CN105504696B - A kind of composite polyester material, preparation method and purposes - Google Patents

A kind of composite polyester material, preparation method and purposes Download PDF

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Publication number
CN105504696B
CN105504696B CN201510705758.XA CN201510705758A CN105504696B CN 105504696 B CN105504696 B CN 105504696B CN 201510705758 A CN201510705758 A CN 201510705758A CN 105504696 B CN105504696 B CN 105504696B
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carbon nano
compound
carbon
polyester
structured compound
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CN201510705758.XA
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CN105504696A (en
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唐林
唐一林
张金柱
张安
栾峰
刘顶
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济南圣泉集团股份有限公司
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Abstract

The present invention relates to a kind of composite polyester material, carbon nano-structured compound is contained in the polyester material;The carbon nano-structured compound contains the second non-carbon nonoxygen element of carbon, 0.5~4wt% the first non-carbon nonoxygen element material and 0~4wt%, and the first non-carbon nonoxygen element is P, Si, Ca, Al and Na;Any a kind or at least two kinds of of combination of the second non-carbon nonoxygen element in Fe, Ni, Mn, K, Mg, Cr, S or Co;The carbon nano-structured compound carbon G peaks and D peaks peak height ratios under Raman spectrum are 1~20.The present invention carrys out composite polyester material, obtains the performance with more excellent antibacterial and Low Temperature Far Infrared by selecting specific carbon nano-structured compound;The compound polyester material preparation method of carbon nano-structured compound provided by the invention is simple.

Description

A kind of composite polyester material, preparation method and purposes

Technical field

The invention belongs to polymeric material field, and in particular to a kind of composite polyester material, preparation method and purposes, especially It is related to a kind of carbon nano-structured compound compound polyester material, preparation method and purposes.

Background technology

Polyester, the polymer general name as obtained by polyalcohol and polyacid polycondensation.Refer mainly to PET (PET) linear thermoplastic's resins such as polybutylene terephthalate (PBT) and polyarylate, are traditionally also included.It is a kind of performance Excellent, widely used engineering plastics.It may be made as polyester fiber and polyester film.Polyester includes polyester resin and polyester Body.Polyester resin includes PET (PET), polybutylene terephthalate (PBT) and polyarylate (PAR) again Deng.Polyester elastomer (TPEE) is typically polymerized by dimethyl terephthalate (DMT), BDO and poly- butanol, and segment includes Hard section part and soft segment part, it is thermoplastic elastomer (TPE).

Carbon nanomaterial refers to the dispersed phase yardstick at least one-dimensional carbon material less than 100nm, such as CNT, graphite Alkene etc..Graphene is a kind of two-dimensional material for the alveolate texture being made up of individual layer sp2 hydbridized carbon atoms, is had many excellent Performance.It has been found since 2004, graphene just becomes a big study hotspot of scientific circles, to the physico of graphene While property is studied, the composite related to graphene emerges in an endless stream.On nano science direction, graphene It is used to prepare the nano combined material of the nano composite material, especially graphene/metal or graphene/metal oxide of correlation Material.Due to the excellent properties of graphene, these nano composite materials are led in novel energy, bio-sensing, catalysis, optical material etc. There are wide Research Prospects in domain.

CN104630928A discloses a kind of preparation method for strengthening fire-retardant regenerative polyester staple fiber based on graphene, including Following steps:The preparation of graphene master batch;The preparation of phosphorus series non-halogen fire-retardant master granule;Weigh graphene master batch and phosphorus series non-halogen is fire-retardant Master batch carries out combination drying with recycled polyester raw material;Melt warp after dried raw material melts under screw extruder effect is molten Body, which is pumped in homogeneous removal of impurities agitator, to carry out uniforming removal of impurities processing;Polyester fondant after homogeneous removal of impurities is pumped to two through melt Level filter, enters spinning manifold after the configured blend melt on pipeline of melt after filtering;Fiber after spinning is entered Row drawing-off is processed, and produces the fire-retardant Regenerated Polyester Fibres of enhancing;Tow is cut off, packaging.Strengthen fire-retardant recycled polyester slice spinning into Type is good, and fiber quality is excellent;The graphene of use can produce synergy with phosphorus flame retardant, can effectively reduce the use of fire retardant Amount, so as to reduce cost, can play humidification, can effectively improve fibrous mechanical property in addition.

