CN105019246B - A kind of finish and preparation method thereof - Google Patents
A kind of finish and preparation method thereof Download PDFInfo
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- CN105019246B CN105019246B CN201510466520.6A CN201510466520A CN105019246B CN 105019246 B CN105019246 B CN 105019246B CN 201510466520 A CN201510466520 A CN 201510466520A CN 105019246 B CN105019246 B CN 105019246B
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Abstract
The present invention relates to a kind of finish and preparation method thereof, the finish at least includes fluorochemical polyether, the 45% of the quality of quality >=finish of fluorochemical polyether；Fluorochemical polyether is the random copolymer of oxirane, [(1,1,2,2 tetrafluoro ethyoxyl) methyl] oxirane and expoxy propane, and its structural formula is：
Description
Technical field
The present invention relates to a kind of finish and preparation method thereof.
Background technology
Polyester fiber has many excellent textile performances and wearability, by people's extensive use.In polyester fiber
, it is necessary to which finish to carry out a certain degree of protection to fiber in production process, make its occur in process of manufacture should not
Performance is damaged.
Conventional use of polyester fiber is 10%-15% with the concentration of finish, and remainder is water, and water is through hot plate
Evaporated mostly during heating, the evaporation of water can take away substantial amounts of heat, add the run time of fiber, while increasing energy consumption and dirt
Contaminate environment.The relatively low key factor of concentration be the problem of the cloud point of finish system in use is considered,
In certain limit, concentration is higher, and the temperature that cloud point occurs is lower, and cloud point causes the even equal property oiled to be deteriorated after occurring, greatly
Influence the effect of finish.
Cloud point be ehter bond on the very important physical parameter of nonionic surfactant, APEO can and moisture
Son forms hydrogen bond, surfactant is had a hydrophily, but when solution by after hot Hydrogen bonding forces weaken until disappearance.A certain
On temperature, nonionic surfactant is no longer combined with water, aggregation number of micelle increase, muddiness occurs in solution, and be separated into
Two liquid phases of micella and poor micella are enriched with, this temperature is cloud point.The cloud point of nonionic surface active agent and oxygen ethene
The factors such as mass fraction, relative molecular mass, the initiator of base are relevant.Spinning oil main component is oxirane (EO)/ring
Ethylene Oxide (PO) copolyether, while polyethers is used as the important high molecular surfactant of a class.Finish of good performance is with dense
The change of degree and temperature, the viscosity of emulsion should change steadily, and the size of viscosity directly influences the flatness of finish, even attached property
And spinnability.
In order to improve the service efficiency of spinning oil, and finish with concentration and the stability of temperature change, in polyethers
[(1,1,2,2- tetrafluoros ethyoxyl) methyl] is introduced on the basis of main component oxirane (EO)/expoxy propane (PO) copolyether
Oxirane, due to the presence of fluorine element, will increase more than the hydrogen chain number formed between hydrone, and can further improve polyethers
The cloud point of the aqueous solution.
Perfluoroalkyl acrylate is introduced in patent CN103469568A, its purpose is to the appropriate table for reducing finish
Face tension force, forms uniform continuous oil film, meets the demand of fluorine-containing production of polyester, but can not change the cloud point of polyethers in finish
And the change for the finish characteristic brought.
The content of the invention
It is an object of the invention to provide a kind of finish and preparation method thereof, finish is by mineral oil, fluorochemical polyether, phosphate potassium
Salt and sodium alkyl sulfonate composition, the concentration of the finish is 10~50wt%.The fluorochemical polyether middle ring used in the present invention
The composition of oxirane group monomer is moderate, while introducing [(1,1,2,2- tetrafluoro ethyoxyl) methyl] oxirane, adds body
Hydrogen bond in system, the increase of hydrogen bond is conducive to the raising of cloud point, remains to protect while the concentration of finish is being increased because a little
Hold the quality of finish.The increase of finish concentration can greatly reduce the consumption of energy in finish drying process, save energy.
A kind of finish, at least including fluorochemical polyether, the 45% of the quality of quality >=finish of fluorochemical polyether；It is described to contain
Perfluoroalkyl polyether is the random copolymer of oxirane, [(1,1,2,2- tetrafluoro ethyoxyl) methyl] oxirane and expoxy propane, its
Structural formula is：
Wherein, m=10~20, n=20~30, k=1~3.
