CN103642013A - Preparation method of polytrimethylene terephthalate - Google Patents
Preparation method of polytrimethylene terephthalate Download PDFInfo
- Publication number
- CN103642013A CN103642013A CN201310580757.8A CN201310580757A CN103642013A CN 103642013 A CN103642013 A CN 103642013A CN 201310580757 A CN201310580757 A CN 201310580757A CN 103642013 A CN103642013 A CN 103642013A
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- CN
- China
- Prior art keywords
- terephthalic acid
- preparation
- reaction
- tetraethyl titanate
- oxalic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 polytrimethylene terephthalate Polymers 0.000 title claims abstract description 50
- 229920002215 polytrimethylene terephthalate Polymers 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 136
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 108
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims abstract description 70
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 36
- 238000005886 esterification reaction Methods 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims abstract 15
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims abstract 9
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims abstract 9
- 238000006068 polycondensation reaction Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- FRHSFOIZFYYLRC-UHFFFAOYSA-N formic acid terephthalic acid Chemical compound OC=O.OC(=O)c1ccc(cc1)C(O)=O FRHSFOIZFYYLRC-UHFFFAOYSA-N 0.000 claims 1
- 230000032050 esterification Effects 0.000 abstract description 10
- 229920000728 polyester Polymers 0.000 abstract description 8
- 239000000835 fiber Substances 0.000 abstract description 4
- 229940035437 1,3-propanediol Drugs 0.000 abstract 2
- 239000000203 mixture Substances 0.000 abstract 2
- 238000012643 polycondensation polymerization Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- GJYPUXPGBAIWQC-UHFFFAOYSA-N C(Cl)(Cl)Cl.C1(=CC=CC=C1)O.C1=CC=CC=C1 Chemical compound C(Cl)(Cl)Cl.C1(=CC=CC=C1)O.C1=CC=CC=C1 GJYPUXPGBAIWQC-UHFFFAOYSA-N 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- SWPSRVKULRXLOX-UHFFFAOYSA-M [OH-].[Na+].C1=CC=CC=C1.CO Chemical compound [OH-].[Na+].C1=CC=CC=C1.CO SWPSRVKULRXLOX-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to technical field of polyester fiber preparation, and specifically relates to a preparation method of polytrimethylene terephthalate. According to the preparation method, terephthalic acid and 1, 3-propanediol are taken as raw materials. The preparation method comprises following steps: (1) titanium ethoxide, terephthalic acid and 1, 3-propanediol are delivered into an esterification reaction tank, oxalic acid is added dropwise so as to obtain a mixture, and the mixture is subjected to normal pressure esterification for 30 to 60min at a temperature of 220 to 240 DEG C; and (2) titanium ethoxide is added for stirring, and at the same time oxalic acid is added dropwise for condensation polymerization for 3 to 5h, at a temperature of 220 to 240 DEG C, under a reaction pressure of 0.01 to 0.05 MPa so as to obtain polytrimethylene terephthalate. Technology of the preparation method is simple, and effect is excellent.
Description
Technical field
The invention belongs to technical field prepared by polyester fiber, be specially a kind of preparation method of Poly(Trimethylene Terephthalate).
Background technology
Poly(Trimethylene Terephthalate) (PTT or PPT) fiber is the polyester tencel of a kind of excellent performance of Shell company exploitation, it is by terephthalic acid (PTA) and 1, ammediol (PDO) polycondensation forms, and its molecular structural formula is ((CH
2) 3O O=C O=CO)).
PPT/PTT is the new polyester after PET, PBT, and advantage is to combine:
1, the flexibility of nylon, (than the better colour fastness of nylon);
2, the fluffiness of acrylic fibers, (avoiding the shortcoming of acrylic fibers balling-up easy to wear);
3, the pollution resistance of terylene, (but having good feel).
4, the feature of own intrinsic good springiness.
Integrate various good wear behavior.The popular novel material that becomes current recent development in the world, is widely used in the fields such as finishing material, textile garment, engineering plastics, film.
