CN105001405B - Prepare method of copolyester ether thin film and application thereof - Google Patents
Prepare method of copolyester ether thin film and application thereof Download PDFInfo
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Abstract
The present invention provides a kind of method for preparing copolyester ether thin film, comprising：Pillar recovery is provided；Dihydroxylic alcohols are added to carry out alcoholysis reaction with Pillar recovery, so that the first intermediate product is obtained, wherein Pillar recovery and the mole ratio of dihydroxylic alcohols are 1:1.8～2.5；Ester exchange reaction is carried out to the first intermediate product, so that the second intermediate product is obtained, and transesterification reaction temperature is between 190 DEG C to 230 DEG C；Add poly-dihydric alcohol and the second intermediate product to carry out polyreaction, so that copolyester ether is obtained, and copolyester ether contains poly-dihydric alcohol composition, calculated with copolyester ether gross weight, wherein poly-dihydric alcohol composition 24 to 55 percentage by weight of accounting；And copolyester ether is made into elastic film.Thin film prepared in accordance with the method for the present invention is elastic water-proof moisture permeable membrane, and young's modulus is 60～210MPa, and rate of perviousness is 600～6000g/m2/day。
Description
Technical field
The invention relates to a kind of method for preparing copolyester ether thin film, in particular to one kind by Pillar recovery system
The method of standby thermoplastic copolyesters ether thin film.
Background technology
With a hard segment structure and that can form crystal region in the basic molecular structure of thermoplastic copolyesters ether
It is able to maintain that its elasticity and soft soft chain segment structure.When the aggregation of hard segment proper alignment can produce crystal region, according to hard
Segment is changed with the composition species of soft chain segment, and adjusts the number that its soft, hard segment constitutes content, in extensive range to manufacture physical property
Thermoplastic copolyesters ether elastomer (Thermoplastic Polyester Elastomer, TPEE), it is therefore soft, hard segment
It is all to determine TPEE things that molecular composition, structure, amount of monomer, size, and soft, hard segment account for the pro rate of total TPEE structures
The key element of rationality matter.
In general, the selection of hard segment is more based on the polyester with crystal property, for example：Poly terephthalic acid second two
Alcohol ester (Polyethylene terephthalate, PET), PTT (Polytrimethylene
Terephthalate, PTT), polybutylene terephthalate (PBT) (Polybutylene terephthalate, PBT) etc., and
Soft chain segment then more uses the poly- alkyl diol of long chain type, for example：Polyethylene Glycol (Polyethylene glycol, PEG), poly- four
Subunit ether glycol (Polytetramethylene glycol, PTMEG) etc..The hard segment of industrial TPEE is constituted at present
It is that soft chain segment composition is, based on PTMEG, to be applied to sports equipment, automobile-used built-in material etc. more with PBT.
In material speciality, PBT is adopted for the TPEE of hard segment main body and there is crystalline rate faster, therefore with injection
The application of forming machine tool part, for example：Automobile oil pipe, electric wire and cable jacket etc., can provide preferable size steady
It is qualitative and shorten the CT Cycle Time time；Adopt PET for hard segment main body TPEE, because PET have higher fusing point, compared to
PBT has higher thermostability for the TPEE of main body, although crystalline rate is slower than PBT, but PET strip has the ethylene of short molecular chain
Base molecule segment, is relatively also easy to produce hypocrystalline (semi-crystalline domain), therefore can regulate and control its hard segment by vinyl
Crystal area proportion, TPEE is integrally crystallized with scalable selectivity.In sum, TPEE is by the knot for regulating and controlling its hard segment
Brilliant firm property and the flexibility and its freedom of movement of molecule segment of its soft chain segment, make both soft, hard segment ratios reach flat
Weighing apparatus, therefore can provide material excellent elasticity, while with good intensity.
Known technology prepare the method for copolyester ether be using dimethyl terephthalate (DMT) (DMT) and dihydroxylic alcohols for example：Fourth
Glycol (BG), carries out ester exchange reaction in the presence of ester exchange catalyst, but known technology has the difficult point that individual need overcome, and is exactly
By-product is produced easily in the ester exchange reaction stage, for example：Low point of methanol and tetrahydrofuran (Tetrahydrofuran, THF) etc.