The fluorochemical polyether can not only provide good smooth, emulsification and wetting function, additionally it is possible to be carried for finish system
For substantial amounts of hydrogen bond, cloud point is improved, is conducive to finish to use the raising of high concentration, energy is saved.Oxirane (EO)/epoxy third
Alkane (PO) ratio is one of most important index of polyethers, and the influence to polyethers performance is also very big.Pfpe molecule chain by multiple EO and
The arrangement of PO chain links is formed, and compared with EO, there is a side base on PO chain links, steric hindrance is larger.EO/PO is than increase, i.e. PO chain links
Reduce, pending methyl group quantity declines, intermolecular space steric hindrance is reduced, the hydrogen chain number formed between hydrone is more, so cloud point
Also raise.The presence of branched structure can reduce surface tension in pfpe molecule chain simultaneously, improve wetting speed, increase with EO/PO,
PO chain links containing branched chain methyl are reduced, thus surface tension rise, and wetting speed slows down, therefore must contain in polyethers macromolecular chain
There is a certain amount of PO.But polyethers relies primarily on the oxygen atom in ether with the hydrogen bond that hydrone is formed, so cloud point rise is limited,
The introducing of [(1,1,2,2- tetrafluoro ethyoxyl) methyl] oxirane, due to the presence of fluorine element, is formed between hydrone
It will increase more than hydrogen bond number, and can further improve the cloud point of polyether aqueous solution；Fluorine element will enter one all in branched positional simultaneously
The surface tension of step reduction polyethers.In finish formation oil film, fluorine element, due to the characteristic of fluorine element, can make in surface enrichment
The flatness of finish is further enhanced.
A kind of finish as described above, the relative molecular weight of the fluorochemical polyether is 1000~4000；The fluorochemical polyether
Cloud point be 50~100 DEG C.
A kind of finish as described above, 25~40dyn/cm of surface tension of the fluorochemical polyether.
Also include mineral oil, phosphate kalium salt and sodium alkyl sulfonate in a kind of finish as described above, the finish；Mineral
Oil has good heat resistance, has good compatibility with other components, and it has uniform, the characteristics of film strength is high that oil,
The coefficient of friction of fiber and metal can also be effectively reduced, increases the cohesive force of fiber, is conducive to boundling.It is anti-using anionic
Electrostatic agent, can realize surface hydrophilic, and relatively good, the good antistatic behaviour of the heat resistance of phosphate kalium salt can strengthen fibre
The antistatic effect of dimension, is conducive to the boundling of fiber.The addition of sodium alkyl sulfonate can improve the penetrating power of finish so that oil
Agent can be uniformly adhered on tow in the short period of time, can effectively reduce lousiness, the appearance of broken end.
By weight：Mineral oil is 25~35 parts；Fluorochemical polyether is 50~70 parts；Phosphate kalium salt is 8~15 parts；Alkane
Base sodium sulfonate is 2~7 parts；
Described mineral oil is one kind in 9#~17# mineral oil；Described phosphate kalium salt is dodecylphosphoric acid
One kind in ester sylvite, isomerous tridecanol polyoxyethylene ether phosphate kalium salt and ten tetracosanol phosphate kalium salts；Described alkane
Base sodium sulfonate is one kind in dodecyl sodium sulfate, pentadecyl sulfonic acid sodium and sodium cetanesulfonate.
The present invention also provides a kind of preparation method of finish, and step is：Initiator and highly basic are blended, then heated to
105~125 DEG C, add well mixed oxirane, [(1,1,2,2- tetrafluoro ethyoxyl) methyl] oxirane and epoxy
Propane, carries out polymerisation under protective atmosphere, and reaction pressure is less than 0.4MPa, reaches and obtains fluorine-containing poly- after predetermined molecular weight
Ether；
Then, fluorochemical polyether, phosphate kalium salt and sodium alkyl sulfonate normal temperature are well mixed, then fed the mixture into again
Into mineral oil, temperature control is 40-55 DEG C, stirs 1~3h, that is, obtains the finish；
By weight：
A kind of preparation method of finish as described above, the initiator is butanol, the amount of the butanol is oxirane,
The 1-5 ‰ of [(1,1,2,2- tetrafluoros ethyoxyl) methyl] oxirane and expoxy propane gross mass；The highly basic is potassium hydroxide
Or sodium hydroxide；The amount of the highly basic is oxirane, [(1,1,2,2- tetrafluoros ethyoxyl) methyl] oxirane and epoxy third
The 1-5 ‰ of alkane gross mass.
