CN106589328B - A kind of polyester elastomer and preparation method thereof - Google Patents
A kind of polyester elastomer and preparation method thereof Download PDFInfo
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- CN106589328B CN106589328B CN201510683371.9A CN201510683371A CN106589328B CN 106589328 B CN106589328 B CN 106589328B CN 201510683371 A CN201510683371 A CN 201510683371A CN 106589328 B CN106589328 B CN 106589328B
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Abstract
The present invention relates to polyester elastomer field, a kind of polyester elastomer and preparation method thereof is disclosed, this method includes：Make to carry out esterification and/or ester exchange reaction containing the mixture of the first dicarboxylic acids (ester) and the first dihydric alcohol, the product after obtaining the first reaction；Make mixture the second esterification of progress and/or ester exchange reaction containing product, the second dicarboxylic acids (ester) and the second dihydric alcohol after first reaction, the product after obtaining the second reaction；In the presence of polycondensation catalyst, the product after making second reaction carries out polycondensation reaction；Wherein, first dicarboxylic acids (ester) contains M-phthalic acid (ester), and second dicarboxylic acids (ester) contains oxalic acid (ester), and first dihydric alcohol and second dihydric alcohol contain ethylene glycol.Polyester elastomer of the invention has bigger molecular weight and better coloration.
Description
Technical field
The present invention relates to a kind of polyester elastomers and preparation method thereof.
Background technique
Elastomer refers to glass transition temperature lower than room temperature, elongation at break>50%, it is preferably high that external force withdraws from rear restoration
Molecular compound.Thermo-setting elastomer and thermoplastic elastomer (TPE) two major classes are divided into according to whether elastomer is plastic.
Polyethylene terephthalate (PET) is typically used as thermoplastic material, the mechanical properties such as crystallinity, intensity,
Chemical resistance, heat resistance, electrical property, transparency etc. are had excellent performance, various in film, fiber, bottle, extrusion molding article etc.
It is used with a large amount of on the way, China's polyethylene terephthalate production capacity has been up to 25,000,000 tons.It is certain be not easily recycled answer
Some white pollutions are caused to exist just because of the above-mentioned excellent properties of polyethylene terephthalate with occasion.In order to keep away
Exempt from this problem, improve the biodegradability of polyester, is the developing direction of polyester material.
Therefore, it is badly in need of that a kind of biodegradability is good and polyester bullet with excellent tensile property and resilience performance
Property body.In order to overcome the above-mentioned problems in the prior art, the applicant mentions in patent application CN201410573539.6
The polyester elastomer good and with excellent tensile property and resilience performance for a kind of biodegradability.But the polyester
The color of elastomer is deeper, and molecular weight needs to be further increased.
Summary of the invention
That the purpose of the present invention is to provide a kind of colors is shallower, molecular weight is larger and with excellent tensile property and returns
The biodegradability polyester elastomer of elastic energy.
The present inventor by in-depth study find, directly by two kinds of dicarboxylic acids (ester) and dihydric alcohol contact into
Row transesterification and esterification, then polycondensation is carried out, the obtained usual color of polymer is deeper, and molecular weight is lower, needs further to add
The modified molecular weight that improves of work just can satisfy processing request.In consideration of it, the present inventor is further to polyester elastomer
Reaction condition is studied, it has surprisingly been found that by the esterification and/or ester exchange reaction of dicarboxylic acids (ester) and dihydric alcohol point
Step carries out, and can obtain that color is shallower, molecular weight is larger, biodegradability is good, and with excellent tensile property and returns
The polyester elastomer of elastic energy, has thus completed the present invention.
That is, in a first aspect, the present invention provides a kind of preparation method of polyester elastomer, wherein this method includes：?
Under conditions of one esterification and/or ester exchange reaction, make the mixture containing the first dicarboxylic acids (ester) and the first dihydric alcohol
Reaction, the product after obtaining the first esterification and/or ester exchange reaction；In the second esterification and/or ester exchange reaction
Under the conditions of, make containing product, the second dicarboxylic acids (ester) and the two or two after first esterification and/or ester exchange reaction
The mixture of first alcohol reacts, the product after obtaining the second esterification and/or ester exchange reaction；Under the conditions of polycondensation reaction,
In the presence of polycondensation catalyst, the product after making second esterification and/or ester exchange reaction carries out polycondensation reaction；Wherein,
First dicarboxylic acids (ester) contains M-phthalic acid (ester), and second dicarboxylic acids (ester) contains oxalic acid (ester), described
First dihydric alcohol and second dihydric alcohol contain ethylene glycol.
