CN107523895A

CN107523895A - A kind of coloured regenerative polyester staple fiber and preparation method thereof

Info

Publication number: CN107523895A
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; National Dong Hwa University
Priority date: 2017-07-20
Filing date: 2017-07-20
Publication date: 2017-12-29
Anticipated expiration: 2037-07-20
Also published as: CN107523895B

Abstract

The present invention relates to a kind of coloured regenerative polyester staple fiber 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 TVOC removing and the reparation of cracking functional group obtains low TVOC contents polyester oligomer melt, then low TVOC contents polyester oligomer melt carries out polycondensation reaction and obtains low TVOC contents recycled polyester melt, the color matching for finally controlling low TVOC contents recycled polyester melt by computer for colouring system obtains coloured recycled polyester melt, coloured regenerative polyester staple fiber is made into fused mass directly spinning system in coloured recycled polyester melt.The aberration of coloured regenerative polyester staple fiber of the invention final obtained is smaller, and TVOC contents are 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, is related to a kind of coloured regenerative polyester staple fiber and preparation method thereof, It is more particularly to a kind of using polyester reclaiming material as raw material and the relatively low coloured regenerative polyester staple fibers of high-quality of TVOC and its efficiently Preparation method.

Background technology

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

The regeneration techniques of polyester can be divided mainly into Physical and the major class of chemical method two.Conventional physical method to waste material by carrying out Regeneration is realized in melting reprocessing, has the characteristics of high efficiency, low cost, is that current polyester regenerates the leading of industrialization technology, but tradition The more primary quality decline of product that Physical regenerates is obvious, and inherent viscosity declines and fluctuated larger.During simultaneously because 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 Can not such as be removed in time in the process of temperature will trigger a variety of irreversible cracking degradeds.Therefore pair of simple physical method regeneration The waste polyester bottle chip higher as being only limitted to degree of purity.

In order to carry out highly efficient regeneration to polyester reclaiming material, prior art has carried out improving upgrading to conventional physical method, its Feature is to add 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 production cost increase compared with conventional physical method and few, and can realize to polyester reclaiming material High efficiency, low cost regeneration, therefore in recent years the Industry Promotion scope of correlation technique also in rapid expansion.It is but also due to molten The limitation of body viscosity, this method still can not effectively be removed for impurity, TVOC contents and other particularly in recycled product The content of organic murder by poisoning thing is higher, and the application of product is still greatly limited, can not comprehensively into take, automotive trim etc. Higher field is required to safety in utilization.

Chemical rule is to realize regeneration by the route of " be depolymerized to monomer-separating-purifying-polymerize again ", during due to poly- Ester is depolymerizated as monomer, technically easily realizes purification more thoroughly, the low waste material such as waste textile can be carried out effective Recovery, recycled product quality can match in excellence or beauty it is primary, but technological process grow, efficiency is low, and 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 correlation technique under the fostering of preferential policy and attempted, wherein representative Patented technology has US5710315, US4609608 and WO2003033581 etc., but because Cost Problems, popularization are seriously made About.

The content of the invention

It is an object of the invention to provide a kind of coloured regenerative polyester staple fiber of high-quality and its high efficiency preparation method, simultaneous In the case of caring for production cost and equipment modification cost, effectively lifting is using polyester reclaiming material as coloured recycled polyester made from raw material The quality of chopped fiber, effectively solves that the existing coloured regenerative polyester staple fiber TVOC contents that are produced of improvement Physical are high to ask Topic.

To reach above-mentioned purpose, the technical solution adopted by the present invention is：

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

1) by polyester reclaiming material and polyester oligomer melt carry out reactive melt blending obtain average degree of polymerization for 20~ 40 preliminary depolymerization melt, the average degree of polymerization of the polyester oligomer melt is 1.5~4, and can be by the product of step afterwards 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 being mixed with ethylene glycol Depolymerization melt；

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

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

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

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

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

As preferable 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 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：It is made up of the different screen layers with parallel angle bead, angle bead on adjacent gate flaggy Direction be mutually perpendicular to, top to the bottom of self-supporting reactor, the interlamellar spacing of adjacent gate flaggy gradually increases, 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 change, 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 being preferred with 50%~80%, the depth depolymerization is melted Residence time of the body in vertical reactor is 10min~2h, the oxygen content in the vertical reactor<0.03v/v%.

A kind of preparation method of coloured regenerative polyester staple fiber as described above, is comprised the following steps that：

1) will be added by fully dry polyester reclaiming material, catalyst and polyester oligomer melt in double screw extruder Reactive melt blending is carried out, in the presence of ester exchange reaction, reversible depolymerization will occur for polyester reclaiming material in Blending Processes Obtain preliminary depolymerization melt；Described polyester reclaiming material by reclaim Lai PET give up cloth be prepared, it is described reactivity melting altogether Mixed temperature is：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 be preferred using 288~293 DEG C of temperature ranges, the time is 1~5min, and atmosphere is nitrogen or gauge pressure is<0.15KPa's Vacuum environment；

Melt is depolymerized using polyester oligomer in step 1), rather than chemical method was carried out frequently with ethylene glycol in the past The main advantage of melting depolymerization is：

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

B) ethylene glycol can be avoided effectively to be reduced again from substantial amounts of autohemagglutination etherificate side reaction occurs in high temperature and high pressure environment The content of diethylene glycol (DEG) in raw product；

C) under the reaction condition that step 1) provides, based on ester exchange reaction, polyester oligomer can equally enter to polyester Row depolymerization, and depolymerization approximation belongs to homogeneous reaction, has the advantages of depolymerization speed is fast, and molecular weight of product is evenly distributed；

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

2) preliminary depolymerization melt feeds reactor after filter I is filtered off except insoluble inert particle impurity through pipeline A, And carry out alcoholysis reaction under nitrogen protection, pressurization and stirring condition after being mixed with ethylene glycol and obtain 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；

It is involved by step 2) it is a technical advantage that：It is fine that depth depolymehzation step can be such that material has at a lower temperature Mobility, in melt in next step TVOC depth remove and suppress diethylene glycol (DEG) generation guarantee is provided；In the present invention Depth depolymerization be different from the regeneration of conventional chemical method frequently with the part of the heterogeneous alcoholysis of low-temperature atmosphere-pressure be：Undergo step 1) This is quickly after preliminary depolymehzation process, depth depolymerization can in low temperature, homogeneous depolymerization is realized close under conditions of normal pressure, simultaneously The degree of polymerization can accurately be adjusted by rate of charge, avoided using excessive ethylene glycol, thus can be lifted depolymerization efficiency, Production cost is saved, and can effectively avoids the generation of diethylene glycol (DEG)；

3) depth depolymerization melt by filter II filtering after by pipeline B feed vertical reactor, and by self gravitation by The bottom of vertical reactor is flowed at the top of vertical reactor, during this period, passes through controlling reaction temperature, pressure and oxygen content TVOC removing and the reparation of cracking functional group in depth depolymerization melt are carried out, sample tap is provided with the bottom of vertical reactor, Depth depolymerization melt passes through after sample tap outflow obtains low TVOC contents by carrying out repetition flowing at the top of pipeline D Returning reactors Polyester oligomer melt；

The control of pressure is by constantly supplementing ethylene glycol simultaneously from vertical from the bottom of vertical reactor in vertical reactor Gas realization is detached at the top of formula reactor, the bottom of vertical reactor keeps communicating by pipeline F and ethylene glycol storage tank II, G is condensed the gas of extraction by condenser by the road, is finally reclaimed by ethylene glycol storage tank I, and ethylene glycol storage tank I passes through pipe respectively Road E and pipeline H connect with ethylene glycol storage tank II and reactor；