Sub- alcohols.This by-product can produce side reaction or back reaction during previous reaction, cause molecular weight of product skewness with
The problems such as mechanical properties are not good.
Taiwan patent of invention the I232226th, discloses a kind of method for manufacturing copolyester ether, its revealing method with
Know technology no significant difference, only using single usual with the mixed catalyst of magnesium acetate replacement known technology of four titanium butoxides
Titanium series catalyst, has an advantage in that and can reduce the polycondensation reaction time, has no and discloses the content for suppressing side reaction.U.S. Patent No.
No. 7795320 are disclosed a kind of poly terephthalic acid Propylene Glycol copolymerized block works respectively with No. 8110609
(Polytrimethylene ether ester block copolymer) and preparation method thereof, both is all with PET bottle piece
(PET Scrap), used as the material of initial action, these technologies are that the alcoholysis of PET bottle piece is formed terephthalic acids dimethyl ester (DMT).
The technology additionally must add the dimethyl isophthalate (DMI) that molecular structure is close but fusing point is relatively low again, use enhancement ester
Exchange reaction conversion ratio (abbreviation ester exchange rate), is subsequently generated with the reaction of poly- four subunits ether glycol (PTMEG) Jing condensation polymerizations again
Copolyester ether block copolymer (block copolymer).However, poly- four subunits ether glycol can be dissociateed in high-temperature reaction process
Tetrahydrofuran (THF), and tetrahydrofuran long-term existence harmful doubt with the doubt endangered to environment He Ermeng, institute
With less suitable for use in the articles for use with human contact, such as fabric pad pasting or family's decorations articles for use pad pasting.Additionally, poly- four subunits ether glycol
Molecular structure for main chain be four carbon numbers straight chain type carbon, straight chain type carbon is easily produced and is forward crystallized, therefore is relatively suitable as
Ejection formed piece (inject molded) or moldings formed therefrom product (extruder molded).Jetting process needs crystallization rate fast
Material behavior to shorten the ejection formation time (cycle time), and moldings formed therefrom product are even more and require that the material of rapid crystallization is special
Property, therefore the material behavior for forward crystallizing easily is produced, relatively it is suitable as ejection formed piece or moldings formed therefrom product.But forward tie
The too fast material behavior of brilliant speed is then unfavorable for the membrane product for being applied to elongation moulding, because in the process for extending film forming, crystallization
Excessive velocities can cause the problem of film breakage or membrane thickness unevenness, more be applied to required by fabric laminating it is difficult to cannot manufacture
Film thickness, the usual usual thickness of moisture-permeability waterproof film in general fabrics field be 20 μm.Other disclose the technology Ze You U.S.
Patent the 6380290th discloses a kind of engineering plastics grade copolyester ether block structure thing, its feature be fusing point higher than 200 DEG C with
On, its technology is to add aromatic series amine system antioxidant (the aromatic amine thermo of high concentration content
Oxidative stabilizer) increase its non-oxidizability, to extend weatherability, but the softness of copolyester ether itself cannot be improved
Property.U.S. Patent No. 7799838 is disclosed and blends the prepared modification copolyester ether of mode with physics, and which cannot also improve copolyesters
The flexibility of ether itself.
The content of the invention
In view of this, it is an object of the invention to provide a kind of method for preparing copolyester ether thin film, can make copolyester ether
Thin film is simultaneously with the characteristic with PBT and PET as hard segment main body, there is provided appropriate crystalline rate, is conducive to enhancement to extend into
The convenient formation of film processing, and while provide thin-film material excellent flexibility, so that the copolyester ether thin film of the present invention
Materials application can possess the wear sense of soft comfortable among dress of fabric.While the copolyester ether thin-film material of the present invention
Preparation method will not dissociate harmful substance in manufacture process, friendly to natural environment, and can feeling at ease, it is long-term to be used in needs
With the haberdashery of human contact.