Due to the excellent properties of PTT, it can be widely used in the every field such as dress material, industry, decoration and engineering plastics, particularly in carpet applications, will become the strong rival of PA.According to relevant expert, estimate, the demand about 55% of ptt fiber is from carpet applications, and remaining 45% is other textile field.The performance condition of PTT has been determined its wide Application Areas, and the market value of PTT is higher at present, thereby limits it and can only aspect the stronger product of cost digestion ability and kind, obtain limited development result; Once can drop to suitable price level, the market development of PTT just will be difficult to the situation of expecting and be shaped up with people.
The method of industrial production PTT mainly contains DMT method (ester-interchange method) and PTA method (direct esterification) at present, no matter is esterification or transesterification reaction, and that obtain is all intermediate product BHPT.BHPT is PTT in stage polycondensation subsequently, and PTA and DMT route are identical in polycondensation phase.The advantage of PTA method is because PTA cost ratio DMT is cheap, makes production of polyester cost, and PTA route by-product methyl alcohol not, can save the operation that reclaims methyl alcohol, saves investment, reduces and pollutes, and is conducive to safety in production, suitable employing PTA method in industrial production.But it is the nonhomogeneous system that solid phase PTA and liquid phase P DO coexist that shortcoming is reaction system, it is large that difficulty is controlled in reaction, along with the growth of molecular chain in PTT polymerization process, some side reactions can affect the molecular weight of polymkeric substance as generated cyclic oligomer, end of the chain degraded, interchain degraded etc.And allyl group and vinyl carbinol that PTT end group reaction generates be reversible transition, end group stabilization, thus suppressed the continuation growth of molecular chain.
Summary of the invention
The object of the invention is to for the problem of above-mentioned existence and a kind of preparation method of Poly(Trimethylene Terephthalate) is provided.The method adopts that to take terephthalic acid and 1,3-PD be raw material, and step (1) is by tetraethyl titanate, terephthalic acid and 1, ammediol adds in esterification reaction tank, drips oxalic acid simultaneously, carries out normal pressure esterification reaction 30-60 minute, wherein, the temperature of esterification is 220-240 ℃; Step (2) then adds tetraethyl titanate to stir, and drips oxalic acid simultaneously and carries out polycondensation, reaction 3-5 hour, temperature of reaction is 220-240 ℃, reaction pressure is the technical scheme of 0.01-0.05MPa, and technique is simple, and the Poly(Trimethylene Terephthalate) obtaining is effective.
Technical scheme of the present invention is:
A preparation method for Poly(Trimethylene Terephthalate), take terephthalic acid and 1,3-PD as raw material, it is characterized in that,
Step (1) adds tetraethyl titanate, terephthalic acid and 1,3-PD in esterification reaction tank, drips oxalic acid simultaneously, carries out normal pressure esterification reaction 30-60 minute, and wherein, the temperature of esterification is 220-240 ℃;
Step (2) then adds tetraethyl titanate to stir, and drip oxalic acid simultaneously and carry out polycondensation, reaction 3-5 hour, temperature of reaction is 220-240 ℃, reaction pressure is 0.01-0.05MPa.
Feature of the present invention also has:
Wherein, in step (1), the mole dosage proportionlity of terephthalic acid and 1,3-PD is, terephthalic acid: 1,3-PD=1:1.05-1.3.
In step (1), the consumption of tetraethyl titanate is the 0.0001-0.001% of terephthalic acid molar weight.
In step (1), the consumption of oxalic acid is the 0.0005-0.001% of terephthalic acid molar weight.
In step (2), the consumption of tetraethyl titanate is the 0.0001-0.001% of terephthalic acid molar weight.
In step (2), the consumption of oxalic acid is the 0.0005-0.001% of terephthalic acid molar weight.
