CN103642013B - A kind of preparation method of Poly(Trimethylene Terephthalate) - Google Patents
A kind of preparation method of Poly(Trimethylene Terephthalate) Download PDFInfo
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- CN103642013B CN103642013B CN201310580757.8A CN201310580757A CN103642013B CN 103642013 B CN103642013 B CN 103642013B CN 201310580757 A CN201310580757 A CN 201310580757A CN 103642013 B CN103642013 B CN 103642013B
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Abstract
The invention belongs to technical field prepared by polyester fiber, be specially a kind of preparation method of Poly(Trimethylene Terephthalate).The method adopts with terephthalic acid and 1,3-PD for 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 DEG C; Step (2) then adds tetraethyl titanate and stirs, and drips oxalic acid simultaneously and carries out polycondensation, reaction 3-5 hour, temperature of reaction is 220-240 DEG C, reaction pressure is the technical scheme of 0.01-0.05MPa, and technique is simple, and the Poly(Trimethylene Terephthalate) obtained is effective.
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) 3OO=CO=CO)).
PPT/PTT is the new polyester after PET, PBT, and advantage combines:
1, the flexibility of nylon, (colour fastness more better than 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 good springiness inherently.
Integrate various excellent wear behavior.Become the popular novel material of current recent development in the world, be 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 will become the strong rival of PA in carpet applications.Estimate according to relevant expert, the demand about 55% of ptt fiber is from carpet applications, and remaining 45% is other textile field.The performance condition of PTT determines its wide Application Areas, and the market value of current PTT is higher, thus limits it and can only obtain limited development result in the stronger product of cost digestion ability and kind; Once suitable price level can be dropped to, the market development of PTT just by with people be difficult to the situation expected and shape up.
The method of current industrial production PTT mainly contains DMT method (ester-interchange method) and PTA method (direct esterification), no matter is esterification or transesterification reaction, and that obtain is all intermediate product BHPT.BHPT is PTT, PTA and DMT route at multi-stage polycondensation is subsequently identical in polycondensation phase.The advantage of PTA method is because PTA cost ratio DMT is cheap, and production of polyester cost is reduced, and PTA route not by-product methyl alcohol, can save the operation reclaiming methyl alcohol, investment reduction, decreasing pollution, be conducive to safety in production, be suitable for adopting PTA method in industrial production.But shortcoming is that reaction system is the nonhomogeneous system that solid phase PTA and liquid phase P DO coexists, reaction controlling difficulty is large, along with the growth of PTT polymerization process Middle molecule chain, some side reactions can affect the molecular weight of polymkeric substance as generated cyclic oligomer, end of the chain degraded, interchain degraded etc.And the allyl group that generates of PTT end group reaction and vinyl carbinol are reversible transitions, end group stabilization, thus inhibit the continuation of molecular chain to increase.
Summary of the invention
The object of the invention is to the preparation method that a kind of Poly(Trimethylene Terephthalate) is provided for above-mentioned Problems existing.The method adopts with terephthalic acid and 1,3-PD for 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 DEG C; Step (2) then adds tetraethyl titanate and stirs, and drips oxalic acid simultaneously and carries out polycondensation, reaction 3-5 hour, temperature of reaction is 220-240 DEG C, reaction pressure is the technical scheme of 0.01-0.05MPa, and technique is simple, and the Poly(Trimethylene Terephthalate) obtained is effective.
Technical scheme of the present invention is:
A preparation method for Poly(Trimethylene Terephthalate), with terephthalic acid and 1,3-PD for raw material, is characterized in that,
Tetraethyl titanate, terephthalic acid and 1,3-PD add in esterification reaction tank by step (1), drip oxalic acid simultaneously, and carry out normal pressure esterification reaction 30-60 minute, wherein, the temperature of esterification is 220-240 DEG C;
Step (2) then adds tetraethyl titanate and stirs, and drips oxalic acid simultaneously and carries out polycondensation, and reaction 3-5 hour, temperature of reaction is 220-240 DEG C, and 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, with terephthalic acid and 1,3-PD for raw material, is characterized in that,
Tetraethyl titanate, terephthalic acid and 1,3-PD add in esterification reaction tank by step (1), drip oxalic acid simultaneously, carry out normal pressure esterification and react 30 minutes, and wherein, the temperature of esterification is 220 DEG C;
Step (2) then adds tetraethyl titanate and stirs, and drip oxalic acid simultaneously and carry out polycondensation, react 5 hours, temperature of reaction is 220 DEG C, and reaction pressure is 0.05MPa.