One specific aspect of the present invention is to provide a kind of method for preparing copolyester ether thin film, comprising：There is provided one and reclaim poly-
Ester；Dihydroxylic alcohols are added to carry out alcoholysis reaction with Pillar recovery, so that the first intermediate product, wherein Pillar recovery and dihydroxylic alcohols is obtained
Mole ratio is 1:1.8～2.5；Ester exchange reaction is carried out to the first intermediate product, so that the second intermediate product, and ester exchange is obtained
Reaction temperature is between 190 DEG C to 230 DEG C；Poly-dihydric alcohol and the second intermediate product is added to carry out polyreaction, so that copolyesters is obtained
Ether, and copolyester ether contains poly-dihydric alcohol composition, is calculated with copolyester ether gross weight, wherein poly-dihydric alcohol constitutes accounting 24 to 55
Percentage by weight；And copolyester ether is made into elastic film.
According to one embodiment of the invention, Pillar recovery is to be made Jing after removing impurity removing, lift the flow processs such as viscosity again, and which can
For polyethylene terephthalate (Polyethylene terephthalate, PET), PTT
(Polytrimethylene terephthalate, PTT), polybutylene terephthalate (PBT) (Polybutylene
Terephthalate, PBT) or any of the above-described combination.
According to one embodiment of the invention, dihydroxylic alcohols have two to ten carbon, aliphatic two of the preferred dihydroxylic alcohols for C2～C10
First alcohol, for example：1,2- ethylene glycol, 1,2- Propylene Glycol, 1,3- Propylene Glycol, 1,4- butanediols, 1,5- pentanediols, 1,6-HD,
1,7- heptandiols, 1,8- ethohexadiols and cyclohexanedimethanol.According to another embodiment of the present invention, dihydroxylic alcohols used in the present invention
Matter of making a living dihydroxylic alcohols.
According to one embodiment of the invention, alcoholysis reaction is to react 3～5 hours in 190 DEG C～200 DEG C, this alcoholysis reaction
Purpose is to block the molecule segment of polyester.When Pillar recovery is PET, double-hydroxyethyl terephthalate (BHET) can be generated.
The functional group of BHET ends is the reactive functional group base required for follow-up transesterification steps, and functional group's number is more, more
Contribute to follow-up ester exchange rate, therefore property more preferably copolyester ether thin film can be obtained.
According to one embodiment of the invention, after aforementioned transesterification steps, further include to go out excess with vacuum extraction
Dihydroxylic alcohols the step of.
According to one embodiment of the invention, poly-dihydric alcohol is Polyethylene Glycol (Polyethylene glycol, PEG).
The preparation method of the present invention can add catalyst to promote reaction rate.In one embodiment, it is anti-in ester exchange
Ester exchange catalyst should be added, wherein ester exchange catalyst is titanium compound, tin compound, antimonial, monovalent metal chemical combination
Thing, bivalent metallic compound or any of the above-described combination.In another embodiment, polymerization catalyst is added in polyreaction, its
Middle polymerization catalyst is antimonial, germanium compound, magnesium compound, manganese compound, phosphorus compound, nitrogen compound, organic peroxy
Compound or any of the above-described combination.
The preparation method of the present invention can add the auxiliary additive of tool specific function to promote material other characteristics.In this reality
Apply in mode, addition antioxidant adds UV absorbent to promote the uvioresistant of material to promote the heat stability of material
Line characteristic.
According to the present invention preparation method obtained by copolyester ether, its fusing point between 150 DEG C to 200 DEG C, its glass
Glass conversion temperature is between -20 DEG C to -40 DEG C.
Method according to the present invention, thin film obtained in which be elastic water-proof moisture permeable membrane, young's modulus be 60～
210MPa, and rate of perviousness is 600～6000g/m2/day。
Description of the drawings
To enable the feature of the present invention, advantage and embodiment to become apparent, appended accompanying drawing is described as follows：
Figure 1A and Figure 1B are illustrated respectively according to copolyester ether obtained in the method for the present invention is soft, rigid structure schematic diagram and its hard
Segment crystalline region microcosmic schematic diagram；
Fig. 2A and Fig. 2 B are the nuclear magnetic resonance, NMR (Nuclearmagnetic of one embodiment of the invention and comparative example respectively
Resonance, NMR) analysis result；
Wherein, symbol description：
100：Copolyester ether 102：Hard segment crystalline phase area's microstructure schematic diagram
110：Hard segment crystalline phase area 112,114：Crystallite phase region
116：Amorphous area 120：Soft chain segment molecule.
