CN104357938B - A kind of preparation method of Regenerated Polyester Fibres - Google Patents

Abstract

The preparation method of a kind of Regenerated Polyester Fibres of disclosure, chemical regeneration field for waste and old polyester, adopt a kind of binary titanium alkoxide alkali metal coordination compound being dissolvable in water ethylene glycol as catalyst, the ethylene glycol depolymerization of catalysis waste and old polyester goods and the repolymerization process of depolymerization product, this catalyst all has higher catalysis activity for ethylene glycol depolymerization and the depolymerization product repolymerization process of polyester, therefore in the preparation method of this Regenerated Polyester Fibres, the process of preparation Regenerated Polyester Fibres just can be used for polycondensation again without being removed from depolymerization product by catalyst, recycled polyester quality is ensure that while being greatly saved depolymerization product separating-purifying cost, color and luster and the intensity of Regenerated Polyester Fibres can be obviously improved, serialization closed loop recovery for waste and old polyester goods provides possibility.

Description

A kind of preparation method of Regenerated Polyester Fibres

Technical field

The invention belongs to the chemical regeneration technical field of polyester, the preparation method relating to a kind of Regenerated Polyester Fibres, particularly relates to a kind of employing and is dissolvable in water the binary titanium alkoxide alkali metal coordination compound of the ethylene glycol Regenerated Polyester Fibres preparation method as the catalyst ethylene glycol depolymerization for waste and old polyester goods polycondensation spinning again.

Background technology

Polyethylene terephthalate (polyethyleneterephthalate, PET, it is called for short polyester) it is the semi-crystalline thermoplastic macromolecule material of a kind of excellent performance, it is widely used in the fields such as chemical fibre, packaging, medicine, electric mechanical, is the first big kind of chemical fibre. 2010, whole world polyester total output reached 56,100,000 tons. While PET industry develops rapidly, the process problem of waste and old polyester goods is comed one after another, and in society, the huge storage of waste polyester goods not only brings huge pressure to ecological environment, causes the serious waste of fossil resources simultaneously. Therefore, it is possible not only to turn waste into wealth to the regeneration recovery of waste polyester goods, alleviates the pressure of the non-renewable resources shortage such as oil, the protection of ecological environment and the sustainable development etc. of PET industry are all significant simultaneously.

In conjunction with the physicochemical characteristic of polyester, its way of recycling is broadly divided into physics regeneration and chemical regeneration two kinds. Physics method of reproduction is based on the thermoplasticity of polyester, the regeneration of polyester is realized by waste and old polyester goods remove impurity, cleaning, pulverizing being carried out after drying the method for melted pelletize again, although physics regeneration has, cost is low, the simple feature of technology, but waste and old polyester goods that are complicated for impurity component and that be not readily separated, the particularly recovery of waste and old polyester textile, physiochemical mutagens can only realize degradation and reclaim, and final generation cannot be recycled the waste, it is impossible to realizes the enclosed circulation of polyester material. The necleophilic reaction mechanism of the chemical regeneration reversibility based on polyester polycondensation reaction and ester exchange reaction, polyester is made to be depolymerized to polymerization single polymerization monomer or intermediate the attack of macromolecular chain by little molecule depolymerizing agent, carrying out repolymerization after separated purification and realize regeneration, the recovery for waste and old polyester textile has clear superiority. Main depolymerization method has hydrolysis, methanol solution and ethylene glycol solution three kinds, and wherein hydrolysis needs acid or the alkali of high concentration, methanol solution reaction needed high temperature and high pressure environment, and therefore that equipment requirements is high, industrialization difficulty is big; By contrast, it is gentleer that ethylene glycol solution has reaction condition, available existing polyester production facility, and technological process is short, it is easy to accomplish the feature that continuous prodution etc. are prominent, thus enjoys industry to favor.

The quality of recycled polyester determines the quality of Regenerated Polyester Fibres, and the technique that therefore polyester chemistry reclaims is particularly important, and the ethylene glycol solution reaction of PET is usually the heterogeneous reaction of normal pressure or the low pressure carried out at 180-220 DEG C.Because reaction temperature is higher, in order to prevent the response time long generation causing the side reactions such as the decomposition of depolymerization, depolymerization product and diethylene glycol generation, it usually needs add alcoholysis catalysts and accelerate reaction. at present, the metallic salt that the alcoholysis catalysts known the most is is representative with zinc acetate, although the alcoholysis catalytic efficiency of zinc acetate is high, but zinc acetate also exists serious defect as depolymerization catalyst, first its consumption is higher, it is generally the 0.5-1.5% of PET mass, and be difficult to after depolymerization remove from product, the zinc ion simultaneously remaining in high-load in depolymerization product can accelerate because the catalytic machine of ketonic oxygen coordination be comprehended side reactions such as causing in repolymerization process thermal degradation by it, molecular weight is increased limited, the viscosity of recycled polyester is low, poor quality, spinnability is poor. the method of the patent of invention CN102584594AC DEG C of ionic liquid-catalyzed alcoholysis polyethylene terephthalate of l42-/NiCl42-type, patent of invention CN102731310A the first transition metal ion liquid catalyst alcoholysis ethylene glycol terephthalate method, and CN200810101969.2 is in polyester alcoholysis catalysts published in the catalyst of alcoholysis polyethylene terephthalate, although having reaction condition gentleness, response speed is fast, conversion ratio is high, catalytic selectivity is high, the advantages such as catalyst can be recycled, but there is a very important defect simultaneously, be exactly in the catalyst of this type of ionic liquid halogen content significantly high, failing to catalyst is removed from depolymerization product, repolymerization process then can cause the decomposition of macromole because producing hydrogen halides, have a strong impact on the quality of repolymerization goods, recycled polyester is made to lose spinnability, and catalyst is removed thoroughly from depolymerization product production cost will be significantly increased, lose more than gain. patent of invention CN200810126347.5SO42-/MO2 type solid super acid catalyst degraded polyethylene terephthalate prepare BHET (bishydroxyethyl terephthalate) although in disclosed a kind of SO42-/MO2 type solid acid catalyst to have product easily separated, catalytic selectivity is high, the feature easily recycled, but because it is heterogeneous catalysis, in catalytic reaction, mass transport process is complicated, causes that catalytic efficiency is relatively low.

Summary of the invention

The preparation method that it is an object of the invention to provide a kind of Regenerated Polyester Fibres, in the preparation method of this Regenerated Polyester Fibres, adopt a kind of binary titanium alkoxide alkali metal coordination compound being dissolvable in water ethylene glycol as catalyst, the ethylene glycol depolymerization of catalysis waste and old polyester goods and the repolymerization process of depolymerization product, therefore the process preparing recycled polyester just can be used for polycondensation again without being removed from depolymerization product by catalyst, recycled polyester quality is ensure that while being greatly saved depolymerization product separating-purifying cost, color and luster and the intensity of recycled polyester spinnability and Regenerated Polyester Fibres can be obviously improved, efficiently high-quality serialization closed loop recovery for waste and old polyester goods provides possibility.

The alcoholysis of PET polyester and polycondensation both reacting quintessences are all realize molecule chain break with the bimolecular reaction mechanism of acyl-oxygen cleavage and increase, but owing to the factor difference such as reactant nature and reaction condition of alcoholysis reaction and polycondensation reaction is bigger, have not yet to see a kind of catalyst in two, under reaction condition, can all realize the catalysis to reaction efficiently and directionally simultaneously, polycondensation process is often had a negative impact by depolymerization catalyst simultaneously, such as serious thermal degradation catalysis etc., so that regenerative PET polyester spinnability is poor, the quality of regenerated fiber is low.Therefore needing catalyst alcoholysis process used to remove to ensure being smoothed out of depolymerization product polycondensation process again in current PET polyester chemistry regenerative process, this process will be added significantly to cost of withdrawing deposit so that the chemical regeneration Difficulty of PET polyester article. the present invention is by adopting bimetallic matching structure design, catalyst is made to combine two kinds of catalytic mechanisms of bimolecular reaction of acyl-oxygen cleavage, i.e. ligand exchange mechanism and metal alkoxide mechanism, making this catalyst all can show efficient and directed catalysis activity in the alcoholysis and polycondensation two kinds reaction of PET, side reaction is few, the catalyst of this bimetallic fit structure provided by the invention is ate complex, preferred electronegativity is suitable and the rational transition metal titanium of outer shell electron distribution is as the central atom of acid group complex ion, make part with di-alcohols structure and promote homogeneity and ligand exchange activity, adopt alkali metal group as cation on the one hand for promoting the ligancy of catalytic center titanium atom, part is more easy to deform upon, thus strengthening titanium catalysis activity in alcoholysis with polycondensation process, on the other hand, alkali metal group cation can be passed through the mode forming metal alkoxide and alcoholysis reaction realizes auxiliary acceleration, PET depolymerization and polycondensation all can be shown high activity reaching this catalyst, without removing it after depolymerization, therefore recycled polyester preparation method provided by the invention can effectively solve foregoing problem.