A kind of preparation method of finish as described above, the oxirane, [(1,1,2,2- tetrafluoro ethyoxyl) methyl]
The consumption of oxirane and expoxy propane is 10~20 in molar ratio:1~3:20~30.
A kind of preparation method of finish as described above, the protective atmosphere is nitrogen atmosphere or inert gas atmosphere；Institute
State predetermined molecular weight and refer to that the relative molecular weight of product is 1000~4000.
A kind of preparation method of finish as described above, the product reached after predetermined molecular weight is also neutralized, inhaled
Attached, vacuum dehydration, drying and filtering.
A kind of preparation method of finish as described above, when in use, it is 10 that oil concentration is configured to water to the finish
~50wt% emulsion.
Beneficial effect：
1. the composition of fluorochemical polyether ethylene oxide base monomer is moderate, while introducing [(1,1,2,2- tetrafluoro ethyoxyl)
Methyl] oxirane, the hydrogen bond in system is added, the increase of hydrogen bond is conducive to the raising of cloud point, because a little in increase finish
Concentration while remain to keep finish quality.
2. in spinning oil formation oil film, fluorine element, due to the characteristic of fluorine element, can make the flat of finish in surface enrichment
Slip is further enhanced, and reduces the damage of fiber in the process of running.Fluorine element will enter all in branched positional simultaneously
One step reduces the surface tension of polyethers.
3. the increase of finish concentration can greatly reduce the consumption of energy in finish drying process, energy is saved.
4. the service efficiency of spinning oil is improved, and finish is with concentration and the stability of temperature change.
Embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
Bright rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, art technology
Personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Fixed scope.
A kind of finish, at least including fluorochemical polyether, the 45% of the quality of quality >=finish of fluorochemical polyether；It is described to contain
Perfluoroalkyl polyether is the random copolymer of oxirane, [(1,1,2,2- tetrafluoro ethyoxyl) methyl] oxirane and expoxy propane, its
Structural formula is：
Wherein, m=10~20, n=20~30, k=1~3.
Wherein, the relative molecular weight of the fluorochemical polyether is 1000~4000；The cloud point of the fluorochemical polyether is 50~100
℃；25~40dyn/cm of surface tension of the fluorochemical polyether；
Also include mineral oil, phosphate kalium salt and sodium alkyl sulfonate in the finish；
By weight：Mineral oil is 25~35 parts；Fluorochemical polyether is 50~70 parts；Phosphate kalium salt is 8~15 parts；Alkane
Base sodium sulfonate is 2~7 parts；
Described mineral oil is one kind in 9#~17# mineral oil；Described phosphate kalium salt is dodecylphosphoric acid
One kind in ester sylvite, isomerous tridecanol polyoxyethylene ether phosphate kalium salt and ten tetracosanol phosphate kalium salts；Described alkane
Base sodium sulfonate is one kind in dodecyl sodium sulfate, pentadecyl sulfonic acid sodium and sodium cetanesulfonate.