Specific embodiment
For make the narration of this disclosure more detailed with it is complete, below for the present invention enforcement aspect be embodied as
Example proposes illustrative description；But this is not implemented or with the unique forms of the specific embodiment of the invention.It is disclosed below
Each embodiment, can be mutually combined in the case of beneficial or replace, also can additional other embodiments in one embodiment, and nothing
Must further record or illustrate.
One aspect of the present invention is to provide a kind of method for preparing copolyester ether thin film, in particular to one kind by reclaiming
The method that polyester prepares thermoplastic copolyesters ether thin film, the method for the present invention for reaction more rapidly one-part form reaction (one-
Shot reaction), compared with known method, the implementation steps of the inventive method seem more simple, more economical excellent
Gesture.The step of the inventive method, is comprising as follows：One Pillar recovery is provided；Dihydroxylic alcohols are added to carry out alcoholysis reaction with Pillar recovery,
Purification step and filter are not needed, the first intermediate product is obtained, wherein Pillar recovery with the mole ratio of dihydroxylic alcohols is
1:1.8～2.5；Ester exchange reaction is carried out to the first intermediate product, so that the second intermediate product is obtained, and transesterification reaction temperature is situated between
In 190 DEG C to 230 DEG C, it is to avoid by-product low molecule alcohol is generated in course of reaction；Add poly-dihydric alcohol and the second intermediate product
Polyreaction is carried out, so that copolyester ether is obtained, and copolyester ether contains poly-dihydric alcohol composition, is calculated with copolyester ether gross weight,
Wherein 24 to 55 percentage by weight of poly-dihydric alcohol weight accounting；And copolyester ether is made into elastic film.
According to one embodiment of the invention, Pillar recovery be Jing after removing impurity removing, lift the flow processs such as viscosity again made by gather
Ester ester grain, which can be PET, PTT, PBT or any of the above-described combination.
According to one embodiment of the invention, dihydroxylic alcohols have two to ten carbon, aliphatic two of the preferred dihydroxylic alcohols for C2～C10
First alcohol, for example：1,2- ethylene glycol, 1,2- Propylene Glycol, 1,3- Propylene Glycol, 1,4- butanediols, 1,5- pentanediols, 1,6-HD,
1,7- heptandiols, 1,8- ethohexadiols and cyclohexanedimethanol.According to another embodiment of the present invention, dihydroxylic alcohols used in the present invention
Matter of making a living dihydroxylic alcohols, which is made of to replace traditional petrochemical material using plant, contributes to lowering the demand to petroleum-based energy.
According to one embodiment of the invention, after aforementioned transesterification steps, further include to go out excess with vacuum extraction
Dihydroxylic alcohols the step of.
According to one embodiment of the invention, poly-dihydric alcohol is PEG.
As start material used in the present invention is Pillar recovery, therefore when Pillar recovery is PET, with alcoholysis reaction
Double-hydroxyethyl terephthalate (BHET) can be obtained, there is provided the reactive functional group base needed for ester exchange reaction.In one embodiment,
Alcoholysis reaction is to react 3～5 hours at a temperature of 190 DEG C～200 DEG C.
The preparation method of the present invention can add catalyst to promote reaction rate.In one embodiment, it is anti-in ester exchange
Ester exchange catalyst should be added, wherein ester exchange catalyst is titanium compound, tin compound, antimonial, monovalent metal chemical combination
Thing, bivalent metallic compound or any of the above-described combination.In another embodiment, polymerization catalyst is added in polyreaction, its
Middle polymerization catalyst is antimonial, germanium compound, magnesium compound, manganese compound, phosphorus compound, nitrogen compound, organic peroxy
Compound or any of the above-described combination.