The preparation method of a kind of Regenerated Polyester Fibres of the present invention, comprises the following steps:

1) PET polyester is carried out ethylene glycol depolymerization:

1.1) alcoholysis catalysts binary titanium alkoxide alkali metal coordination compound is dissolved in depolymerizing agent ethylene glycol, is formed and solve poly solution;

1.2) mol ratio that solution poly solution and PET polyester are mixed and stirred for carrying out depolymerization reaction, depolymerizing agent ethylene glycol consumption and PET polyester is 4-50:1, and depolymerization reaction temperature is 160-240 DEG C, and reaction system pressure is 1-2.5atm, and the response time is 30min-8h;

The structural formula of described alcoholysis catalysts binary titanium alkoxide alkali metal coordination compound is:

Wherein, M+ is IA race metal cation, for Li+, Na+, K+ or Rb+;

R ' is saturated hydrocarbon chains structure that carbon number is 2-4.

This kind of structural design has following advantage:

A)-O-R '-O-structure can make this Titanium series catalyst have solubility in depolymerizing agent ethylene glycol, to guarantee that depolymehzation process is for homogeneous catalysis, promotes catalytic efficiency.

B) introducing of M+IA race metal cation can be prevented effectively from Ti and-(-O-R '-O-)-3 structure autohemagglutinations and forms the catalysis activity that the chain structure of one-dimensional prolongation causes and reduce.

C) introducing of M+IA race metal cation can so that in catalyst Ti atom ligancy improve, thus causing that the stability of catalyst space structure reduces, it is more easy to and due to coordination, ligand exchange reaction occurs with the ester bond in depolymerizing agent and polyester, thus causing macromole chain rupture. Simultaneously, the coordination of Ti and ester bond can increase the electrophilicity of carbonyl carbon in macromolecular chain, and M+ can have an effect with the hydroxyl in depolymerizing agent ethylene glycol and can increase the nucleophilicity of hydroxyl oxygen, therefore the mutual promoting action of both Ti and M+ makes to be more easy to attack polyester macromolecule at ethylene glycol and acyl-oxygen bond fission occurs, the i.e. alcoholysis of PET, therefore has very high alcoholysis catalysis activity.

D) high in reaction temperature, reactant is mainly in the polycondensation process of polyester oligomer, and the titanium ethylene glycolate acid group part of this catalyst can make still have efficient catalysis activity in its polycondensation process by ligand exchange effect.

2) to the decolouring of depolymerization product and purification, step is as follows:

2.1) in step 1) gained solution add containing the ethylene glycol dispersion liquid that quality of activated carbon mark is 0.5-5%, at temperature is 150-220 DEG C, atmospheric pressure reflux stirring decolouring 1-5h;

2.2) the elimination removal of impurity and the activated carbon of decolouring it are then passed through;

2.3) step 2.1 is repeated) and 2.2) 2-5 time, namely decolour and filter process is repeatedly performed 2-5 time, obtain the ethylene glycol solution of depolymerizing substance after remove impurity is decoloured;

2.4) ethylene glycol in solution, when temperature is 190-210 DEG C and pressure is 0.5-0.8atm, is evaporated completely by the ethylene glycol solution of the depolymerizing substance after remove impurity being decoloured, it is thus achieved that purification and the depolymerization product after decolouring;

3) repolymerization of depolymerization product, concrete step is as follows:

3.1) in step 2) depolymerization product after the purification that obtains and decolouring adds polycondensation catalyst and heat stabilizer, when 220-240 DEG C and pressure 1atm, and under inert gas shielding, stirring mixing;

3.2) then, reaction temperature is increased to 240-250 DEG C, continues reaction 5-30min, simultaneously this period, make pressure in system at the uniform velocity be reduced to 1kPa.

3.3) then, reaction temperature is increased to 265-290 DEG C, makes after pressure is reduced to 20Pa in system, continue reaction 10-60min, namely obtain recycled polyester.

4) by step 3) prepare recycled polyester dry after obtain Regenerated Polyester Fibres through circular port or Special-shaped hole spinneret plate melt spinning molding.

As preferred technical scheme:

The preparation method of a kind of Regenerated Polyester Fibres as above, the molal weight of PET polyester calculates with 192g/mol, the preferred 8-20:1 of mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester, too much ethylene glycol can cause that the side reaction generating diethylene glycol occurs, the very few productivity that will reduce depolymerization speed and monomer, preferred 180-210 DEG C of depolymerization reaction temperature, the too low depolymerization rate that can reduce of reaction temperature, too high, the generation of side reaction can be caused; In described solution poly solution, the 0.1%-1% that consumption is quality of glycol of described binary titanium alkoxide alkali metal coordination compound; Stirring during described depolymerization reaction, stir speed (S.S.) is that 50-1500 turns/min; Described depolymerization reaction carries out under inert gas shielding.

The preparation method of a kind of Regenerated Polyester Fibres as above, described binary titanium alkoxide alkali metal coordination compound is prepared by following steps:

A) by titanium compound that formula is Ti (OR) 4 when 50-150 DEG C and nitrogen protection, with dihydroxylic alcohols the HO-R '-OH Homogeneous phase mixing that carbon number is 2-4; Wherein, R is carbon number is the saturated hydrocarbon chains structure of 2-4, and R ' is saturated hydrocarbon chains structure that carbon number is 2-4; In conjunction with synthetic reaction activity, catalysis activity, raw material stability and price factor, the preferred butyl titanate of Ti (OR) 4, tetraisopropyl titanate; The preferred ethylene glycol of dihydroxylic alcohols, 1,2-PD;

B) add IA race metal hydroxides MOH, after continuing stirring until the liquid that reaction system is transparent and homogeneous, raise reaction temperature to 180-250 DEG C;

C) in course of reaction, backflow dihydroxylic alcohols also gets rid of low boiling monohydric alcohol R-OH and the water that reaction generates, and the response time is 2-5 hour, and the dihydroxylic alcohols in system is quickly evaporated after terminating and obtains white or slightly yellow solid completely by reaction;

D) above-mentioned solid utilizes ethanol-Gossypol recrystallized from chloroform repeatedly obtain colourless or light yellow crystal and is described binary titanium alkoxide alkali metal coordination compound.

The preparation method of a kind of Regenerated Polyester Fibres as above, the mol ratio of Ti (OR) 4 and HO-R '-OH is 1:20-100; The mol ratio of MOH and Ti (OR) 4 is 2.01-2.05:1; In step c), described quickly referring at temperature is 190-210 DEG C, reaction system pressure is under 0.5-0.8atm, in 0.5-5min by dihydroxylic alcohols evaporation in system completely.

The preparation method of a kind of Regenerated Polyester Fibres as above, described PET polyester is be containing any type of goods made by polyethylene terephthalate and waste and old product by composition.

The preparation method of a kind of Regenerated Polyester Fibres as above, the decolouring of described depolymerization product and the step of purification, step 2.1) in, the addition of the ethylene glycol solution containing activated carbon is 0.5-5 times of depolymerizing substance ethylene glycol solution quality.

The preparation method of a kind of Regenerated Polyester Fibres as above, step 3.1) in, described polycondensation catalyst is one or more in binary titanium alkoxide alkali metal coordination compound catalyst, antimony glycol, antimony acetate, antimony oxide, Germanium tetraacetate., germanium dioxide, tetraisopropyl titanate, tetra-n-butyl titanate, titanium ethylene glycolate; The addition of described catalyst is the 0-200ppm of the depolymerization product quality after purifying and decolouring; Described heat stabilizer is one or more in trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite, ammonium phosphite, ammonium dihydrogen phosphate, phosphoric acid, phosphorous acid, ortho phosphorous acid, pyrophosphoric acid, ammonium phosphate; The addition of described heat stabilizer is the 50ppm-500ppm of the depolymerization product quality after purifying and decolouring.