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

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

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

B) because melt viscosity is low, at a set temperature, by negative pressure TVOC can quickly escaped from melt, After negative pressure certain time, to storage tank VII supply ethylene glycol, now ethylene glycol can because of negative pressure fast vaporizing, in the environment of pumping Under to top fast transferring and can be constantly updated from reactor lower part, during the glycol steam that flows can capture (dissolving) with And drive the TVOC even some higher murder by poisoning organic matters of boiling point (such as：Nonylphenol class and its isomer) thoroughly move out；

C) temperature of vertical reactor lower semisection is controlled to be slightly above upper semisection, more conducively bottom-up inverse of glycol steam Melt stream migration, screen in reactor under spacing is cumulative layer by layer and angle bead between the structure of gap decrescence so that melt Surface Renewal speed gradually increases, and falls film length increase, with reference to the higher condition of temperature of lower, it is ensured that in depth depolymerization melt Fail to poison organic matter (such as in reactor top effectively removing higher boiling net to the greatest extent：Nonyl phenol and its isomer) flowing through Thoroughly depart from melt during reactor lower part and enter the glycol steam phase of flowing；

D) the pressure change cycle in vertical reactor is controlled to be equal to stop of the depth depolymerization melt in vertical reactor Time, it is ensured that the uniformity of continuous flow procedure material devolatilization degree, while under this technique, depth solution in whole 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 has preferable exchange reaction activity with ethylene glycol so that mistake The structure that some in journey contain cracking end group can be repaired by exchange reaction, the low boiling containing cracking end group being replaced Monomer structure can be taken out of in devolatilization processes by glycol steam；

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

5) low TVOC contents precondensation polyester fondant is delivered in final polycondensation reaction kettle via pipeline I carries out final polycondensation reaction Obtain the low TVOC contents 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 reactor) is 100~180min；

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

7) coloured regenerative polyester staple fiber is made into fused mass directly spinning system via pipeline J in coloured recycled polyester melt, spins Silk technique be：Melt conveying → spinning → cooling → winding falling-barrel → seal wire → one of drawing-off → bis- drawing-offs → thermal finalization → volume Song cut-out packing；Spinning technology parameter is：270~290 DEG C, 800~1500m/min of spinning speed of spinning temperature, 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 fully drying 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 stir speed (S.S.) 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 contents polyester oligomer melt, the addition of catalyst Measure as 10~300ppm；

The antioxidant is the different certain herbaceous plants with big flowers ester of pentaerythritol diphosphite two, double (2.4- di-tert-butyl-phenyls) pentaerythrites two Phosphite ester；Three (2,4- di-t-butyl) phenyl-phosphites more than one, with the matter of low TVOC contents polyester oligomer melt On the basis of amount, the addition 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 More than kind, on the basis of the quality of low TVOC contents polyester oligomer melt, the addition of heat stabilizer is 50~200ppm；

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

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

Present invention also offers a kind of coloured regenerative polyester staple fiber, the fiber number of coloured regenerative polyester staple fiber for 1.1~ 5.5dtex, length are 30~50mm, and the aberration grade of the coloured regenerative polyester staple fiber is 4-5 levels, and color fastness is 4-5 levels, TVOC contents are 30~300ppm, and the content of nonyl phenol and its isomer is 80~200ppm.

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

Beneficial effect：

(1) a kind of preparation method of coloured regenerative polyester staple fiber of the invention can be reduced effectively using 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 Color needed for online allotment, and the requirement to regenerative raw materials quality is low, strong adaptability；

(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 are polyester industry metaplasia production Equipment Foundations to carry out reform strengthening, the more existing long-time melt devolatilization thickening method of reproduction of cost and chain extension It is few to regenerate the increase of thickening method, but the product quality and added value that are obtained can be obviously improved, therefore with extraordinary Industry Promotion advantage and environmental benefit.

Brief description of the drawings

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

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

Embodiment

The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair Bright rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, art technology Personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited Fixed scope.

Embodiment 1

A kind of preparation method of coloured Regenerated Polyester Fibres, step 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 and 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, catalyst is titanium ethylene glycolate, with metallic element quality phase in catalyst Calculated for polyester oligomer melt quality, the content of catalyst is 50ppm；The temperature of reactive melt blending is：Twin-screw 268 DEG C of feed zone temperature, 288 DEG C of twin-screw compression section, 288 DEG C, time 2min of homogenizing zone temperature, screw rod is interior to be protected for nitrogen Shield；

2) reactor 13 is fed through pipeline A1 after the filter I12 filterings that the filtered precision of preliminary depolymerization melt is 50 μm, And carry out alcoholysis reaction 60min, preliminary depolymerization at 200 DEG C under nitrogen protection, pressurization and stirring condition after being mixed with ethylene glycol The mass ratio of melt and ethylene glycol is 3.5:1, the pressure after pressurization is 120KPa, stir speed (S.S.) 50Hz, and stirring uses sheet frame Formula agitating paddle, the depth depolymerization melt that average degree of polymerization is 2 is obtained after reaction；

3) vertical reactor is fed by pipeline B2 after the filter II14 filterings that the filtered precision of depth depolymerization melt is 1 μm 15, and flow to by the top of vertical reactor 15 bottom of vertical reactor 15, during this period, by controlling reaction temperature, Pressure and oxygen content carry out TVOC removing and the reparation of cracking functional group in depth depolymerization melt, at the bottom of vertical reactor 15 Portion is provided with sample tap, and depth depolymerization melt passes through after sample tap outflow carries out repetitive stream by the top of pipeline D4 Returning reactors 15 Move until the TVOC contents of melt obtain low TVOC contents polyester oligomer melt for 10ppm；

Vertical reactor 15 is that grid falls membrane type devolatilization reactor, and bleeding point is located at reactor head, internal grid knot Structure is：It is made up of the different screen layers with parallel angle bead, the direction of angle bead is mutually perpendicular on adjacent gate flaggy, and self-supporting is anti- Top to the bottom of device is answered, the interlamellar spacing of adjacent gate flaggy gradually increases, and the gap of angle bead is gradually reduced on different screen layers；

The temperature of the lower semisection of vertical reactor 15 is higher than the temperature of upper semisection, and the temperature of vertical reactor is：Upper semisection temperature Spend for 190~195 DEG C, 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 bottom of vertical reactor 15 Top detach gas realization, the bottom of vertical reactor 15 is communicated by pipeline F6 and ethylene glycol storage tank II17 holdings, taken out G7 is condensed the gas gone out by condenser 18 by the road, is finally reclaimed by ethylene glycol storage tank I16, ethylene glycol storage tank I16 difference Connected by pipeline E5 and pipeline H8 with ethylene glycol storage tank II17 and reactor 13, oxygen content is 0.01v/v% vertical response Pressure generating period change in the range of 1~80KPa in device 15, cycle 110min, wherein 1KPa pressure are kept Time is 88min；

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

5) low TVOC contents precondensation polyester fondant is delivered to progress final minification in final polycondensation reaction kettle 21 via pipeline I9 and gathered Reaction obtains the low TVOC contents 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 contents recycled polyester melt are carried out on pipeline J 10, by calculating Machine color matching system calculates the color masterbatch species and dosage obtained required for target form and aspect, and it is corresponding molten to control color masterbatch melt group 23 to convey Body obtains coloured recycled polyester melt with low TVOC contents recycled polyester melt mixed；

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：The drawing-off of melt conveying → spinning → cooling → winding falling-barrel → seal wire → one of drawing-off → bis- → heat is fixed Type → curling cut-out packing；Spinning technology parameter is：290 DEG C, spinning speed 1500m/min of spinning temperature, 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 obtained coloured Regenerated Polyester Fibres is 1.1dtex, length 30mm, coloured Regenerated Polyester Fibres TVOC contents be 30ppm, the content of nonyl phenol and its isomer is 92ppm, and the fracture of coloured Regenerated Polyester Fibres is strong It is 7.0% to spend for 4.52cN/dtex, elongation at break 23.3%, line density deviation ratio, aberration class 4 .5 levels, color fastness etc. 4.5 grades of level.

