CN107523895B

CN107523895B - A kind of coloured regenerative polyester staple fiber and preparation method thereof

Info

Publication number: CN107523895B
Application number: CN201710595770.9A
Authority: CN
Inventors: 陈烨; 王朝生; 王华平; 王少博; 吉鹏; 刘顶
Original assignee: Donghua University
Current assignee: Donghua University
Priority date: 2017-07-20
Filing date: 2017-07-20
Publication date: 2019-01-11
Anticipated expiration: 2037-07-20
Also published as: CN107523895A

Abstract

The present invention relates to a kind of coloured regenerative polyester staple fibers and preparation method thereof, polyester reclaiming material and polyester oligomer melt are subjected to reactive melt blending first and obtain preliminary depolymerization melt, then preliminary depolymerization melt mixes progress alcoholysis reaction with ethylene glycol and obtains depth depolymerization melt, depth depolymerization melt carries out the removing of TVOC and the reparation of cracking functional group obtains low TVOC content polyester oligomer melt, then low TVOC content polyester oligomer melt carries out polycondensation reaction and obtains low TVOC content recycled polyester melt, coloured recycled polyester melt is finally obtained by the color matching that computer for colouring system controls low TVOC content recycled polyester melt, coloured recycled polyester melt enters fused mass directly spinning system and coloured regenerative polyester staple fiber is made.The color difference of the final obtained coloured regenerative polyester staple fiber of the present invention is smaller, and TVOC content is 30~300ppm, and the content of nonyl phenol and its isomer is 80~200ppm.

Description

A kind of coloured regenerative polyester staple fiber and preparation method thereof

Technical field

The invention belongs to the regeneration field of waste and old polyester, it is related to a kind of coloured regenerative polyester staple fiber and preparation method thereof, In particular to one kind is using polyester reclaiming material as raw material and the coloured regenerative polyester staple fiber of the lower high-quality of TVOC and its efficient Preparation method.

Background technique

Polyethylene terephthalate (Polyethylene Terephthalate, PET, abbreviation polyester) is that one kind is answered With extensive synthesis high molecular material, whole world PET yield is more than 4,000 ten thousand tons within 2015, is only second to polyolefin, be synthetic fibers with Dominate material used in food packaging applications (proportion is more than 80%).However it is closed as a kind of not degradable petroleum base At high molecular material, the social reserves of polyester discarded product are also very huge, and it is waste and old that especially dopant species are complicated, content is high Polyester-containing textiles are just being increased every year with million tons of speed, but the current rate of recovery is also less than 3%, the fossil resources thus caused Waste and noxious waste pollution problem are also increasingly serious.Therefore (especially waste and old polyester textile etc. is low-quality for waste polyester Waste material) high-efficiency high-quality regeneration techniques be of great significance for the sustainable development of industry.

The regeneration techniques of polyester can be divided mainly into physical method and chemical method two major classes.Conventional physical method is by carrying out waste material Regeneration is realized in melting reprocessing, has the characteristics that high efficiency, low cost, is that current polyester regenerates the leading of industrialization technology, but tradition The more primary quality decline of the product that physical method regenerates is obvious, and inherent viscosity declines and fluctuates larger.Simultaneously because in the process Melt viscosity is larger, so that the filtering of infusibility impurity and volatile impurity removing are all extremely difficult, while excessive levels of impurities is in height Cannot such as remove in time in the process of temperature will cause a variety of irreversible cracking degradations.Therefore simple physical method is regenerated right As being only limitted to the higher waste polyester bottle chip of degree of purity.

In order to carry out highly efficient regeneration to polyester reclaiming material, the prior art has carried out conventional physical method to improve upgrading, Feature is to increase thickening link in melt stage.Such as patent of invention CN201210006794.3 passes through chain extender, invention Patent CN201210399804.4 more can effectively increase regeneration by the method for long-time high-specific surface area high vacuum polycondensation The inherent viscosity of product.It is such to improve to the production cost increases compared with conventional physical method and few, and can realize to polyester reclaiming material High efficiency, low cost regeneration, therefore in recent years the industrialization promotion range of the relevant technologies also in rapid expansion.But also due to molten The limitation of body viscosity, this method still cannot effectively remove impurity, TVOC content and other especially in recycled product The content of organic murder by poisoning object is higher, and the application range of product is still greatly limited, can not comprehensively into take, automobile interior decoration etc. The field more demanding to safety in utilization.

Chemical rule is to realize regeneration by the route of " being depolymerized to monomer-separating-purifying-to polymerize again ", in the process due to poly- Ester is depolymerizated as monomer, technical purification more thoroughly easy to accomplish, can carry out to the low waste material such as waste textile effective Recycling, recycled product quality can match in excellence or beauty primary, but process flow is long, and low efficiency, cost is very high, loses more than gain.Only the U.S. and The developed countries such as Japan have carried out small-scale industrialization to the relevant technologies under the fostering of preferential policy and have attempted, wherein representative Patented technology has US5710315, US4609608 and WO2003033581 etc., but due to cost problem, popularization is seriously made About.

Summary of the invention

The purpose of the present invention is to provide a kind of coloured regenerative polyester staple fiber of high-quality and its high efficiency preparation methods, simultaneous In the case where caring for production cost and equipment modification cost, effectively promoted using polyester reclaiming material as coloured recycled polyester made from raw material The quality of staple fiber, effectively solves that existing improvement physical method coloured regenerative polyester staple fiber TVOC content produced is high to ask Topic.

In order to achieve the above objectives, the technical solution adopted by the present invention are as follows:

A kind of preparation method of coloured regenerative polyester staple fiber, steps are as follows:

1) by polyester reclaiming material and polyester oligomer melt carry out reactive melt blending obtain average degree of polymerization be 20~ 40 preliminary depolymerization melt, the average degree of polymerization of the polyester oligomer melt are 1.5~4, and can be by the product of step later It is continuous to provide；

2) preliminary depolymerization melt carries out alcoholysis reaction and obtains the depth that average degree of polymerization is 1.5~4 after mixing with ethylene glycol Depolymerization melt；

3) depth depolymerization melt is under conditions of temperature is 190~205 DEG C, pressure is 1~80KPa and glycol steam pair Stream flowing carries out the removing of TVOC and the reparation of cracking functional group obtains the low TVOC content polyester oligomeric of TVOC content < 20ppm Object melt；

4) low TVOC content polyester oligomer melt carries out prepolymerization reaction and obtains low TVOC content precondensation polyester fondant；

5) low TVOC content precondensation polyester fondant carries out final polycondensation reaction and obtains low TVOC content recycled polyester melt；

6) the form and aspect data for obtaining low TVOC content recycled polyester melt obtain aim colour by computer for colouring system-computed Color masterbatch type and dosage required for phase, and convey corresponding melt and low TVOC content recycled polyester melt mixed obtain it is coloured again Raw polyester fondant；

7) coloured recycled polyester melt enters fused mass directly spinning system coloured regenerative polyester staple fiber is made.

As a preferred technical scheme:

A kind of preparation method of coloured regenerative polyester staple fiber as described above, the removing of the TVOC and cracking functional group Reparation be to be carried out in vertical reactor, the vertical reactor be grid fall membrane type devolatilization reactor, bleeding point is located at Reactor head, internal cell structure are as follows: be made of the different screen layers with parallel angle bead, angle bead on adjacent screen layer Direction be mutually perpendicular to, the interlamellar spacing of top to the bottom of self-supporting reactor, adjacent screen layer is gradually increased, different screen layers The gap of upper angle bead is gradually reduced.

A kind of preparation method of coloured regenerative polyester staple fiber as described above, the temperature of the vertical reactor lower semisection Higher than the temperature of upper semisection, upper semisection temperature is 190~200 DEG C, and lower semisection temperature is 200~205 DEG C；The vertical reactor Interior pressure generating period variation, cycle length are equal to residence time of the depth depolymerization melt in vertical reactor, 1KPa's Pressure hold time accounts for the 20%~90% of cycle time length, wherein with 50%~80% be it is preferred, the depth depolymerization is molten Residence time of the body in vertical reactor is 10min~2h, oxygen content < 0.03v/v% in the vertical reactor.

A kind of preparation method of coloured regenerative polyester staple fiber as described above, the specific steps are as follows:

1) it will be added twin-screw extrude by sufficiently dry polyester reclaiming material, catalyst and polyester oligomer melt Reactive melt blending is carried out, under the action of ester exchange reaction, reversible depolymerization will occur for polyester reclaiming material in Blending Processes Obtain preliminary depolymerization melt；The polyester reclaiming material by recycle Lai PET give up cloth be prepared, it is described reactivity melting altogether Mixed temperature are as follows: 260~275 DEG C of twin-screw feed zone temperature, 275~300 DEG C of twin-screw compression section, homogenizing zone temperature 275~ 295 DEG C, and with 288~293 DEG C of temperature ranges be it is preferred, the time is 1~5min, and atmosphere is nitrogen or gauge pressure is < 0.15KPa Vacuum environment；

It is depolymerized using polyester oligomer to melt in step 1), rather than previous chemical method is carried out frequently with ethylene glycol The main advantage of melting depolymerization is:

A) it can avoid adding the ethylene glycol generation unaffordable reaction pressure of conventional screw into high temperature double-screw rod；

B) it can avoid ethylene glycol from a large amount of autohemagglutination etherificate side reaction occurs in high temperature and high pressure environment, be effectively reduced again The content of diethylene glycol (DEG) in raw product；

C) step 1) provide reaction condition under, be based on ester exchange reaction, polyester oligomer equally can to polyester into The advantages of row depolymerization, and depolymerization approximation belongs to homogeneous reaction has depolymerization speed fast, and molecular weight of product is evenly distributed；

D) the preliminary depolymerization melt generated after step 1) has preferable dissolubility in ethylene glycol, can make next The alcoholysis reaction of step is changed into homogeneous depolymerization by heterogeneous depolymerization rapidly, effectively promotion reaction rate；

2) preliminary depolymerization melt feeds reaction kettle through pipeline A after filter I filtering removes insoluble inert particle impurity, And alcoholysis reaction is carried out under nitrogen protection, pressurization and stirring condition after mixing with ethylene glycol and obtains depth depolymerization melt；It is described The temperature of alcoholysis reaction is 190~205 DEG C, and the time of alcoholysis reaction is 40~80min；

Involved in step 2) it is a technical advantage that: depth depolymehzation step, which can make material at a lower temperature, to be had very well Mobility, in melt in next step TVOC depth removal and inhibit diethylene glycol (DEG) generation guarantee is provided；In the present invention Depth depolymerization be different from the regeneration of previous chemical method frequently with the part of the heterogeneous alcoholysis of low-temperature atmosphere-pressure be: experience step 1) This is quickly after preliminary depolymehzation process, depth depolymerization can low temperature, close to normal pressure under conditions of realize homogeneous depolymerization, simultaneously The degree of polymerization can accurately be adjusted by feed ratio, avoided using excessive ethylene glycol, thus can be promoted depolymerization efficiency, Production cost is saved, and can effectively avoid the generation of diethylene glycol (DEG)；

3) depth depolymerization melt through filter II filtering after by pipeline B feed vertical reactor, and by self gravity by The bottom of vertical reactor is flowed at the top of vertical reactor, during this period, passes through control reaction temperature, pressure and oxygen content The removing of TVOC and the reparation of cracking functional group in depth depolymerization melt are carried out, is equipped with sample tap in the bottom of vertical reactor, Depth depolymerization melt is after sample tap outflow through by carrying out repeating to flow at the top of pipeline D Returning reactor obtaining low TVOC content Polyester oligomer melt；

The control of pressure is by constantly supplementing ethylene glycol simultaneously from vertical from the lower part of vertical reactor in vertical reactor Gas realization is detached at the top of formula reactor, the lower part of vertical reactor is communicated by pipeline F with ethylene glycol storage tank II holding, G is condensed the gas of extraction by condenser by the road, is finally recycled by ethylene glycol storage tank I, and ethylene glycol storage tank I passes through pipe respectively Road E and pipeline H are connected to ethylene glycol storage tank II and reaction kettle；