The auxiliary additive that the preparation method of the present invention can add tool specific function is special needed for other to promote material
Property.In the present embodiment, add antioxidant to promote the heat stability of material, add UV absorbent to promote material
Uvioresistant characteristic.
The preparation method is that to reclaim raw material of the obtained polyester as initial action again, and add dihydroxylic alcohols
Alcoholysis reaction is carried out with Pillar recovery, the purpose of alcoholysis reaction is to block the segment molecular moiety of polyester.If Pillar recovery
For PET, its chain segment molecule partly can be blocked, and be allowed to form double-hydroxyethyl terephthalate (BHET).The concrete reality of the present invention
It is using relatively simple one-part form reaction (one-shot reaction) of reaction more rapid and processing procedure to apply example, it is not necessary to Jing
Cross purification step and filter；The ester exchange catalyst that add again of continuing carries out ester exchange reaction, its object is to import different
Carbon number molecules structure makes its part replace the structure in original hard segment area of above-mentioned polyester ether.Therefore, the molecule knot in hard segment area
Cover the alkyl structure arrangement of two kinds of different carbon numbers in structure simultaneously, therefore cause crystallite area to be separated, the phase separation degree in crystallite area is got over
Greatly, and then can obtain the better thin film of poisture-penetrability, if but be separated and spend big, then become can the tensile strength physical property of thin film
Difference, so phase separation degree should control to be in proper range.
Referring to Figure 1A and Figure 1B, illustrate respectively according to copolyester ether obtained in the method for the present invention 100 it is soft, scleroma
Figure 102 is illustrated in structure schematic diagram and its area's microstructure of hard segment crystalline phase.Copolyester ether 100 have can form the hard of crystal region
Segment crystalline phase area 110 and it is able to maintain that its elasticity and soft soft chain segment molecule 120.Refer to Figure 1B, hard segment crystalline phase area 110
In ordered arrangement structure simultaneously exist because of two kinds of alkyl molecules, produce two kinds of crystallite phase regions 112,114 structural arrangement, and due to
The carbon number of two kinds of crystallite phase regions 112,114 is different, is studded with unordered amorphous area between two adjacent crystallite phase regions 112,114
(amorphous) 116, the ordered structure ratio in the overall crystalline phase area of destruction.Therefore, the change of crystallite kenel affects integral material
Property so that melting temperature is moved toward low temperature direction, and glass transition temperature is because being limited by the process effects that crystallite area is separated,
Also move toward subzero temperature area.Additionally, the crystallite kenel change in copolyester ether hard segment area also increases overall free volume, hard chain is made
The strand activity in section area is more flexible, with good elasticity and flexibility, is conducive to preparing the processing forming of thin film.
According to one embodiment of the invention, the Pillar recovery for using is that PET, dihydroxylic alcohols are BDO and poly-dihydric alcohol is
PEG, according to the preparation method of aforementioned copolyester ether, the ethylene glycol segment for blocking PET parts imports butanediol segment again, makes fourth two
Alcohol segment part replaces the molecular structure of original segmented structure, Gu Yinglianduanqu to cover ethyoxyl (C simultaneously2H4O) segment and
Butoxy (C4H6O) two kinds of structures, obtained copolyester ether fusing point be 150 DEG C to 200 DEG C between, and glass transition temperature be -20
DEG C between -40 DEG C.
Known technology is to prepare copolyester ether using dimethyl terephthalate (DMT) (DMT) and butanediol (BG), and which is with fourth oxygen
Base molecule segment is hard segment main body, using PolyTHF dihydroxylic alcohols (PTMEG) as soft chain segment main body, with this hard and soft chain segment group
Lack flexibility into made thin film, material is more firm, and PTMEG high temperature can dissociate tetrahydrofuran
(Tetrahydrofuran, THF), and THF has the doubt that harm is produced to human body always.In one embodiment, according to this
Invention preparation method adopts recycled PET for start material, and obtained thin film includes ethoxy based structures due to hard segment area part,
Therefore can have good elasticity, and the function of water proofing property that copolyester ether materials can be maintained excellent and poisture-penetrability, therefore it is obtained thin
Film is elastic water-proof moisture permeable membrane, and young's modulus is 60～210MPa, and rate of perviousness is 600～6000g/m2/day。
The film preparation mode of the present invention can be commonly known masking technique, for example：Melting extrusion mode or blown film side
Formula.