Comparative example 1

A kind of preparation method of coloured Regenerated Polyester Fibres, using polyester reclaiming material same as Example 1, through superfusion Melting, 275 DEG C of melts homogenize 30min, in mouse-cage type reactor, 272 DEG C, air pressure<50Pa high vacuum devolatilization 150min, process melt It is brown to know from experience automatic, 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 fracture strengths of coloured Regenerated Polyester Fibres are 1.2cN/dtex, elongation at break 11.2%, line density deviation ratio For 9%, aberration grade is 3.5 grades, and color fastness grade is 4 grades.Comparative example 1 and embodiment 1 are contrasted as can be seen that using this hair The TVOC contents and the content of nonyl phenol and its isomer of coloured Regenerated Polyester Fibres made from bright preparation method are relative Reduced substantially in 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 Reactive melt blending is carried out in addition double screw extruder and obtains the preliminary depolymerization melt that average degree of polymerization is 20, wherein, gather The mass ratio of ester reclaimed materials and polyester oligomer melt is 0.1:1, catalyst is tetra-n-butyl titanate, with metal member in catalyst Quality amount calculates relative to polyester oligomer melt quality, and the content of catalyst is 50ppm；The temperature of reactive melt blending For：260 DEG C of twin-screw feed zone temperature, 275 DEG C of twin-screw compression section, 275 DEG C, time 5min of homogenizing zone temperature, atmosphere are Nitrogen；

2) through pipeline A feeding reactors after the filter I filterings that the filtered precision of preliminary depolymerization melt is 100 μm, and with After ethylene glycol mixing alcoholysis reaction 80min, preliminary depolymerization melt are carried out under nitrogen protection, pressurization and stirring condition at 190 DEG C Mass ratio with ethylene glycol is 3:1, the pressure after pressurization is 101KPa, stir speed (S.S.) 35Hz, and stirring is stirred using plate and frame Oar, the depth depolymerization melt that average degree of polymerization is 1.5 is obtained after reaction；

1) 3) the filtered precision of depth depolymerization melt feeds vertical reactor after being filtered for 1 μm of filter II by pipeline B, And by flowing to the bottom of vertical reactor at the top of vertical reactor, during this period, by controlling reaction temperature, pressure and contain Oxygen amount carries out TVOC removing and the reparation of cracking functional group in depth depolymerization melt, and sampling is provided with the bottom of vertical reactor Mouthful, it is 10ppm's that depth depolymerization melt repeats flowing to obtain TVOC contents after sample tap outflow through path same as Example 1 Low TVOC contents polyester oligomer melt, the structure and pressure control path of vertical reactor are the same as embodiment 1；Vertical reactor Temperature is：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 change in the range of 1~80KPa in reactor, cycle 70min, wherein 1KPa pressure are kept Time is 35min；

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

5) low TVOC contents precondensation polyester fondant is averagely gathered through path same as Example 1 progress final polycondensation reaction It is right be 95 low TVOC contents recycled polyester melt；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：270 DEG C, spinning speed 800m/min of spinning temperature, 60 DEG C of draft temperature, preliminary draft multiplying power are 1.02, one of draft ratio is 1.8, and two draft ratios are 1.02.

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

Comparative example 2

A kind of preparation method of coloured Regenerated Polyester Fibres, using polyester reclaiming material same as Example 2, through superfusion Melt, 270 DEG C of air pressure<50Pa, vertical falling-film reactor high vacuum devolatilization and homogenizing 80min, the 272 DEG C of polycondensations of mouse-cage type reactor increase Viscous 120min, process melt can be automatically brown, 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 are 650ppm, and nonyl phenol and its isomer contain Measure as 556ppm, the fracture 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 aberration grade, color fastness grade 3.5.Comparative example 2 and embodiment 2 are contrasted as can be seen that using this hair The TVOC contents and the content of nonyl phenol and its isomer of coloured Regenerated Polyester Fibres made from bright preparation method are relative Reduced substantially in 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 and 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, catalyst is tetraisopropyl titanate, with metallic element matter in catalyst Amount calculates relative to polyester oligomer melt quality, and the content of catalyst is 10ppm；The temperature of reactive melt blending is：It is 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) reactor, and and second are fed through pipeline A after the filter I filterings that the filtered precision of preliminary depolymerization melt is 50 μm Glycol mixing after nitrogen protection, pressurization and stirring condition under 205 DEG C carry out alcoholysis reaction 40min, preliminary depolymerization melt with The mass ratio of ethylene glycol is 4.5:1, the pressure after pressurization is 150KPa, stir speed (S.S.) 75Hz, and stirring is stirred using plate and frame Oar, the depth depolymerization melt that average degree of polymerization is 4 is obtained after reaction；

3) vertical reactor is fed by pipeline B after the filter II filterings that the filtered precision of depth depolymerization melt is 10 μm, And by flowing to the bottom of vertical reactor at the top of vertical reactor, during this period, by controlling reaction temperature, pressure and contain Oxygen amount carries out TVOC removing and the reparation of cracking functional group in depth depolymerization melt, and sampling is provided with the bottom of vertical reactor Mouthful, it is 15ppm's that depth depolymerization melt repeats flowing to obtain TVOC contents after sample tap outflow through path same as Example 1 Low TVOC contents polyester oligomer melt, the structure and pressure control path of vertical reactor are the same as embodiment 1；Vertical reactor Temperature is：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% The generating period in the range of 1~80KPa of the pressure in device is answered to change, cycle 120min, wherein 1KPa pressure are kept Time is 108min；

4) low TVOC contents polyester oligomer melt is continuously fed into twin-screw as the raw material of step 1) via pipeline D and squeezed Go out machine, or prepolymerization reaction kettle is fed through pipeline C after the filter III filterings that filtered precision is 10 μm, add catalyst Tetraisopropyl titanate, heat stabilizer triphenyl phosphate, anti-ether agent sodium acetate and antioxidant double (2.4- di-tert-butyl-phenyls) seasons penta Prepolymerization reaction is carried out after tetrol diphosphites and obtains the low TVOC contents precondensation polyester fondant that average degree of polymerization is 30；In advance The temperature of polycondensation reaction is：265 DEG C of upper chamber, lower 275 DEG C of room；Pressure is：Upper chamber 4.5KPa, lower room 2.5KPa；Time is 60min；On the basis of the quality of low TVOC contents polyester oligomer melt, the addition of catalyst is 10ppm, heat stabilizer Addition is 200ppm, and the addition of sodium acetate is 200ppm, and the addition of antioxidant is 100pmm；

5) low TVOC contents precondensation polyester fondant is averagely gathered through path same as Example 1 progress final polycondensation reaction It is right be 100 low TVOC contents recycled polyester melt；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：290 DEG C, spinning speed 850m/min of spinning temperature, 70 DEG C of draft temperature, preliminary draft multiplying power are 1.05, one of draft ratio is 2.3, and two draft ratios are 1.05.