Oxygen content < 0.03v/v% in the vertical reactor；

Step 3) can efficiently realize in depth depolymerization melt the deep removal of TVOC and the Principles of cracking functional group and Technical advantage is as follows:

A) technological temperature is lower, even if depth depolymerization melt will not occur further to polymerize in subnormal ambient, because This fluidity of molten is good, while melt flows, via a large amount of cell structures, liquid-gas interface renewal speed is very fast；

B) since melt viscosity is low, at a set temperature, by negative pressure TVOC can quickly escaped from melt, Negative pressure after a certain period of time, to storage tank VII supply ethylene glycol, at this time ethylene glycol can due to negative pressure fast vaporizing, in the environment of pumping Under to top fast transferring and can be constantly updated from reactor lower part, the glycol steam flowed in the process can capture (dissolution) with And drive thoroughly moving out for the TVOC even some higher murder by poisoning organic matter of boiling point (such as: nonylphenol class and its isomer)；

C) temperature for controlling vertical reactor lower semisection is slightly above upper semisection, more conducively bottom-up inverse of glycol steam Melt stream migration, screen in reactor under the structure of gap decrescence between spacing is cumulative layer by layer and angle bead, so that melt Surface Renewal speed is gradually increased, and film length increase is fallen, in conjunction with the higher condition of temperature of lower, it is ensured that in depth depolymerization melt Fail effectively to remove net higher boiling to the greatest extent on reactor top and poison organic matter (such as: nonyl phenol and its isomer) flowing through It is thoroughly detached from melt when reactor lower part and enters the glycol steam phase of flowing；

D) the pressure change period controlled in vertical reactor is equal to stop of the depth depolymerization melt in vertical reactor Time, it is ensured that the uniformity of continuous production process material devolatilization degree, while under this technique, depth solution in entire devolatilization processes The dynamic viscosity of poly- melt does not change substantially, the accurate control for devolatilization condition of being more convenient for；

E) in Process temperature ranges, depth depolymerization melt and ethylene glycol have preferable exchange reaction activity, so that mistake Some structures containing cracking end group can be repaired by exchange reaction in journey, the low boiling point containing cracking end group being replaced Monomer structure can be taken out of in devolatilization processes by glycol steam；

4) low TVOC content polyester oligomer melt is continuously fed into twin-screw as the raw material of step 1) via pipeline D and squeezes Machine out, or prepolymerization reaction kettle is fed through pipeline C after filter III filtering, catalyst, heat stabilizer, anti-ether agent is added Prepolymerization reaction, which is carried out, with antioxidant obtains the low TVOC content precondensation polyester fondant that average degree of polymerization is 20~30；It is described pre- The temperature of polycondensation reaction are as follows: 255~265 DEG C of upper chamber, 265~275 DEG C of lower room；The pressure of the prepolymerization reaction are as follows: upper chamber 2.5 ~4.5KPa, lower 1~2.5KPa of room；The time (residence time of the melt in reaction kettle) of the prepolymerization reaction be 60~ 120min；

5) low TVOC content precondensation polyester fondant is delivered in final polycondensation reaction kettle via pipeline I carries out final polycondensation reaction Obtain the low TVOC content recycled polyester melt that average degree of polymerization is 95~110；The temperature of the final polycondensation reaction be 280~ 285 DEG C, pressure is 50~500Pa, and the time (residence time of the melt in reaction kettle) is 100~180min；

6) the form and aspect data that on-line monitoring obtains low TVOC content recycled polyester melt are carried out on pipeline J, by computer Color matching system calculates color masterbatch type and dosage required for obtaining target form and aspect, and control color masterbatch melt group convey corresponding melt with Low TVOC content recycled polyester melt mixed obtains coloured recycled polyester melt；

7) coloured recycled polyester melt enters fused mass directly spinning system via pipeline J coloured regenerative polyester staple fiber is made, and spins Silk technique are as follows: melt conveying → spinning → cooling → winding falling-barrel → seal wire → one of drawing-off → bis- drawing-offs → thermal finalization → volume Song cutting is packaged；Spinning technology parameter are as follows: 270~290 DEG C of spinning temperature, 800~1500m/min of spinning speed, draft temperature 60~80 DEG C, preliminary draft multiplying power is 1.02~1.10, and one draft ratio is 1.8~2.5, two draft ratios are 1.02~ 1.1。

A kind of preparation method of coloured regenerative polyester staple fiber as described above, it is described by sufficiently dry in step 1) Polyester reclaiming material refer to moisture content < 100ppm polyester reclaiming material；

The catalyst is tetra-n-butyl titanate, tetraisopropyl titanate, titanium ethylene glycolate, ethylene glycol sodium titanate, titanium ethylene glycolate One or more of sour potassium, zinc acetate and manganese acetate, with metallic element quality in catalyst relative to polyester oligomer melt matter Amount calculates, and the content of catalyst is 10~300ppm；

The mass ratio of the polyester reclaiming material and polyester oligomer melt is 0.1~3:1.

A kind of preparation method of coloured regenerative polyester staple fiber as described above, in step 2), the preliminary depolymerization melt Mass ratio with ethylene glycol is 3~4.5:1；Pressure after pressurization is 101~150KPa, and stirring rate is 35~75Hz, stirring Using plate and frame agitating paddle.

A kind of preparation method of coloured regenerative polyester staple fiber as described above, in step 4), the catalyst is metatitanic acid Four N-butyls, tetraisopropyl titanate, titanium ethylene glycolate, ethylene glycol sodium titanate, ethylene glycol potassium titanate, antimony acetate, antimony oxide, second One or more of sour germanium and germanium oxide, on the basis of the quality of low TVOC content polyester oligomer melt, the addition of catalyst Amount is 10~300ppm；

The antioxidant is the different certain herbaceous plants with big flowers ester of pentaerythritol diphosphite two, bis- (2.4- di-tert-butyl-phenyl) pentaerythrites two Phosphite ester；Three (2,4- di-t-butyl) phenyl-phosphites more than one, with the matter of low TVOC content polyester oligomer melt On the basis of amount, the additive amount of antioxidant is 10~100ppm；

The heat stabilizer is trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, phosphorous triphenyl phosphate One in ester, diphenyl phosphite, ammonium phosphite, ammonium dihydrogen phosphate, phosphoric acid, phosphorous acid, ortho phosphorous acid, pyrophosphoric acid and ammonium phosphate Kind or more, on the basis of the quality of low TVOC content polyester oligomer melt, the additive amount of heat stabilizer is 50~200ppm；

The anti-ether agent is sodium acetate, on the basis of the quality of low TVOC content polyester oligomer melt, additive amount 50 ~200ppm.

A kind of preparation method of coloured regenerative polyester staple fiber as described above, filter I, filter II and filter The filtering accuracy of III is respectively 50~100 μm, 1~15 μm and 1~15 μm.

The present invention also provides a kind of coloured regenerative polyester staple fiber, the fiber number of coloured regenerative polyester staple fiber is 1.1~ 5.5dtex, length are 30~50mm, and the color difference grade of the coloured regenerative polyester staple fiber is 4-5 grades, and color fastness is 4-5 grades, TVOC content is 30~300ppm, and the content of nonyl phenol and its isomer is 80~200ppm.

Coloured regenerative polyester staple fiber as described above, the breaking strength of the coloured regenerative polyester staple fiber is 2.8~ 4.8cN/dtex, elongation at break are 22.0~65.0%, and line density deviation ratio is 6.0~8.0%.

The utility model has the advantages that

(1) a kind of preparation method of coloured regenerative polyester staple fiber of the invention can effectively reduce with polyester reclaiming material as original The content of TVOC, nonyl phenol and its isomer in the prepared coloured regenerative polyester staple fiber of material, while can stablize It is online to deploy required color, and the requirement to regenerative raw materials quality is low, it is adaptable；

(2) a kind of preparation method of coloured regenerative polyester staple fiber of the invention is the cyclic regeneration work of " waste material to fiber " Skill, overall flow length and technique controlling difficulty are moderate, have high efficiency；

(3) production equipment needed for a kind of preparation method of coloured regenerative polyester staple fiber of the invention can make full use of existing There is polyester industry metaplasia to produce Equipment Foundations and is transformed construction, the more existing long-time melt devolatilization thickening method of reproduction of cost and chain extension It regenerates thickening method to increase seldom, but product quality obtained and added value can be obviously improved, therefore has extraordinary Industrialization promotion advantage and environmental benefit.

Detailed description of the invention

Fig. 1 is the preparation method schematic diagram of the coloured regenerative polyester staple fiber of the present invention；

Wherein, 1- pipeline A, 2- pipeline B, 3- pipeline C, 4- pipeline D, 5- pipeline E, 6- pipeline F, 7- pipeline G, 8- pipeline H, 9- pipeline I, 10- pipeline J, 11- double screw extruder, 12- filter I, 13- reaction kettle, 14- filter II, 15- vertical response Device, 16- ethylene glycol storage tank I, 17- ethylene glycol storage tank II, 18- condenser, 19- filter III, 20- prepolymerization reaction kettle, 21- Final polycondensation reaction kettle, 22- fused mass directly spinning system, 23- color masterbatch melt group.

Specific embodiment

The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Fixed range.

Embodiment 1

A kind of preparation method of coloured Regenerated Polyester Fibres, steps are as follows:

1) the polyester oligomer melt that polyester reclaiming material, catalyst and average degree of polymerization that moisture content is 50ppm are 2 is added Enter to carry out reactive melt blending in double screw extruder to obtain the preliminary depolymerization melt that average degree of polymerization is 40, wherein polyester The mass ratio of reclaimed materials and polyester oligomer melt is 1:1, and catalyst is titanium ethylene glycolate, with metallic element quality phase in catalyst Polyester oligomer melt quality is calculated, the content of catalyst is 50ppm；The temperature of reactive melt blending are as follows: twin-screw 268 DEG C of feed zone temperature, 288 DEG C of twin-screw compression section, 288 DEG C of homogenizing zone temperature, time 2min, screw rod is interior to be protected for nitrogen Shield；

2) preliminary depolymerization melt feeds reaction kettle 13 through pipeline A1 after the filter I12 filtering that filtering accuracy is 50 μm, And after being mixed with ethylene glycol under nitrogen protection, pressurization and stirring condition in 200 DEG C of progress alcoholysis reaction 60min, preliminary depolymerization The mass ratio of melt and ethylene glycol is 3.5:1, and the pressure after pressurization is 120KPa, stirring rate 50Hz, and stirring uses sheet frame Formula agitating paddle obtains the depth depolymerization melt that average degree of polymerization is 2 after reaction；

3) depth depolymerization melt feeds vertical reactor by pipeline B2 after the filter II14 filtering that filtering accuracy is 1 μm 15, and flow to by the top of vertical reactor 15 bottom of vertical reactor 15, during this period, by control reaction temperature, Pressure and oxygen content carry out the removing of TVOC and the reparation of cracking functional group in depth depolymerization melt, at the bottom of vertical reactor 15 Portion is equipped with sample tap, and depth depolymerization melt is after sample tap outflow through carrying out repetitive stream by the top of pipeline D4 Returning reactor 15 It moves until the TVOC content of melt is that 10ppm obtains low TVOC content polyester oligomer melt；

Vertical reactor 15 is that grid falls membrane type devolatilization reactor, and bleeding point is located at reactor head, internal grid knot Structure are as follows: be made of the different screen layers with parallel angle bead, the direction of angle bead is mutually perpendicular on adjacent screen layer, and self-supporting is anti- The top of device to bottom is answered, the interlamellar spacing of adjacent screen layer is gradually increased, and the gap of angle bead is gradually reduced on different screen layers；