But the compound polyester material of graphene disclosed in prior art, purpose are mostly that its prominent fire-retardant or raising mechanics is strong Degree, rarely have report for work its it is compound after antibacterial and far-infrared effect.

CN103938293A discloses a kind of far-infrared polyester fiber and preparation method thereof, the original of the far-infrared polyester fiber Material includes according to parts by weight configuration:15~35 parts of 65~85 parts of polyester slice and far-infrared matrix, the far-infrared matrix Raw material includes according to parts by weight configuration:75~90 parts of polyester slice, 10~20 parts of nano-far-infrared powder, silane coupler 0.5~5 part, 0.5~5 part of Tissuemat E, three 0.05~1 part of [2.4- di-tert-butyl-phenyls] phosphite esters and four [β-(3,5- bis- Tert-butyl-hydroxy phenyl) propionic acid] 0.05~1 part of pentaerythritol ester.

CN1308148A discloses a kind of far infrared radiating hollow 3-D crimped polyester fiber and preparation method thereof, by 0.3 ~0.5 μm of composite inorganic far infrared super-fine material, high-speed stirring is together added to titante coupling agent and surfactant Progress dry surface processing, the super-fine material powder after surface treatment in machine is mixed to mix in high-speed mixer with polyester support, Obtained mixed powder is sent to blending extrusion in double screw extruder, its operating temperature is more conventional make Masterbatch temperature it is low 10~ 30 DEG C, far-infrared matrix obtained above and polyester slice are delivered into blender through feeder charging and mixed, is then sent to The extruder type spinning machine for making hollow 3-D crimped fiber carries out spinning, and the finished product finally obtained is that Far-infrared spoke of the present invention is hit Empty 3-D crimped polyester fiber.A variety of far infrared inorganic material, its fundamental component are silica, alundum (Al2O3), two The mixture of titanium oxide, zirconium dioxide, is crushed with superfine jet mill, its particle diameter is crushed at 0.3-0.5 μm, after crushing Far infrared inorganic material powder be placed in high temperature furnace and sinter, sintering temperature is 800-1100 DEG C, crushes, makes again after sintering cooling Particle diameter still controls and at 0.3-0.5 μm, obtains 0.3-0.5 μm of composite inorganic far infrared super-fine material.

The content of the invention

The present invention is solution problem above, it is an object of the present invention to provide a kind of composite polyester material, the polyester Contain carbon nano-structured compound in material;

The carbon nano-structured compound contains carbon, 0.5~4wt% the first non-carbon nonoxygen element material and 0 ~4wt% the second non-carbon nonoxygen element, the first non-carbon nonoxygen element material are the simple substance of the first non-carbon nonoxygen element, changed Any a kind or at least two kinds of of combination in compound;The first non-carbon nonoxygen element is P, Si, Ca, Al and Na;Described second Non-carbon nonoxygen element exists in the form of any a kind or at least two kinds of in simple substance, compound of combination;Second non-carbon is non- Any a kind or at least two kinds of of combination of the oxygen element in Fe, Ni, Mn, K, Mg, Cr, S or Co;

The carbon nano-structured compound carbon G peaks and D peaks peak height ratios under Raman spectrum are 1~20, such as 2nd, 5,7,8,10,12,13,16,18 etc.;Alternatively, under Raman spectrum also there is 2D peaks in the carbon nano-structured compound;

The carbon nano-structured compound far infrared detection normal emittance be more than 0.85, such as 0.87,0.89, 0.91st, 0.92,0.93 etc.;Preferably, the far infrared detection normal emittance of carbon nano-structured compound is more than 0.88.

Carbon G peaks embody sp2 hydridization degree under Raman spectrum;D peaks embody lattice defect, such as sp3 carbon knot Structure;2D peaks embody graphene film thickness degree.

Carbon nano-structured compound of the present invention is a kind of compound containing impurity element based on carbon, Wherein carbon mainly exists in the form of sp2 hydridization.

The present invention from specific carbon nano-structured compound as compound material, it is compound with polyester material, it is exemplary Complex method can use in-situ polymerization, melting mixing or solution mixing in any a kind, it is preferred that without to carbon nanometer The compound of structure is modified, it is only necessary to the polymerized monomer of polyester material and carbon nano-structured compound is simply mixed, or Polyester material and carbon nano-structured compound is simply mixed in person.

In the carbon nano-structured compound, content >=80wt% of the carbon, such as 82wt%, 86wt%, 89wt%, 91wt%, 94wt%, 97wt%, 99wt% etc., preferably 85~97wt%, further preferred 90~95wt%.