Embodiment 1
A kind of preparation method of finish, step is：Initiator butanol and highly basic potassium hydroxide are blended, then heated to
105 DEG C, well mixed oxirane, [(1,1,2,2- tetrafluoro ethyoxyl) methyl] oxirane and expoxy propane are added,
The amount of butanol is the 1 ‰ of oxirane, [(1,1,2,2- tetrafluoro ethyoxyl) methyl] oxirane and expoxy propane gross mass, by force
The amount of alkali potassium hydroxide is oxirane, [(1,1,2,2- tetrafluoros ethyoxyl) methyl] oxirane and expoxy propane gross mass
1 ‰, the consumption of oxirane, [(1,1,2,2- tetrafluoro ethyoxyl) methyl] oxirane and expoxy propane is 10 in molar ratio:
1:20, polymerisation is carried out in the case where protective atmosphere is nitrogen atmosphere, reaction pressure is 0.4MPa, it is 1000 to reach relative molecular weight
Afterwards, that is, fluorochemical polyether is obtained, its cloud point is 50 DEG C, its surface tension 25dyn/cm；
Then, by fluorochemical polyether, phosphate kalium salt 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and sodium alkyl sulfonate dodecyl sodium sulfonate
Sodium normal temperature is well mixed, and is then added mixture to again in mineral oil, and temperature control is 40 DEG C, stirs 1h, that is, obtains finish,
Finish when in use, the emulsion that oil concentration is 10wt% is configured to water；
By weight：
Embodiment 2
A kind of preparation method of finish, step is：Initiator butanol and highly basic sodium hydroxide are blended, then heated to
125 DEG C, well mixed oxirane, [(1,1,2,2- tetrafluoro ethyoxyl) methyl] oxirane and expoxy propane are added,
The amount of butanol is the 5 ‰ of oxirane, [(1,1,2,2- tetrafluoro ethyoxyl) methyl] oxirane and expoxy propane gross mass, by force
The amount of alkali sodium hydroxide is oxirane, [(1,1,2,2- tetrafluoros ethyoxyl) methyl] oxirane and expoxy propane gross mass
5 ‰, the consumption of oxirane, [(1,1,2,2- tetrafluoro ethyoxyl) methyl] oxirane and expoxy propane is 20 in molar ratio:
3:30, polymerisation is carried out in the case where protective atmosphere is inert gas atmosphere, reaction pressure is 0.5MPa, reaches that relative molecular weight is
After 4000, neutralized, adsorbed, vacuum dehydration, drying and filtering, that is, obtain fluorochemical polyether, its cloud point is 100 DEG C, its surface
Tension force 32dyn/cm；
Then, by fluorochemical polyether, phosphate kalium salt isomerous tridecanol polyoxyethylene ether phosphate kalium salt and sodium alkyl sulfonate
Dodecyl sodium sulfate normal temperature is well mixed, and is then added mixture to again in mineral oil, and temperature control is 55 DEG C, stirring
3h, that is, obtain finish, and finish when in use, the emulsion that oil concentration is 50wt% is configured to water；
By weight：
Embodiment 3
A kind of preparation method of finish, step is：Initiator butanol and highly basic sodium hydroxide are blended, then heated to
115 DEG C, well mixed oxirane, [(1,1,2,2- tetrafluoro ethyoxyl) methyl] oxirane and expoxy propane are added,
The amount of butanol is the 2 ‰ of oxirane, [(1,1,2,2- tetrafluoro ethyoxyl) methyl] oxirane and expoxy propane gross mass, by force
The amount of alkali sodium hydroxide is oxirane, [(1,1,2,2- tetrafluoros ethyoxyl) methyl] oxirane and expoxy propane gross mass
1.5 ‰, the consumption of oxirane, [(1,1,2,2- tetrafluoro ethyoxyl) methyl] oxirane and expoxy propane is in molar ratio
12:1:30, polymerisation is carried out in the case where protective atmosphere is inert gas atmosphere, reaction pressure is 0.8MPa, reaches average molecular
Measure after 3000, to be neutralized, being adsorbed, vacuum dehydration, drying and filtering, that is, obtain fluorochemical polyether, its cloud point is 100 DEG C, its
Surface tension 40dyn/cm；
Then, by fluorochemical polyether, the tetracosanol phosphate kalium salt of phosphate kalium salt ten and sodium alkyl sulfonate cetyl sulphur
Sour sodium normal temperature is well mixed, and is then added mixture to again in mineral oil, and temperature control is 45 DEG C, stirs 2h, that is, obtains oil
Agent, finish when in use, the emulsion that oil concentration is 18wt% is configured to water；
By weight：
Embodiment 4
A kind of preparation method of finish, step is：Initiator butanol and highly basic potassium hydroxide are blended, then heated to
120 DEG C, well mixed oxirane, [(1,1,2,2- tetrafluoro ethyoxyl) methyl] oxirane and expoxy propane are added,