The temperature of 15 lower semisection of vertical reactor is higher than the temperature of upper semisection, the temperature of vertical reactor are as follows: upper semisection temperature Degree is 190~195 DEG C, and lower semisection temperature is 195~205 DEG C；

The control of pressure is by constantly supplementing ethylene glycol simultaneously from vertical reactor 15 from the lower part of vertical reactor 15 Top detach gas realization, the lower part of vertical reactor 15 is communicated by pipeline F6 with ethylene glycol storage tank II17 holding, pumping G7 is condensed gas out by condenser 18 by the road, is finally recycled by ethylene glycol storage tank I16, ethylene glycol storage tank I16 difference It is connected to by pipeline E5 and pipeline H8 with ethylene glycol storage tank II17 and reaction kettle 13, oxygen content is the vertical response of 0.01v/v% Pressure generating period variation in the range of 1~80KPa in device 15, period 110min, wherein the pressure of 1KPa is kept Time is 88min；

4) low TVOC content polyester oligomer melt is continuously fed into twin-screw as the raw material of step 1) via pipeline D4 Extruder, or prepolymerization reaction kettle 20 is fed through pipeline C3 after the filter III19 filtering that filtering accuracy is 1 μm, it is added Catalyst glycol titanium, heat stabilizer triphenyl phosphite, anti-ether agent sodium acetate and antioxidant three (2,4- di-t-butyl) phosphorous Prepolymerization reaction is carried out after acid phenenyl ester obtains the low TVOC content precondensation polyester fondant that average degree of polymerization is 30；Prepolymerization reaction Temperature are as follows: 260 DEG C of upper chamber, 267 DEG C of lower room；The pressure of prepolymerization reaction are as follows: upper chamber 2.6KPa, lower room 1.1KPa；Precondensation The time of reaction is 64min；On the basis of the quality of low TVOC content polyester oligomer melt, the additive amount of catalyst is 10ppm, the additive amount of heat stabilizer are 200ppm, and the additive amount of sodium acetate is 200ppm, and the additive amount of antioxidant is 100pmm；

5) low TVOC content precondensation polyester fondant is delivered to progress final minification in final polycondensation reaction kettle 21 via pipeline I9 and gathers Reaction obtains the low TVOC content recycled polyester melt that average degree of polymerization is 110；The temperature of final polycondensation reaction is 285 DEG C, pressure For 50Pa, time 100min；

6) the form and aspect data that on-line monitoring obtains low TVOC content recycled polyester melt are carried out on pipeline J 10, by calculating Machine color matching system calculates color masterbatch type and dosage required for obtaining target form and aspect, and controls color masterbatch melt group 23 and convey corresponding melt Body and low TVOC content recycled polyester melt mixed obtain coloured recycled polyester melt；

7) the short fibre of coloured recycled polyester is made into fused mass directly spinning system 22 via pipeline J 10 in coloured recycled polyester melt Dimension, spinning technique are as follows: melt conveying → spinning → cooling → winding falling-barrel → seal wire → one of drawing-off → bis- drawing-offs → heat is fixed Type → curling cutting is packaged；Spinning technology parameter are as follows: 290 DEG C of spinning temperature, spinning speed 1500m/min, 80 DEG C of draft temperature, Preliminary draft multiplying power is 1.10, and one of draft ratio is 2.5, and two draft ratios are 1.1.

The fiber number of final coloured Regenerated Polyester Fibres obtained is 1.1dtex, length 30mm, coloured Regenerated Polyester Fibres TVOC content be 30ppm, the content of nonyl phenol and its isomer is 92ppm, and the fracture of coloured Regenerated Polyester Fibres is strong Degree be 4.52cN/dtex, elongation at break 23.3%, line density deviation ratio be 7.0% .5 grades of color difference class 4, color fastness etc. 4.5 grades of grade.

Comparative example 1

A kind of preparation method of coloured Regenerated Polyester Fibres, using polyester reclaiming material same as Example 1, through superfusing Melt, 275 DEG C of melts homogenize 30min, and in mouse-cage type reactor, 272 DEG C, air pressure < 50Pa high vacuum devolatilization 150min, process is molten Know from experience is brown automatically, and regeneration coloured polyester fiber is made after melt spinning, and the fiber number of coloured Regenerated Polyester Fibres is 5.0dtex, the TVOC contents of coloured Regenerated Polyester Fibres are 758ppm, and the content of nonyl phenol and its isomer is 633ppm, the breaking strength of coloured Regenerated Polyester Fibres are 1.2cN/dtex, elongation at break 11.2%, line density deviation ratio It is 9%, color difference grade is 3.5 grades, and color fastness grade is 4 grades.By comparative example 1 and the comparison of embodiment 1 as can be seen that using this hair The TVOC content and nonyl phenol of coloured Regenerated Polyester Fibres made from bright preparation method and its content of isomer are opposite It is reduced obviously in the prior art, the quality of colored fibre is more excellent.

Embodiment 2

1) the polyester oligomer melt for being 1.5 by polyester reclaiming material, catalyst and average degree of polymerization that moisture content is 90ppm It adds twin-screw extrude the reactive melt blending of progress and obtains the preliminary depolymerization melt that average degree of polymerization is 20, wherein is poly- The mass ratio of ester reclaimed materials and polyester oligomer melt is 0.1:1, and catalyst is tetra-n-butyl titanate, with metal member in catalyst Quality amount is calculated relative to polyester oligomer melt quality, and the content of catalyst is 50ppm；The temperature of reactive melt blending Are as follows: 260 DEG C of twin-screw feed zone temperature, 275 DEG C of twin-screw compression section, 275 DEG C of homogenizing zone temperature, time 5min, atmosphere is Nitrogen；

2) preliminary depolymerization melt feeds reaction kettle through pipeline A after the filter I filtering that filtering accuracy is 100 μm, and with In 190 DEG C of progress alcoholysis reaction 80min, preliminary depolymerization melt under nitrogen protection, pressurization and stirring condition after ethylene glycol mixing Mass ratio with ethylene glycol is 3:1, and the pressure after pressurization is 101KPa, stirring rate 35Hz, and stirring is stirred using plate and frame Paddle obtains the depth depolymerization melt that average degree of polymerization is 1.5 after reaction；

1) 3) depth depolymerization melt through filter II filtering that filtering accuracy be 1 μm after by pipeline B feed vertical reactor, And the bottom by flowing to vertical reactor at the top of vertical reactor by control reaction temperature, pressure and contains during this period Oxygen amount carries out the removing of TVOC and the reparation of cracking functional group in depth depolymerization melt, is equipped with sampling in the bottom of vertical reactor Mouthful, depth depolymerization melt repeats flowing to obtain TVOC content to be 10ppm's after sample tap outflow through path same as Example 1 Low TVOC content polyester oligomer melt, the structure and pressure control path of vertical reactor are the same as embodiment 1；Vertical reactor Temperature are as follows: upper semisection temperature is 190~200 DEG C, and lower semisection temperature is 200~203 DEG C；Oxygen content is the vertical of 0.02v/v% Pressure generating period variation in the range of 1~80KPa in reactor, period 70min, wherein the pressure of 1KPa is kept Time is 35min；

4) low TVOC content polyester oligomer melt is continuously fed into twin-screw as the raw material of step 1) via pipeline D and squeezes Machine 11 out, or prepolymerization reaction kettle is fed through pipeline C after the filter III filtering that filtering accuracy is 1 μm, catalyst is added Tetra-n-butyl titanate, heat stabilizer trimethyl phosphate, anti-ether agent sodium acetate and the different certain herbaceous plants with big flowers of antioxidant pentaerythritol diphosphite two Prepolymerization reaction is carried out after ester obtains the low TVOC content precondensation polyester fondant that average degree of polymerization is 20；The temperature of prepolymerization reaction Degree are as follows: 255 DEG C of upper chamber, 265 DEG C of lower room；Pressure are as follows: upper chamber 2.5KPa, lower room 1KPa；Time is 120min；With low TVOC content On the basis of the quality of polyester oligomer melt, the additive amount of catalyst is 20ppm, and the additive amount of heat stabilizer is 50ppm, acetic acid The additive amount of sodium is 50ppm, and the additive amount of antioxidant is 10pmm；

5) low TVOC content precondensation polyester fondant is averagely gathered through path same as Example 1 progress final polycondensation reaction The right low TVOC content recycled polyester melt for being 95；The temperature of reaction is 280 DEG C, pressure 50Pa, time 150min；

6) coloured recycled polyester melt is obtained using method same as Example 1；

7) the short fibre of coloured recycled polyester is made through path same as Example 1 and spinning technique in coloured recycled polyester melt Dimension, spinning technology parameter are as follows: 270 DEG C of spinning temperature, spinning speed 800m/min, 60 DEG C of draft temperature, preliminary draft multiplying power is 1.02, one of draft ratio is 1.8, and two draft ratios are 1.02.

The fiber number of final coloured Regenerated Polyester Fibres obtained is 5.5dtex, length 50mm, coloured Regenerated Polyester Fibres TVOC content be 30ppm, the content of nonyl phenol and its isomer is 80ppm, and the fracture of coloured Regenerated Polyester Fibres is strong Degree is 3.0cN/dtex, and elongation at break 65.0%, line density deviation ratio is 7.3%, color difference class 4 grade, color fastness grade 4.5 grade.

Comparative example 2

A kind of preparation method of coloured Regenerated Polyester Fibres, using polyester reclaiming material same as Example 2, through superfusing Melt, 270 DEG C of air pressure < 50Pa, vertical falling-film reaction kettle high vacuum devolatilization and homogenizing 80min, 272 DEG C of polycondensations of mouse-cage type reaction kettle increase Viscous 120min, process melt can be brown automatically, and coloured Regenerated Polyester Fibres are made after melt spinning, and coloured recycled polyester is fine The fiber number of dimension is 5.5dtex, and the TVOC contents of coloured Regenerated Polyester Fibres is 650ppm, and nonyl phenol and its isomer contain Amount is 556ppm, and the breaking strength of coloured Regenerated Polyester Fibres is 2.0cN/dtex, and elongation at break 28.6%, line density is inclined Rate is 8%, 3.5 grades of color difference grade, color fastness grade 3.5.By comparative example 2 and the comparison of embodiment 2 as can be seen that using this hair The TVOC content and nonyl phenol of coloured Regenerated Polyester Fibres made from bright preparation method and its content of isomer are opposite It is reduced obviously in the prior art, the quality of colored fibre is more excellent.