Preferably, carbon nano-structured compound carbon G peaks and D peaks peak height ratios under Raman spectrum be 2~ 20, preferably 3~20.

Preferably, carbon nano-structured compound has hexatomic ring cellular lamella knot of the thickness in below 100nm carbon Structure, preferably with thickness below 20nm carbon the cellular lamellar structure of hexatomic ring, further preferably have the number of plies be 1~10 Any a kind or at least two kinds of of combination in the cellular lamellar structure of hexatomic ring of layer carbon, preferred single layer, bilayer or 3~10 layers of knot Any a kind or at least two kinds of of combination in structure.

The number of plies is more than 10 layers, the thickness cellular lamellar structure of the hexatomic ring of carbon, referred to as graphene nanometer sheet within 100nm Layer, using biomass be the number of plies for preparing of carbon source more than 10 layers, thickness cellular lamellar structure of the hexatomic ring of carbon within 100nm, Referred to as biomass graphene nano lamella;The number of plies is the cellular lamellar structure of hexatomic ring of 1~10 layer of carbon, referred to as graphene, with Biomass is the cellular lamellar structure of hexatomic ring that the number of plies prepared by carbon source is 1~10 layer of carbon, referred to as biomass graphene.

Preferably, the microcosmic upper presentation warpage of the cellular lamellar structure of hexatomic ring of carbon, curling, folding structure in the compound Any a kind or at least two kinds of of the combination as in.

Microscopic appearance on the lamellar structure in compound can typically be obtained by electron microscope observation, can be with It is transmission electron microscope or ESEM.

Preferably, in the carbon nano-structured compound, the first non-carbon nonoxygen element is with simple substance, oxide or carbide In any a kind or at least two kinds of of combination form adsorb on carbon nano-structured surface or inside.

Preferably, in the carbon nano-structured compound, the first non-carbon nonoxygen element is introduced by carbon source;The carbon source It is preferred that biomass carbon source, any a kind or at least two kinds of of combination of the biomass resource in plant and/or agriculture and forestry organic waste material;It is excellent Select any a kind or at least two kinds of of combination in needlebush, leaf wood, Lin Yemu, agriculture and forestry organic waste material;The agriculture and forestry organic waste material is excellent In cornstalk, corncob, kaoliang stalk, megasse, bagasse, furfural dregs, xylose residue, wood chip, cotton stalk, shell and reed Any a kind or at least two kinds of of combination, preferred corncob.

Preferably, in the composite polyester material, the content of carbon nano-structured compound is 0.1~10wt%, such as 0.2wt%, 1wt%, 3wt%, 4wt%, 6wt%, 8wt%, 9wt% etc., preferably 0.5~7wt%, further preferred 1~ 5wt%, particularly preferred 2~4wt%.

Preferably, the far infrared detection normal emittance of the carbon nano-structured compound is more than 0.88.

The present invention is not specifically limited to the species of polyester, and typical but non-limiting polyester includes poly terephthalic acid second It is diester, polybutylene terephthalate (PBT), polytrimethylene terephthalate, polycyclohexane terephthalate, poly- 2,6- naphthalenes diacid second diester and the PET of a variety of modifications are (such as:CDP, ECDP, EDDP) etc., Ren Heyi The polyester that kind those skilled in the art can be known is used equally for the present invention;Preferably industrial mass production PET polyester of the invention.

The two of the object of the invention are to provide a kind of preparation method of the composite polyester material as described in the first purpose, methods described For:Polyester material is melted, then adds carbon nano-structured compound thereto, is obtained after cooling multiple as described in the first purpose Close polyester material;Preferably, carbon nano-structured compound need not be modified.

Preferably, the addition of the carbon nano-structured compound is 0.1~10wt% of polyester material, such as 0.2wt%, 1wt%, 3wt%, 4wt%, 6wt%, 8wt%, 9wt% etc., preferably 0.5~7wt%, further preferred 1~ 5wt%, particularly preferred 2~4wt%.

The three of the object of the invention are to provide the preparation method of second of composite polyester material as described in the first purpose, the side Method is:Polyester material is dissolved in solvent, then adds carbon nano-structured compound thereto, remove obtain after solvent as Composite polyester material described in the first purpose;Preferably, carbon nano-structured compound need not be modified.