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

Comparative example 3

A kind of preparation method of coloured Regenerated Polyester Fibres, using polyester reclaiming material same as Example 3, through superfusion Melt, 275 DEG C of air pressure<50Pa, vertical falling-film reactor high vacuum devolatilization and homogenizing 50min, the 268 DEG C of polycondensations of mouse-cage type reactor increase Viscous 180min, process melt can be automatically brown, 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 are 683ppm, and nonyl phenol and its isomer contain Measure as 658ppm, the fracture 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 aberration grade, 3.5 grades of color fastness grade.Comparative example 3 is contrasted as can be seen that adopting with embodiment 3 The TVOC contents of coloured Regenerated Polyester Fibres made from the preparation method of the present invention and nonyl phenol and its isomer contain Amount reduces substantially relative to prior art, 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 and 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, catalyst is ethylene glycol sodium titanate, with metallic element in catalyst Quality calculates relative to polyester oligomer melt quality, and the content of catalyst is 80ppm；The temperature of reactive melt blending is： 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) reactor, and and second are fed through pipeline A after the filter I filterings that the filtered precision of preliminary depolymerization melt is 80 μm Glycol mixing after nitrogen protection, pressurization and stirring condition under 202 DEG C carry out alcoholysis reaction 50min, preliminary depolymerization melt with The mass ratio of ethylene glycol is 4:1, the pressure after pressurization is 120KPa, stir speed (S.S.) 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) vertical reactor is fed by pipeline B after the filter II filterings that the filtered precision of depth depolymerization melt is 15 μm, And by flowing to the bottom of vertical reactor at the top of vertical reactor, during this period, by controlling reaction temperature, pressure and contain Oxygen amount carries out TVOC removing and the reparation of cracking functional group in depth depolymerization melt, and sampling is provided with the bottom of vertical reactor Mouthful, depth depolymerization melt passes through after sample tap outflow to be repeated flowing to obtain TVOC contents to be 10ppm by path same as Example 1 Low TVOC contents polyester oligomer melt, the structure and pressure control path of vertical reactor are the same as embodiment 1；Vertical reactor Temperature be：Upper semisection temperature is 200~203 DEG C, and lower semisection temperature is 203~205 DEG C；Oxygen content is the vertical of 0.02v/v% Pressure generating period change in the range of 1~80KPa in formula reactor, cycle 10min, wherein 1KPa pressure are protected It is 2min to hold the time；

4) low TVOC contents polyester oligomer melt is continuously fed into twin-screw as the raw material of step 1) via pipeline D and squeezed Go out machine, or prepolymerization reaction kettle is fed through pipeline C after the filter III filterings that filtered precision is 10 μm, add catalyst Ethylene glycol sodium titanate, heat stabilizer diphenyl phosphate, anti-ether agent sodium acetate and antioxidant double (2.4- di-tert-butyl-phenyls) seasons penta The different certain herbaceous plants with big flowers ester of tetrol diphosphites, pentaerythritol diphosphite two and three (2,4- di-t-butyls) phenyl-phosphite (mass ratioes 1:1:2) prepolymerization reaction is carried out afterwards obtain the low TVOC contents precondensation polyester fondant that average degree of polymerization is 25；Prepolymerization reaction Temperature be：260 DEG C of upper chamber, lower 265 DEG C of room；Pressure is：Upper chamber 3.5KPa, lower room 1.5KPa；Time is 80min；With low On the basis of the quality of TVOC content polyester oligomer melts, the addition of catalyst is 50ppm, and the addition of heat stabilizer is 100ppm, the addition of sodium acetate is 150ppm, and the addition of antioxidant is 80pmm；

5) low TVOC contents precondensation polyester fondant is averagely gathered through path same as Example 1 progress final polycondensation reaction It is right be 100 low TVOC contents recycled polyester melt；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：292 DEG C, spinning speed 1150m/min of spinning temperature, 75 DEG C of draft temperature, preliminary draft multiplying power are 1.03, one of draft ratio is 2.3, and two draft ratios are 1.05.

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

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 Reactive melt blending is carried out in addition double screw extruder and obtains the preliminary depolymerization melt that average degree of polymerization is 25, wherein, gather The mass ratio of ester reclaimed materials and polyester oligomer melt is 1.5:1, catalyst is ethylene glycol potassium titanate, with metal member in catalyst Quality amount calculates relative to polyester oligomer melt quality, and the content of catalyst is 300ppm；The temperature of reactive melt blending For：260 DEG C of twin-screw feed zone temperature, 275 DEG C of twin-screw compression section, 275 DEG C, time 3min of homogenizing zone temperature, atmosphere are Nitrogen；

2) through pipeline A feeding reactors after the filter I filterings that the filtered precision of preliminary depolymerization melt is 100 μm, and with After ethylene glycol mixing alcoholysis reaction 60min, preliminary depolymerization melt are carried out under nitrogen protection, pressurization and stirring condition at 205 DEG C Mass ratio with ethylene glycol is 4:1, the pressure after pressurization is 150KPa, stir speed (S.S.) 50Hz, and stirring is stirred using plate and frame Oar, the depth depolymerization melt that average degree of polymerization is 2.5 is obtained after reaction；

3) vertical reactor is fed by pipeline B after the filter II filterings that the filtered precision of depth depolymerization melt is 10 μm, And by flowing to the bottom of vertical reactor at the top of vertical reactor, during this period, by controlling reaction temperature, pressure and contain Oxygen amount carries out TVOC removing and the reparation of cracking functional group in depth depolymerization melt, and sampling is provided with the bottom of vertical reactor Mouthful, it is 18ppm's that depth depolymerization melt repeats flowing to obtain TVOC contents after sample tap outflow through path same as Example 1 Low TVOC contents polyester oligomer melt, the structure and pressure control path of vertical reactor are the same as embodiment 1；Vertical reactor Temperature is：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 change in the range of 1~80KPa in reactor, cycle 100min, wherein 1KPa pressure are protected It is 75min to hold the time；

4) low TVOC contents polyester oligomer melt is continuously fed into twin-screw as the raw material of step 1) via pipeline D and squeezed Go out machine, or prepolymerization reaction kettle is fed through pipeline C after the filter III filterings that filtered precision is 10 μm, add catalyst Ethylene glycol potassium titanate, two different certain herbaceous plants with big flowers of heat stabilizer dimethyl phosphate, anti-ether agent sodium acetate and antioxidant pentaerythritol diphosphite Prepolymerization reaction is carried out after ester and obtains the low TVOC contents precondensation polyester fondant that average degree of polymerization is 28；The temperature of prepolymerization reaction Spend and be：265 DEG C of upper chamber, lower 275 DEG C of room；Pressure is：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 addition of catalyst is 300ppm, and the addition of heat stabilizer is 100ppm, The addition of sodium acetate is 100ppm, and the addition of antioxidant is 100pmm；

5) low TVOC contents precondensation polyester fondant is averagely gathered through path same as Example 1 progress final polycondensation reaction It is right be 105 low TVOC contents recycled polyester melt；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：298 DEG C, spinning speed 1500m/min of spinning temperature, 80 DEG C of draft temperature, preliminary draft multiplying power are 1.08, one of draft ratio is 2.4, and two draft ratios are 1.1.