The preparation method of a kind of Regenerated Polyester Fibres as above, step 3.1) in, stirring mixing refers to that speed of agitator is that 50-80 turns/min, stirring mixing 30-60min; Step 3.2) in, at the uniform velocity reduction pressure is 0.5kPa-10kPa/min to the air pressure drop low rate of 1kPa, needs stirring during reaction, and speed of agitator is that 50-80 turns/min; Step 3.3) in, continuation at the uniform velocity reduction pressure is 100Pa-1kPa/min to the air pressure drop low rate of 20Pa, and continues stirring when reacting, and speed of agitator is that 80-120 turns/min.

The preparation method of a kind of Regenerated Polyester Fibres as above, described Regenerated Polyester Fibres type is POY, FDY, DTY or short fibre, and its spinning technique is as follows respectively:

By step 3) recycled polyester for preparing carries out melt spinning, its POY spinning technique is: spinning temperature is 270-290 DEG C, spinning speed is 2000-2500m/min, draft temperature is 60-80 DEG C, total draft multiplying power is 1.5-4.5, prepare recycled polyester POY long filament, by POY long filament after 8h balances, respectively through first roller, first hot tank, coldplate, scroll tube, second roller, network nozzle, second hot phase, 3rd roller, oil tanker, regeneration DTY is prepared after winding, wherein the linear velocity of first roller is 200-500m/min, the linear velocity of the second roller is 400-500m/min, the linear velocity of the 3rd roller is 200-500m/min, the linear velocity of Wound-up roller is 300-600m/min, draw ratio 1.1-1.5, false twisting D/Y is than for 1.2-2.5, the recycled polyester DTY of system,

By step 3) recycled polyester for preparing carries out melt spinning, its FDY spinning technique is: spinning temperature is 270-290 DEG C, spinning speed is 3000-3500m/min, the speed of hot-rolling one is 1100-1500m/min, temperature is 80-110 DEG C, the speed of hot-rolling two is 3000-3500m/min, and temperature is 115-135 DEG C, prepares recycled polyester FDY filament;

By step 3) recycled polyester for preparing carries out melt spinning, its short fine spinning technique is: spinning temperature is 270-290 DEG C, spinning speed is 800-1500m/min, draft temperature is 60-80 DEG C, preliminary draft multiplying power is 1.02-1.10, and one draft ratio is 1.8-2.5, and two road draft ratio are 1.02-1.1, then being 0.5-5dtex through cutting off prepared fiber number, length is the short fibre of recycled polyester of 30mm-50mm.

Special-shaped hole spinneret plate as above is hollow shape, pancake, triangle and the one in cross.

Beneficial effect:

(1) catalyst that the preparation method of a kind of Regenerated Polyester Fibres of the present invention adopts, both can the ethylene glycol depolymerization reaction of the PET of catalysis efficiently, it is possible to the polycondensation reaction again of efficient its depolymerization product of catalysis. The catalyst residual that commonly used at present zinc acetate, zinc-containing metal salt, ionic liquid class catalyst alcoholysis containing halogen cause can be avoided to cause the difficulty of polycondensation again, thus the quality of Regenerated Polyester Fibres can be greatly promoted.

(2) Regenerated Polyester Fibres preparation method provided by the present invention is adopted, can overcome and adopt the catalytic efficiency that mass transport process complicated in solid heterogeneous catalyst alcoholysis and polymerization process causes low, significantly simplify process for separating and purifying and cost, serialization chemical regeneration for PET goods provides possibility, has good application prospect.

(3) the binary titanium alkoxide alkali metal composite salt catalyst used in recycled polyester preparation method provided by the present invention is without heavy metal, and for nontoxic or lower toxicity, the Regenerated Polyester Fibres that therefore this method prepares is safe and reliable.

(4) process for synthetic catalyst used in recycled polyester preparation method provided by the present invention is relatively easy, and reaction condition is gentle, and course of reaction is easily controllable, has good popularizing application prospect.

Detailed description of the invention

Below in conjunction with detailed description of the invention, the present invention is expanded on further. Should be understood that these embodiments are merely to illustrate the present invention rather than restriction the scope of the present invention. In addition, it is to be understood that after having read the content that the present invention lectures, the present invention can be made various changes or modifications by those skilled in the art, and these equivalent form of values fall within the application appended claims limited range equally.

Embodiment 1

First carrying out producing of ethylene glycol lithium titanate, it comprises the following steps:

A) by tetraethyl titanate when 50 DEG C and nitrogen protection, it is 1:100 with the mol ratio of ethylene glycol Homogeneous phase mixing, tetraethyl titanate and ethylene glycol;

B) mol ratio adding Lithium hydrate, Lithium hydrate and tetraethyl titanate is 2.05:1, after continuing stirring until the liquid that reaction system is transparent and homogeneous, raises reaction temperature to 180 DEG C;

C) in course of reaction, backflow ethylene glycol also gets rid of the lower boiling second alcohol and water that reaction generates, response time is 3 hours, reaction is at 190 DEG C in temperature after terminating, reaction system pressure is under 0.5atm, evaporates completely by the ethylene glycol in system in 0.5min, is evaporated by the dihydroxylic alcohols in system and obtains white solid completely, this solid utilizes ethanol-Gossypol recrystallized from chloroform obtain clear crystal three times, namely prepares ethylene glycol lithium titanate;

The structural formula of described alcoholysis catalysts ethylene glycol lithium titanate is:

Then the preparation method carrying out a kind of Regenerated Polyester Fibres, comprises the following steps:

1) being dissolved in depolymerizing agent ethylene glycol by alcoholysis catalysts ethylene glycol lithium titanate produced above, the consumption of ethylene glycol lithium titanate is the 0.1% of quality of glycol, is formed and solves poly solution;

2) mix solving poly solution with waste and old terylene polyester textile and carry out the depolymerization reaction under inert gas shielding; stir simultaneously; stir speed (S.S.) is 1500 turns/min; the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 20:1; the molal weight of PET polyester calculates with 192g/mol; depolymerization reaction temperature is 190 DEG C, and reaction system pressure is 1atm, and the response time is 3h.

3) in step 2) gained solution add containing the ethylene glycol dispersion liquid that quality of activated carbon mark is 0.5%, addition is depolymerization solution quality 1.5 times of activated carbon ethylene glycol dispersion liquid, it is at 150 DEG C in temperature, after atmospheric pressure reflux stirring decolouring 5h, through the activated carbon of the elimination removal of impurity and decolouring, decolouring and filter process are repeatedly performed 2 times;

4) ethylene glycol in solution, when temperature is 190 DEG C and pressure is 0.5atm, is evaporated completely by the ethylene glycol solution of the depolymerizing substance after remove impurity being decoloured, it is thus achieved that purification and the depolymerization product after decolouring;

5) in step 4) depolymerization product after the purification that obtains and decolouring adds 50ppm ethylene glycol lithium titanate as polycondensation catalyst and 50ppm tripotassium phosphate ester heat stabilizer, when 220 DEG C and pressure 1atm, and under inert gas shielding, stirring mixing; Then, reaction temperature is increased to 240 DEG C, continues reaction 60min, simultaneously this period, make pressure in system at the uniform velocity be reduced to 1kPa; Then, reaction temperature is increased to 265 DEG C, makes after pressure is reduced to 20Pa in system, continue reaction 120min, namely obtain recycled polyester.

6) by 5) recycled polyester that obtains carries out melt spinning through circular port spinneret, and its POY spinning technique is: spinning temperature is 270 DEG C, and spinning speed is 2000m/min, and draft temperature is 60 DEG C, and total stretching ratio is 1.5. Prepare recycled polyester POY long filament, by POY long filament after 8h balances, respectively through first roller, the first hot tank, coldplate, scroll tube, the second roller, network nozzle, the second hot phase, the 3rd roller, oil tanker, prepare regeneration DTY after winding. Wherein the linear velocity of first roller is 200m/min, and the linear velocity of the second roller is 400m/min, and the linear velocity of the 3rd roller is 200m/min, and the linear velocity of Wound-up roller is 300m/min, draw ratio 1.1, and false twisting D/Y ratio is 1.2, prepares recycled polyester DTY.