Preferably, the addition of the carbon nano-structured compound is 0.1~10wt% of polyester material, such as 0.2wt%, 1wt%, 3wt%, 4wt%, 6wt%, 8wt%, 9wt% etc., preferably 0.5~7wt%, further preferred 1~ 5wt%, particularly preferred 2~4wt%.

Preferably, the solvent is any a kind in fluoroacetic acid, the mixed solution of phenol and tetrachloroethanes, tetrahydrofuran Or at least two kinds of combination;The typical but non-limiting combination including fluoroacetic acid and phenol of combination, phenol and tetrachloroethanes Mixed solution and tetrahydrofuran combination, the combination of fluoroacetic acid and tetrahydrofuran etc..

Preferably, the mode for removing solvent is distillation.

The four of the object of the invention are to provide the preparation method of the third composite polyester material as described in the first purpose, the side Method comprises the following steps:

Carbon nano-structured compound is introduced in polyester material polymerization process and carries out In-situ reaction, reaction, which finishes, is melted Body, melt discharge to obtain the composite polyester material as described in the first purpose;Preferably, carbon nano-structured compound need not be changed Property.

Preferably, the addition of the carbon nano-structured compound is 0.1~10wt% of polyester material, such as 0.2wt%, 1wt%, 3wt%, 4wt%, 6wt%, 8wt%, 9wt% etc..

Preferably, the carbon nano-structured compound is added in the form of carbon nano-structured compound dry powder, or Added in the form of carbon nano-structured compound dispersion liquid.

Preferably, the dispersant of the carbon nano-structured compound dispersion liquid be selected from deionized water, distilled water, ethanol, Any a kind in ethylene glycol, terephthalic acid (TPA), sodium acetate solution, DBSA, castor oil polyoxyethylene ether or at least 2 kinds of combination.

Preferably, the opportunity for introducing carbon nano-structured compound is selected from the raw material pulping stage, is esterified prepolymerisation stage, is pre- Any a kind or at least two kinds of of combination in polycondensation phase, whole polycondensation phase, preferably raw material pulping stage.

Preferably, the condition of the melt discharging is:In 20~75 DEG C of cooling waters, the condition of 0.01~1m/s draft speeds Bottom discharge.

As the optimal technical scheme of the fourth purpose, the preparation method of composite polyester material of the present invention includes following step Suddenly:

(1) reactor is put into after the mashing of polyacid, polyalcohol and carbon nano-structured compound is mixed, afterwards by ester Change prepolymerisation stage, precondensation stage, whole polycondensation phase and complete polymerisation, obtain melt;

(2) melt discharges under conditions of 20~75 DEG C of cooling waters, 0.01~1m/s draft speeds, is directly granulated and obtains mesh One of the composite polyester material.

In the preparation method for the composite polyester material that one of the object of the invention, the second purpose and the third purpose provide, institute Carbon nano-structured compound is stated to obtain by the following method:

(i) mixing biomass carbon source and catalyst, after stirring carries out catalytic treatment, it is dried to obtain presoma;

(ii) in protective atmosphere, by presoma at 280~350 DEG C, such as 282 DEG C, 288 DEG C, 295 DEG C, 300 DEG C, 332 DEG C, 340 DEG C etc., be incubated 1.5~2.5h, such as 1.6h, 1.8h, 2h, 2.2h, 2.4h etc., temperature programming afterwards to 950~1050 DEG C, such as 960 DEG C, 970 DEG C, 980 DEG C, 990 DEG C, 1010 DEG C, 1020 DEG C, 1030 DEG C, 1040 DEG C etc., 3~4h is incubated, such as 3.1h, 3.3h, 3.5h, 3.8h, 3.9h etc., obtain crude product;The heating rate of described program heating is 15~20 DEG C/min, such as 16 DEG C/min, 18 DEG C/min, 19 DEG C/min etc.;

(iii) after crude product is washed, carbon nano-structured compound is obtained.

Preferably, the mass ratio of the biomass carbon source and catalyst is 1:0.1~10, such as 1:2、1:4、1:6、1:8 Deng preferably 1:0.5~5, further preferred 1:1~3.

Preferably, in compound of the catalyst selected from manganese, iron containing compoundses, cobalt compound and nickel compound containing Any a kind or at least two kinds of of combination;The iron containing compoundses are selected from the halogen compounds of iron, the cyanide and iron content hydrochlorate of iron In any a kind or at least two kinds of of combination;Halogen compounds of the cobalt compound selected from cobalt and containing any in cobaltatess 1 kind or at least two kinds of of combination;Chlorate of the nickel compound containing selected from nickel and containing any a kind in nickelate or at least two kinds of Combination.