Second aspect, the present invention provide a kind of preparation method of polyester elastomer, wherein this method includes：In the first ester
Under conditions of changing reaction and/or ester exchange reaction, make to react containing the mixture of the first dicarboxylic acids (ester) and the first dihydric alcohol,
Product after obtaining the first esterification and/or ester exchange reaction；In the second esterification and/or the condition of ester exchange reaction
Under, make to react containing the mixture of the second dicarboxylic acids (ester) and the second dihydric alcohol, obtains the second esterification and/or transesterification
Product after reaction；Under the conditions of polycondensation reaction, in the presence of polycondensation catalyst, hand over first esterification and/or ester
The mixture of product after changing reaction and the product after second esterification and/or ester exchange reaction carries out polycondensation reaction；
Wherein, first dicarboxylic acids (ester) contains M-phthalic acid (ester), and second dicarboxylic acids (ester) contains oxalic acid (ester),
First dihydric alcohol and second dihydric alcohol contain ethylene glycol.
The third aspect, the present invention also provides one kind to pass through polyester elastomer obtained by the above method.
It is mixed in the preparation method of polyester elastomer according to the present invention, with aforementioned patent applications CN201410573539.6
Conjunction object directly carries out reaction and compares, and obtained polymer molecular weight is bigger, color is more preferable, polymer quality is more preferable.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The preparation method of the polyester elastomer provided according to the first aspect of the invention includes：The first esterification and/
Or under conditions of ester exchange reaction, makes to react containing the mixture of the first dicarboxylic acids (ester) and the first dihydric alcohol, obtain first
Product after esterification and/or ester exchange reaction；Under conditions of the second esterification and/or ester exchange reaction, make containing
The mixture of product, the second dicarboxylic acids (ester) and the second dihydric alcohol after first esterification and/or ester exchange reaction
Reaction, the product after obtaining the second esterification and/or ester exchange reaction；Under the conditions of polycondensation reaction, deposited in polycondensation catalyst
Under, the product after making second esterification and/or ester exchange reaction carries out polycondensation reaction；Wherein, first binary
Carboxylic acid (ester) contain M-phthalic acid (ester), second dicarboxylic acids (ester) contain oxalic acid (ester), first dihydric alcohol and
Second dihydric alcohol contains ethylene glycol.
The preparation method provided according to the second aspect of the invention includes：In the first esterification and/or ester exchange reaction
Under conditions of, make containing the mixture of the first dicarboxylic acids (ester) and the first dihydric alcohol react, obtain the first esterification and/or
Product after ester exchange reaction；Under conditions of the second esterification and/or ester exchange reaction, make containing the second dicarboxylic acids
The reaction of the mixture of (ester) and the second dihydric alcohol, the product after obtaining the second esterification and/or ester exchange reaction；It is anti-in polycondensation
Under the conditions of answering, in the presence of polycondensation catalyst, the product after making first esterification and/or ester exchange reaction and described
The mixture of product after class reaction and/or ester exchange reaction carries out polycondensation reaction；Wherein, first dicarboxylic acids
(ester) contains M-phthalic acid (ester), and second dicarboxylic acids (ester) contains oxalic acid (ester), first dihydric alcohol and described
Second dihydric alcohol contains ethylene glycol.
In the present invention, dicarboxylic acids (ester) indicates dicarboxylic acids and/or dicarboxylic esters, similarly, the oxalic acid
(ester) indicates oxalic acid and/or oxalate, and the M-phthalic acid (ester) indicates M-phthalic acid and/or isophthalic acid ester.Separately
Outside, in the present invention, expression similar to the above also illustrates that identical meaning.
According to the present invention, first dicarboxylic acids (ester) contains M-phthalic acid (ester) as neccessary composition.
It is M-phthalic acid, M-phthalic acid monoalkyl ester and isophthalic two preferably as the M-phthalic acid (ester)
One of formic acid dialkyl ester is a variety of, and in the M-phthalic acid monoalkyl ester and the dialkyl isophthalate
Alkyl be carbon atom number be 1-4 straight chained alkyl (more preferably carbon atom number be 1-3 straight chained alkyl)；It is highly preferred that described
M-phthalic acid (ester) is M-phthalic acid, dimethyl isophthalate, dimethyl isophthalate and M-phthalic acid dipropyl
One of ester is a variety of；It is further preferred that the M-phthalic acid (ester) is M-phthalic acid and/or M-phthalic acid two
Methyl esters.