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

Embodiment 6

A kind of preparation method of coloured Regenerated Polyester Fibres, as shown in figure 1, step is 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 Reactive melt blending is carried out in addition double screw extruder and obtains the preliminary depolymerization melt that average degree of polymerization is 20, wherein, gather The mass ratio of ester reclaimed materials and polyester oligomer melt is 0.1:1, catalyst is zinc acetate, with metallic element quality in catalyst Calculated relative to polyester oligomer melt quality, the content of catalyst is 50ppm；The temperature of reactive melt blending is：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) through pipeline A feeding reactors after the filter I filterings that the filtered precision of preliminary depolymerization melt is 100 μm, and with After ethylene glycol mixing alcoholysis reaction 60min, preliminary depolymerization melt are carried out under nitrogen protection, pressurization and stirring condition at 195 DEG C Mass ratio with ethylene glycol is 3:1, the pressure after pressurization is 101KPa, stir speed (S.S.) 35Hz, and stirring is stirred using plate and frame Oar, the depth depolymerization melt that average degree of polymerization is 1.5 is obtained after reaction；

3) vertical reactor is fed by pipeline B after the filter II filterings that the filtered precision of depth depolymerization melt is 1 μm, and By flowing to the bottom of vertical reactor at the top of vertical reactor, during this period, pass through controlling reaction temperature, pressure and oxygen-containing Amount carries out TVOC removing and the reparation of cracking functional group in depth depolymerization melt, and sampling is provided with the bottom of vertical reactor Mouthful, it is 15ppm's that depth depolymerization melt repeats flowing to obtain TVOC contents after sample tap outflow through path same as Example 1 Low TVOC contents polyester oligomer melt, the structure and pressure control path of vertical reactor are the same as embodiment 1；Vertical reactor Temperature is：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 change in the range of 1~80KPa in reactor, cycle 85min, wherein 1KPa pressure are kept Time is 51min；

4) low TVOC contents polyester oligomer melt is continuously fed into twin-screw as the raw material of step 1) via pipeline D and squeezed Go out machine 11, or prepolymerization reaction kettle is fed through pipeline C after the filter III filterings that filtered precision is 2 μm, add catalyst 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 Carry out prepolymerization reaction and obtain the low TVOC contents precondensation polyester fondant that average degree of polymerization is 28；The temperature of prepolymerization reaction For：260 DEG C of upper chamber, lower 265 DEG C of room；Pressure is：Upper chamber 3.0KPa, lower room 1.5KPa；Time is 120min；With low TVOC contents On the basis of the quality of polyester oligomer melt, the addition of catalyst is 200ppm, and the addition of heat stabilizer is 200ppm, second The addition of sour sodium is 200ppm, and the addition of antioxidant is 10pmm；

5) low TVOC contents precondensation polyester fondant is averagely gathered through path same as Example 1 progress final polycondensation reaction It is right be 95 low TVOC contents recycled polyester melt；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：275 DEG C, spinning speed 1000m/min of spinning temperature, 65 DEG C of draft temperature, preliminary draft multiplying power are 1.02, one of draft ratio is 1.8, and two draft ratios are 1.02.

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

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 Reactive melt blending is carried out in addition double screw extruder and obtains the preliminary depolymerization melt that average degree of polymerization is 25, wherein, gather The mass ratio of ester reclaimed materials and polyester oligomer melt is 1.0:1, catalyst is manganese acetate, with metallic element quality in catalyst Calculated relative to polyester oligomer melt quality, the content of catalyst is 150ppm；The temperature of reactive melt blending is：Double spiral shells 266 DEG C of bar feed zone temperature, 285 DEG C of twin-screw compression section, 282 DEG C, time 3min of homogenizing zone temperature, atmosphere is that gauge pressure is 0.1KPa vacuum environment；

3) reactor, and and second are fed through pipeline A after the filter I filterings that the filtered precision of preliminary depolymerization melt is 70 μm Glycol mixing after nitrogen protection, pressurization and stirring condition under 196 DEG C carry out alcoholysis reaction 55min, preliminary depolymerization melt with The mass ratio of ethylene glycol is 3.6:1, the pressure after pressurization is 121KPa, stir speed (S.S.) 55Hz, and stirring is stirred using plate and frame Oar, the depth depolymerization melt that average degree of polymerization is 2.5 is obtained after reaction；

3) vertical reactor is fed by pipeline B after the filter II filterings that the filtered precision of depth depolymerization melt is 8 μm, and By flowing to the bottom of vertical reactor at the top of vertical reactor, during this period, pass through controlling reaction temperature, pressure and oxygen-containing Amount carries out TVOC removing and the reparation of cracking functional group in depth depolymerization melt, and sampling is provided with the bottom of vertical reactor Mouthful, depth depolymerization melt obtains TVOC contents through path same as Example 1 repetition flowing after sample tap outflow and obtained for 15ppm The low TVOC contents 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 is：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 the vertical reactor generating period in the range of 1~80KPa changes, cycle 10min, wherein 1KPa pressure Retention time is 2min；

4) low TVOC contents polyester oligomer melt is continuously fed into twin-screw as the raw material of step 1) via pipeline D and squeezed Go out machine 11, or prepolymerization reaction kettle 20 is fed through pipeline C 3 after the filterings of filter III 19 that filtered precision 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 contents 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 is：260 DEG C of upper chamber, lower 265 DEG C of room；Pressure is：Upper chamber 3.0KPa, lower room 1.5KPa；Time is 120min；On the basis of the quality of low TVOC contents polyester oligomer melt, the addition of catalyst is 200ppm, the addition of heat stabilizer is 200ppm, and the addition of sodium acetate is 200ppm, and the addition 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：275 DEG C, spinning speed 1200m/min of spinning temperature, 70 DEG C of draft temperature, preliminary draft multiplying power are 1.02, one of draft ratio is 2.0, and two draft ratios are 1.02.

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

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 Reactive melt blending is carried out in addition double screw extruder and obtains the preliminary depolymerization melt that average degree of polymerization is 26, wherein, gather The mass ratio of ester reclaimed materials and polyester oligomer melt is 1.5:1, catalyst is titanium ethylene glycolate, with metallic element matter in catalyst Amount calculates relative to polyester oligomer melt quality, and the content of catalyst is 160ppm；The temperature of reactive melt blending is：It is double 267 DEG C of screw feed section temperature, 286 DEG C of twin-screw compression section, 285 DEG C, time 4min of homogenizing zone temperature, atmosphere are nitrogen ring Border；

2) reactor, and and second are fed through pipeline A after the filter I filterings that the filtered precision of preliminary depolymerization melt is 73 μm Glycol mixing after nitrogen protection, pressurization and stirring condition under 198 DEG C carry out alcoholysis reaction 80min, preliminary depolymerization melt with The mass ratio of ethylene glycol is 3.8:1, the pressure after pressurization is 125KPa, stir speed (S.S.) 60Hz, and stirring is stirred using plate and frame Oar, the depth depolymerization melt that average degree of polymerization is 2.5 is obtained after reaction；

3) vertical reactor is fed by pipeline B after the filter II filterings that the filtered precision of depth depolymerization melt is 10 μm, And by flowing to the bottom of vertical reactor at the top of vertical reactor, during this period, by controlling reaction temperature, pressure and contain Oxygen amount carries out TVOC removing and the reparation of cracking functional group in depth depolymerization melt, and sampling is provided with the bottom of vertical reactor Mouthful, it is 12ppm's that depth depolymerization melt repeats flowing to obtain TVOC contents after sample tap outflow through path same as Example 1 Low TVOC contents polyester oligomer melt, the structure and pressure control path of vertical reactor are the same as embodiment 1；Vertical reactor Temperature is：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 change in the range of 1~80KPa in reactor, cycle 80min, wherein 1KPa pressure are kept Time is 44min；