It is further preferred that the catalyst is selected from iron chloride, frerrous chloride, ferric nitrate, ferrous nitrate, ferric sulfate, sulphur Sour ferrous iron, the potassium ferricyanide, potassium ferrocyanide, three oxalic acid conjunction potassium ferrite, cobalt chloride, cobalt nitrate, cobaltous sulfate, cobalt acetate, nickel chloride, Any a kind or at least two kinds of of combination in nickel nitrate, nickel sulfate and nickel acetate.

The typical but non-limiting example of combination of catalyst of the present invention has the combination of frerrous chloride and ferric sulfate, iron Potassium cyanide and three oxalic acid close the combination of potassium ferrite, the combination of cobalt chloride, cobalt nitrate and iron chloride, cobaltous sulfate, cobalt acetate and nitric acid The combination of nickel, the combination of iron chloride, cobalt chloride and nickel acetate etc..

Preferably, step (i) it is described stirring carry out catalytic treatment temperature be 150~200 DEG C, such as 160 DEG C, 170 DEG C, 180 DEG C 190 DEG C etc., the time >=4h, such as 4.2h, 7h, 9h, 12h, 16h, 19h, 23h etc., preferably 4~14h;The presoma In moisture be preferably below 10wt%, such as 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 1wt% etc.;The heating rate that step (ii) described presoma is warming up to 280~350 DEG C is preferably 3~5 DEG C/min, example Such as 3.5 DEG C/min, 3.8 DEG C/min, 4.2 DEG C/min, 4.5 DEG C/min, 4.8 DEG C/min;The protective atmosphere is nitrogen, helium Any a kind or at least two kinds of of combination in gas, argon gas, preferably nitrogen;Step (iii) the crude product washing is carried out successively Pickling and washing;The preferred concentration of pickling is 3~6wt% hydrochloric acid, and further preferred concentration is 5wt% hydrochloric acid; The washing preferably uses deionized water and/or distilled water;The temperature of the washing be 55~65 DEG C, such as 56 DEG C, 57 DEG C, 58 DEG C, 60 DEG C, 63 DEG C etc., preferably 60 DEG C.

Preferably, the biomass carbon source is cellulose and/or lignin, preferred cellulose, further preferred porous fibre Dimension element.

Porous cellulose of the present invention can be obtained by prior art, typical but non-limiting acquisition porous fibre The prior art of element has:Such as method disclosed in patent publication No. CN104016341A prepares porous cellulose, use Method prepares cellulose disclosed in CN103898782A.

Preferably, the porous cellulose obtains by the following method:

Biomass resource progress sour water solution is obtained into lignocellulosic, post-processes to obtain porous fibre afterwards by porous Element;Alternatively, porous cellulose uses after bleaching;The biomass resource preferably is selected from plant and/or agriculture and forestry organic waste material Any a kind or at least two kinds of of combination;It is preferred that any a kind or at least two kinds of of combination in agriculture and forestry organic waste material;The agricultural are discarded Thing preferably is selected from cornstalk, corncob, kaoliang stalk, megasse, bagasse, furfural dregs, xylose residue, wood chip, cotton stalk and reed Any a kind or at least two kinds of of combination, preferably corncob.

The typical but non-limiting example combinations of biomass resource of the present invention include the combination of cornstalk and corncob, The combination of bagasse, kaoliang stalk and wood chip, megasse, the combination of bagasse and corncob, kaoliang stalk, megasse and xylose residue Combination etc..

The five of the object of the invention are to provide the purposes of the composite polyester material as described in the first purpose, the complex polyester Material prepares polyester fiber by melt spinning, and the composite polyester material prepares polyester film by being cast knife coating, described Composite polyester material is used to prepare tubing, furniture, section bar, the further purposes of including but not limited to above-mentioned composite polyester material, As long as the composite polyester material and its masterbatch that are prepared using the present invention, are further prepared by the method for reprocessing Polyester product belong to protection scope of the present invention.

Compared with prior art, the invention has the advantages that:

(1) present invention carrys out composite polyester material, obtained with more by selecting specific carbon nano-structured compound The performance of excellent antibacterial and Low Temperature Far Infrared, far infrared normal emittance are more than 0.85;

(2) the compound polyester material preparation method of carbon nano-structured compound provided by the invention is simple, carbon nano-structured Compound need not be modified processing, the melt of the composite polyester material obtained after polymerization directly discharges, without carrying out Post processing, technique are simple.