Second dicarboxylic acids (ester) contains oxalic acid (ester) as neccessary composition.
It preferably as the oxalic acid (ester) is one of oxalic acid, oxalic acid monoalkyl ester and dialkyl oxalate or more
Kind, and the alkyl in the oxalic acid monoalkyl ester and the dialkyl oxalate is that the straight chained alkyl that carbon atom number is 1-4 is (more excellent
It is selected as the straight chained alkyl that carbon atom number is 1-3)；It is highly preferred that the oxalic acid (ester) is oxalic acid, dimethyl oxalate, oxalic acid diethyl
One of ester and dipropyl oxalate are a variety of；It is further preferred that the oxalic acid (ester) is oxalic acid, dimethyl oxalate and oxalic acid
One of diethylester is a variety of.
According to the present invention, for the elastic property of the elastomer further increased, it is preferable that with first binary
The integral molar quantity of carboxylic acid (ester) and second dicarboxylic acids (ester) is 100 moles of %, and the mole of the oxalic acid (ester) is 9-
90 moles of %, the mole of the M-phthalic acid (ester) are 10-91 moles of %；It is highly preferred that with first dicarboxylic acids
The integral molar quantity of (ester) and second dicarboxylic acids (ester) is 100 moles of %, and the mole of the oxalic acid (ester) is rubbed for 9-45
You are %, and the mole of the M-phthalic acid (ester) is 55-91 moles of %.
According to the present invention, for the performance of the mechanics of the elastomer improved, it is preferable that first dicarboxylic acids
(ester) and/or second dicarboxylic acids (ester) are also containing the binary removed other than the oxalic acid (ester) and M-phthalic acid (ester)
Carboxylic acid (ester) (hereinafter also referred to third carboxylic acid (ester)).It can be terephthalic acid (TPA), to benzene two as the third carboxylic acid (ester)
Formic acid esters, phthalic acid, phthalic acid ester, 5- sodium sulfonate-terephthalic acid (TPA) (ester), 1,4- succinic acid (ester) and 1,6- oneself
One of diacid (ester), decanedioic acid (ester) are a variety of；Preferably 1,4- succinic acid (ester) and/or decanedioic acid (ester).
According to the present invention, also contain third in first dicarboxylic acids (ester) and/or second dicarboxylic acids (ester)
When carboxylic acid (ester), with the integral molar quantity of first dicarboxylic acids (ester) and second dicarboxylic acids (ester) for 100 moles of %,
The mole of the oxalic acid (ester) is 10-90 moles of %, and the mole of the M-phthalic acid (ester) is 9-80 moles of %, described
The mole of third carboxylic acid (ester) is 1-10 moles of %；Preferably, with first dicarboxylic acids (ester) and second binary
The integral molar quantity of carboxylic acid (ester) is 100 moles of %, and the mole of the oxalic acid (ester) is 9-45 moles of %, the M-phthalic acid
The mole of (ester) is 50-81 moles of %, and the mole of the third carboxylic acid (ester) is 5-10 moles of %.
In the present invention, the third carboxylic acid (ester) if dosage meet above-mentioned dosage, may be embodied in institute
It states in the first dicarboxylic acids (ester), also may be embodied in second dicarboxylic acids (ester), be further included in described first
In dicarboxylic acids (ester) and second dicarboxylic acids (ester).
According to the present invention, first dihydric alcohol and/or the second dihydric alcohol can be ethylene glycol.But in order to keep giving birth to
On the basis of object degradation property, the fusing point of copolymer is further decreased, preferably described first dihydric alcohol and/or the second dihydric alcohol are
Ethylene glycol and the dihydric alcohol other than ethylene glycol.
In the present invention, when first dihydric alcohol and/or the second dihydric alcohol also contain the binary other than ethylene glycol
It is preferably 1,2-PD, 1,3-PD, 2- methyl-1,3- third as the dihydric alcohol other than ethylene glycol when alcohol
Glycol, 2,2- dimethyl -1,3- propylene glycol, 2- ethyl -2- butyl -1,3- propylene glycol, 1,3 butylene glycol, 1,4- butanediol, 1,
One of 4- cyclohexanedimethanol, diethylene glycol (DEG) and triethylene glycol are a variety of；More preferably 1,3- propylene glycol, 1,4- butanediol and two
One of glycol is a variety of.