4) low TVOC contents polyester oligomer melt is continuously fed into twin-screw as the raw material of step 1) via pipeline D and squeezed Go out machine 11, or prepolymerization reaction kettle is fed through pipeline C after the filter III filterings that filtered precision is 2 μm, add catalyst 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 two phosphorous Prepolymerization reaction is carried out after the sour different certain herbaceous plants with big flowers ester of pentaerythritol ester two and obtains the low TVOC contents precondensation polyester that average degree of polymerization is 25 Melt；The temperature of prepolymerization reaction is：260 DEG C of upper chamber, lower 265 DEG C of room；Pressure is：Upper chamber 3.0KPa, lower room 1.0KPa；Time For 90min；On the basis of the quality of low TVOC contents polyester oligomer melt, the addition of catalyst is 300ppm, thermostabilization The addition of agent is 100ppm, and the addition of sodium acetate is 50ppm, and the addition of antioxidant is 10pmm；

5) low TVOC contents precondensation polyester fondant is averagely gathered through path same as Example 1 progress final polycondensation reaction It is right be 100 low TVOC contents recycled polyester melt；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：290 DEG C, spinning speed 1150m/min of spinning temperature, 68 DEG C of draft temperature, preliminary draft multiplying power are 1.07, one of draft ratio is 1.8, and two draft ratios are 1.07.

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

Embodiment 9

2) reactor is fed after the filter I 12 that the filtered precision of preliminary depolymerization melt is 100 μm is filtered through pipeline A 1 13, and carry out alcoholysis reaction 60min, preliminary solution after being mixed with ethylene glycol at 195 DEG C under nitrogen protection, pressurization and stirring condition The mass ratio of poly- melt and ethylene glycol is 3:1, the pressure after pressurization is 101KPa, stir speed (S.S.) 35Hz, and stirring uses sheet frame Formula agitating paddle, the depth depolymerization melt that average degree of polymerization is 1.5 is obtained after reaction；

3) vertical reactor is fed by pipeline B after the filter II filterings that the filtered precision of depth depolymerization melt is 2 μm, and By flowing to the bottom of vertical reactor at the top of vertical reactor, during this period, pass through controlling reaction temperature, pressure and oxygen-containing Amount carries out TVOC removing and the reparation of cracking functional group in depth depolymerization melt, and sampling is provided with the bottom of vertical reactor Mouthful, it is 12ppm's that depth depolymerization melt repeats flowing to obtain TVOC contents after sample tap outflow through path same as Example 1 Low TVOC contents polyester oligomer melt, the structure and pressure control path of vertical reactor are the same as embodiment 1；Vertical reactor Temperature is：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 change in the range of 1~80KPa in reactor, cycle 85min, wherein 1KPa pressure are kept Time is 51min；

4) low TVOC contents polyester oligomer melt is continuously fed into twin-screw as the raw material of step 1) via pipeline D and squeezed Go out machine 11, or prepolymerization reaction kettle is fed through pipeline C after the filter III filterings that filtered precision is 2 μm, add catalyst 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 (2.4- di-tert-butyl-phenyls) pentaerythritol diphosphites and three (2,4- di-t-butyls) phenyl-phosphite (mass ratioes 1：1) after Carry out prepolymerization reaction and obtain the low TVOC contents precondensation polyester fondant that average degree of polymerization is 28；The temperature of prepolymerization reaction For：260 DEG C of upper chamber, lower 265 DEG C of room；Pressure is：Upper chamber 3.0KPa, lower room 1.0KPa；Time is 120min；With low TVOC contents On the basis of the quality of polyester oligomer melt, the addition of catalyst is 280ppm, and the addition of heat stabilizer is 100ppm, second The addition of sour sodium is 50ppm, and the addition 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：288 DEG C, spinning speed 1120m/min of spinning temperature, 72 DEG C of draft temperature, preliminary draft multiplying power are 1.08, one of draft ratio is 2.5, and two draft ratios are 1.07.

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

Embodiment 10

3) vertical reactor is fed by pipeline B after the filter II filterings that the filtered precision of depth depolymerization melt is 10 μm, And by flowing to the bottom of vertical reactor at the top of vertical reactor, during this period, by controlling reaction temperature, pressure and contain Oxygen amount carries out TVOC removing and the reparation of cracking functional group in depth depolymerization melt, and sampling is provided with the bottom of vertical reactor Mouthful, it is 10ppm's that depth depolymerization melt repeats flowing to obtain TVOC contents after sample tap outflow through path same as Example 1 Low TVOC contents polyester oligomer melt, the structure and pressure control path of vertical reactor are the same as embodiment 1；Vertical reactor Temperature is：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 change in the range of 1~80KPa in reactor, cycle 90min, wherein 1KPa pressure are kept Time is 59min；

4) low TVOC contents polyester oligomer melt is continuously fed into twin-screw as the raw material of step 1) via pipeline D and squeezed Go out machine 11, or prepolymerization reaction kettle is fed through pipeline C after the filter III filterings that filtered precision is 1 μm, add catalyst 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-butyls) phenyl-phosphite (mass ratio 1:1) prepolymerization reaction is carried out afterwards obtain the low TVOC that average degree of polymerization is 30 Content precondensation polyester fondant；The temperature of prepolymerization reaction is：260 DEG C of upper chamber, lower 265 DEG C of room；Pressure is：Upper chamber 3.0KPa, Lower room 1.0KPa；Time is 70min；On the basis of the quality of low TVOC contents polyester oligomer melt, the addition of catalyst For 100ppm, the addition of heat stabilizer is 200ppm, and the addition of sodium acetate is 50ppm, and the addition of antioxidant is 20pmm；

5) low TVOC contents precondensation polyester fondant is averagely gathered through path same as Example 1 progress final polycondensation reaction It is right be 110 low TVOC contents recycled polyester melt；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：295 DEG C, spinning speed 1500m/min of spinning temperature, 75 DEG C of draft temperature, preliminary draft multiplying power are 1.08, one of draft ratio is 2.25, and two draft ratios are 1.08.

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

Embodiment 11

3) vertical reactor is fed by pipeline B after the filter II filterings that the filtered precision of depth depolymerization melt is 8 μm, and By flowing to the bottom of vertical reactor at the top of vertical reactor, during this period, pass through controlling reaction temperature, pressure and oxygen-containing Amount carries out TVOC removing and the reparation of cracking functional group in depth depolymerization melt, and sampling is provided with the bottom of vertical reactor Mouthful, it is 12ppm's that depth depolymerization melt repeats flowing to obtain TVOC contents after sample tap outflow through path same as Example 1 Low TVOC contents polyester oligomer melt, the structure and pressure control path of vertical reactor are the same as embodiment 1；Vertical reactor Temperature is：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 change in the range of 1~80KPa in reactor, cycle 95min, wherein 1KPa pressure are kept Time is 63min；

4) low TVOC contents polyester oligomer melt is continuously fed into twin-screw as the raw material of step 1) via pipeline D and squeezed Go out machine 11, or prepolymerization reaction kettle is fed through pipeline C after the filter III filterings that filtered precision is 1 μm, add catalyst 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 Carry out prepolymerization reaction and obtain the low TVOC contents precondensation polyester fondant that average degree of polymerization is 30；The temperature of prepolymerization reaction For：260 DEG C of upper chamber, lower 265 DEG C of room；Pressure is：Upper chamber 3.0KPa, lower room 1.0KPa；Time is 90min；With low TVOC contents On the basis of the quality of polyester oligomer melt, the addition of catalyst is 120ppm, and the addition of heat stabilizer is 200ppm, second The addition of sour sodium is 50ppm, and the addition of antioxidant is 20pmm；

5) low TVOC contents precondensation polyester fondant is averagely gathered through path same as Example 1 progress final polycondensation reaction It is right be 100 low TVOC contents recycled polyester melt；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：288 DEG C, spinning speed 1300m/min of spinning temperature, 776 DEG C of draft temperature, preliminary draft multiplying power are 1.10, one of draft ratio is 2.3, and two draft ratios are 1.08.