Tensile strength of single fiber: 3.19CN/dtex, colour: L:78.21, b:6.23

Embodiment 2

First carrying out producing of ethylene glycol sodium titanate, it comprises the following steps:

A) by tetra-n-butyl titanate when 150 DEG C and nitrogen protection, it is 1:50 with the mol ratio of ethylene glycol Homogeneous phase mixing, tetra-n-butyl titanate and ethylene glycol;

B) mol ratio adding sodium hydroxide, sodium hydroxide and tetra-n-butyl titanate is 2.03:1, after continuing stirring until the liquid that reaction system is transparent and homogeneous, raises reaction temperature to 210 DEG C;

C) in course of reaction, backflow ethylene glycol also gets rid of lower boiling n-butyl alcohol and the water that reaction generates, response time is 2 hours, reaction is at 210 DEG C in temperature after terminating, reaction system pressure is under 0.8atm, evaporates completely by the ethylene glycol in system in 1min, is evaporated by the dihydroxylic alcohols in system and obtains white solid completely, this solid utilizes ethanol-Gossypol recrystallized from chloroform obtain clear crystal three times, namely prepares ethylene glycol sodium titanate;

The structural formula of described alcoholysis catalysts ethylene glycol sodium titanate is:

Then the preparation method carrying out a kind of Regenerated Polyester Fibres, comprises the following steps:

1) being dissolved in depolymerizing agent ethylene glycol by alcoholysis catalysts ethylene glycol sodium titanate produced above, the consumption of ethylene glycol sodium titanate is the 1% of quality of glycol, is formed and solves poly solution;

2) mix solving poly solution with waste pure polyester fabric fragment and carry out the depolymerization reaction under inert gas shielding; stir simultaneously; stir speed (S.S.) is 1000 turns/min; the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 10:1; the molal weight of PET polyester calculates with 192g/mol; depolymerization reaction temperature is 180 DEG C, and reaction system pressure is 1atm, and the response time is 1h.

3) in step 2) gained solution add containing the ethylene glycol dispersion liquid that quality of activated carbon mark is 5%, addition is depolymerization solution quality 5 times of activated carbon ethylene glycol dispersion liquid, it is at 220 DEG C in temperature, after atmospheric pressure reflux stirring decolouring 1h, through the activated carbon of the elimination removal of impurity and decolouring, decolouring and filter process are repeatedly performed 5 times;

4) ethylene glycol in solution, when temperature is 210 DEG C and pressure is 0.8atm, is evaporated completely by the ethylene glycol solution of the depolymerizing substance after remove impurity being decoloured, it is thus achieved that purification and the depolymerization product after decolouring;

5) in step 4) depolymerization product after the purification that obtains and decolouring adds 500ppm triphenyl phosphate heat stabilizer, when 240 DEG C and pressure 1atm, and under inert gas shielding, stirring mixing; Then, reaction temperature is increased to 250 DEG C, continues reaction 20min, simultaneously this period, make pressure in system at the uniform velocity be reduced to 1kPa; Then, reaction temperature is increased to 290 DEG C, makes after pressure is reduced to 20Pa in system, continue reaction 40min, namely obtain recycled polyester.

6) by 5) recycled polyester that obtains carries out melt spinning through pancake spinneret, and its POY spinning technique is: spinning temperature is 290 DEG C, and spinning speed is 2500m/min, and draft temperature is 80 DEG C, and total stretching ratio is 4.5. Prepare recycled polyester POY long filament, by POY long filament after 8h balances, respectively through first roller, the first hot tank, coldplate, scroll tube, the second roller, network nozzle, the second hot phase, the 3rd roller, oil tanker, prepare regeneration DTY after winding. Wherein the linear velocity of first roller is 500m/min, and the linear velocity of the second roller is 500m/min, and the linear velocity of the 3rd roller is 500m/min, and the linear velocity of Wound-up roller is 600m/min, draw ratio 1.5, and false twisting D/Y ratio is 2.5, prepares recycled polyester DTY.

Tensile strength of single fiber: 3.25CN/dtex, colour: L:79.13, b:7.58

Embodiment 3

First carrying out producing of propylene glycol potassium titanate, it comprises the following steps:

A) by tetraisopropyl titanate when 100 DEG C and nitrogen protection, it is 1:80 with the mol ratio of 1,2-PD Homogeneous phase mixing, tetraisopropyl titanate and 1,2-PD;

B) mol ratio adding potassium hydroxide, potassium hydroxide and tetraisopropyl titanate is 2.02:1, after continuing stirring until the liquid that reaction system is transparent and homogeneous, raises reaction temperature to 200 DEG C;

C) in course of reaction, backflow 1,2-propylene glycol also gets rid of the lower boiling isopropyl alcohol and water that reaction generates, response time is 4 hours, and reaction is at 200 DEG C in temperature after terminating, and reaction system pressure is under 0.7atm, in in 1min, the ethylene glycol in system is evaporated completely, dihydroxylic alcohols in system is evaporated and obtains faint yellow solid completely, this solid utilizes ethanol-Gossypol recrystallized from chloroform obtain clear crystal three times, namely prepare propylene glycol potassium titanate;

The structural formula of described alcoholysis catalysts propylene glycol potassium titanate is:

Then the preparation method carrying out a kind of Regenerated Polyester Fibres, comprises the following steps:

1) being dissolved in depolymerizing agent ethylene glycol by alcoholysis catalysts propylene glycol potassium titanate produced above, the consumption of propylene glycol potassium titanate is the 0.5% of quality of glycol, is formed and solves poly solution;

2) mix solving poly solution with containing the polyester cotton fragment washing 65% and carry out the depolymerization reaction under inert gas shielding, stir simultaneously, stir speed (S.S.) is 600 turns/min, the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 50:1, the molal weight of PET polyester calculates with 192g/mol, depolymerization reaction temperature is 160 DEG C, and reaction system pressure is 1atm, and the response time is 8h;

3) in step 2) gained solution add containing the ethylene glycol dispersion liquid that quality of activated carbon mark is 4%, addition is depolymerization solution quality 4 times of activated carbon ethylene glycol dispersion liquid, it is at 200 DEG C in temperature, after atmospheric pressure reflux stirring decolouring 2h, through the activated carbon of the elimination removal of impurity and decolouring, decolouring and filter process are repeatedly performed 5 times;

4) ethylene glycol in solution, when temperature is 200 DEG C and pressure is 0.6atm, is evaporated completely by the ethylene glycol solution of the depolymerizing substance after remove impurity being decoloured, it is thus achieved that purification and the depolymerization product after decolouring;

5) in step 4) depolymerization product after the purification that obtains and decolouring adds 50ppm propylene glycol potassium titanate as polycondensation catalyst and 500ppm triphenyl phosphite heat stabilizer, when 230 DEG C and pressure 1atm, and under inert gas shielding, stirring mixing; Then, reaction temperature is increased to 250 DEG C, continues reaction 20min, simultaneously this period, make pressure in system at the uniform velocity be reduced to 1kPa; Then, reaction temperature is increased to 275 DEG C, makes after pressure is reduced to 20Pa in system, continue reaction 60min, namely obtain recycled polyester.

6) by 5) recycled polyester that obtains carries out melt spinning through pancake spinneret, its FDY spinning technique is: spinning temperature is 290 DEG C, spinning speed is 3500m/min, the speed of hot-rolling one is 1500m/min, temperature is 110 DEG C, the speed of hot-rolling two is 3500m/min, and temperature is 135 DEG C, prepares recycled polyester FDY filament.