In the present invention, when first dihydric alcohol and/or second dihydric alcohol also contain other than ethylene glycol
When dihydric alcohol, with the integral molar quantity of first dihydric alcohol and second dihydric alcohol for 100 moles of %, the ethylene glycol rubs
Your amount is 90-99.9 moles of %, and the mole for removing the dihydric alcohol other than ethylene glycol is 0.1-10 moles of %.
It in the present invention, can as long as the dosage for removing the dihydric alcohol other than ethylene glycol meets above-mentioned dosage
To be included in first dihydric alcohol, it also may be embodied in second dihydric alcohol, be further included in the described 1st
In first alcohol and second dihydric alcohol.
According to the present invention, the amount ratio of first dicarboxylic acids (ester) and first dihydric alcohol can be in wider model
Enclose interior variation, it is preferable that the molar ratio of first dicarboxylic acids (ester) and first dihydric alcohol is 1：0.8-4, more preferably
It is 1：0.8-1.5.
According to the present invention, the amount ratio of second dicarboxylic acids (ester) and second dihydric alcohol can be in wider model
Enclose interior variation, it is preferable that the molar ratio of second dicarboxylic acids (ester) and second dihydric alcohol is 1：0.8-4, more preferably
It is 1：0.8-1.5.
According to the present invention, for the stability, resilience and mechanical property of the elastomer further increased, preferably
Ground, first esterification and/or ester exchange reaction, in one of polyalcohol, polyacid, unsaturated acids and unsaturated alcohol
Or it is a variety of in the presence of carry out.
According to the present invention, the polyacid and polyalcohol refer to compound of the functional group number greater than 2 of carboxyl and hydroxyl,
The including but not limited to inclined benzene front three of citric acid, glycerol, gluconic acid, trimethylolpropane, 1,3,5- trimesic acid, 1,2,4-
Acid, 1,2,4- inclined benzene three acid anhydrides, pentaerythrites, dipentaerythritol etc., preferably trimethylolpropane, citric acid, 1,3,5- is equal
One of benzenetricarboxylic acid is a variety of.
According to the present invention, the unsaturated acids (ester) or unsaturated alcohol refer to alcohol or acid (ester) chemical combination with olefinic double bonds
Object, including but not limited to epoxidized soybean oil, fumaric acid, fumarate, itaconic acid or itaconate.Preferably fumaric acid and/or
Dimethyl fumarate.
As the dosage of the polyalcohol, polyacid, unsaturated acids (ester) or unsaturated alcohol, preferably with first binary
On the basis of the integral molar quantity of carboxylic acid (ester) and second dicarboxylic acids (ester), the polyalcohol, polyacid, unsaturated acids (ester)
Or the dosage of unsaturated alcohol is 0.1-10 moles of %, more preferably 0.5-5 moles of %, further preferably 2-5 moles of %.
According to the present invention, for first esterification and/or ester exchange reaction and described in the second esterification
And/or there is no particular limitation for the condition of ester exchange reaction, can be condition commonly used in the art.Such as first esterification is instead
Answer and/or ester exchange reaction and it is described can be carried out under catalyst in the second esterification and/or ester exchange reaction,
It can not be carried out under catalyst.Whether carried out under catalyst, those skilled in the art can be appropriate according to the raw material of reaction
Ground is selected.In addition, first esterification and/or ester exchange reaction and described in the second esterification and/or ester
The actual conditions of exchange reaction for example including：Reaction temperature is 100-280 DEG C, and reaction absolute pressure is 0-0.5MPa, when reaction
Between be 1-10 hours；Preferably, reaction temperature is 140-250 DEG C, and reaction absolute pressure is 0.1-0.4MPa, reaction time 2-
6 hours.
According to the present invention, first esterification and/or ester exchange reaction and it is described the second esterification and/
Or ester exchange reaction can carry out in the presence of a catalyst, it can also be without being carried out in the case where catalyst.It is preferred that described
One esterification and/or ester exchange reaction and it is described the second esterification and/or ester exchange reaction catalyst presence
Lower progress, ester exchange catalyst are selected from one of metal hydroxides, metal oxide, metal salt or titanate compound
Or a variety of, preferably metal acetate salt or titanate esters.The more preferable catalyst be manganese acetate, magnesium acetate, antimony oxide and
One of titanate esters are a variety of.