As further preferably, the preparation method of Poly(Trimethylene Terephthalate) of the present invention, with terephthalic acid and 1,3-PD for raw material, is characterized in that,
Tetraethyl titanate, terephthalic acid and 1,3-PD add in esterification reaction tank by step (1), drip oxalic acid simultaneously, carry out normal pressure esterification and react 30 minutes, and wherein, the temperature of esterification is 220 DEG C; 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 and stirs, and drip oxalic acid simultaneously and carry out polycondensation, react 5 hours, temperature of reaction is 220 DEG C, 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 amounts relation and catalyst type carry out improvement and bring new ideas, by the acting in conjunction of each factor, obtain the preparation method of a kind of high-performance poly propylene glycol ester terephthalate, 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 obtained, 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) obtained is effective, has outstanding substantive distinguishing features and significant progress, 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) obtained 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 25mL phenol and 1,1,2,2, and waiting in the solution of mass mixing thing of-tetrachloroethane, utilizes Ubbelohde viscometer to measure in 25 ± 0.1 DEG C of waters bath with thermostatic control.
Content of carboxyl end group
Be dissolved in by the PTT polyester powder of certain mass (about 0.25g) in phenol chloroform (volume ratio is 2:3) mixed solvent, 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, with terephthalic acid and 1,3-PD for raw material,
Tetraethyl titanate, terephthalic acid and 1,3-PD add in esterification reaction tank by step (1), drip oxalic acid simultaneously, carry out normal pressure esterification and react 30 minutes, and wherein, the temperature of esterification is 220 DEG C; 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 and stirs, and drip oxalic acid simultaneously and carry out polycondensation, react 5 hours, temperature of reaction is 220 DEG C, 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) obtained 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, with terephthalic acid and 1,3-PD for raw material,
Tetraethyl titanate, terephthalic acid and 1,3-PD add in esterification reaction tank by step (1), drip oxalic acid simultaneously, carry out normal pressure esterification and react 60 minutes, and wherein, the temperature of esterification is 240 DEG C; 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 and stirs, and drip oxalic acid simultaneously and carry out polycondensation, react 3 hours, temperature of reaction is 240 DEG C, 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) obtained 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, with terephthalic acid and 1,3-PD for raw material,
Tetraethyl titanate, terephthalic acid and 1,3-PD add in esterification reaction tank by step (1), drip oxalic acid simultaneously, carry out normal pressure esterification and react 45 minutes, and wherein, the temperature of esterification is 230 DEG C; 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 and stirs, and drip oxalic acid simultaneously and carry out polycondensation, react 4 hours, temperature of reaction is 230 DEG C, 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) obtained are as follows: limiting viscosity 0.8524dL/g, and content of carboxyl end group 23mol/t, color is pale yellow.
Claims (1)
1. a preparation method for Poly(Trimethylene Terephthalate), with terephthalic acid and 1,3-PD for raw material, is characterized in that,
Tetraethyl titanate, terephthalic acid and 1,3-PD add in esterification reaction tank by step (1), drip oxalic acid simultaneously, carry out normal pressure esterification and react 30 minutes, and wherein, the temperature of esterification is 220 DEG C; 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 and stirs, and drip oxalic acid simultaneously and carry out polycondensation, react 5 hours, temperature of reaction is 220 DEG C, 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.
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Effective date of registration: 20191114 Address after: 207-3, floor 2, No.19 B, Chegongzhuang West Road, Haidian District, Beijing 100044 Patentee after: Beijing Sino European Institute of science and technology Address before: 250000, No. 11, building 2, north section of Qilihe Road, Licheng District, Shandong, Ji'nan Patentee before: Xinghuo Sci. & Tech. Research Inst., Jinan Dev. Zone |
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