The amount of butanol is the 4 ‰ of oxirane, [(1,1,2,2- tetrafluoro ethyoxyl) methyl] oxirane and expoxy propane gross mass, by force
The amount of alkali potassium hydroxide is oxirane, [(1,1,2,2- tetrafluoros ethyoxyl) methyl] oxirane and expoxy propane gross mass
4 ‰, the consumption of oxirane, [(1,1,2,2- tetrafluoro ethyoxyl) methyl] oxirane and expoxy propane is 20 in molar ratio:
2:26, polymerisation is carried out in the case where protective atmosphere is inert gas atmosphere, reaction pressure is 0.8MPa, reaches that relative molecular weight is
After 2500, neutralized, adsorbed, vacuum dehydration, drying and filtering, that is, obtain fluorochemical polyether, its cloud point is 80 DEG C, its surface
Power 37dyn/cm；
Then, by fluorochemical polyether, phosphate kalium salt 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite and sodium alkyl sulfonate dodecyl sodium sulfonate
Sodium normal temperature is well mixed, and is then added mixture to again in mineral oil, and temperature control is 45 DEG C, stirs 2h, that is, obtains finish,
Finish when in use, the emulsion that oil concentration is 35wt% is configured to water；
By weight：
Embodiment 5
A kind of preparation method of finish, step is：Initiator butanol and highly basic potassium hydroxide are blended, then heated to
125 DEG C, well mixed oxirane, [(1,1,2,2- tetrafluoro ethyoxyl) methyl] oxirane and expoxy propane are added,
The amount of butanol is the 3 ‰ of oxirane, [(1,1,2,2- tetrafluoro ethyoxyl) methyl] oxirane and expoxy propane gross mass, by force
The amount of alkali is the 3 ‰ of oxirane, [(1,1,2,2- tetrafluoro ethyoxyl) methyl] oxirane and expoxy propane gross mass, epoxy
The consumption of ethane, [(1,1,2,2- tetrafluoros ethyoxyl) methyl] oxirane and expoxy propane is 18 in molar ratio:2:20, protecting
Shield atmosphere be nitrogen atmosphere under carry out polymerisation, reaction pressure is 0.9MPa, reach relative molecular weight be 2500 after, in progress
With, absorption, vacuum dehydration, drying and filtering, that is, fluorochemical polyether is obtained, its cloud point is 70 DEG C, its surface tension 29dyn/cm；
Then, by fluorochemical polyether, phosphate kalium salt isomerous tridecanol polyoxyethylene ether phosphate kalium salt and sodium alkyl sulfonate
Pentadecyl sulfonic acid sodium normal temperature is well mixed, and is then added mixture to again in mineral oil, and temperature control is 48 DEG C, stirring
1h, that is, obtain finish, and finish when in use, the emulsion that oil concentration is 50wt% is configured to water；
By weight：
Embodiment 6
A kind of preparation method of finish, step is：Initiator butanol and highly basic sodium hydroxide are blended, then heated to
123 DEG C, well mixed oxirane, [(1,1,2,2- tetrafluoro ethyoxyl) methyl] oxirane and expoxy propane are added,
The amount of butanol is the 4 ‰ of oxirane, [(1,1,2,2- tetrafluoro ethyoxyl) methyl] oxirane and expoxy propane gross mass, by force
The amount of alkali is the 2 ‰ of oxirane, [(1,1,2,2- tetrafluoro ethyoxyl) methyl] oxirane and expoxy propane gross mass, epoxy
The consumption of ethane, [(1,1,2,2- tetrafluoros ethyoxyl) methyl] oxirane and expoxy propane is 18 in molar ratio:2:26, protecting
Shield atmosphere be nitrogen atmosphere under carry out polymerisation, reaction pressure is 1.0MPa, reach relative molecular weight be 1600 after, in progress
With, absorption, vacuum dehydration, drying and filtering, that is, fluorochemical polyether is obtained, its cloud point is 82 DEG C, its surface tension 33dyn/cm；
Then, by fluorochemical polyether, the tetracosanol phosphate kalium salt of phosphate kalium salt ten and sodium alkyl sulfonate cetyl sulphur
Sour sodium normal temperature is well mixed, and is then added mixture to again in mineral oil, and temperature control is 48 DEG C, stirs 2h, that is, obtains oil
Agent, finish when in use, the emulsion that oil concentration is 16wt% is configured to water；
By weight：
Claims (8)
1. a kind of finish, it is characterized in that：At least include fluorochemical polyether, the quality of quality >=finish of fluorochemical polyether
45%；The fluorochemical polyether is the nothing of oxirane, [(1,1,2,2- tetrafluoros ethyoxyl) methyl] oxirane and expoxy propane
Copolymer is advised, its structural formula is：
Wherein, m=10~20, n=20~30, k=1~3；
The cloud point of the fluorochemical polyether is 50~100 DEG C；25~40dyn/cm of surface tension of the fluorochemical polyether；
The relative molecular weight of the fluorochemical polyether is 1000~4000.