As above-mentioned catalyst dosage can be this field conventional amount used, for example, first esterification and/
Or in ester exchange reaction, on the basis of the weight of first dicarboxylic acids (ester), the dosage of the catalyst is 0.01-1 weight
Measure %, preferably 0.03-0.2 weight %, more preferably 0.03-0.1 weight %.It is handed in second esterification and/or ester
It changes in reaction, on the basis of the weight of second dicarboxylic acids (ester), the dosage of the catalyst is 0.01-1 weight %, excellent
It is selected as 0.03-0.2 weight %, more preferably 0.03-0.1 weight %.
According to the present invention, the polymerizing condition is that reaction absolute pressure is less than 45kPa, and polymerization temperature is 200-300 DEG C, is gathered
Closing the time is 0.5-10 hours.
In order to preferably control polymer quality, the polycondensation can be divided into prepolymerization and final minification poly- two stages.It is described pre-
Esterification products are carried out prepolymerization reaction under the vacuum condition of 45kPa~5kPa by the poly- stage.Preferably, the precondensation
Condition includes that reaction temperature is 200-240 DEG C, reacts absolute pressure between 30kPa-5kPa, and the reaction time is 0.5-4 hours
In order to preferably carry out polycondensation reaction, increase polymer molecular weight, the polymer by precondensation is also needed into one
The reduction pressure of step improves temperature, carries out melt polycondensation.Preferably, the condition of the melt polycondensation reaction includes：Reaction temperature
It is 220-300 DEG C, reaction absolute pressure is 1500Pa hereinafter, the reaction time is 0.5-6 hours.
The polycondensation catalyst can be the various catalyst for ester polycondensation commonly used in the art, such as the polycondensation is urged
Agent can be selected from one of metal hydroxides, metal oxide, metal salt or titanate compound or a variety of, preferably
For antimony glycol, antimony oxide, selenium dioxide, carbon atom number be 1-12 alkyl aluminum, acetate, titanate esters, trifluoro methylsulphur
One of hydrochlorate and organic tin compound are a variety of；More preferably in antimony glycol, butyl titanate and selenium dioxide
It is one or more.
Dosage as the polycondensation catalyst can be the conventional amount used of this field, for example, with the first binary carboxylic
On the basis of the total weight of sour (ester) and second dicarboxylic acids (ester), the dosage of the catalyst is 0.005-1 weight %, excellent
It is selected as 0.03-0.2 weight %, more preferably 0.03-0.1 weight %.
According to the present invention, the present invention does not specially require the adding manner of polycondensation catalyst, and polycondensation catalyst can be with one
Secondary addition can also be continuously added in batches.It, can be in addition, the addition opportunity for polycondensation catalyst does not also require particularly
It is added in first esterification and/or ester exchange reaction or described anti-in the second esterification and/or transesterification
Middle addition is answered, or is added in polycondensation reaction.
In the case where, according to the invention it is preferred to, the polycondensation reaction carries out in the presence of heat stabilizer and/or antioxidant.
The stabilizer and antioxidant can be various stabilizers and antioxidant commonly used in the art.The stabilizer is preferably that phosphatization is closed
Object, the phosphorus compound are preferably phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acids, phosphate n-butyl, p isopropylbenzoic acid ester, tricresyl phosphate
Ethyl ester, trimethyl phosphate, triphenyl phosphate etc. it is one or more.The antioxidant can be double for hindered phenol, thio-2 acid
The one or more of ester and aromatic amine antioxidant, preferably 2,6- three-level butyl -4- methylphenol, bis- (3,5- three-level fourths
Base -4- hydroxy phenyl) thioether, four (β-(3,5- three-level butyl -4- hydroxy phenyl) propionic acid) pentaerythritol esters, 1222 and of antioxidant
One of antioxidant 1010 is a variety of.