Embodiment 3

1) the polyester oligomer melt that polyester reclaiming material, catalyst and average degree of polymerization that moisture content is 80ppm are 4 is added Enter to carry out reactive melt blending in double screw extruder to obtain the preliminary depolymerization melt that average degree of polymerization is 30, wherein polyester The mass ratio of reclaimed materials and polyester oligomer melt is 3:1, and catalyst is tetraisopropyl titanate, with metallic element matter in catalyst Amount is calculated relative to polyester oligomer melt quality, and the content of catalyst is 10ppm；The temperature of reactive melt blending are as follows: double 275 DEG C of screw feed section temperature, 300 DEG C of twin-screw compression section, 295 DEG C of homogenizing zone temperature, time 1min, atmosphere is nitrogen；

2) preliminary depolymerization melt feeds reaction kettle, and and second through pipeline A after the filter I filtering that filtering accuracy is 50 μm In 205 DEG C of progresss alcoholysis reaction 40min under nitrogen protection, pressurization and stirring condition after glycol mixing, preliminary depolymerization melt and The mass ratio of ethylene glycol is 4.5:1, and the pressure after pressurization is 150KPa, stirring rate 75Hz, and stirring is stirred using plate and frame Paddle obtains the depth depolymerization melt that average degree of polymerization is 4 after reaction；

3) depth depolymerization melt feeds vertical reactor by pipeline B after the filter II filtering that filtering accuracy is 10 μm, And the bottom by flowing to vertical reactor at the top of vertical reactor by control reaction temperature, pressure and contains during this period Oxygen amount carries out the removing of TVOC and the reparation of cracking functional group in depth depolymerization melt, is equipped with sampling in the bottom of vertical reactor Mouthful, depth depolymerization melt repeats flowing to obtain TVOC content to be 15ppm's after sample tap outflow through path same as Example 1 Low TVOC content polyester oligomer melt, the structure and pressure control path of vertical reactor are the same as embodiment 1；Vertical reactor Temperature are as follows: upper semisection temperature is 200~202 DEG C, 202~205 DEG C of lower semisection temperature；Oxygen content is the vertical anti-of 0.02v/v% Generating period in the range of 1~80KPa of the pressure in device is answered to change, period 120min, wherein the pressure of 1KPa is kept Time is 108min；

4) low TVOC content polyester oligomer melt is continuously fed into twin-screw as the raw material of step 1) via pipeline D and squeezes Machine out, or prepolymerization reaction kettle is fed through pipeline C after the filter III filtering that filtering accuracy is 10 μm, catalyst is added Tetraisopropyl titanate, heat stabilizer triphenyl phosphate, anti-ether agent sodium acetate and antioxidant bis- (2.4- di-tert-butyl-phenyl) seasons penta Prepolymerization reaction is carried out after tetrol diphosphites obtains the low TVOC content precondensation polyester fondant that average degree of polymerization is 30；In advance The temperature of polycondensation reaction are as follows: 265 DEG C of upper chamber, 275 DEG C of lower room；Pressure are as follows: upper chamber 4.5KPa, lower room 2.5KPa；Time is 60min；On the basis of the quality of low TVOC content polyester oligomer melt, the additive amount of catalyst is 10ppm, heat stabilizer Additive amount is 200ppm, and the additive amount of sodium acetate is 200ppm, and the additive amount of antioxidant is 100pmm；

5) low TVOC content precondensation polyester fondant is averagely gathered through path same as Example 1 progress final polycondensation reaction The right low TVOC content recycled polyester melt for being 100；The temperature of reaction is 285 DEG C, pressure 500Pa, time 180min；

7) the short fibre of coloured recycled polyester is made through path same as Example 1 and spinning technique in coloured recycled polyester melt Dimension, spinning technology parameter are as follows: 290 DEG C of spinning temperature, spinning speed 850m/min, 70 DEG C of draft temperature, preliminary draft multiplying power is 1.05, one of draft ratio is 2.3, and two draft ratios are 1.05.

The fiber number of final coloured Regenerated Polyester Fibres obtained is 3.5dtex, length 30mm, coloured Regenerated Polyester Fibres TVOC content be 300ppm, the content of nonyl phenol and its isomer is 200ppm, the fracture of coloured Regenerated Polyester Fibres Intensity is 3.2cN/dtex, elongation at break 25.6%, and line density deviation ratio is 6.5% .5 grades of color difference class 4, color fastness .5 grades of class 4.

Comparative example 3

A kind of preparation method of coloured Regenerated Polyester Fibres, using polyester reclaiming material same as Example 3, through superfusing Melt, 275 DEG C of air pressure < 50Pa, vertical falling-film reaction kettle high vacuum devolatilization and homogenizing 50min, 268 DEG C of polycondensations of mouse-cage type reaction kettle increase Viscous 180min, process melt can be brown automatically, and coloured Regenerated Polyester Fibres are made after melt spinning, and coloured recycled polyester is fine The fiber number of dimension is 5.0dtex, and the TVOC contents of coloured Regenerated Polyester Fibres is 683ppm, and nonyl phenol and its isomer contain Amount is 658ppm, and the breaking strength of coloured Regenerated Polyester Fibres is 2.2cN/dtex, and elongation at break 32.7%, line density is inclined Rate is 10.2%, 3.5 grades of color difference grade, 3.5 grades of color fastness grade.Comparative example 3 is compared with embodiment 3 as can be seen that adopting The TVOC content and nonyl phenol of the coloured Regenerated Polyester Fibres made from preparation method of the invention and its containing for isomer Amount reduces obviously compared with the existing technology, and the quality of colored fibre is more excellent.

Embodiment 4

1) the polyester oligomer melt that polyester reclaiming material, catalyst and average degree of polymerization that moisture content is 80ppm are 3 is added Enter to carry out reactive melt blending in double screw extruder to obtain the preliminary depolymerization melt that average degree of polymerization is 30, wherein polyester The mass ratio of reclaimed materials and polyester oligomer melt is 1.5:1, and catalyst is ethylene glycol sodium titanate, with metallic element in catalyst Quality is calculated relative to polyester oligomer melt quality, and the content of catalyst is 80ppm；The temperature of reactive melt blending are as follows: 270 DEG C of twin-screw feed zone temperature, 290 DEG C of twin-screw compression section, 295 DEG C of homogenizing zone temperature, time 2.5min, atmosphere is nitrogen Gas；

2) preliminary depolymerization melt feeds reaction kettle, and and second through pipeline A after the filter I filtering that filtering accuracy is 80 μm In 202 DEG C of progresss alcoholysis reaction 50min under nitrogen protection, pressurization and stirring condition after glycol mixing, preliminary depolymerization melt and The mass ratio of ethylene glycol is 4:1, and the pressure after pressurization is 120KPa, stirring rate 50Hz, and stirring uses plate and frame agitating paddle, The depth depolymerization melt that average degree of polymerization is 3 is obtained after reaction；

3) depth depolymerization melt feeds vertical reactor by pipeline B after the filter II filtering that filtering accuracy is 15 μm, And the bottom by flowing to vertical reactor at the top of vertical reactor by control reaction temperature, pressure and contains during this period Oxygen amount carries out the removing of TVOC and the reparation of cracking functional group in depth depolymerization melt, is equipped with sampling in the bottom of vertical reactor Mouthful, depth depolymerization melt is after sample tap outflow through repeating flowing to obtain TVOC content to be 10ppm by path same as Example 1 Low TVOC content polyester oligomer melt, the structure and pressure control path of vertical reactor are the same as embodiment 1；Vertical reactor Temperature are as follows: upper semisection temperature be 200~203 DEG C, lower semisection temperature be 203~205 DEG C；Oxygen content is the vertical of 0.02v/v% Pressure generating period variation in the range of 1~80KPa in formula reactor, period 10min, wherein the pressure of 1KPa is protected Holding the time is 2min；

4) low TVOC content polyester oligomer melt is continuously fed into twin-screw as the raw material of step 1) via pipeline D and squeezes Machine out, or prepolymerization reaction kettle is fed through pipeline C after the filter III filtering that filtering accuracy is 10 μm, catalyst is added Ethylene glycol sodium titanate, heat stabilizer diphenyl phosphate, anti-ether agent sodium acetate and antioxidant bis- (2.4- di-tert-butyl-phenyl) seasons penta Tetrol diphosphites, the different certain herbaceous plants with big flowers ester of pentaerythritol diphosphite two and three (2,4- di-t-butyl) phenyl-phosphite (mass ratioes Prepolymerization reaction 1:1:2) is carried out afterwards obtains the low TVOC content precondensation polyester fondant that average degree of polymerization is 25；Prepolymerization reaction Temperature are as follows: 260 DEG C of upper chamber, 265 DEG C of lower room；Pressure are as follows: upper chamber 3.5KPa, lower room 1.5KPa；Time is 80min；With low On the basis of the quality of TVOC content polyester oligomer melt, the additive amount of catalyst is 50ppm, and the additive amount of heat stabilizer is 100ppm, the additive amount of sodium acetate are 150ppm, and the additive amount of antioxidant is 80pmm；

5) low TVOC content precondensation polyester fondant is averagely gathered through path same as Example 1 progress final polycondensation reaction The right low TVOC content recycled polyester melt for being 100；The temperature of reaction is 280 DEG C, pressure 300Pa, time 180min；

7) the short fibre of coloured recycled polyester is made through path same as Example 1 and spinning technique in coloured recycled polyester melt Dimension, spinning technology parameter are as follows: 292 DEG C of spinning temperature, spinning speed 1150m/min, 75 DEG C of draft temperature, preliminary draft multiplying power is 1.03, one of draft ratio is 2.3, and two draft ratios are 1.05.

The fiber number of final coloured Regenerated Polyester Fibres obtained is 3.5dtex, length 45mm, coloured Regenerated Polyester Fibres TVOC content be 253ppm, the content of nonyl phenol and its isomer is 190ppm, the fracture of coloured Regenerated Polyester Fibres Intensity is 3.1cN/dtex, elongation at break 27.1%, and line density deviation ratio is 6.5% .5 grades of color difference class 4, color fastness .5 grades of class 4.

Embodiment 5

1) the polyester oligomer melt for being 2.5 by polyester reclaiming material, catalyst and average degree of polymerization that moisture content is 80ppm It adds twin-screw extrude the reactive melt blending of progress and obtains the preliminary depolymerization melt that average degree of polymerization is 25, wherein is poly- The mass ratio of ester reclaimed materials and polyester oligomer melt is 1.5:1, and catalyst is ethylene glycol potassium titanate, with metal member in catalyst Quality amount is calculated relative to polyester oligomer melt quality, and the content of catalyst is 300ppm；The temperature of reactive melt blending Are as follows: 260 DEG C of twin-screw feed zone temperature, 275 DEG C of twin-screw compression section, 275 DEG C of homogenizing zone temperature, time 3min, atmosphere is Nitrogen；

2) preliminary depolymerization melt feeds reaction kettle through pipeline A after the filter I filtering that filtering accuracy is 100 μm, and with In 205 DEG C of progress alcoholysis reaction 60min, preliminary depolymerization melt under nitrogen protection, pressurization and stirring condition after ethylene glycol mixing Mass ratio with ethylene glycol is 4:1, and the pressure after pressurization is 150KPa, stirring rate 50Hz, and stirring is stirred using plate and frame Paddle obtains the depth depolymerization melt that average degree of polymerization is 2.5 after reaction；

3) depth depolymerization melt feeds vertical reactor by pipeline B after the filter II filtering that filtering accuracy is 10 μm, And the bottom by flowing to vertical reactor at the top of vertical reactor by control reaction temperature, pressure and contains during this period Oxygen amount carries out the removing of TVOC and the reparation of cracking functional group in depth depolymerization melt, is equipped with sampling in the bottom of vertical reactor Mouthful, depth depolymerization melt repeats flowing to obtain TVOC content to be 18ppm's after sample tap outflow through path same as Example 1 Low TVOC content polyester oligomer melt, the structure and pressure control path of vertical reactor are the same as embodiment 1；Vertical reactor Temperature are as follows: upper semisection temperature is 200~202 DEG C, and lower semisection temperature is 202~205 DEG C；Oxygen content is the vertical of 0.02v/v% Pressure generating period variation in the range of 1~80KPa in reactor, period 100min, wherein the pressure of 1KPa is protected Holding the time is 75min；

4) low TVOC content polyester oligomer melt is continuously fed into twin-screw as the raw material of step 1) via pipeline D and squeezes Machine out, or prepolymerization reaction kettle is fed through pipeline C after the filter III filtering that filtering accuracy is 10 μm, catalyst is added Ethylene glycol potassium titanate, heat stabilizer dimethyl phosphate, anti-ether agent sodium acetate and the different certain herbaceous plants with big flowers of antioxidant pentaerythritol diphosphite two Prepolymerization reaction is carried out after ester obtains the low TVOC content precondensation polyester fondant that average degree of polymerization is 28；The temperature of prepolymerization reaction Degree are as follows: 265 DEG C of upper chamber, 275 DEG C of lower room；Pressure are as follows: upper chamber 2.5KPa, lower room 1.5KPa；Time is 100min；Contained with low TVOC On the basis of the quality of weight polyester oligomer melt, the additive amount of catalyst is 300ppm, and the additive amount of heat stabilizer is 100ppm, The additive amount of sodium acetate is 100ppm, and the additive amount of antioxidant is 100pmm；

5) low TVOC content precondensation polyester fondant is averagely gathered through path same as Example 1 progress final polycondensation reaction The right low TVOC content recycled polyester melt for being 105；The temperature of reaction is 285 DEG C, pressure 300Pa, time 150min；

7) the short fibre of coloured recycled polyester is made through path same as Example 1 and spinning technique in coloured recycled polyester melt Dimension, spinning technology parameter are as follows: 298 DEG C of spinning temperature, spinning speed 1500m/min, 80 DEG C of draft temperature, preliminary draft multiplying power is 1.08, one of draft ratio is 2.4, and two draft ratios are 1.1.

