature of reaction is controlled at 270～285 ℃, 1～2 hour reaction times.
2. the preparation method of a kind of fluorine polyester according to claim 1, is characterized in that, the add-on of described inhibitor is 0.01%～0.05% of described fluorine-containing terephthalic acid weight.
3. the preparation method of a kind of fluorine polyester according to claim 1, is characterized in that, described ethylene glycol and the mol ratio of fluorine-containing terephthalic acid are 1.2～2.0: 1.
4. the preparation method of a kind of fluorine polyester according to claim 1, is characterized in that, described catalyzer is selected from a kind of in antimonous oxide, antimony glycol and antimony acetate, and catalyst levels is 0.01%～0.05% of described fluorine-containing terephthalic acid weight.
5. the preparation method of a kind of fluorine polyester according to claim 1, it is characterized in that, described stablizer is selected from a kind of in triphenylphosphate, trimethyl phosphite 99 and trimethyl phosphite, and stabilizing agent dosage is 0.01%～0.05% of described fluorine-containing terephthalic acid weight.
6. the fluorine polyester that preparation method as claimed in claim 1 makes, is characterized in that: described fluorine polyester refers to the polyethylene terephthalate that benzene ring hydrogen is replaced by fluorine, and its general structure is
Or
N=80～200 wherein.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106008940A (en) * | 2016-05-30 | 2016-10-12 | 江苏双星彩塑新材料股份有限公司 | Solar battery backplane, and preparation method of film polyester used for backplane |
| CN109233583A (en) * | 2018-09-27 | 2019-01-18 | 韶关市合众化工有限公司 | A kind of hydrophobic fire-retardant ordor removing PE piano woodcare paint of high adhesion force |
| CN109337057A (en) * | 2018-09-28 | 2019-02-15 | 韶关市合众化工有限公司 | A kind of Organic fluoride boron and the hydrophobic flame-retarded unsaturated polyester resin of epoxy-modified high adhesion force |
| CN109722736A (en) * | 2018-12-27 | 2019-05-07 | 江苏恒力化纤股份有限公司 | A kind of fluorine-containing binary acid modified poly ester FDY fiber and preparation method thereof |
| CN111286004A (en) * | 2020-03-31 | 2020-06-16 | 中电保力（北京）科技有限公司 | Hydrophobic polyurethane anti-condensation air-tight sealing material and preparation method thereof |
| CN113072699A (en) * | 2021-03-09 | 2021-07-06 | 东莞市华盈新材料有限公司 | Low-hygroscopicity PA10T and synthesis method thereof |
| CN117343303A (en) * | 2023-12-05 | 2024-01-05 | 山东广垠新材料有限公司 | Ultraviolet-resistant polyester elastomer and preparation method thereof |
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| CN106008940A (en) * | 2016-05-30 | 2016-10-12 | 江苏双星彩塑新材料股份有限公司 | Solar battery backplane, and preparation method of film polyester used for backplane |
| CN109233583A (en) * | 2018-09-27 | 2019-01-18 | 韶关市合众化工有限公司 | A kind of hydrophobic fire-retardant ordor removing PE piano woodcare paint of high adhesion force |
| CN109337057A (en) * | 2018-09-28 | 2019-02-15 | 韶关市合众化工有限公司 | A kind of Organic fluoride boron and the hydrophobic flame-retarded unsaturated polyester resin of epoxy-modified high adhesion force |
| CN109722736A (en) * | 2018-12-27 | 2019-05-07 | 江苏恒力化纤股份有限公司 | A kind of fluorine-containing binary acid modified poly ester FDY fiber and preparation method thereof |
| CN109722736B (en) * | 2018-12-27 | 2020-07-07 | 江苏恒力化纤股份有限公司 | Fluorine-containing diacid modified polyester FDY fiber and preparation method thereof |
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