In the present invention, (for the polyester elastomer of the first aspect of the present invention on the basis of the weight of polycondensation reaction raw material
Preparation method when, in this way obtained in product after the second esterification and/or ester exchange reaction weight on the basis of；
When the preparation method of the polyester elastomer of the second aspect of the present invention, in this way obtained in the first esterification and/or ester
On the basis of the weight of the mixture of the product after product and the second esterification and/or ester exchange reaction after exchange reaction), institute
The dosage for stating heat stabilizer is 0.1-10 weight %, preferably 0.3-8 weight %, further preferably 0.5-5 weight %；It is described
The dosage of antioxidant is 0.1-5 weight %, preferably 0.3-3 weight %, further preferably 0.5-2.5 weight %.
In accordance with the present invention it is preferred that this method further includes in first esterification and/or ester-exchange reaction
In or it is described in the second esterification and/or ester exchange reaction during, or in polycondensation process, chain extender is added
To increase the reaction rate of end group, the molecular weight of product is improved.Preferably, the chain extender, which is selected from, includes two or more
One of epoxy group, the compound of isocyanate groups, double oxazolines or organic acid acid anhydrides are a variety of.Further preferred institute
Stating chain extender is at least one in diisocyanate, phthalic anhydride, pyromellitic dianhydride, double oxazolines and epoxy resin
Kind.In addition, the dosage of chain extender can be the conventional amount used of this field, such as with first dicarboxylic acids (ester) and described the
It is 0.1-3 weight % on the basis of the total weight of two dicarboxylic acids (ester).
According to the present invention, a small amount of other functional additives, such as ultraviolet absorbing agent, resistance can also be contained as needed
Fire agent, fluorescent whitening agent, delustering agent, antistatic agent, antibacterial agent, opening agent etc..It is not special for the dosage of above-mentioned additive
Restriction, can be the conventional amount used of this field, not stated herein tired.
In the case where, according to the invention it is preferred to, this method further includes：After polycondensation reaction, being passed through inert gas will
Pressure rises to 0.1-1MPa, then carries out cooling and pelletizing.The cooling and pelletizing are well known in the art, no longer tired herein
It states.
The present invention also provides a kind of polyester elastomers being prepared by the above method.
Polyester elastomer according to the present invention, for glass transition temperature at -60~-8 DEG C, tensile strength is 0.3MPa or more,
Elongation at break is 390% or more, and intrinsic viscosity is in 0.1dl/L or more, with glass transition temperature is low, mechanical property is good, color
The advantages that good and resilience is good.
The present invention will be described in detail by way of examples below.
In following embodiment and comparative example, using the glass transition temperature of DSC method test polyester elastomer；Using GB/T
The tensile strength and elongation at break of the method test polyester elastomer of 528-2009；It is tested using 14855 compost of standard ISO
Measure the biodegradability of polyester.
The measurement of coloration is carried out by color difference meter.By the way that by sample, after 110 DEG C 4 hours dry, taking-up is cooled to 25
After DEG C, the particle of 350~833um is taken, sample particle is put into specimen cup and is accumulated closely, specimen cup is placed on measured hole,
The coloration (L, a, b) of sample is measured, 120 degree of measurements of every rotation are primary, survey altogether at 3 points, take 3 points of average value.
Molecular weight of polyesters is indicated with intrinsic viscosity.
Pressure is absolute pressure in following embodiment and comparative example.
Embodiment 1
The M-phthalic acid of 182.6g (1.1mol), the ethylene glycol and second of 93g (1.5mol) are added in batch reactor
Glycol antimony (on the basis of the weight of above-mentioned dicarboxylic acids (ester), dosage is 0.01 weight %), in 220~250 DEG C, pressure
Esterification and end esterification after transesterification 1 hour, reactor pressure is let out to normal pressure, 10g (0.11mol) is added under 0.25MPa
Oxalic acid and 7.6g (0.12mol) ethylene glycol, antimony glycol (on the basis of the weight of above-mentioned oxalic acid, dosage be 0.01 weight
Measure %), it is esterified under 160-200 degree under normal pressure, trimethyl phosphate is added after esterification (after esterification and ester exchange reaction
Product weight on the basis of, dosage be 0.1 weight %) after, gradually decompression heating, 200 DEG C, pressure be 30kPa condition
Then lower polycondensation 0.5 hour continues to heat up and depressurize, reaction kettle vacuum reaches 1500Pa after 45 minutes, and reaction temperature is maintained
250~260 DEG C, using polymerization reaction is terminated after polymerization in 110 minutes, vacuum is eliminated with nitrogen, water cooled, pelletizing can obtain polyester
Elastomer A1.A1 is measured, glass transition temperature, tensile strength, elongation at break, intrinsic viscosity, color and biology drop
It is as shown in table 1 to solve performance.