The fiber number of final coloured Regenerated Polyester Fibres obtained is 3.6dtex, length 42mm, coloured Regenerated Polyester Fibres TVOC content be 195ppm, the content of nonyl phenol and its isomer is 200ppm, the fracture of coloured Regenerated Polyester Fibres Intensity is 3.2cN/dtex, elongation at break 25.2%, and line density deviation ratio is 7.3% .5 grades of color difference class 4, color fastness .5 grades of class 4.

Embodiment 6

A kind of preparation method of coloured Regenerated Polyester Fibres, as shown in Figure 1, steps are as follows:

1) the polyester oligomer melt for being 1.5 by polyester reclaiming material, catalyst and average degree of polymerization that moisture content is 80ppm It adds twin-screw extrude the reactive melt blending of progress and obtains the preliminary depolymerization melt that average degree of polymerization is 20, wherein is poly- The mass ratio of ester reclaimed materials and polyester oligomer melt is 0.1:1, and catalyst is zinc acetate, with metallic element quality in catalyst It is calculated relative to polyester oligomer melt quality, the content of catalyst is 50ppm；The temperature of reactive melt blending are as follows: double spiral shells 265 DEG C of bar feed zone temperature, 280 DEG C of twin-screw compression section, 280 DEG C of homogenizing zone temperature, time 4min, atmosphere is nitrogen；

2) preliminary depolymerization melt feeds reaction kettle through pipeline A after the filter I filtering that filtering accuracy is 100 μm, and with In 195 DEG C of progress alcoholysis reaction 60min, preliminary depolymerization melt under nitrogen protection, pressurization and stirring condition after ethylene glycol mixing Mass ratio with ethylene glycol is 3:1, and the pressure after pressurization is 101KPa, stirring rate 35Hz, and stirring is stirred using plate and frame Paddle obtains the depth depolymerization melt that average degree of polymerization is 1.5 after reaction；

3) depth depolymerization melt feeds vertical reactor by pipeline B after the filter II filtering that filtering accuracy is 1 μm, and By flowing to the bottom of vertical reactor at the top of vertical reactor, during this period, pass through control reaction temperature, pressure and oxygen-containing Amount carries out the removing of TVOC and the reparation of cracking functional group in depth depolymerization melt, is equipped with sampling in the bottom of vertical reactor Mouthful, depth depolymerization melt repeats flowing to obtain TVOC content to be 15ppm's after sample tap outflow through path same as Example 1 Low TVOC content polyester oligomer melt, the structure and pressure control path of vertical reactor are the same as embodiment 1；Vertical reactor Temperature are as follows: upper semisection temperature is 190~195 DEG C, and lower semisection temperature is 195~200 DEG C；Oxygen content is the vertical of 0.02v/v% Pressure generating period variation in the range of 1~80KPa in reactor, period 85min, wherein the pressure of 1KPa is kept Time is 51min；

4) low TVOC content polyester oligomer melt is continuously fed into twin-screw as the raw material of step 1) via pipeline D and squeezes Machine 11 out, or prepolymerization reaction kettle is fed through pipeline C after the filter III filtering that filtering accuracy is 2 μm, catalyst is added After antimony acetate, heat stabilizer diphenyl phosphite, anti-ether agent sodium acetate and the different certain herbaceous plants with big flowers ester of antioxidant pentaerythritol diphosphite two It carries out prepolymerization reaction and obtains the low TVOC content precondensation polyester fondant that average degree of polymerization is 28；The temperature of prepolymerization reaction Are as follows: 260 DEG C of upper chamber, 265 DEG C of lower room；Pressure are as follows: upper chamber 3.0KPa, lower room 1.5KPa；Time is 120min；With low TVOC content On the basis of the quality of polyester oligomer melt, the additive amount of catalyst is 200ppm, and the additive amount of heat stabilizer is 200ppm, second The additive amount of sour sodium is 200ppm, and the additive amount of antioxidant is 10pmm；

5) low TVOC content precondensation polyester fondant is averagely gathered through path same as Example 1 progress final polycondensation reaction The right low TVOC content recycled polyester melt for being 95；The temperature of reaction is 285 DEG C, pressure 100Pa, time 100min；

7) the short fibre of coloured recycled polyester is made through path same as Example 1 and spinning technique in coloured recycled polyester melt Dimension, spinning technology parameter are as follows: 275 DEG C of spinning temperature, spinning speed 1000m/min, 65 DEG C of draft temperature, preliminary draft multiplying power is 1.02, one of draft ratio is 1.8, and two draft ratios are 1.02.

The fiber number of final coloured Regenerated Polyester Fibres obtained is 3.5dtex, length 50mm, coloured Regenerated Polyester Fibres TVOC content be 193ppm, the content of nonyl phenol and its isomer is 183ppm, the fracture of coloured Regenerated Polyester Fibres Intensity is 3.2cN/dtex, elongation at break 32.5%, and line density deviation ratio is 7.9% .5 grades of color difference class 4, color fastness Class 4 grade.

Embodiment 7

2) the polyester oligomer melt for being 2.5 by polyester reclaiming material, catalyst and average degree of polymerization that moisture content is 90ppm It adds twin-screw extrude the reactive melt blending of progress and obtains the preliminary depolymerization melt that average degree of polymerization is 25, wherein is poly- The mass ratio of ester reclaimed materials and polyester oligomer melt is 1.0:1, and catalyst is manganese acetate, with metallic element quality in catalyst It is calculated relative to polyester oligomer melt quality, the content of catalyst is 150ppm；The temperature of reactive melt blending are as follows: double spiral shells 266 DEG C of bar feed zone temperature, 285 DEG C of twin-screw compression section, 282 DEG C of homogenizing zone temperature, time 3min, atmosphere is that gauge pressure is The vacuum environment of 0.1KPa；

3) preliminary depolymerization melt feeds reaction kettle, and and second through pipeline A after the filter I filtering that filtering accuracy is 70 μm In 196 DEG C of progresss alcoholysis reaction 55min under nitrogen protection, pressurization and stirring condition after glycol mixing, preliminary depolymerization melt and The mass ratio of ethylene glycol is 3.6:1, and the pressure after pressurization is 121KPa, stirring rate 55Hz, and stirring is stirred using plate and frame Paddle obtains the depth depolymerization melt that average degree of polymerization is 2.5 after reaction；

3) depth depolymerization melt feeds vertical reactor by pipeline B after the filter II filtering that filtering accuracy is 8 μm, and By flowing to the bottom of vertical reactor at the top of vertical reactor, during this period, pass through control reaction temperature, pressure and oxygen-containing Amount carries out the removing of TVOC and the reparation of cracking functional group in depth depolymerization melt, is equipped with sampling in the bottom of vertical reactor Mouthful, depth depolymerization melt obtains TVOC content through path same as Example 1 repetition flowing after sample tap outflow and obtains for 15ppm The low TVOC content polyester oligomer melt arrived, the structure and pressure control path of vertical reactor are the same as embodiment 1；Vertical response The temperature of device are as follows: upper semisection temperature is 194~198 DEG C, and lower semisection temperature is 198~202 DEG C；Oxygen content is 0.015v/v%'s Pressure in vertical reactor generating period in the range of 1~80KPa changes, period 10min, wherein the pressure of 1KPa Retention time is 2min；

4) low TVOC content polyester oligomer melt is continuously fed into twin-screw as the raw material of step 1) via pipeline D and squeezes Machine 11 out, or prepolymerization reaction kettle 20 is fed through pipeline C 3 after the filtering of filter III 19 that filtering accuracy is 2 μm, add Enter the catalytic antimony trioxide, heat stabilizer ammonium phosphite and ammonium dihydrogen phosphate (mass ratio 1:1), anti-ether agent sodium acetate and antioxygen It is pre- to obtain the low TVOC content that average degree of polymerization is 28 for progress prepolymerization reaction after the different certain herbaceous plants with big flowers ester of agent pentaerythritol diphosphite two Polycondensation polyester fondant；The temperature of prepolymerization reaction are as follows: 260 DEG C of upper chamber, 265 DEG C of lower room；Pressure are as follows: upper chamber 3.0KPa, lower room 1.5KPa；Time is 120min；On the basis of the quality of low TVOC content polyester oligomer melt, the additive amount of catalyst is 200ppm, the additive amount of heat stabilizer are 200ppm, and the additive amount of sodium acetate is 200ppm, and the additive amount of antioxidant is 10pmm；

7) the short fibre of coloured recycled polyester is made through path same as Example 1 and spinning technique in coloured recycled polyester melt Dimension, spinning technology parameter are as follows: 275 DEG C of spinning temperature, spinning speed 1200m/min, 70 DEG C of draft temperature, preliminary draft multiplying power is 1.02, one of draft ratio is 2.0, and two draft ratios are 1.02.

The fiber number of final coloured Regenerated Polyester Fibres obtained is 3.5dtex, length 50mm, coloured Regenerated Polyester Fibres TVOC content be 233ppm, the content of nonyl phenol and its isomer is 171ppm, the fracture of coloured Regenerated Polyester Fibres Intensity is 2.8cN/dtex, elongation at break 31.5%, and line density deviation ratio is 7.6% .5 grades of color difference class 4, color fastness .5 grades of class 4.

Embodiment 8

1) the polyester oligomer melt for being 2.5 by polyester reclaiming material, catalyst and average degree of polymerization that moisture content is 50ppm It adds twin-screw extrude the reactive melt blending of progress and obtains the preliminary depolymerization melt that average degree of polymerization is 26, wherein is poly- The mass ratio of ester reclaimed materials and polyester oligomer melt is 1.5:1, and catalyst is titanium ethylene glycolate, with metallic element matter in catalyst Amount is calculated relative to polyester oligomer melt quality, and the content of catalyst is 160ppm；The temperature of reactive melt blending are as follows: double 267 DEG C of screw feed section temperature, 286 DEG C of twin-screw compression section, 285 DEG C of homogenizing zone temperature, time 4min, atmosphere is nitrogen ring Border；

2) preliminary depolymerization melt feeds reaction kettle, and and second through pipeline A after the filter I filtering that filtering accuracy is 73 μm In 198 DEG C of progresss alcoholysis reaction 80min under nitrogen protection, pressurization and stirring condition after glycol mixing, preliminary depolymerization melt and The mass ratio of ethylene glycol is 3.8:1, and the pressure after pressurization is 125KPa, stirring rate 60Hz, and stirring is stirred using plate and frame Paddle obtains the depth depolymerization melt that average degree of polymerization is 2.5 after reaction；

3) depth depolymerization melt feeds vertical reactor by pipeline B after the filter II filtering that filtering accuracy is 10 μm, And the bottom by flowing to vertical reactor at the top of vertical reactor by control reaction temperature, pressure and contains during this period Oxygen amount carries out the removing of TVOC and the reparation of cracking functional group in depth depolymerization melt, is equipped with sampling in the bottom of vertical reactor Mouthful, depth depolymerization melt repeats flowing to obtain TVOC content to be 12ppm's after sample tap outflow through path same as Example 1 Low TVOC content polyester oligomer melt, the structure and pressure control path of vertical reactor are the same as embodiment 1；Vertical reactor Temperature are as follows: upper semisection temperature is 195~199 DEG C, and lower semisection temperature is 199~203 DEG C；Oxygen content is the vertical of 0.015v/v% Pressure generating period variation in the range of 1~80KPa in reactor, period 80min, wherein the pressure of 1KPa is kept Time is 44min；