Tensile strength of single fiber: 3.42CN/dtex, colour: L:79.13, b:7.58

Embodiment 4

First carrying out producing of butanediol metatitanic acid rubidium, it comprises the following steps:

A) by metatitanic acid tetra-tert ester when 50 DEG C and nitrogen protection, it is 1:20 with 1,3 butylene glycol Homogeneous phase mixing, metatitanic acid tetra-tert ester and 1,3 butanediol mol ratio;

B) mol ratio adding rubidium hydroxide, rubidium hydroxide and metatitanic acid tetra-tert ester is 2.01:1, after continuing stirring until the liquid that reaction system is transparent and homogeneous, raises reaction temperature to 250 DEG C;

C) in course of reaction, backflow 1, the lower boiling tert-butyl alcohol and the water that reaction generates also got rid of by 2-propylene glycol, and the response time is 5 hours, and reaction is at 210 DEG C in temperature after terminating, reaction system pressure is under 0.8atm, in in 5min, the 1,3 butylene glycol in system is evaporated completely, the dihydroxylic alcohols in system is evaporated and obtains yellow solid completely, this solid utilizes ethanol-Gossypol recrystallized from chloroform obtain light yellow crystal three times, namely prepares butanediol metatitanic acid rubidium;

The structural formula of described alcoholysis catalysts butanediol metatitanic acid rubidium is:

Then the preparation method carrying out a kind of Regenerated Polyester Fibres, comprises the following steps:

1) alcoholysis catalysts butanediol metatitanic acid rubidium produced above is dissolved in depolymerizing agent ethylene glycol, consumption is quality of glycol the 1% of butanediol metatitanic acid rubidium, formed and solve poly solution;

2) mix solving poly solution with PET mylar and carry out the depolymerization reaction under inert gas shielding, stir simultaneously, stir speed (S.S.) is 50 turns/min, the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 4:1, the molal weight of PET polyester calculates with 192g/mol, depolymerization reaction temperature is 240 DEG C, and reaction system pressure is 2.5atm, and the response time is 30min;

3) in step 2) gained solution add containing the ethylene glycol dispersion liquid that quality of activated carbon mark is 0.9%, addition is depolymerization solution quality 0.5 times of activated carbon ethylene glycol dispersion liquid, it is at 200 DEG C in temperature, after atmospheric pressure reflux stirring decolouring 2h, through the activated carbon of the elimination removal of impurity and decolouring, decolouring and filter process are repeatedly performed 2 times;

4) ethylene glycol in solution, when temperature is 210 DEG C and pressure is 0.8atm, is evaporated completely by the ethylene glycol solution of the depolymerizing substance after remove impurity being decoloured, it is thus achieved that purification and the depolymerization product after decolouring;

5) in step 4) depolymerization product after the purification that obtains and decolouring adds 50ppm butanediol metatitanic acid rubidium as polycondensation catalyst and 500ppm diphenyl phosphite heat stabilizer, when 240 DEG C and pressure 1atm, and under inert gas shielding, stirring mixing; Then, reaction temperature is increased to 245 DEG C, continues reaction 30min, simultaneously this period, make pressure in system at the uniform velocity be reduced to 1kPa; Then, reaction temperature is increased to 275 DEG C, makes after pressure is reduced to 20Pa in system, continue reaction 70min, namely obtain recycled polyester.

6) by 5) recycled polyester that obtains carries out melt spinning through triangle spinneret, its FDY spinning technique is: spinning temperature is 270 DEG C, spinning speed is 3000m/min, the speed of hot-rolling one is 1100m/min, temperature is 80 DEG C, the speed of hot-rolling two is 3000m/min, and temperature is 115 DEG C, prepares recycled polyester FDY filament.

Tensile strength of single fiber: 3.39CN/dtex, colour: L:79.50, b:6.97

Embodiment 5

First carrying out producing of ethylene glycol sodium titanate, it comprises the following steps:

A) by tetra-n-butyl titanate when 150 DEG C and nitrogen protection, it is 1:60 with the mol ratio of ethylene glycol Homogeneous phase mixing, tetra-n-butyl titanate and ethylene glycol;

B) mol ratio adding sodium hydroxide, sodium hydroxide and tetra-n-butyl titanate is 2.01:1, after continuing stirring until the liquid that reaction system is transparent and homogeneous, raises reaction temperature to 210 DEG C;

C) in course of reaction, backflow ethylene glycol also gets rid of lower boiling n-butyl alcohol and the water that reaction generates, response time is 2 hours, reaction is at 205 DEG C in temperature after terminating, reaction system pressure is under 0.6atm, evaporates completely by the ethylene glycol in system in 2min, is evaporated by the dihydroxylic alcohols in system and obtains white solid completely, this solid utilizes ethanol-Gossypol recrystallized from chloroform obtain clear crystal three times, namely prepares ethylene glycol sodium titanate;

The structural formula of described alcoholysis catalysts ethylene glycol sodium titanate is:

Then the preparation method carrying out a kind of Regenerated Polyester Fibres, comprises the following steps:

1) being dissolved in depolymerizing agent ethylene glycol by alcoholysis catalysts ethylene glycol sodium titanate produced above, the consumption of ethylene glycol sodium titanate is the 1% of quality of glycol, is formed and solves poly solution;

2) mix solving poly solution with waste polyester bottle chip and carry out the depolymerization reaction under inert gas shielding, stir simultaneously, stir speed (S.S.) is 50 turns/min, the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 4:1, the molal weight of PET polyester calculates with 192g/mol, depolymerization reaction temperature is 230 DEG C, and reaction system pressure is 2.5atm, and the response time is 30min;

3) in step 2) gained solution add containing the ethylene glycol dispersion liquid that quality of activated carbon mark is 3%, addition is depolymerization solution quality 5 times of activated carbon ethylene glycol dispersion liquid, it is at 200 DEG C in temperature, after atmospheric pressure reflux stirring decolouring 1h, through the activated carbon of the elimination removal of impurity and decolouring, decolouring and filter process are repeatedly performed 3 times;

4) ethylene glycol in solution, when temperature is 210 DEG C and pressure is 0.8atm, is evaporated completely by the ethylene glycol solution of the depolymerizing substance after remove impurity being decoloured, it is thus achieved that purification and the depolymerization product after decolouring;

5) in step 4) depolymerization product after the purification that obtains and decolouring adds 400ppm ammonium dihydrogen phosphate make heat stabilizer, when 240 DEG C and pressure 1atm, and under inert gas shielding, stirring mixing;Then, reaction temperature is increased to 248 DEG C, continues reaction 50min, simultaneously this period, make pressure in system at the uniform velocity be reduced to 1kPa; Then, reaction temperature is increased to 270 DEG C, makes after pressure is reduced to 20Pa in system, continue reaction 80min, namely obtain recycled polyester.

6) by 5) recycled polyester that obtains carries out melt spinning through hollow shape spinneret, spinning temperature is 270 DEG C, spinning speed is 800m/min, draft temperature is 60 DEG C, preliminary draft multiplying power is 1.02, and one draft ratio is 1.8, and two road draft ratio are 1.02, then being 5dtex through cutting off prepared fiber number, length is the short fibre of recycled polyester of 50mm.

Tensile strength of single fiber: 2.71CN/dtex, colour: L:79.03, b:5.12

Embodiment 6

First carrying out producing of ethylene glycol potassium titanate, it comprises the following steps:

A) by tetraisopropyl titanate when 120 DEG C and nitrogen protection, it is 1:50 with the mol ratio of ethylene glycol Homogeneous phase mixing, tetraisopropyl titanate and ethylene glycol;

B) mol ratio adding potassium hydroxide, potassium hydroxide and tetraisopropyl titanate is 2.02:1, after continuing stirring until the liquid that reaction system is transparent and homogeneous, raises reaction temperature to 220 DEG C;

C) in course of reaction, backflow ethylene glycol also gets rid of the lower boiling isopropyl alcohol and water that reaction generates, response time is 2 hours, reaction is at 205 DEG C in temperature after terminating, reaction system pressure is under 0.6atm, evaporates completely by the ethylene glycol in system in 0.5min, is evaporated by the dihydroxylic alcohols in system and obtains white solid completely, this solid utilizes ethanol-Gossypol recrystallized from chloroform obtain clear crystal three times, namely prepares ethylene glycol potassium titanate;

The structural formula of described alcoholysis catalysts ethylene glycol potassium titanate is:

Then the preparation method carrying out a kind of Regenerated Polyester Fibres, comprises the following steps:

1) being dissolved in depolymerizing agent ethylene glycol by alcoholysis catalysts ethylene glycol potassium titanate produced above, the consumption of ethylene glycol potassium titanate is the 0.3% of quality of glycol, is formed and solves poly solution;

2) poly solution will be solved and knit the depolymerization reaction mixing and carrying out under inert gas shielding containing the polyester cotton blending washing 85%, stir simultaneously, stir speed (S.S.) is 200 turns/min, the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 50:1, the molal weight of PET polyester calculates with 192g/mol, depolymerization reaction temperature is 200 DEG C, and reaction system pressure is 1.5atm, and the response time is 1h;

3) in step 2) gained solution add containing the ethylene glycol dispersion liquid that quality of activated carbon mark is 5%, addition is depolymerization solution quality 5 times of activated carbon ethylene glycol dispersion liquid, it is at 200 DEG C in temperature, after atmospheric pressure reflux stirring decolouring 1h, through the activated carbon of the elimination removal of impurity and decolouring, decolouring and filter process are repeatedly performed 3 times;

4) ethylene glycol in solution, when temperature is 210 DEG C and pressure is 0.8atm, is evaporated completely by the ethylene glycol solution of the depolymerizing substance after remove impurity being decoloured, it is thus achieved that purification and the depolymerization product after decolouring;

5) in step 4) depolymerization product after the purification that obtains and decolouring adds 100ppm Germanium tetraacetate., 50ppm titanium ethylene glycolate is as polycondensation catalyst, and 500ppm pyrophosphoric acid makes heat stabilizer, when 240 DEG C and pressure 1atm, and under inert gas shielding, stirring mixing; Then, reaction temperature is increased to 250 DEG C, continues reaction 50min, simultaneously this period, make pressure in system at the uniform velocity be reduced to 1kPa; Then, reaction temperature is increased to 280 DEG C, makes after pressure is reduced to 20Pa in system, continue reaction 80min, namely obtain recycled polyester.