Embodiment

Technical scheme is further illustrated below by embodiment.

Those skilled in the art it will be clearly understood that the embodiment be only to aid in understand the present invention, be not construed as to this hair Bright concrete restriction.

The preparation of carbon nano-structured compound

(1) it is specially with reference to CN104016341A index porous celluloses:

At 90 DEG C, with the sulfuric acid adjusting corn core aqueous solution to pH=3, immersion 10min is hydrolyzed, and obtains wood fibre Element, the quality of the sulfuric acid are the 3% of the corncob quality;Then, at 70 DEG C, obtained lignocellulosic is immersed in 1h in acid accumulator sulfite, obtains porous cellulose;Wherein, acid is sulfuric acid, and sulphite is magnesium sulfite, the matter of the sulfuric acid Measure as the 4% of the lignocellulosic quality, liquid-solid ratio 2:1;It is made rear standby;

(2) carbon nano-structured compound is prepared, is specially:

In mass ratio 1:0.1~10 mixing porous cellulose and catalyst, stir at 150~200 DEG C and carry out at catalysis More than 4h is managed, dries to below presoma moisture 10wt%, obtains presoma;Then, in protective atmosphere, with 3~5 DEG C/presoma is warming up to 280~350 DEG C by min speed, 1.5~2.5h is incubated, temperature programming afterwards is protected to 950~1200 DEG C 3~4h of temperature obtains crude product;The heating rate of described program heating is 15~20 DEG C/min;At 55~65 DEG C, crude product is passed through After concentration is 3~6wt% chlorohydric acid pickling, washing obtains carbon nano-structured compound.

The preparation condition of compound carbon nano-structured 1# is:

In step (2), catalyst is frerrous chloride;The mixing quality of porous cellulose and catalyst ratio is 1:0.1;Catalysis Treatment temperature is 150 DEG C, time 4h;Moisture in presoma is 10wt%;

The process for obtaining crude product is:280 DEG C are warming up to 3 DEG C/min speed, 2h is incubated, afterwards with 15 DEG C/min speed Rate is warming up to 950 DEG C, is incubated 3h;

Pickling temperature is 55 DEG C, and the concentration of hydrochloric acid that pickling uses is 4wt%;

P, Si, Ca, Al, Na, Fe, Mg element are mainly contained in compound carbon nano-structured 1#;And Raman spectrum shows G Peak, D peaks peak height ratios are highly than being 7;2D peaks be present;

The difference of the preparation process of compound carbon nano-structured 2# and the preparation process of compound carbon nano-structured 1# It is only that:The ratio of porous cellulose and frerrous chloride is changed into 1 in step (2):10;Compound carbon nano-structured obtained 2# In mainly contain P, Si, Ca, Al, Na, Fe, Mg element;And Raman spectrum shows G peaks, D peaks peak height ratios highly than being 20.

The difference of the preparation process of compound carbon nano-structured 3# and the preparation process of compound carbon nano-structured 1# It is only that:The ratio of porous cellulose and frerrous chloride is changed into 1 in step (2):0.5;Carbon nano-structured compound of obtained 2# P, Si, Ca, Al, Na, Fe, Mg element are mainly contained in thing;And Raman spectrum shows G peaks, D peaks peak height ratios highly than being 1.5.

Embodiment 1

A kind of composite polyester material, it is prepared via a method which to obtain:

(1) compound carbon nano-structured 100g and 8.52kg PTA, 3.5L ethylene glycol are fed intake mixing, ball-milling treatment Mashing kettle mashing 30min is introduced directly into after 20min, is reacted, polymerize instead according to using three kettle PET polymerization techniques Should, polymerisation finishes to obtain melt;

(2) melt obtains carbon nano-structured multiple in 40 DEG C of cooling waters, directly 0.5m/s draft speed condition bottom discharges, granulation The compound PET material of compound;

Respectively with compound carbon nano-structured 1#, 2# carbon nano-structured compound, 3# carbon nano-structured compound Polyester material is prepared, is designated as product 1a (the compound PET material of compound carbon nano-structured 1#) respectively, product 1b (receive by 1# carbon The compound PET material of compound of rice structure) and product 1c (the compound PET material of compound carbon nano-structured 3#);