4) low TVOC content polyester oligomer melt is continuously fed into twin-screw as the raw material of step 1) via pipeline D and squeezes Machine 11 out, or prepolymerization reaction kettle is fed through pipeline C after the filter III filtering that filtering accuracy is 2 μm, catalyst is added Two phosphorous of acetic acid germanium, heat stabilizer phosphoric acid, phosphorous acid and ortho phosphorous acid (mass ratio 1:1:1), anti-ether agent sodium acetate and antioxidant Prepolymerization reaction is carried out after the different certain herbaceous plants with big flowers ester of sour pentaerythritol ester two obtains the low TVOC content precondensation polyester that average degree of polymerization is 25 Melt；The temperature of prepolymerization reaction are as follows: 260 DEG C of upper chamber, 265 DEG C of lower room；Pressure are as follows: upper chamber 3.0KPa, lower room 1.0KPa；Time For 90min；On the basis of the quality of low TVOC content polyester oligomer melt, the additive amount of catalyst is 300ppm, thermostabilization The additive amount of agent is 100ppm, and the additive amount of sodium acetate is 50ppm, and the additive amount of antioxidant is 10pmm；

5) low TVOC content precondensation polyester fondant is averagely gathered through path same as Example 1 progress final polycondensation reaction The right low TVOC content recycled polyester melt for being 100；The temperature of reaction is 285 DEG C, pressure 80Pa, time 100min；

7) the short fibre of coloured recycled polyester is made through path same as Example 1 and spinning technique in coloured recycled polyester melt Dimension, spinning technology parameter are as follows: 290 DEG C of spinning temperature, spinning speed 1150m/min, 68 DEG C of draft temperature, preliminary draft multiplying power is 1.07, one of draft ratio is 1.8, and two draft ratios are 1.07.

The fiber number of final coloured Regenerated Polyester Fibres obtained is 2.9dtex, length 42mm, coloured Regenerated Polyester Fibres TVOC content be 288ppm, the content of nonyl phenol and its isomer is 200ppm, the fracture of coloured Regenerated Polyester Fibres Intensity is 3.5cN/dtex, elongation at break 46.1%, and line density deviation ratio is 6.5% .5 grades of color difference class 4, color fastness .5 grades of class 4.

Embodiment 9

2) preliminary depolymerization melt feeds reaction kettle through pipeline A 1 after the filter I 12 that filtering accuracy is 100 μm is filtered 13, and after being mixed with ethylene glycol under nitrogen protection, pressurization and stirring condition in 195 DEG C of progress alcoholysis reaction 60min, it is preliminary to solve The mass ratio of poly- melt and ethylene glycol is 3:1, and the pressure after pressurization is 101KPa, stirring rate 35Hz, and stirring uses sheet frame Formula agitating paddle obtains the depth depolymerization melt that average degree of polymerization is 1.5 after reaction；

3) depth depolymerization melt feeds vertical reactor by pipeline B after the filter II filtering that filtering accuracy is 2 μm, and By flowing to the bottom of vertical reactor at the top of vertical reactor, during this period, pass through control reaction temperature, pressure and oxygen-containing Amount carries out the removing of TVOC and the reparation of cracking functional group in depth depolymerization melt, is equipped with sampling in the bottom of vertical reactor Mouthful, depth depolymerization melt repeats flowing to obtain TVOC content to be 12ppm's after sample tap outflow through path same as Example 1 Low TVOC content polyester oligomer melt, the structure and pressure control path of vertical reactor are the same as embodiment 1；Vertical reactor Temperature are as follows: upper semisection temperature is 195~199 DEG C, and lower semisection temperature is 199~203 DEG C；Oxygen content is the vertical of 0.015v/v% Pressure generating period variation in the range of 1~80KPa in reactor, period 85min, wherein the pressure of 1KPa is kept Time is 51min；

4) low TVOC content polyester oligomer melt is continuously fed into twin-screw as the raw material of step 1) via pipeline D and squeezes Machine 11 out, or prepolymerization reaction kettle is fed through pipeline C after the filter III filtering that filtering accuracy is 2 μm, catalyst is added Antimony acetate, antimony oxide and acetic acid germanium (mass ratio 3:1:1), heat stabilizer ammonium phosphate, anti-ether agent sodium acetate and antioxidant are double After (2.4- di-tert-butyl-phenyl) pentaerythritol diphosphites and three (2,4- di-t-butyl) phenyl-phosphites (mass ratio 1:1) It carries out prepolymerization reaction and obtains the low TVOC content precondensation polyester fondant that average degree of polymerization is 28；The temperature of prepolymerization reaction Are as follows: 260 DEG C of upper chamber, 265 DEG C of lower room；Pressure are as follows: upper chamber 3.0KPa, lower room 1.0KPa；Time is 120min；With low TVOC content On the basis of the quality of polyester oligomer melt, the additive amount of catalyst is 280ppm, and the additive amount of heat stabilizer is 100ppm, second The additive amount of sour sodium is 50ppm, and the additive amount of antioxidant is 10pmm；

7) the short fibre of coloured recycled polyester is made through path same as Example 1 and spinning technique in coloured recycled polyester melt Dimension, spinning technology parameter are as follows: 288 DEG C of spinning temperature, spinning speed 1120m/min, 72 DEG C of draft temperature, preliminary draft multiplying power is 1.08, one of draft ratio is 2.5, and two draft ratios are 1.07.

The fiber number of final coloured Regenerated Polyester Fibres obtained is 2.6dtex, length 40mm, coloured Regenerated Polyester Fibres TVOC content be 135ppm, the content of nonyl phenol and its isomer is 110ppm, the fracture of coloured Regenerated Polyester Fibres Intensity is 3.4cN/dtex, elongation at break 26.7%, and line density deviation ratio is 7.0% .5 grades of color difference class 4, color fastness .5 grades of class 4.

Embodiment 10

3) depth depolymerization melt feeds vertical reactor by pipeline B after the filter II filtering that filtering accuracy is 10 μm, And the bottom by flowing to vertical reactor at the top of vertical reactor by control reaction temperature, pressure and contains during this period Oxygen amount carries out the removing of TVOC and the reparation of cracking functional group in depth depolymerization melt, is equipped with sampling in the bottom of vertical reactor Mouthful, depth depolymerization melt repeats flowing to obtain TVOC content to be 10ppm's after sample tap outflow through path same as Example 1 Low TVOC content polyester oligomer melt, the structure and pressure control path of vertical reactor are the same as embodiment 1；Vertical reactor Temperature are as follows: upper semisection temperature is 196~198 DEG C, and lower semisection temperature is 198~203 DEG C；Oxygen content is the vertical of 0.01v/v% Pressure generating period variation in the range of 1~80KPa in reactor, period 90min, wherein the pressure of 1KPa is kept Time is 59min；

4) low TVOC content polyester oligomer melt is continuously fed into twin-screw as the raw material of step 1) via pipeline D and squeezes Machine 11 out, or prepolymerization reaction kettle is fed through pipeline C after the filter III filtering that filtering accuracy is 1 μm, catalyst is added Titanium ethylene glycolate, heat stabilizer ammonium phosphite, anti-ether agent sodium acetate and the different certain herbaceous plants with big flowers ester of antioxidant pentaerythritol diphosphite two and three (2,4- di-t-butyl) phenyl-phosphite (mass ratio 1:1) carries out prepolymerization reaction afterwards and obtains the low TVOC that average degree of polymerization is 30 Content precondensation polyester fondant；The temperature of prepolymerization reaction are as follows: 260 DEG C of upper chamber, 265 DEG C of lower room；Pressure are as follows: upper chamber 3.0KPa, Lower room 1.0KPa；Time is 70min；On the basis of the quality of low TVOC content polyester oligomer melt, the additive amount of catalyst For 100ppm, the additive amount of heat stabilizer is 200ppm, and the additive amount of sodium acetate is 50ppm, and the additive amount of antioxidant is 20pmm；

5) low TVOC content precondensation polyester fondant is averagely gathered through path same as Example 1 progress final polycondensation reaction The right low TVOC content recycled polyester melt for being 110；The temperature of reaction is 285 DEG C, pressure 50Pa, time 120min；

7) the short fibre of coloured recycled polyester is made through path same as Example 1 and spinning technique in coloured recycled polyester melt Dimension, spinning technology parameter are as follows: 295 DEG C of spinning temperature, spinning speed 1500m/min, 75 DEG C of draft temperature, preliminary draft multiplying power is 1.08, one of draft ratio is 2.25, and two draft ratios are 1.08.

The fiber number of final coloured Regenerated Polyester Fibres obtained is 1.5dtex, length 39mm, coloured Regenerated Polyester Fibres TVOC content be 182ppm, the content of nonyl phenol and its isomer is 158ppm, the fracture of coloured Regenerated Polyester Fibres Intensity is 4.3cN/dtex, elongation at break 37.6%, and line density deviation ratio is 6.8% .5 grades of color difference class 4, color fastness .5 grades of class 4.

Embodiment 11

3) depth depolymerization melt feeds vertical reactor by pipeline B after the filter II filtering that filtering accuracy is 8 μm, and By flowing to the bottom of vertical reactor at the top of vertical reactor, during this period, pass through control reaction temperature, pressure and oxygen-containing Amount carries out the removing of TVOC and the reparation of cracking functional group in depth depolymerization melt, is equipped with sampling in the bottom of vertical reactor Mouthful, depth depolymerization melt repeats flowing to obtain TVOC content to be 12ppm's after sample tap outflow through path same as Example 1 Low TVOC content polyester oligomer melt, the structure and pressure control path of vertical reactor are the same as embodiment 1；Vertical reactor Temperature are as follows: upper semisection temperature is 197~200 DEG C, and lower semisection temperature is 200~204 DEG C；Oxygen content is the vertical of 0.01v/v% Pressure generating period variation in the range of 1~80KPa in reactor, period 95min, wherein the pressure of 1KPa is kept Time is 63min；

4) low TVOC content polyester oligomer melt is continuously fed into twin-screw as the raw material of step 1) via pipeline D and squeezes Machine 11 out, or prepolymerization reaction kettle is fed through pipeline C after the filter III filtering that filtering accuracy is 1 μm, catalyst is added After tetra-n-butyl titanate, heat stabilizer pyrophosphoric acid, anti-ether agent sodium acetate and the different certain herbaceous plants with big flowers ester of antioxidant pentaerythritol diphosphite two It carries out prepolymerization reaction and obtains the low TVOC content precondensation polyester fondant that average degree of polymerization is 30；The temperature of prepolymerization reaction Are as follows: 260 DEG C of upper chamber, 265 DEG C of lower room；Pressure are as follows: upper chamber 3.0KPa, lower room 1.0KPa；Time is 90min；With low TVOC content On the basis of the quality of polyester oligomer melt, the additive amount of catalyst is 120ppm, and the additive amount of heat stabilizer is 200ppm, second The additive amount of sour sodium is 50ppm, and the additive amount of antioxidant is 20pmm；

5) low TVOC content precondensation polyester fondant is averagely gathered through path same as Example 1 progress final polycondensation reaction The right low TVOC content recycled polyester melt for being 100；The temperature of reaction is 285 DEG C, pressure 50Pa, time 100min；

7) the short fibre of coloured recycled polyester is made through path same as Example 1 and spinning technique in coloured recycled polyester melt Dimension, spinning technology parameter are as follows: 288 DEG C of spinning temperature, spinning speed 1300m/min, 776 DEG C of draft temperature, preliminary draft multiplying power is 1.10, one of draft ratio is 2.3, and two draft ratios are 1.08.