6) by 5) recycled polyester that obtains carries out melt spinning through cross spinneret, spinning temperature is 290 DEG C, spinning speed is 1500m/min, draft temperature is 80 DEG C, preliminary draft multiplying power is 1.10, and one draft ratio is 2.5, and two road draft ratio are 1.1, then being 0.5dtex through cutting off prepared fiber number, length is the short fibre of recycled polyester of 30mm.

Tensile strength of single fiber: 2.85CN/dtex, colour: L:79.96, b:6.37

Embodiment 7

First carrying out producing of ethylene glycol lithium titanate, it comprises the following steps:

A) by tetraethyl titanate when 80 DEG C and nitrogen protection, it is 1:80 with the mol ratio of ethylene glycol Homogeneous phase mixing, tetraethyl titanate and ethylene glycol;

B) mol ratio adding Lithium hydrate, Lithium hydrate and tetraethyl titanate is 2.05:1, after continuing stirring until the liquid that reaction system is transparent and homogeneous, raises reaction temperature to 180 DEG C;

C) in course of reaction, backflow ethylene glycol also gets rid of the lower boiling second alcohol and water that reaction generates, response time is 3 hours, reaction is at 190 DEG C in temperature after terminating, reaction system pressure is under 0.5atm, evaporates completely by the ethylene glycol in system in 0.5min, is evaporated by the dihydroxylic alcohols in system and obtains white solid completely, this solid utilizes ethanol-Gossypol recrystallized from chloroform obtain clear crystal three times, namely prepares ethylene glycol lithium titanate;

The structural formula of described alcoholysis catalysts ethylene glycol lithium titanate is:

Then the preparation method carrying out a kind of recycled polyester, comprises the following steps:

1) being dissolved in depolymerizing agent ethylene glycol by alcoholysis catalysts ethylene glycol lithium titanate produced above, the consumption of ethylene glycol lithium titanate is the 1% of quality of glycol, is formed and solves poly solution;

2) mix solving poly solution with waste PET polyester bottles fragment and carry out the depolymerization reaction under inert gas shielding; stir simultaneously; stir speed (S.S.) is 1500 turns/min; the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 20:1; the molal weight of PET polyester calculates with 192g/mol; depolymerization reaction temperature is 190 DEG C, and reaction system pressure is 1atm, and the response time is 3h.

3) in step 2) gained solution add containing the ethylene glycol dispersion liquid that quality of activated carbon mark is 0.5%, addition is depolymerization solution quality 1.5 times of activated carbon ethylene glycol dispersion liquid, it is at 150 DEG C in temperature, after atmospheric pressure reflux stirring decolouring 5h, through the activated carbon of the elimination removal of impurity and decolouring, decolouring and filter process are repeatedly performed 2 times;

4) ethylene glycol in solution, when temperature is 190 DEG C and pressure is 0.5atm, is evaporated completely by the ethylene glycol solution of the depolymerizing substance after remove impurity being decoloured, it is thus achieved that purification and the depolymerization product after decolouring;

5) in step 4) depolymerization product after the purification that obtains and decolouring adds 50ppm dimethyl phosphate heat stabilizer, when 220 DEG C and pressure 1atm, and under inert gas shielding, stirring mixing; Then, reaction temperature is increased to 240 DEG C, continues reaction 60min, simultaneously this period, make pressure in system at the uniform velocity be reduced to 1kPa; Then, reaction temperature is increased to 265 DEG C, makes after pressure is reduced to 20Pa in system, continue reaction 120min, namely obtain recycled polyester.

6) by 5) recycled polyester that obtains carries out melt spinning through circular port spinneret, and its POY spinning technique is: spinning temperature is 280 DEG C, and spinning speed is 2200m/min, and draft temperature is 70 DEG C, and total stretching ratio is 3. Prepare recycled polyester POY long filament, by POY long filament after 8h balances, respectively through first roller, the first hot tank, coldplate, scroll tube, the second roller, network nozzle, the second hot phase, the 3rd roller, oil tanker, prepare regeneration DTY after winding.Wherein the linear velocity of first roller is 300m/min, and the linear velocity of the second roller is 450m/min, and the linear velocity of the 3rd roller is 300m/min, and the linear velocity of Wound-up roller is 400m/min, draw ratio 1.2, and false twisting D/Y ratio is 1.5, prepares recycled polyester DTY.

Tensile strength of single fiber: 3.19CN/dtex, colour: L:78.21, b:6.23

Embodiment 8

First carrying out producing of ethylene glycol sodium titanate, it comprises the following steps:

A) by tetra-n-butyl titanate when 120 DEG C and nitrogen protection, it is 1:60 with the mol ratio of ethylene glycol Homogeneous phase mixing, tetra-n-butyl titanate and ethylene glycol;

B) mol ratio adding sodium hydroxide, sodium hydroxide and tetra-n-butyl titanate is 2.03:1, after continuing stirring until the liquid that reaction system is transparent and homogeneous, raises reaction temperature to 210 DEG C;

C) in course of reaction, backflow ethylene glycol also gets rid of lower boiling n-butyl alcohol and the water that reaction generates, response time is 2 hours, reaction is at 210 DEG C in temperature after terminating, reaction system pressure is under 0.8atm, evaporates completely by the ethylene glycol in system in 5min, is evaporated by the dihydroxylic alcohols in system and obtains white solid completely, this solid utilizes ethanol-Gossypol recrystallized from chloroform obtain clear crystal three times, namely prepares ethylene glycol sodium titanate;

The structural formula of described alcoholysis catalysts ethylene glycol sodium titanate is:

Then the preparation method carrying out a kind of recycled polyester, comprises the following steps:

1) being dissolved in depolymerizing agent ethylene glycol by alcoholysis catalysts ethylene glycol sodium titanate produced above, the consumption of ethylene glycol sodium titanate is the 0.1% of quality of glycol, is formed and solves poly solution;

2) mix solving poly solution with waste pure polyester fabric fragment and carry out the depolymerization reaction under inert gas shielding; stir simultaneously; stir speed (S.S.) is 1000 turns/min; the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 10:1; the molal weight of PET polyester calculates with 192g/mol; depolymerization reaction temperature is 180 DEG C, and reaction system pressure is 1atm, and the response time is 1h.

3) in step 2) gained solution add containing the ethylene glycol dispersion liquid that quality of activated carbon mark is 5%, addition is depolymerization solution quality 5 times of activated carbon ethylene glycol dispersion liquid, it is at 220 DEG C in temperature, after atmospheric pressure reflux stirring decolouring 1h, through the activated carbon of the elimination removal of impurity and decolouring, decolouring and filter process are repeatedly performed 5 times;

4) ethylene glycol in solution, when temperature is 210 DEG C and pressure is 0.8atm, is evaporated completely by the ethylene glycol solution of the depolymerizing substance after remove impurity being decoloured, it is thus achieved that purification and the depolymerization product after decolouring;

5) in step 4) depolymerization product after the purification that obtains and decolouring adds 100ppm butyl titanate as polycondensation catalyst and 100ppm diphenyl phosphate heat stabilizer, when 240 DEG C and pressure 1atm, and under inert gas shielding, stirring mixing; Then, reaction temperature is increased to 250 DEG C, continues reaction 20min, simultaneously this period, make pressure in system at the uniform velocity be reduced to 1kPa; Then, reaction temperature is increased to 290 DEG C, makes after pressure is reduced to 20Pa in system, continue reaction 40min, namely obtain recycled polyester.