Several embodiments are exemplified below with the more elaboration method of the present invention, so which is only and illustrates to be used, not
To limit the present invention, protection scope of the present invention is defined when the scope defined by appended claims.
Chemicals
The chemicals prepared needed for the embodiment of the present invention are as follows：
1. Pillar recovery (polyethylene terephthalate, PET)：Model C FF-290Recycle PETchip；Repeat
Unit molecular weight is 192；Originate as Far East New Era Company.
2.1,4- butanediols (1,4-butanediol, BG)：Molecular weight is 92.
3. Polyethylene Glycol (Polyethylene glycol, PEG)：Molecular weight is 1000 and 2000.
4. tetrabutyl titanium (Titanium (IV)-n-butoxide).
5. antimony oxide (Antimony trioxide, Sb2O3)。
6. antioxidant：Marque IRGANIX1010 and GA80.
7. UV absorbent：Marque EVERSORB761.
Inspection project and test specification method
The inspection project and method used by test material characteristic is as follows：
1. tensile strength test：ASTM D42.
2. moisture permeability test：ASTM E96BW and JIS L1099A1.
3. water pressure resistance test：JIS L1092.
4. film feel test：Artificial sensory evaluation is taken, by determinand with the gripping action of handss, by bending flexure repeatedly
Change, there is provided the soft or hard information of film feel.
5.NMR is analyzed：To verify in hard segment crystal region containing ethyoxyl and two kinds of segmented structure of butoxy.
Embodiment 1
The preparation method of embodiment 1 is as follows：
1. the BDO of the recycled PET and 23.44kg that take 20kg carries out alcoholysis reaction, is entered using 50kg consersion units
OK, first stage glycolysis temperature is 190 DEG C～200 DEG C, 5 hours alcoholysis time.
2. continue and be warming up to 230 DEG C and add appropriate ester exchange catalyst tetrabutyl titanium to carry out ester exchange reaction, by PET
Ethyoxyl (C2H4O) segment molecular moiety imports butoxy (C4H6O).Transesterification temperature need to control below 230 DEG C to avoid
Because reaction temperature it is too high so that BDO cracks to form THF.
3. treat ester exchange degree up to more than 95%, the excessive BDO of vacuum drawn, move to polymerization tank carry out being polymerized it is anti-
Should, polymerization temperature is 250 DEG C, and the polyreaction initial stage keeps 2 hours atmospheric pressure states, after determining tower top without distillation, adds 4kg
Polyethylene Glycol (molecular weight is 1000), to promote polymerization rate, another addition is anti-for another addition polymerization catalyst antimony oxide
Oxidant promotes the uvioresistant characteristic of material to promote heat stability and UV absorbent.Polymerization tank vacuum control
Below 1torr, polymerization time about 5 hours treat the relative viscosity of copolymer up to 2.3～3.55, you can to obtain copolyester ether.
4. above-mentioned copolyester ether is made into the thin film that thickness is 20 μm, as embodiment 1, and carry out subsequent survey project.
Embodiment 2～4
The preparation method of embodiment 2～4 is substantially same as Example 1, is only changed to the operating condition of Polyethylene Glycol respectively
The Polyethylene Glycol 14kg that addition molecular weight is 1000 Polyethylene Glycol 6kg, 10kg and molecular weight is 2000.
Comparative example
Comparative example is made of to prepare thermoplastic polyester ether method using known, and step is as follows：
1. esterification：Take 21.6kg dimethyl terephthalate (DMT) (Dimethyl terephthalate, DMT),
The Polyethylene Glycol (molecular weight 1000) of the BDO and 8kg of 11.7kg carries out esterification, is carried out with 50kg consersion units,
The tetrabutyl titanium catalyst of addition 16g, to avoid reactant in Esterification Stage thermal cracking, another addition antioxidant and ultraviolet are inhaled
Receive agent.Esterification temperature initial setting adopts stage intensification at 150 DEG C.