The fiber number of final coloured Regenerated Polyester Fibres obtained is 2.2dtex, length 38mm, coloured Regenerated Polyester Fibres TVOC content be 117ppm, the content of nonyl phenol and its isomer is 156ppm, the fracture of coloured Regenerated Polyester Fibres Intensity is 4.0cN/dtex, elongation at break 46.0%, and line density deviation ratio is 7.0% .5 grades of color difference class 4, color fastness .5 grades of class 4.

Embodiment 12

3) depth depolymerization melt feeds vertical reactor by pipeline B after the filter II filtering that filtering accuracy is 12 μm, And the bottom by flowing to vertical reactor at the top of vertical reactor by control reaction temperature, pressure and contains during this period Oxygen amount carries out the removing of TVOC and the reparation of cracking functional group in depth depolymerization melt, is equipped with sampling in the bottom of vertical reactor Mouthful, depth depolymerization melt repeats flowing to obtain TVOC content to be 13ppm's after sample tap outflow through path same as Example 1 Low TVOC content polyester oligomer melt, the structure and pressure control path of vertical reactor are the same as embodiment 1；Vertical reactor Temperature are as follows: upper semisection temperature is 197~201 DEG C, and lower semisection temperature is 201~204 DEG C；Oxygen content is the vertical of 0.01v/v% Pressure generating period variation in the range of 1~80KPa in reactor, period 100min, wherein the pressure of 1KPa is protected Holding the time is 75min；

4) low TVOC content polyester oligomer melt is continuously fed into twin-screw as the raw material of step 1) via pipeline D and squeezes Machine 11 out, or prepolymerization reaction kettle is fed through pipeline C after the filter III filtering that filtering accuracy is 1 μm, catalyst is added Ethylene glycol sodium titanate, heat stabilizer ammonium dihydrogen phosphate, anti-ether agent sodium acetate and the different certain herbaceous plants with big flowers of antioxidant pentaerythritol diphosphite two Prepolymerization reaction is carried out after ester obtains the low TVOC content precondensation polyester fondant that average degree of polymerization is 30；The temperature of prepolymerization reaction Degree are as follows: 260 DEG C of upper chamber, 270 DEG C of lower room；Pressure are as follows: upper chamber 3.0KPa, lower room 1.0KPa；Time is 90min；Contained with low TVOC On the basis of the quality of weight polyester oligomer melt, the additive amount of catalyst is 100ppm, and the additive amount of heat stabilizer is 100ppm, The additive amount of sodium acetate is 50ppm, and the additive amount of antioxidant is 20pmm；

5) low TVOC content precondensation polyester fondant is averagely gathered through path same as Example 1 progress final polycondensation reaction The right low TVOC content recycled polyester melt for being 105；The temperature of reaction is 288 DEG C, pressure 80Pa, time 120min；

7) the short fibre of coloured recycled polyester is made through path same as Example 1 and spinning technique in coloured recycled polyester melt Dimension, spinning technology parameter are as follows: 288 DEG C of spinning temperature, spinning speed 1300m/min, 78 DEG C of draft temperature, preliminary draft multiplying power is 1.09, one of draft ratio is 2.5, and two draft ratios are 1.09.

The fiber number of final Regenerated Polyester Fibres obtained is 2.5dtex, and the TVOC of length 38mm, Regenerated Polyester Fibres contain Measuring is 168ppm, and the content of nonyl phenol and its isomer is 139ppm, and the breaking strength of Regenerated Polyester Fibres is 3.5cN/ Dtex, elongation at break 26.2%, line density deviation ratio are 6.8%, color difference class 5 grade .5 grades of color fastness class 4.

Embodiment 13

3) depth depolymerization melt feeds vertical reactor by pipeline B after the filter II filtering that filtering accuracy is 10 μm, And the bottom by flowing to vertical reactor at the top of vertical reactor by control reaction temperature, pressure and contains during this period Oxygen amount carries out the removing of TVOC and the reparation of cracking functional group in depth depolymerization melt, is equipped with sampling in the bottom of vertical reactor Mouthful, depth depolymerization melt repeats flowing to obtain TVOC content to be 10ppm's after sample tap outflow through path same as Example 1 Low TVOC content polyester oligomer melt, the structure and pressure control path of vertical reactor are the same as embodiment 1；Vertical reactor Temperature are as follows: upper semisection temperature is 198~202 DEG C, and lower semisection temperature is 202~205 DEG C；Oxygen content is the vertical of 0.01v/v% Pressure generating period variation in the range of 1~80KPa in reactor, period 110min, wherein the pressure of 1KPa is protected Holding the time is 88min；

4) low TVOC content polyester oligomer melt is continuously fed into twin-screw as the raw material of step 1) via pipeline D and squeezes Machine 11 out, or prepolymerization reaction kettle is fed through pipeline C after the filter III filtering that filtering accuracy is 2 μm, catalyst is added Tetra-n-butyl titanate and ethylene glycol potassium titanate (mass ratio 1:1), two phosphorous of heat stabilizer phosphoric acid, anti-ether agent sodium acetate and antioxidant Prepolymerization reaction is carried out after the different certain herbaceous plants with big flowers ester of sour pentaerythritol ester two obtains the low TVOC content precondensation polyester that average degree of polymerization is 30 Melt；The temperature of prepolymerization reaction are as follows: 260 DEG C of upper chamber, 270 DEG C of lower room；Pressure are as follows: upper chamber 3.0KPa, lower room 1.0KPa；Time For 120min；On the basis of the quality of low TVOC content polyester oligomer melt, the additive amount of catalyst is 100ppm, thermostabilization The additive amount of agent is 200ppm, and the additive amount of sodium acetate is 50ppm, and the additive amount of antioxidant is 20pmm；

5) low TVOC content precondensation polyester fondant is averagely gathered through path same as Example 1 progress final polycondensation reaction The right low TVOC content recycled polyester melt for being 110；The temperature of reaction is 280 DEG C, pressure 50Pa, time 180min；

7) the short fibre of coloured recycled polyester is made through path same as Example 1 and spinning technique in coloured recycled polyester melt Dimension, spinning technology parameter are as follows: 292 DEG C of spinning temperature, spinning speed 1400m/min, 80 DEG C of draft temperature, preliminary draft multiplying power is 1.09, one of draft ratio is 2.5, and two draft ratios are 1.1.

The fiber number of final coloured Regenerated Polyester Fibres obtained is 1.8dtex, length 35mm, coloured Regenerated Polyester Fibres TVOC content be 66ppm, the content of nonyl phenol and its isomer is 110ppm, and the breaking strength of Regenerated Polyester Fibres is 4.7cN/dtex, elongation at break 23.6%, line density deviation ratio be 6.6% .5 grades of color difference class 4, color fastness class 5 Grade.

Embodiment 14

A kind of preparation method of Regenerated Polyester Fibres, steps are as follows:

2) preliminary depolymerization melt feeds reaction kettle through pipeline A 1 after the filter I 12 that filtering accuracy is 50 μm is filtered 13, and after being mixed with ethylene glycol under nitrogen protection, pressurization and stirring condition in 195 DEG C of progress alcoholysis reaction 60min, it is preliminary to solve The mass ratio of poly- melt and ethylene glycol is 3:1, and the pressure after pressurization is 101KPa, stirring rate 35Hz, and stirring uses sheet frame Formula agitating paddle obtains the depth depolymerization melt that average degree of polymerization is 1.5 after reaction；

3) depth depolymerization melt feeds vertical reactor by pipeline B after the filter II filtering that filtering accuracy is 10 μm, And the bottom by flowing to vertical reactor at the top of vertical reactor by control reaction temperature, pressure and contains during this period Oxygen amount carries out the removing of TVOC and the reparation of cracking functional group in depth depolymerization melt, is equipped with sampling in the bottom of vertical reactor Mouthful, depth depolymerization melt repeats flowing to obtain TVOC content to be 8ppm's from path same as Example 1 after sample tap outflow TVOC content polyester oligomer melt, the structure and pressure control path of vertical reactor are the same as embodiment 1；The temperature of vertical reactor Degree are as follows: upper semisection temperature is 199~202 DEG C, and lower semisection temperature is 202~205 DEG C；Oxygen content is the vertical anti-of 0.01v/v% Generating period in the range of 1~80KPa of the pressure in device is answered to change, period 105min, wherein the pressure of 1KPa is kept Time is 89min；

4) low TVOC content polyester oligomer melt is continuously fed into twin-screw as the raw material of step 1) via pipeline D and squeezes Machine 11 out, or prepolymerization reaction kettle is fed through pipeline C after the filter III filtering that filtering accuracy is 2 μm, catalyst is added After ethylene glycol potassium titanate, heat stabilizer phosphorous acid, anti-ether agent sodium acetate and the different certain herbaceous plants with big flowers ester of antioxidant pentaerythritol diphosphite two It carries out prepolymerization reaction and obtains the low TVOC content precondensation polyester fondant that average degree of polymerization is 30；The temperature of prepolymerization reaction Are as follows: 260 DEG C of upper chamber, 270 DEG C of lower room；Pressure are as follows: upper chamber 3.0KPa, lower room 1.0KPa；Time is 120min；With low TVOC content On the basis of the quality of polyester oligomer melt, the additive amount of catalyst is 100ppm, and the additive amount of heat stabilizer is 200ppm, second The additive amount of sour sodium is 100ppm, and the additive amount of antioxidant is 20pmm；

7) regenerative polyester staple fiber is made through path same as Example 1 and spinning technique in coloured recycled polyester melt, spins Silk technological parameter are as follows: 290 DEG C of spinning temperature, spinning speed 1500m/min, 75 DEG C of draft temperature, preliminary draft multiplying power is 1.1, one Road draft ratio is 2.5, and two draft ratios are 1.1.

The fiber number of final Regenerated Polyester Fibres obtained is 1.2dtex, and the TVOC of length 35mm, Regenerated Polyester Fibres contain Measuring is 50ppm, and the content of nonyl phenol and its isomer is 90ppm, and the breaking strength of Regenerated Polyester Fibres is 4.2cN/ Dtex, elongation at break 25.6%, line density deviation ratio be 6.2% .5 grades of color difference class 4 .5 grades of color fastness class 4.

Embodiment 15

1) the polyester oligomer melt for being 1.5 by polyester reclaiming material, catalyst and average degree of polymerization that moisture content is 80ppm It adds twin-screw extrude the reactive melt blending of progress and obtains the preliminary depolymerization melt that average degree of polymerization is 20, wherein is poly- The mass ratio of ester reclaimed materials and polyester oligomer melt is 0.1:1, and catalyst is zinc acetate and titanium ethylene glycolate (mass ratio 1:1), It is calculated with metallic element quality in catalyst relative to polyester oligomer melt quality, the content of catalyst is 80ppm；Reactivity The temperature of melt blending are as follows: 265 DEG C of twin-screw feed zone temperature, 275 DEG C of twin-screw compression section, 275 DEG C of homogenizing zone temperature, the time For 4min, atmosphere is nitrogen；

2) preliminary depolymerization melt feeds reaction kettle, and and second through pipeline A after the filter I filtering that filtering accuracy is 50 μm In 195 DEG C of progresss alcoholysis reaction 60min under nitrogen protection, pressurization and stirring condition after glycol mixing, preliminary depolymerization melt and The mass ratio of ethylene glycol is 3:1, and the pressure after pressurization is 101KPa, stirring rate 35Hz, and stirring uses plate and frame agitating paddle, The depth depolymerization melt that average degree of polymerization is 1.5 is obtained after reaction；

3) depth depolymerization melt feeds vertical reactor by pipeline B after the filter II filtering that filtering accuracy is 2 μm, and By flowing to the bottom of vertical reactor at the top of vertical reactor, during this period, pass through control reaction temperature, pressure and oxygen-containing Amount carries out the removing of TVOC and the reparation of cracking functional group in depth depolymerization melt, is equipped with sampling in the bottom of vertical reactor Mouthful, depth depolymerization melt repeats flowing to obtain TVOC content to be the low of 12ppm from path same as Example 1 after sample tap outflow TVOC content polyester oligomer melt, the structure and pressure control path of vertical reactor are the same as embodiment 1；The temperature of vertical reactor Degree are as follows: upper semisection temperature is 200~202 DEG C, and lower semisection temperature is 202~205 DEG C；Oxygen content is the vertical anti-of 0.01v/v% Answer the pressure in device in 1~80KPa generating period change, period 115min, wherein the pressure hold time of 1KPa be 103.5min；