6) by 5) recycled polyester that obtains carries out melt spinning through circular port spinneret, and its POY spinning technique is: spinning temperature is 275 DEG C, and spinning speed is 2100m/min, and draft temperature is 60 DEG C, and total stretching ratio is 1.5. Prepare recycled polyester POY long filament, by POY long filament after 8h balances, respectively through first roller, the first hot tank, coldplate, scroll tube, the second roller, network nozzle, the second hot phase, the 3rd roller, oil tanker, prepare regeneration DTY after winding.Wherein the linear velocity of first roller is 300m/min, and the linear velocity of the second roller is 400m/min, and the linear velocity of the 3rd roller is 250m/min, and the linear velocity of Wound-up roller is 500m/min, draw ratio 1.2, and false twisting D/Y ratio is 1.8, prepares recycled polyester DTY.

Tensile strength of single fiber: 3.19CN/dtex, colour: L:78.21, b:6.23

Embodiment 9

First carrying out producing of propylene glycol potassium titanate, it comprises the following steps:

A) by tetraisopropyl titanate when 100 DEG C and nitrogen protection, it is 1:80 with the mol ratio of 1,2-PD Homogeneous phase mixing, tetraisopropyl titanate and 1,2-PD;

B) mol ratio adding potassium hydroxide, potassium hydroxide and tetraisopropyl titanate is 2.02:1, after continuing stirring until the liquid that reaction system is transparent and homogeneous, raises reaction temperature to 200 DEG C;

C) in course of reaction, backflow 1,2-propylene glycol also gets rid of the lower boiling isopropyl alcohol and water that reaction generates, response time is 4 hours, and reaction is at 200 DEG C in temperature after terminating, and reaction system pressure is under 0.7atm, in in 1min, the ethylene glycol in system is evaporated completely, dihydroxylic alcohols in system is evaporated and obtains faint yellow solid completely, this solid utilizes ethanol-Gossypol recrystallized from chloroform obtain clear crystal three times, namely prepare propylene glycol potassium titanate;

The structural formula of described alcoholysis catalysts propylene glycol potassium titanate is:

Then the preparation method carrying out a kind of recycled polyester, comprises the following steps:

1) being dissolved in depolymerizing agent ethylene glycol by alcoholysis catalysts propylene glycol potassium titanate produced above, the consumption of propylene glycol potassium titanate is the 0.4% of quality of glycol, is formed and solves poly solution;

2) mix solving poly solution with containing the polyester cotton fragment washing 65% and carry out the depolymerization reaction under inert gas shielding, stir simultaneously, stir speed (S.S.) is 600 turns/min, the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 30:1, the molal weight of PET polyester calculates with 192g/mol, depolymerization reaction temperature is 160 DEG C, and reaction system pressure is 1atm, and the response time is 5h;

3) in step 2) gained solution add containing the ethylene glycol dispersion liquid that quality of activated carbon mark is 4%, addition is depolymerization solution quality 4 times of activated carbon ethylene glycol dispersion liquid, it is at 200 DEG C in temperature, after atmospheric pressure reflux stirring decolouring 2h, through the activated carbon of the elimination removal of impurity and decolouring, decolouring and filter process are repeatedly performed 5 times;

4) ethylene glycol in solution, when temperature is 200 DEG C and pressure is 0.6atm, is evaporated completely by the ethylene glycol solution of the depolymerizing substance after remove impurity being decoloured, it is thus achieved that purification and the depolymerization product after decolouring;

5) in step 4) depolymerization product after the purification that obtains and decolouring adds the tetraisopropyl titanate of 10ppm germanium dioxide and 50ppm as polycondensation catalyst and 250ppm ammonium phosphite heat stabilizer, when 230 DEG C and pressure 1atm, and under inert gas shielding, stirring mixing; Then, reaction temperature is increased to 250 DEG C, continues reaction 20min, simultaneously this period, make pressure in system at the uniform velocity be reduced to 1kPa; Then, reaction temperature is increased to 275 DEG C, makes after pressure is reduced to 20Pa in system, continue reaction 60min, namely obtain recycled polyester.

6) by 5) recycled polyester that obtains carries out melt spinning through pancake spinneret, its FDY spinning technique is: spinning temperature is 280 DEG C, spinning speed is 3200m/min, the speed of hot-rolling one is 1200m/min, temperature is 90 DEG C, the speed of hot-rolling two is 3200m/min, and temperature is 120 DEG C, prepares recycled polyester FDY filament.

Tensile strength of single fiber: 3.42CN/dtex, colour: L:79.13, b:7.58

Embodiment 10

First carrying out producing of butanediol metatitanic acid rubidium, it comprises the following steps:

A) by metatitanic acid tetra-tert ester when 50 DEG C and nitrogen protection, it is 1:20 with 1,3 butylene glycol Homogeneous phase mixing, metatitanic acid tetra-tert ester and 1,3 butanediol mol ratio;

B) mol ratio adding rubidium hydroxide, rubidium hydroxide and metatitanic acid tetra-tert ester is 2.01:1, after continuing stirring until the liquid that reaction system is transparent and homogeneous, raises reaction temperature to 250 DEG C;

C) in course of reaction, backflow 1, the lower boiling tert-butyl alcohol and the water that reaction generates also got rid of by 2-propylene glycol, and the response time is 5 hours, and reaction is at 210 DEG C in temperature after terminating, reaction system pressure is under 0.5atm, in in 5min, the 1,3 butylene glycol in system is evaporated completely, the dihydroxylic alcohols in system is evaporated and obtains yellow solid completely, this solid utilizes ethanol-Gossypol recrystallized from chloroform obtain light yellow crystal three times, namely prepares butanediol metatitanic acid rubidium;

The structural formula of described alcoholysis catalysts butanediol metatitanic acid rubidium is:

Then the preparation method carrying out a kind of recycled polyester, comprises the following steps:

1) alcoholysis catalysts butanediol metatitanic acid rubidium produced above is dissolved in depolymerizing agent ethylene glycol, consumption is quality of glycol the 0.2% of butanediol metatitanic acid rubidium, formed and solve poly solution;

2) mix solving poly solution with PET mylar and carry out the depolymerization reaction under inert gas shielding, stir simultaneously, stir speed (S.S.) is 600 turns/min, the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 16:1, the molal weight of PET polyester calculates with 192g/mol, depolymerization reaction temperature is 240 DEG C, and reaction system pressure is 2atm, and the response time is 30min;

3) in step 2) gained solution add containing the ethylene glycol dispersion liquid that quality of activated carbon mark is 0.9%, addition is depolymerization solution quality 0.5 times of activated carbon ethylene glycol dispersion liquid, it is at 200 DEG C in temperature, after atmospheric pressure reflux stirring decolouring 2h, through the activated carbon of the elimination removal of impurity and decolouring, decolouring and filter process are repeatedly performed 2 times;

4) ethylene glycol in solution, when temperature is 210 DEG C and pressure is 0.8atm, is evaporated completely by the ethylene glycol solution of the depolymerizing substance after remove impurity being decoloured, it is thus achieved that purification and the depolymerization product after decolouring;

5) in step 4) depolymerization product after the purification that obtains and decolouring adds 100ppm Germanium tetraacetate., 20ppm antimony glycol, 20ppm antimony oxide, 20ppm antimony acetate is as polycondensation catalyst and 50 ammonium phosphites, 60 ammonium dihydrogen phosphates, 70 phosphoric acid, 80 phosphorous acid, 90 ortho phosphorous acids, 100 pyrophosphoric acids, 20 ammonium phosphate heat stabilizers, when 240 DEG C and pressure 1atm, and under inert gas shielding, stirring mixing; Then, reaction temperature is increased to 245 DEG C, continues reaction 30min, simultaneously this period, make pressure in system at the uniform velocity be reduced to 1kPa; Then, reaction temperature is increased to 275 DEG C, makes after pressure is reduced to 20Pa in system, continue reaction 70min, namely obtain recycled polyester.

6) by 5) recycled polyester that obtains carries out melt spinning through cross spinneret, spinning temperature is 280 DEG C, spinning speed is 1000m/min, draft temperature is 70 DEG C, preliminary draft multiplying power is 1.08, and one draft ratio is 2.0, and two road draft ratio are 1.08, then being 0.8dtex through cutting off prepared fiber number, length is the short fibre of recycled polyester of 40mm.

Tensile strength of single fiber: 2.85CN/dtex, colour: L:79.96, b:6.37.