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

Embodiment 12

3) vertical reactor is fed by pipeline B after the filter II filterings that the filtered precision of depth depolymerization melt is 12 μm, And by flowing to the bottom of vertical reactor at the top of vertical reactor, during this period, by controlling reaction temperature, pressure and contain Oxygen amount carries out TVOC removing and the reparation of cracking functional group in depth depolymerization melt, and sampling is provided with the bottom of vertical reactor Mouthful, it is 13ppm's that depth depolymerization melt repeats flowing to obtain TVOC contents after sample tap outflow through path same as Example 1 Low TVOC contents polyester oligomer melt, the structure and pressure control path of vertical reactor are the same as embodiment 1；Vertical reactor Temperature is：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 change in the range of 1~80KPa in reactor, cycle 100min, wherein 1KPa pressure are protected It is 75min to hold the time；

4) low TVOC contents polyester oligomer melt is continuously fed into twin-screw as the raw material of step 1) via pipeline D and squeezed Go out machine 11, or prepolymerization reaction kettle is fed through pipeline C after the filter III filterings that filtered precision is 1 μm, add catalyst Ethylene glycol sodium titanate, two different certain herbaceous plants with big flowers of heat stabilizer ammonium dihydrogen phosphate, anti-ether agent sodium acetate and antioxidant pentaerythritol diphosphite Prepolymerization reaction is carried out after ester and obtains the low TVOC contents precondensation polyester fondant that average degree of polymerization is 30；The temperature of prepolymerization reaction Spend and be：260 DEG C of upper chamber, lower 270 DEG C of room；Pressure is：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 addition of catalyst is 100ppm, and the addition of heat stabilizer is 100ppm, The addition of sodium acetate is 50ppm, and the addition of antioxidant is 20pmm；

5) low TVOC contents precondensation polyester fondant is averagely gathered through path same as Example 1 progress final polycondensation reaction It is right be 105 low TVOC contents recycled polyester melt；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：288 DEG C, spinning speed 1300m/min of spinning temperature, 78 DEG C of draft temperature, preliminary draft multiplying power are 1.09, one of draft ratio is 2.5, and two draft ratios are 1.09.

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

Embodiment 13

3) vertical reactor is fed by pipeline B after the filter II filterings that the filtered precision of depth depolymerization melt is 10 μm, And by flowing to the bottom of vertical reactor at the top of vertical reactor, during this period, by controlling reaction temperature, pressure and contain Oxygen amount carries out TVOC removing and the reparation of cracking functional group in depth depolymerization melt, and sampling is provided with the bottom of vertical reactor Mouthful, it is 10ppm's that depth depolymerization melt repeats flowing to obtain TVOC contents after sample tap outflow through path same as Example 1 Low TVOC contents polyester oligomer melt, the structure and pressure control path of vertical reactor are the same as embodiment 1；Vertical reactor Temperature is：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 change in the range of 1~80KPa in reactor, cycle 110min, wherein 1KPa pressure are protected It is 88min to hold the time；

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

5) low TVOC contents precondensation polyester fondant is averagely gathered through path same as Example 1 progress final polycondensation reaction It is right be 110 low TVOC contents recycled polyester melt；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：292 DEG C, spinning speed 1400m/min of spinning temperature, 80 DEG C of draft temperature, preliminary draft multiplying power are 1.09, one of draft ratio is 2.5, and two draft ratios are 1.1.

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

Embodiment 14

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

2) reactor is fed after the filter I 12 that the filtered precision of preliminary depolymerization melt is 50 μm is filtered through pipeline A 1 13, and carry out alcoholysis reaction 60min, preliminary solution after being mixed with ethylene glycol at 195 DEG C under nitrogen protection, pressurization and stirring condition The mass ratio of poly- melt and ethylene glycol is 3:1, the pressure after pressurization is 101KPa, stir speed (S.S.) 35Hz, and stirring uses sheet frame Formula agitating paddle, the depth depolymerization melt that average degree of polymerization is 1.5 is obtained after reaction；

3) vertical reactor is fed by pipeline B after the filter II filterings that the filtered precision of depth depolymerization melt is 10 μm, And by flowing to the bottom of vertical reactor at the top of vertical reactor, during this period, by controlling reaction temperature, pressure and contain Oxygen amount carries out TVOC removing and the reparation of cracking functional group in depth depolymerization melt, and sampling is provided with the bottom of vertical reactor Mouthful, it is 8ppm's that depth depolymerization melt repeats flowing to obtain TVOC contents from path same as Example 1 after sample tap outflow TVOC content polyester oligomer melts, the structure and pressure control path of vertical reactor are the same as embodiment 1；The temperature of vertical reactor Spend and be：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% The generating period in the range of 1~80KPa of the pressure in device is answered to change, cycle 105min, wherein 1KPa pressure are kept Time is 89min；

4) low TVOC contents polyester oligomer melt is continuously fed into twin-screw as the raw material of step 1) via pipeline D and squeezed Go out machine 11, or prepolymerization reaction kettle is fed through pipeline C after the filter III filterings that filtered precision is 2 μm, add catalyst 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 Carry out prepolymerization reaction and obtain the low TVOC contents precondensation polyester fondant that average degree of polymerization is 30；The temperature of prepolymerization reaction For：260 DEG C of upper chamber, lower 270 DEG C of room；Pressure is：Upper chamber 3.0KPa, lower room 1.0KPa；Time is 120min；With low TVOC contents On the basis of the quality of polyester oligomer melt, the addition of catalyst is 100ppm, and the addition of heat stabilizer is 200ppm, second The addition of sour sodium is 100ppm, and the addition 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 be：290 DEG C, spinning speed 1500m/min of spinning temperature, 75 DEG C of draft temperature, preliminary draft multiplying power are 1.1, one Road draft ratio is 2.5, and two draft ratios are 1.1.