4) low TVOC content polyester oligomer melt is continuously fed into twin-screw as the raw material of step 1) via pipeline D and squeezes Machine 11 out, or prepolymerization reaction kettle is fed through pipeline C after the filter III filtering that filtering accuracy is 2 μm, catalyst is added It is carried out after germanium oxide, heat stabilizer ortho phosphorous acid, anti-ether agent sodium acetate and the different certain herbaceous plants with big flowers ester of antioxidant pentaerythritol diphosphite two Prepolymerization reaction obtains the low TVOC content precondensation polyester fondant that average degree of polymerization is 30；Temperature are as follows: 260 DEG C of upper chamber, lower room 270℃；Pressure are as follows: upper chamber 3.0KPa, lower room 1.0KPa；The time of prepolymerization reaction is 120min；Contain weight polyester with low TVOC On the basis of the quality of oligomer melt, the additive amount of catalyst is 80ppm, and the additive amount of heat stabilizer is 200ppm, sodium acetate Additive amount be 100ppm, the additive amount of antioxidant is 20pmm；

5) low TVOC content precondensation polyester fondant is averagely gathered through path same as Example 1 progress final polycondensation reaction The right low TVOC content recycled polyester melt for being 110；The temperature of reaction is 285 DEG C, pressure 50Pa, time 160min；

7) the short fibre of coloured recycled polyester is made through path same as Example 1 and spinning technique in coloured recycled polyester melt Dimension, spinning technology parameter are as follows: 288 DEG C of spinning temperature, spinning speed 1500m/min, 80 DEG C of draft temperature, preliminary draft multiplying power is 1.1, one of draft ratio is 2.5, and two draft ratios are 1.1.

The fiber number of final Regenerated Polyester Fibres obtained is 1.8dtex, and the TVOC of length 35mm, Regenerated Polyester Fibres contain Measuring is 85ppm, and the content of nonyl phenol and its isomer is 138ppm, and the breaking strength of Regenerated Polyester Fibres is 4.2cN/ Dtex, elongation at break 24.1%, line density deviation ratio be 7.1% .5 grades of color difference class 4 .5 grades of color fastness class 4.

Claims

1. a kind of preparation method of coloured regenerative polyester staple fiber, characterized in that steps are as follows:

1) polyester reclaiming material and polyester oligomer melt are carried out reactive melt blending to obtain average degree of polymerization being 20~40 Preliminary depolymerization melt, the average degree of polymerization of the polyester oligomer melt are 1.5~4；

2) preliminary depolymerization melt carries out alcoholysis reaction and obtains the depth depolymerization that average degree of polymerization is 1.5~4 after mixing with ethylene glycol Melt；

3) depth depolymerization melt is under conditions of temperature is 190~205 DEG C, pressure is 1~80KPa and glycol steam convection current It is molten that the dynamic removing for carrying out TVOC and the reparation of cracking functional group obtain the low TVOC content polyester oligomer of TVOC content < 20ppm Body；

6) the form and aspect data for obtaining low TVOC content recycled polyester melt obtain target form and aspect institute by computer for colouring system-computed The color masterbatch type and dosage needed, and convey corresponding melt and low TVOC content recycled polyester melt mixed to obtain coloured regeneration poly- Ester melt；

7) coloured recycled polyester melt enters fused mass directly spinning system coloured regenerative polyester staple fiber is made；

The removing of the TVOC and the reparation of cracking functional group are carried out in vertical reactor, and the vertical reactor is lattice Grid fall membrane type devolatilization reactor, and bleeding point is located at reactor head, internal cell structure are as follows: have parallel angle bead by different Screen layer constitute, the direction of angle bead is mutually perpendicular on adjacent screen layer, top to the bottom of self-supporting reactor, adjacent screen The interlamellar spacing of layer is gradually increased, and the gap of angle bead is gradually reduced on different screen layers.

2. a kind of preparation method of coloured regenerative polyester staple fiber according to claim 1, which is characterized in that described vertical The temperature of reactor lower semisection be higher than upper semisection temperature, upper semisection temperature be 190~200 DEG C, lower semisection temperature be 200~ 205℃；Pressure generating period changes in the vertical reactor, and cycle length is equal to depth depolymerization melt in vertical reactor In residence time, the pressure hold time of 1KPa accounts for the 20%~90% of cycle time length, and the depth depolymerization melt exists Residence time in vertical reactor is 10min~2h, oxygen content < 0.03v/v% in the vertical reactor.

3. a kind of preparation method of coloured regenerative polyester staple fiber according to claim 2, which is characterized in that specific steps It is as follows:

1) progress will be added twin-screw extrude by sufficiently dry polyester reclaiming material, catalyst and polyester oligomer melt Reactive melt blending obtains preliminary depolymerization melt；The temperature of the reactivity melt blending are as follows: twin-screw feed zone temperature 260 ~275 DEG C, 275~300 DEG C of twin-screw compression section, 275~295 DEG C of homogenizing zone temperature, the time is 1~5min, and atmosphere is nitrogen Or gauge pressure is the < vacuum environment of 0.15KPa；

2) preliminary depolymerization melt feeds reaction kettle through pipeline A after filter I filtering, and protects after mixing with ethylene glycol in nitrogen Alcoholysis reaction, which is carried out, under shield, pressurization and stirring condition obtains depth depolymerization melt；The temperature of the alcoholysis reaction is 190~205 DEG C, the time of alcoholysis reaction is 40~80min；

3) depth depolymerization melt feeds vertical reactor by pipeline B after filter II filtering, and by the top of vertical reactor The bottom for flowing to vertical reactor is equipped with sample tap in the bottom of vertical reactor, and depth depolymerization melt is flowed out from sample tap By by carrying out repeating to flow at the top of pipeline D Returning reactor obtaining low TVOC content polyester oligomer melt；

The control of pressure is by constantly supplementing ethylene glycol simultaneously from vertical anti-from the lower part of vertical reactor in vertical reactor It answers and detaches gas realization at the top of device, the lower part of vertical reactor is communicated by pipeline F with ethylene glycol storage tank II holding, is extracted out Gas G is condensed by condenser by the road, finally recycled by ethylene glycol storage tank I, ethylene glycol storage tank I passes through pipeline E respectively It is connected to pipeline H with ethylene glycol storage tank II and reaction kettle；

4) low TVOC content polyester oligomer melt is continuously fed into twin-screw extrusion as the raw material of step 1) via pipeline D Machine, or through filter III filtering after through pipeline C feed prepolymerization reaction kettle, be added catalyst, heat stabilizer, anti-ether agent and Prepolymerization reaction is carried out after antioxidant obtains the low TVOC content precondensation polyester fondant that average degree of polymerization is 20~30；It is described pre- The temperature of polycondensation reaction are as follows: 255~265 DEG C of upper chamber, 265~275 DEG C of lower room；The pressure of the prepolymerization reaction are as follows: upper chamber 2.5 ~4.5KPa, lower 1~2.5KPa of room；The time of the prepolymerization reaction is 60~120min；

5) low TVOC content precondensation polyester fondant is delivered to progress final polycondensation reaction in final polycondensation reaction kettle via pipeline I and obtains The low TVOC content recycled polyester melt that average degree of polymerization is 95~110；The temperature of the final polycondensation reaction is 280~285 DEG C, Pressure is 50~500Pa, and the time is 100~180min；

6) the form and aspect data that on-line monitoring obtains low TVOC content recycled polyester melt are carried out on pipeline J, by computer for colouring System-computed obtains color masterbatch type and dosage required for target form and aspect, and control color masterbatch melt group convey corresponding melt with it is low TVOC content recycled polyester melt mixed obtains coloured recycled polyester melt；

7) coloured recycled polyester melt enters fused mass directly spinning system via pipeline J coloured regenerative polyester staple fiber, spinning work is made Skill are as follows: melt conveying → spinning → cooling → winding falling-barrel → seal wire → one of drawing-off → bis- drawing-offs → thermal finalization → curling is cut It is disconnected to be packaged；Spinning technology parameter are as follows: 270~290 DEG C of spinning temperature, 800~1500m/min of spinning speed, draft temperature 60~ 80 DEG C, preliminary draft multiplying power is 1.02~1.10, and one of draft ratio is 1.8~2.5, and two draft ratios are 1.02~1.1.

4. a kind of preparation method of coloured regenerative polyester staple fiber according to claim 3, which is characterized in that step 1) In, it is described to refer to moisture content < 100ppm polyester reclaiming material by sufficiently dry polyester reclaiming material；

The catalyst be tetra-n-butyl titanate, tetraisopropyl titanate, titanium ethylene glycolate, ethylene glycol sodium titanate, ethylene glycol potassium titanate, One or more of zinc acetate and manganese acetate, by metallic element quality in catalyst based on polyester oligomer melt quality It calculates, the content of catalyst is 10~300ppm；

5. a kind of preparation method of coloured regenerative polyester staple fiber according to claim 3, which is characterized in that step 2) In, the mass ratio of the preliminary depolymerization melt and ethylene glycol is 3~4.5:1；Pressure after pressurization is 101~150KPa, stirring Rate is 35~75Hz, and stirring uses plate and frame agitating paddle.

6. a kind of preparation method of coloured regenerative polyester staple fiber according to claim 3, which is characterized in that step 4) In, the catalyst be tetra-n-butyl titanate, tetraisopropyl titanate, titanium ethylene glycolate, ethylene glycol sodium titanate, ethylene glycol potassium titanate, One or more of antimony acetate, antimony oxide, acetic acid germanium and germanium oxide, with the quality of low TVOC content polyester oligomer melt On the basis of, the additional amount of catalyst is 10~300ppm；

The antioxidant is the different certain herbaceous plants with big flowers ester of pentaerythritol diphosphite two, bis- two phosphorous of (2.4- di-tert-butyl-phenyl) pentaerythrite One or more of acid esters and three (2,4- di-t-butyl) phenyl-phosphites, with the quality of low TVOC content polyester oligomer melt On the basis of, the additive amount of antioxidant is 10~100ppm；

The heat stabilizer is trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite, Asia One of diphenyl phosphate, ammonium phosphite, ammonium dihydrogen phosphate, phosphoric acid, phosphorous acid, ortho phosphorous acid, pyrophosphoric acid and ammonium phosphate with On, on the basis of the quality of low TVOC content polyester oligomer melt, the additive amount of heat stabilizer is 50~200ppm；

The anti-ether agent be sodium acetate, on the basis of the quality of low TVOC content polyester oligomer melt, additive amount be 50~ 200ppm。

7. a kind of preparation method of coloured regenerative polyester staple fiber according to claim 3, which is characterized in that filter I, The filtering accuracy of filter II and filter III are respectively 50~100 μm, 1~15 μm and 1~15 μm.

8. the preparation method of a kind of coloured regenerative polyester staple fiber according to claim 1, it is characterized in that: coloured regeneration is poly- The fiber number of ester staple fiber is 1.1~5.5dtex, and length is 30~50mm, the color difference grade of the coloured regenerative polyester staple fiber Be 4-5 grades, color fastness is 4-5 grade, and TVOC content is 30~300ppm, the content of nonyl phenol and its isomer for 80~ 200ppm。

9. a kind of preparation method of coloured regenerative polyester staple fiber according to claim 8, which is characterized in that described coloured The breaking strength of regenerative polyester staple fiber is 2.8~4.8cN/dtex, and elongation at break is 22.0~65.0%, line density deviation Rate is 6.0~8.0%.