Claims (9)

1. a preparation method for Regenerated Polyester Fibres, is characterized in that comprising the following steps:

1) PET polyester is carried out ethylene glycol depolymerization:

1.1) alcoholysis catalysts binary titanium alkoxide alkali metal coordination compound is dissolved in depolymerizing agent ethylene glycol, is formed and solve poly solution;

1.2) mol ratio that solution poly solution and PET polyester are mixed and stirred for carrying out depolymerization reaction, depolymerizing agent ethylene glycol consumption and PET polyester is 4-50:1, and depolymerization reaction temperature is 160-240 DEG C, and reaction system pressure is 1-2.5atm, and the response time is 30min-8h;

The structural formula of described alcoholysis catalysts binary titanium alkoxide alkali metal coordination compound is:

Wherein, M+ is IA race metal cation, for Li+, Na+, K+ or Rb+;

R ' is saturated hydrocarbon chains structure that carbon number is 2-4;

2) to the decolouring of depolymerization product and purification, step is as follows:

2.1) in step 1) gained solution add containing the ethylene glycol dispersion liquid that quality of activated carbon mark is 0.5-5%, at temperature is 150-220 DEG C, atmospheric pressure reflux stirring decolouring 1-5h;

2.2) the elimination removal of impurity and the activated carbon of decolouring it are then passed through;

2.3) step 2.1 is repeated) and 2.2) 2-5 time, namely decolour and filter process is repeatedly performed 2-5 time, obtain the ethylene glycol solution of depolymerizing substance after remove impurity is decoloured;

2.4) ethylene glycol in solution is evaporated completely when temperature is 190-210 DEG C and pressure is 0.5-0.8atm by the ethylene glycol solution of the depolymerizing substance after remove impurity being decoloured, it is thus achieved that purification and the depolymerization product after decolouring;

3) repolymerization of depolymerization product, concrete step is as follows:

3.1) in step 2) depolymerization product after the purification that obtains and decolouring adds polycondensation catalyst and heat stabilizer, when 220-240 DEG C and pressure 1atm, and under inert gas shielding, stirring mixing;

3.2) then, reaction temperature is increased to 240-250 DEG C, continues reaction 20-60min, simultaneously this period, make pressure in system at the uniform velocity be reduced to 1kPa;

3.3) then, reaction temperature is increased to 265-290 DEG C, makes after pressure is reduced to 20Pa in system, continue reaction 40-120min, namely obtain recycled polyester;

4) by step 3) prepare recycled polyester dry after obtain Regenerated Polyester Fibres through circular port or Special-shaped hole spinneret plate melt spinning molding;

Described step 3.1) in, described polycondensation catalyst is one or more in binary titanium alkoxide alkali metal coordination compound catalyst, antimony glycol, antimony acetate, antimony oxide, Germanium tetraacetate., germanium dioxide, tetraisopropyl titanate, tetra-n-butyl titanate, titanium ethylene glycolate; The addition of described catalyst is the 0-200ppm of the depolymerization product quality after purifying and decolouring;

In described solution poly solution, the 0.1%-1% that consumption is quality of glycol of described binary titanium alkoxide alkali metal coordination compound; The molal weight of PET polyester calculates with 192g/mol; The preferred 8-20:1 of mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester, preferred 180-210 DEG C of depolymerization reaction temperature; Stirring during described depolymerization reaction, stir speed (S.S.) is that 50-1500 turns/min; Described depolymerization reaction carries out under inert gas shielding.

2. the preparation method of a kind of Regenerated Polyester Fibres according to claim 1, it is characterised in that described binary titanium alkoxide alkali metal coordination compound is prepared by following steps:

A) by titanium compound that formula is Ti (OR) 4 when 50-150 DEG C and nitrogen protection, with dihydroxylic alcohols the HO-R '-OH Homogeneous phase mixing that carbon number is 2-4;Wherein, R is carbon number is the saturated hydrocarbon chains structure of 2-4, and R ' is saturated hydrocarbon chains structure that carbon number is 2-4;

B) add IA race metal hydroxides MOH, after continuing stirring until the liquid that reaction system is transparent and homogeneous, raise reaction temperature to 180-250 DEG C;

C), in course of reaction, backflow dihydroxylic alcohols also gets rid of low boiling monohydric alcohol R-OH and the water that reaction generates, and the response time is 2-5 hour, and the dihydroxylic alcohols in system is quickly evaporated completely after terminating by reaction, it is thus achieved that white or slightly yellow solid;

D) above-mentioned solid utilizes ethanol-Gossypol recrystallized from chloroform repeatedly obtain colourless or light yellow crystal and is described binary titanium alkoxide alkali metal coordination compound.

3. the preparation method of a kind of Regenerated Polyester Fibres according to claim 2, it is characterised in that the mol ratio of Ti (OR) 4 and HO-R '-OH is 1:20-100; The mol ratio of MOH and Ti (OR) 4 is 2.01-2.05:1; In step c), described quickly referring at temperature is 190-210 DEG C, reaction system pressure is under 0.5-0.8atm, in 0.5-5min by dihydroxylic alcohols evaporation in system completely.

4. the preparation method of a kind of Regenerated Polyester Fibres according to claim 1, it is characterised in that described PET polyester is any type of goods made by polyethylene terephthalate and waste and old product.

5. the preparation method of a kind of Regenerated Polyester Fibres according to claim 1, it is characterized in that, the decolouring of described depolymerization product and the step of purification, step 2.1) in, the addition of the ethylene glycol solution containing activated carbon is 0.5-5 times of depolymerizing substance ethylene glycol solution quality.

6. the preparation method of a kind of Regenerated Polyester Fibres according to claim 1, it is characterized in that, described heat stabilizer is one or more in trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite, ammonium phosphite, ammonium dihydrogen phosphate, phosphoric acid, phosphorous acid, ortho phosphorous acid, pyrophosphoric acid, ammonium phosphate; The addition of described heat stabilizer is the 50ppm-500ppm of the depolymerization product quality after purifying and decolouring.

7. the preparation method of a kind of Regenerated Polyester Fibres according to claim 1, it is characterised in that step 3.1) in, stirring mixing refers to that speed of agitator is that 50-80 turns/min, stirring mixing 30-60min; Step 3.2) in, at the uniform velocity reduction pressure is 0.5kPa-10kPa/min to the air pressure drop low rate of 1kPa, needs stirring during reaction, and speed of agitator is that 50-80 turns/min; Step 3.3) in, continuation at the uniform velocity reduction pressure is 100Pa-1kPa/min to the air pressure drop low rate of 20Pa, and continues stirring when reacting, and speed of agitator is that 80-120 turns/min.

8. the preparation method of a kind of Regenerated Polyester Fibres according to claim 1, it is characterised in that described Regenerated Polyester Fibres type is POY, FDY, DTY or short fibre, and its spinning technique is respectively as follows:

By step 3) recycled polyester for preparing carries out melt spinning, its POY spinning technique is: spinning temperature is 270-290 DEG C, spinning speed is 2000-2500m/min, draft temperature is 60-80 DEG C, total draft multiplying power is 1.5-4.5, prepare recycled polyester POY long filament, by POY long filament after 8h balances, respectively through first roller, first hot tank, coldplate, scroll tube, second roller, network nozzle, second hot tank, 3rd roller, oil tanker, regeneration DTY is prepared after winding, wherein the linear velocity of first roller is 200-500m/min, the linear velocity of the second roller is 400-500m/min, the linear velocity of the 3rd roller is 200-500m/min, the linear velocity of Wound-up roller is 300-600m/min, draw ratio 1.1-1.5, false twisting D/Y is than for 1.2-2.5, prepare recycled polyester DTY,

By step 3) recycled polyester for preparing carries out melt spinning, its FDY spinning technique is: spinning temperature is 270-290 DEG C, spinning speed is 3000-3500m/min, the speed of hot-rolling one is 1100-1500m/min, temperature is 80-110 DEG C, the speed of hot-rolling two is 3000-3500m/min, and temperature is 115-135 DEG C, prepares recycled polyester FDY filament;

By step 3) recycled polyester for preparing carries out melt spinning, its short fine spinning technique is: spinning temperature is 270-290 DEG C, spinning speed is 800-1500m/min, draft temperature is 60-80 DEG C, preliminary draft multiplying power is 1.02-1.10, and one draft ratio is 1.8-2.5, and two road draft ratio are 1.02-1.1, then being 0.5-5dtex through cutting off prepared fiber number, length is the short fibre of recycled polyester of 30mm-50mm.

9. the preparation method of a kind of Regenerated Polyester Fibres according to claim 1, it is characterised in that described Special-shaped hole spinneret plate is hollow type, pancake, triangle and the one in cross.