As preferably, the preparation method of Poly(Trimethylene Terephthalate) of the present invention, take terephthalic acid and 1,3-PD as raw material, it is characterized in that,
Step (1) adds tetraethyl titanate, terephthalic acid and 1,3-PD in esterification reaction tank, drips oxalic acid simultaneously, carries out normal pressure esterification reaction 30 minutes, and wherein, the temperature of esterification is 220 ℃;
Step (2) then adds tetraethyl titanate to stir, and drips oxalic acid simultaneously and carries out polycondensation, reacts 5 hours, and temperature of reaction is 220 ℃, and reaction pressure is 0.05MPa.
As further preferred, the preparation method of Poly(Trimethylene Terephthalate) of the present invention, take terephthalic acid and 1,3-PD as raw material, it is characterized in that,
Step (1) adds tetraethyl titanate, terephthalic acid and 1,3-PD in esterification reaction tank, drips oxalic acid simultaneously, carries out normal pressure esterification reaction 30 minutes, and wherein, the temperature of esterification is 220 ℃; The mole dosage proportionlity of terephthalic acid and 1,3-PD is, terephthalic acid: 1,3-PD=1:1.05; The consumption of tetraethyl titanate is 0.001% of terephthalic acid molar weight; The consumption of oxalic acid is 0.0005% of terephthalic acid molar weight.
Step (2) then adds tetraethyl titanate to stir, and drips oxalic acid simultaneously and carries out polycondensation, reacts 5 hours, and temperature of reaction is 220 ℃, and reaction pressure is 0.05MPa; The consumption of tetraethyl titanate is 0.0001% of terephthalic acid molar weight; The consumption of oxalic acid is 0.0005% of terephthalic acid molar weight.
Beneficial effect of the present invention is:
Preparation method of the present invention passes through processing condition, material carries out improvement and bring new ideas by magnitude relation and catalyst type, by the acting in conjunction of each factor, has obtained a kind of high-performance poly propylene glycol ester terephthalate's preparation method, this preparation method's catalyst levels is little, speed of reaction is very fast, and reaction conditions is gentle, the excellent property of the polyester obtaining, content of carboxyl end group is low, limiting viscosity is high, between 0.85-0.86dL/g, and lighter color.
In a word, the preparation method of Poly(Trimethylene Terephthalate) of the present invention, technique is simple, and the Poly(Trimethylene Terephthalate) obtaining is effective, has outstanding substantive distinguishing features and significant progressive, possesses creativeness.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in detail.
The testing method of each index of Poly(Trimethylene Terephthalate) obtaining is as follows:
Reaction unit:
Adopt reaction rectification integrated experimental device, be furnished with electric mixer, nitrogen protection and vacuum system.
Limiting viscosity
0.1250gPTT polyester product is dissolved in to 25mL phenol and 1,1,2,2, in the solution that waits mass mixing thing of-tetrachloroethane, utilizes Ubbelohde viscometer to measure in 25 ± 0.1 ℃ of waters bath with thermostatic control.
Content of carboxyl end group
The PTT polyester powder of certain mass (about 0.25g) is dissolved in benzene phenol-chloroform (volume ratio is 2:3) mixed solvent, and heating in water bath, to all dissolving, is titrated to 0.2% bromjophenol blue indicator discoloration with sodium hydroxide-Methanol-benzene methyl alcohol standardized solution.
embodiment 1
the preparation method of Poly(Trimethylene Terephthalate) of the present invention, take terephthalic acid and 1,3-PD as raw material,
Step (1) adds tetraethyl titanate, terephthalic acid and 1,3-PD in esterification reaction tank, drips oxalic acid simultaneously, carries out normal pressure esterification reaction 30 minutes, and wherein, the temperature of esterification is 220 ℃; The mole dosage proportionlity of terephthalic acid and 1,3-PD is, terephthalic acid: 1,3-PD=1:1.05; The consumption of tetraethyl titanate is 0.001% of terephthalic acid molar weight; The consumption of oxalic acid is 0.0005% of terephthalic acid molar weight.
Step (2) then adds tetraethyl titanate to stir, and drips oxalic acid simultaneously and carries out polycondensation, reacts 5 hours, and temperature of reaction is 220 ℃, and reaction pressure is 0.05MPa; The consumption of tetraethyl titanate is 0.0001% of terephthalic acid molar weight; The consumption of oxalic acid is 0.0005% of terephthalic acid molar weight.