2. a kind of finish according to claim 1, it is characterised in that also include mineral oil, phosphate potassium in the finish
Salt and sodium alkyl sulfonate；
By weight：Mineral oil is 25~35 parts；Fluorochemical polyether is 50~70 parts；Phosphate kalium salt is 8~15 parts；Alkyl sulphur
Sour sodium is 2~7 parts；
Described mineral oil is one kind in 9#~17# mineral oil；Described phosphate kalium salt is 1-isobutyl-3,5-dimethylhexylphosphoric acid potassium
One kind in salt and isomerous tridecanol polyoxyethylene ether phosphate kalium salt；Described sodium alkyl sulfonate be dodecyl sodium sulfate,
One kind in pentadecyl sulfonic acid sodium and sodium cetanesulfonate.
3. a kind of preparation method of finish as claimed in claim 1, it is characterized in that step is：Butanol and highly basic are blended, so
After be warming up to 105~125 DEG C, add well mixed oxirane, [(1,1,2,2- tetrafluoro ethyoxyl) methyl] epoxy second
Alkane and expoxy propane, carry out polymerisation under protective atmosphere, and reaction pressure is less than 0.4MPa, reaches and produced after predetermined molecular weight
To fluorochemical polyether；
Then, fluorochemical polyether, phosphate kalium salt and sodium alkyl sulfonate normal temperature are well mixed, ore deposit is then added mixture to again
In thing oil, temperature control is 40-55 DEG C, stirs 1~3h, that is, obtains the finish；
By weight：
4. the preparation method of a kind of finish according to claim 3, it is characterised in that the amount of the butanol is epoxy second
The 1-5 ‰ of alkane, [(1,1,2,2- tetrafluoros ethyoxyl) methyl] oxirane and expoxy propane gross mass；The highly basic is hydroxide
Potassium or sodium hydroxide；The amount of the highly basic is oxirane, [(1,1,2,2- tetrafluoros ethyoxyl) methyl] oxirane and epoxy
The 1-5 ‰ of propane gross mass.
5. a kind of preparation method of finish according to claim 3, it is characterised in that the oxirane, [(1,1,2,
2- tetrafluoros ethyoxyl) methyl] consumption of oxirane and expoxy propane is 10~20 in molar ratio:1~3:20~30.
6. the preparation method of a kind of finish according to claim 3, it is characterised in that the protective atmosphere is nitrogen atmosphere
Or inert gas atmosphere；The predetermined molecular weight refers to that the relative molecular weight of product is 1000~4000.
7. the preparation method of a kind of finish according to claim 3, it is characterised in that described to reach after predetermined molecular weight
Product is also neutralized, adsorbed, vacuum dehydration, drying and filtering.
8. the preparation method of a kind of finish according to claim 3, it is characterised in that the finish when in use, uses water
It is configured to the emulsion that oil concentration is 10~50wt%.
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| CN101929068A (en) * | 2010-08-24 | 2010-12-29 | 上虞市皇马化学有限公司 | Polyester POY spinning finish and production method thereof |
| CN102767075A (en) * | 2012-06-25 | 2012-11-07 | 桐乡市恒隆化工有限公司 | Oiling agent for producing high-F terylene DTY and production method thereof |
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| JPH10182814A (en) * | 1996-12-25 | 1998-07-07 | Kao Corp | Fluoro polyether graft polymer and its production |
| EP2231747A1 (en) * | 2007-12-21 | 2010-09-29 | 3M Innovative Properties Company | Fluorinated polymer compositions and methods for treating hydrocarbon-bearing formations using the same |
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| CN101929068A (en) * | 2010-08-24 | 2010-12-29 | 上虞市皇马化学有限公司 | Polyester POY spinning finish and production method thereof |
| CN102767075A (en) * | 2012-06-25 | 2012-11-07 | 桐乡市恒隆化工有限公司 | Oiling agent for producing high-F terylene DTY and production method thereof |
| CN102978934A (en) * | 2012-11-28 | 2013-03-20 | 浙江天圣控股集团有限公司 | Low-smoke FDY (Fully Drawn Yarn) oiling agent and preparation method thereof |
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