2. polyreaction：After esterification reaction temperature rises to 220 DEG C and lasts about 6 hours, i.e. by-product distillation reaches
6.7kg, the intermediate product by esterification degree up to 95% moves to polymerization tank carries out polyreaction.Polymerization temperature is set in 250 DEG C, separately adds
Plus the tetrabutyl titanium catalyst of 24g, below polymerization tank vacuum control 1torr, polymerization time about 5 hours.
3. treat the relative viscosity of copolymer up to 2.3～3.55, i.e. sample analysis.
Table 1 is to utilize to show that Differential scanning calorimetry instrument (Differential scanning calorimeter, DSC) is measured
The knot that the fusing point (Tm) of embodiment 1～4 and comparative example, cold crystallization temperature (Tcc) and glass transition temperature (Tg) are analyzed with NMR
Really, wherein TPA is p-phthalic acid；DMT is dimethyl terephthalate (DMT)；EG is ethyoxyl；BG is butoxy；PEG is poly- second
Glycol.
Table 1
From above-mentioned table 1, according to copolyester ether obtained in the inventive method due to hard segment area contain simultaneously ethyoxyl and
Butoxy structure, causes crystallite area to be separated, and smaller than 200 DEG C of 1～4 fusing point of embodiment, and glass transition temperature is all located at
- 20 DEG C～-40 ° DEG C of subzero temperature area, and two kinds of chains of ethyoxyl and butoxy are contained really simultaneously with NMR analysis verifications embodiment 1～4
Segment structure.
Fig. 2A and Fig. 2 B are refer to, which is respectively the NMR analysis results of embodiment 1 and comparative example, embodiment 1 is understood by which
Hard segment crystal region in really containing ethyoxyl and two kinds of segmented structure of butoxy, and in the hard segment crystal region of comparative example only
Containing butoxy segmented structure.
Table 2 is embodiment 1～4 and the test of comparative example tensile strength, young's modulus, moisture permeability test and water pressure resistance test
As a result, wherein young's modulus is a modulus of elasticity, and material is harder, more crisp, more do not have elasticity, and its young ' is bigger；Material is more soft
Soft, more flexible, its young ' is less.In the present embodiment, with young ' represent obtained in film surface elastic and
Feel.
Table 2
From above-mentioned table 2, embodiment 1～4 is represented according to present invention side with compared to the less young ' of comparative example
Copolyester ether obtained in method has good elasticity and pliability, and obtained copolyester ether thin film feel is soft compared with comparative example,
Wherein embodiment 1～4 is to add the Polyethylene Glycol of different proportion and molecular weight, and Polyethylene Glycol is the main knot of soft chain segment composition
Structure, from upper table result, can be obtained the copolyester ether of the different elasticity of tool and pliability by regulation and control soft chain segment proportion of composing.
Separately, the copolyester ether thin film by obtained in moisture permeability and water pressure resistance test result understand according to the inventive method have simultaneously water proofing property and
Poisture-penetrability.
In sum, the of the invention method for preparing copolyester ether is to carry out alcoholysis reaction using polyester and dihydroxylic alcohols, in
Polyester portion imports dihydroxylic alcohols as copolyester ether hard segment area, changes the crystallite kenel in copolyester ether hard segment area, increases whole
The free volume of body, subchain activity is more flexible to distinguish hard segment, with good elasticity and flexibility, is conducive to heat to extend into
The processing forming of film, and the fusing point of obtained copolyester ether is less than 200 DEG C, when making processing, material is easily heated evenly and completely
Melting.Additionally, polyester raw material used in the present invention comes from Pillar recovery, reuse polyester material, can effective energy-conservation
Subtract carbon, mitigate pollution and burden to earth environment.In addition, the dihydroxylic alcohols that the present invention adds in alcoholysis reaction also can be using life
The dihydroxylic alcohols in matter source, contribute to lowering the demand to petroleum-based energy, to reach the purpose of environmental protection.