The performance index of the Poly(Trimethylene Terephthalate) obtaining are as follows: limiting viscosity 0.8589dL/g, and content of carboxyl end group 22mol/t, color is pale yellow.
embodiment 2
?the preparation method of Poly(Trimethylene Terephthalate) of the present invention, take terephthalic acid and 1,3-PD as raw material,
Step (1) adds tetraethyl titanate, terephthalic acid and 1,3-PD in esterification reaction tank, drips oxalic acid simultaneously, carries out normal pressure esterification reaction 60 minutes, and wherein, the temperature of esterification is 240 ℃; The mole dosage proportionlity of terephthalic acid and 1,3-PD is, terephthalic acid: 1,3-PD=1:1.3; The consumption of tetraethyl titanate is 0.0001% of terephthalic acid molar weight; The consumption of oxalic acid is 0.001% of terephthalic acid molar weight.
Step (2) then adds tetraethyl titanate to stir, and drips oxalic acid simultaneously and carries out polycondensation, reacts 3 hours, and temperature of reaction is 240 ℃, and reaction pressure is 0.01MPa; The consumption of tetraethyl titanate is 0.001% of terephthalic acid molar weight; The consumption of oxalic acid is 0.001% of terephthalic acid molar weight.
The performance index of the Poly(Trimethylene Terephthalate) obtaining are as follows: limiting viscosity 0.8512dL/g, and content of carboxyl end group 23mol/t, color is pale yellow.
embodiment 3
?the preparation method of Poly(Trimethylene Terephthalate) of the present invention, take terephthalic acid and 1,3-PD as raw material,
Step (1) adds tetraethyl titanate, terephthalic acid and 1,3-PD in esterification reaction tank, drips oxalic acid simultaneously, carries out normal pressure esterification reaction 45 minutes, and wherein, the temperature of esterification is 230 ℃; The mole dosage proportionlity of terephthalic acid and 1,3-PD is, terephthalic acid: 1,3-PD=1:1.1; The consumption of tetraethyl titanate is 0.0005% of terephthalic acid molar weight; The consumption of oxalic acid is 0.0008% of terephthalic acid molar weight.
Step (2) then adds tetraethyl titanate to stir, and drips oxalic acid simultaneously and carries out polycondensation, reacts 4 hours, and temperature of reaction is 230 ℃, and reaction pressure is 0.03MPa; The consumption of tetraethyl titanate is 0.0005% of terephthalic acid molar weight; The consumption of oxalic acid is 0.0008% of terephthalic acid molar weight.
The performance index of the Poly(Trimethylene Terephthalate) obtaining are as follows: limiting viscosity 0.8524dL/g, and content of carboxyl end group 23mol/t, color is pale yellow.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310580757.8A CN103642013B (en) | 2013-11-19 | 2013-11-19 | A kind of preparation method of Poly(Trimethylene Terephthalate) |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310580757.8A CN103642013B (en) | 2013-11-19 | 2013-11-19 | A kind of preparation method of Poly(Trimethylene Terephthalate) |
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| CN103642013A true CN103642013A (en) | 2014-03-19 |
| CN103642013B CN103642013B (en) | 2016-01-20 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117187977A (en) * | 2023-09-15 | 2023-12-08 | 邵阳阳光发品有限公司 | Chemical fiber filament and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1643032A (en) * | 2002-03-18 | 2005-07-20 | 旭化成纤维株式会社 | Polytrimethylene terephthalate composition particles and process for producing the same |
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- 2013-11-19 CN CN201310580757.8A patent/CN103642013B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1643032A (en) * | 2002-03-18 | 2005-07-20 | 旭化成纤维株式会社 | Polytrimethylene terephthalate composition particles and process for producing the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117187977A (en) * | 2023-09-15 | 2023-12-08 | 邵阳阳光发品有限公司 | Chemical fiber filament and preparation method thereof |
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| CN103642013B (en) | 2016-01-20 |
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