Product 1a far infrareds normal emittance can reach 0.87;It is 70% to staphylococcus aureus antibacterial bacteriostatic rate;Production Product 1b far infrareds normal emittance can reach 0.89;It is 82% to staphylococcus aureus antibacterial bacteriostatic rate;Product 1c far infrareds Normal emittance can reach 0.85;It is 60% to staphylococcus aureus antibacterial bacteriostatic rate;

Wherein, infrared detection data foundation:GBT 7286.1-1987《Metal tries with the full normal emittance of nonmetallic materials Proved recipe method》;

Antibacterial detection data foundation:GB/T 31402-2015《Plastics, frosting Anti-microbial Performance Tests method》, with gold Exemplified by staphylococcus aureus.

Embodiment 2

A kind of composite polyester material, it is prepared via a method which to obtain:

(1) compound carbon nano-structured 200g and 8.52kg PTA, 3.5L ethylene glycol are fed intake mixing, ball-milling treatment Mashing kettle mashing 30min is introduced directly into after 20min, is reacted, polymerize instead according to using three kettle PET polymerization techniques Should, polymerisation finishes to obtain melt;

(2) melt obtains carbon nano-structured multiple in 40 DEG C of cooling waters, directly 0.5m/s draft speed condition bottom discharges, granulation The compound PET material of compound;

Respectively with compound carbon nano-structured 1#, 2# carbon nano-structured compound, 3# carbon nano-structured compound Polyester material is prepared, is designated as product 2a (the compound PET material of compound carbon nano-structured 1#) respectively, product 2b (receive by 1# carbon The compound PET material of compound of rice structure) and product 2c (the compound PET material of compound carbon nano-structured 3#);

Product 2a far infrareds normal emittance can reach 0.90;It is 95% to staphylococcus aureus antibacterial bacteriostatic rate;Production Product 2b far infrareds normal emittance can reach 0.92;It is 97% to staphylococcus aureus antibacterial bacteriostatic rate;Product 2c far infrareds Normal emittance can reach 0.88;It is 90% to staphylococcus aureus antibacterial bacteriostatic rate;

Method of testing is same as Example 1.

Embodiment 3:

A kind of composite polyester material, it is prepared via a method which to obtain:

(1) PTA 8.52kg, EG 3.5L and catalyst glycol antimony 3.8g, 30min is beaten, is gathered according to using three kettle PET Close technique to be reacted, carry out polymerisation, polymerisation finishes to obtain melt;

(2) melt is dissolved in trifluoroacetic acid, adds the carbon nano-structured compound grinding 10min of 200g, disperse equal It is even;

In 40 DEG C of cooling waters, 0.5m/s draft speed condition bottom discharges, directly it is granulated and obtains carbon nano-structured compound Compound PET material.

Respectively with compound carbon nano-structured 1#, 2# carbon nano-structured compound, 3# carbon nano-structured compound Polyester material is prepared, is designated as product 3a (the compound PET material of compound carbon nano-structured 1#) respectively, product 3b (receive by 1# carbon The compound PET material of compound of rice structure) and product 3c (the compound PET material of compound carbon nano-structured 3#);

Its far infrared normal emittance of product 3a can reach 0.89;It is 90% to staphylococcus aureus antibacterial bacteriostatic rate; Its far infrared normal emittance of product 3b can reach 0.90;It is 95% to staphylococcus aureus antibacterial bacteriostatic rate;Product 3c its Far infrared normal emittance can reach 0.87;It is 88% to staphylococcus aureus antibacterial bacteriostatic rate;

Method of testing is same as Example 1.

Embodiment 4:

A kind of composite polyester material, it is prepared via a method which to obtain:

(1) 600mL ethylene glycol is incorporated into the mashing kettle containing 8.52kg PTA and 3L ethylene glycol, adds antimony glycol 3.8g Continue to be beaten 30min, reacted according to using three kettle PET polymerization techniques, carry out polymerisation, polymerisation, which finishes, to be melted Body;Excessive EG should be excluded in the class and polycondensation of polymerisation;

(2) the carbon nano-structured compound grinding 10min of 300g will after melt heating melting, be added;

(3) melt obtains carbon nano-structured in 40 DEG C of cooling waters, directly 0.5m/s draft speed condition bottom discharges, granulation The compound PET material of compound.

Respectively with compound carbon nano-structured 1#, 2# carbon nano-structured compound, 3# carbon nano-structured compound Polyester mater