Although the present invention is disclosed above with embodiment, so which is not limited to the present invention, any to be familiar with this skill
Person, without departing from the spirit and scope of the present invention, when can be used for a variety of modifications and variations, therefore protection scope of the present invention is worked as
It is defined depending on the scope defined by appended claims.
Claims (7)
1. a kind of method for preparing copolyester ether thin film, comprising：
(A) provide and reclaim polyethylene terephthalate, the wherein polyethylene terephthalate is via going the removal of impurity
And reprocessing is made the step of lifting viscosity；
(B) BDO is added to carry out alcoholysis reaction with the recovery polyethylene terephthalate, in 190 DEG C～200 DEG C
At a temperature of react 3～5 hours, so that the first intermediate product is obtained, the alcoholysis degree of wherein first intermediate product is not less than 80%,
And the recovery polyethylene terephthalate and the mole ratio of the 1,4- butanediols are 1:1.8～2.5；
(C) ester exchange reaction is carried out to first intermediate product, so that the second intermediate product is obtained, and the transesterification reaction temperature is situated between
In 190 DEG C to 230 DEG C, tetrahydrofuran, wherein the hard segment area of second intermediate product are formed to avoid BDO from cracking
Molecular structure simultaneously cover ethyoxyl (C2H4O) segment and butoxy (C4H6O) segment；
(D) Polyethylene Glycol is added to second intermediate product, and carry out polyreaction copolymerization is obtained with second intermediate product
The molecular structure in the hard segment area of ester ether, the wherein copolyester ether covers the ethyoxyl (C simultaneously2H4O) segment and the butoxy
(C4H6O) segment, the copolyester ether contain Polyethylene Glycol composition, are calculated with the copolyester ether gross weight, and the Polyethylene Glycol composition is accounted for
Than 24 to 55 percentage by weights, and the ethyoxyl (C2H4O) 1.5 to 3.1 percentage by weight of segment accounting；And
(E) copolyester ether is made into elastic film, the wherein rate of perviousness of the elastic film is 600～6000g/m2/day。
2. the BDO the method for claim 1, wherein described in the step (B) is taken from giving birth to matter source.
3. the method for claim 1, the ester exchange reaction of wherein step (C) further include to add ester exchange catalysis
Agent to promote which to react, and the ester exchange catalyst be titanium compound, tin compound, antimonial, monovalent metal compound, two
Divalent metal compound or any of the above-described combination.
4. the method for claim 1, wherein after the ester exchange reaction of the step (C), further includes with vacuum extraction
The step of going out excessive dihydroxylic alcohols.
5. the method for claim 1, the polyreaction of wherein step (D) further include that adding polymerization catalyst promotees
Enter reaction, and the polymerization catalyst be antimonial, germanium compound, magnesium compound, manganese compound, phosphorus compound, nitrogen compound,
Organic peroxide or any of the above-described combination.
6. the method for claim 1, the fusing point of the wherein copolyester ether of the step (D) be between 150 DEG C to 200 DEG C it
Between, and glass transition temperature is between -20 DEG C to -40 DEG C.
7. the method for claim 1, the wherein young ' of the elastic film of the step (E) are 60～210MPa.
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| CN101376702A (en) * | 2008-10-09 | 2009-03-04 | 东华大学 | Polyester based phase-change material having uvioresistant function and preparation thereof |
| CN101636427A (en) * | 2006-01-27 | 2010-01-27 | 沙伯基础创新塑料知识产权有限公司 | Copolyether ester derived from polyethylene terephthalate |
| CN103304792A (en) * | 2013-06-06 | 2013-09-18 | 张家港市宝田新型材料科技有限公司 | Preparation method of polyester resin for epoxy hybrid powder coating |
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| CN101376702A (en) * | 2008-10-09 | 2009-03-04 | 东华大学 | Polyester based phase-change material having uvioresistant function and preparation thereof |
| CN103304792A (en) * | 2013-06-06 | 2013-09-18 | 张家港市宝田新型材料科技有限公司 | Preparation method of polyester resin for epoxy hybrid powder coating |
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