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

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 Reactive melt blending is carried out in addition double screw extruder and obtains the preliminary depolymerization melt that average degree of polymerization is 20, wherein, gather The mass ratio of ester reclaimed materials and polyester oligomer melt is 0.1:1, catalyst is zinc acetate and titanium ethylene glycolate (mass ratio 1:1), 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 is：265 DEG C of twin-screw feed zone temperature, 275 DEG C of twin-screw compression section, 275 DEG C of homogenizing zone temperature, time For 4min, atmosphere is nitrogen；

2) reactor, and and second are fed through pipeline A after the filter I filterings that the filtered precision of preliminary depolymerization melt is 50 μm Glycol mixing after nitrogen protection, pressurization and stirring condition under 195 DEG C carry out alcoholysis reaction 60min, preliminary depolymerization melt with The mass ratio of ethylene glycol is 3:1, the pressure after pressurization is 101KPa, stir speed (S.S.) 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) vertical reactor is fed by pipeline B after the filter II filterings that the filtered precision of depth depolymerization melt is 2 μm, and By flowing to the bottom of vertical reactor at the top of vertical reactor, during this period, pass through controlling reaction temperature, pressure and oxygen-containing Amount carries out TVOC removing and the reparation of cracking functional group in depth depolymerization melt, and sampling is provided with the bottom of vertical reactor Mouthful, it is the low of 12ppm that depth depolymerization melt repeats flowing to obtain TVOC contents from path same as Example 1 after sample tap outflow TVOC content polyester oligomer melts, the structure and pressure control path of vertical reactor are the same as embodiment 1；The temperature of vertical reactor Spend and be：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% The generating period in 1~80KPa of the pressure in device is answered to change, cycle 115min, wherein 1KPa pressure hold time are 103.5min；

4) low TVOC contents polyester oligomer melt is continuously fed into twin-screw as the raw material of step 1) via pipeline D and squeezed Go out machine 11, or prepolymerization reaction kettle is fed through pipeline C after the filter III filterings that filtered precision is 2 μm, add catalyst 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 contents precondensation polyester fondant that average degree of polymerization is 30；Temperature is：260 DEG C of upper chamber, lower room 270℃；Pressure is：Upper chamber 3.0KPa, lower room 1.0KPa；The time of prepolymerization reaction is 120min；Weight polyester is contained with low TVOC On the basis of the quality of oligomer melt, the addition of catalyst is 80ppm, and the addition of heat stabilizer is 200ppm, sodium acetate Addition be 100ppm, the addition of antioxidant is 20pmm；

5) low TVOC contents precondensation polyester fondant is averagely gathered through path same as Example 1 progress final polycondensation reaction It is right be 110 low TVOC contents recycled polyester melt；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：288 DEG C, spinning speed 1500m/min of spinning temperature, 80 DEG C of draft temperature, preliminary draft multiplying power are 1.1, one of draft ratio is 2.5, and two draft ratios are 1.1.

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

Claims

1. a kind of preparation method of coloured regenerative polyester staple fiber, it is characterized in that, step is as follows：

1) it is 20~40 to carry out reactive melt blending to obtain average degree of polymerization by polyester reclaiming material and polyester oligomer melt Preliminary depolymerization melt, the average degree of polymerization of the polyester oligomer melt is 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 being mixed with ethylene glycol Melt；

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

6) the form and aspect data of low TVOC contents recycled polyester melt are obtained, target form and aspect institute is obtained by computer for colouring system-computed The color masterbatch species and dosage needed, and convey corresponding melt and obtain coloured regeneration with low TVOC contents recycled polyester melt mixed and gather Ester melt；

A kind of 2. preparation method of coloured regenerative polyester staple fiber according to claim 1, it is characterised in that the TVOC Removing and the reparation of cracking functional group carried out in vertical reactor, the vertical reactor is that grid falls membrane type devolatilization Reactor, bleeding point are located at reactor head, and internal cell structure is：By the different screen layer structures with parallel angle bead Into the direction of angle bead is mutually perpendicular on adjacent gate flaggy, top to the bottom of self-supporting reactor, the interlamellar spacing of adjacent gate flaggy Gradually increase, the gap of angle bead is gradually reduced on different screen layers.

3. the preparation method of a kind of coloured regenerative polyester staple fiber according to claim 2, it is characterised 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, 1KPa pressure hold time accounts for the 20%~90% of cycle time length, and the depth depolymerization melt exists Residence time in vertical reactor is 10min~2h, the oxygen content in the vertical reactor<0.03v/v%.

A kind of 4. preparation method of coloured regenerative polyester staple fiber according to claim 3, it is characterised in that specific steps It is as follows：

1) it will add in double screw extruder and carry out by fully dry polyester reclaiming material, catalyst and polyester oligomer melt Reactive melt blending obtains preliminary depolymerization melt；The temperature of the reactive melt blending is：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<0.15KPa vacuum environment；

2) preliminary depolymerization melt feeds reactor after filter I filterings through pipeline A, and is protected after being mixed 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 after filter II filterings by pipeline B, and by the top of vertical reactor The bottom of vertical reactor is flowed to, sample tap is provided with the bottom of vertical reactor, depth depolymerization melt flows out from sample tap Low TVOC contents polyester oligomer melt is obtained by by carrying out repetition flowing at the top of pipeline D Returning reactors；

The control of pressure is by constantly supplementing ethylene glycol simultaneously from vertical anti-from the bottom of vertical reactor in vertical reactor Answer and gas realization is detached at the top of device, the bottom of vertical reactor keeps communicating by pipeline F and ethylene glycol storage tank II, extracts out Gas G is condensed by condenser by the road, finally reclaimed by ethylene glycol storage tank I, ethylene glycol storage tank I passes through pipeline E respectively Connected with pipeline H with ethylene glycol storage tank II and reactor；

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

5) low TVOC contents precondensation polyester fondant is delivered to progress final polycondensation reaction in final polycondensation reaction kettle via pipeline I and obtained Average degree of polymerization is 95~110 low TVOC contents recycled polyester melt；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 contents recycled polyester melt are carried out on pipeline J, by computer for colouring System-computed obtains the color masterbatch species 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 mixeds obtain coloured recycled polyester melt；

7) coloured regenerative polyester staple fiber, spinning work is made into fused mass directly spinning system via pipeline J in coloured recycled polyester melt Skill is：Melt conveying → spinning → cooling → winding falling-barrel → seal wire → one of drawing-off → bis- drawing-offs → thermal finalization → curling is cut Disconnected packing；Spinning technology parameter is：270~290 DEG C, 800~1500m/min of spinning speed of spinning temperature, 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.

A kind of 5. preparation method of coloured regenerative polyester staple fiber according to claim 4, it is characterised in that step 1) In, it is described to refer to moisture content by fully dry polyester reclaiming material<100ppm 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 Calculate, the content of catalyst is 10~300ppm；

A kind of 6. preparation method of coloured regenerative polyester staple fiber according to claim 4, it is characterised 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 Speed is 35~75Hz, and stirring uses plate and frame agitating paddle.

A kind of 7. preparation method of coloured regenerative polyester staple fiber according to claim 4, it is characterised 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 contents polyester oligomer melt On the basis of, the addition of catalyst is 10~300ppm；

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

The heat stabilizer is trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite, Asia In diphenyl phosphate, ammonium phosphite, ammonium dihydrogen phosphate, phosphoric acid, phosphorous acid, ortho phosphorous acid, pyrophosphoric acid and ammonium phosphate it is a kind of with On, on the basis of the quality of low TVOC contents polyester oligomer melt, the addition of heat stabilizer is 50~200ppm；

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

A kind of 8. preparation method of coloured regenerative polyester staple fiber according to claim 4, it is characterised in that filter I, Filter II and filter III filtering accuracy are respectively 50~100 μm, 1~15 μm and 1~15 μm.

9. using coloured regenerative polyester staple fiber, its feature made from the preparation method as described in any one of claim 1~8 It is：The fiber number of coloured regenerative polyester staple fiber is 1.1~5.5dtex, and length is 30~50mm, the coloured short fibre of recycled polyester The aberration grade of dimension is 4-5 levels, and color fastness is 4-5 levels, and TVOC contents are 30~300ppm, nonyl phenol and its isomer Content is 80~200ppm.

10. coloured regenerative polyester staple fiber according to claim 9, it is characterised in that the coloured short fibre of recycled polyester The fracture strength of dimension is 2.8~4.8cN/dtex, and elongation at break is 22.0~65.0%, line density deviation ratio is 6.0~ 8.0%.