Embodiment 2
The M-phthalic acid of 182.6g (1.1mol), the ethylene glycol and vinegar of 93g (1.5mol) are added in batch reactor
Sour magnesium (on the basis of the weight of above-mentioned dicarboxylic acids (ester), dosage is 0.01 weight %), in 220~250 DEG C, pressure
Esterification and end esterification after transesterification 1 hour, reactor pressure is let out to normal pressure, adds 81g's (0.9mol) under 0.25MPa
It is esterified under 160-200 degree under oxalic acid and 62g (1.0mol) ethylene glycol normal pressure, phosphoric acid is then added after esterification (with ester
Change on the basis of the weight of the product after ester exchange reaction, dosage is 0.5 weight %), antimony glycol (with above-mentioned dicarboxylic acids
On the basis of the weight of (ester), dosage is 0.03 weight %) and after mixing evenly, in 240 DEG C, pressure to contract under conditions of 30kPa
Poly- 4 hours, then, continue to heat up and depressurize, reaction kettle vacuum reaches 90Pa after 15 minutes, and reaction temperature is maintained 250~260
DEG C, vacuum is eliminated using polymerization reaction nitrogen is terminated after 80 minutes, water cooled, pelletizing can obtain polyester elastomer A2.To A2
It is measured, glass transition temperature, tensile strength, elongation at break, intrinsic viscosity, color and biodegradability such as 1 institute of table
Show.
Embodiment 3
The diethy-aceto oxalate of 146g (1.0mol), the ethylene glycol and acetic acid of 93g (1.5mol) are added in batch reactor
Magnesium (on the basis of the weight of above-mentioned dicarboxylic acids (ester), dosage be 0.01 weight %), under 160~220 DEG C, normal pressure esterification and
Terminate esterification after transesterification 1 hour, the M-phthalic acid and 62g (1.0mol) ethylene glycol for adding 198.2g (1.2mol) exist
220~250 DEG C, be esterified and terminate esterification after transesterification 4 hours under pressure 0.25MPa, be then added after esterification phosphoric acid (with
On the basis of the weight of product after esterification and ester exchange reaction, dosage is 0.5 weight %), antimony glycol (with above-mentioned dicarboxylic acids
On the basis of the weight of (ester), dosage is 0.03 weight %) and after mixing evenly, gradually decompression heating is in 200 DEG C, pressure
Then polycondensation 0.5 hour under conditions of 30kPa is continued to heat up and be depressurized, reaction kettle vacuum reaches 600Pa after 15 minutes, will react
Temperature maintains 240-250 DEG C, using polymerization reaction is terminated after polymerization in 90 minutes, eliminates vacuum, water cooled, pelletizing with nitrogen
Polyester elastomer A3 can be obtained.A3 is measured, glass transition temperature, tensile strength, elongation at break, intrinsic viscosity, color
It is as shown in table 1 with biodegradability.
Embodiment 4
It carries out according to the method for embodiment 1, unlike：The M-phthalic acid of part is replaced with terephthalic acid (TPA), and right
The dosage of phthalic acid is 10 moles of % of dosage of the dicarboxylic acids (ester) in embodiment 1；Part is replaced with 1,4- butanediol
Ethylene glycol, and the dosage of 1,4-butanediol is 10 moles of % of dosage of the dihydric alcohol in embodiment 1, obtains polyester elastomer A4.
A4 is measured, glass transition temperature, tensile strength, elongation at break, intrinsic viscosity, color and biodegradability such as table
Shown in 1.
Embodiment 5
It is carried out according to the method for embodiment 3, unlike：The oxalic acid of part, and the dosage of adipic acid are replaced with adipic acid
For 5 moles of % of dosage of the dicarboxylic acids (ester) in embodiment 1；The ethylene glycol of part, and the use of diethylene glycol (DEG) are replaced with diethylene glycol (DEG)
Amount is 5 moles of % of dosage of the dihydric alcohol in embodiment 1, obtains polyester elastomer A5.A5 is measured, vitrifying temperature
Degree, tensile strength, elongation at break, intrinsic viscosity, color and biodegradability are as shown in table 1.
Embodiment 6
Unlike carrying out according to the method for embodiment 1, citric acid, and lemon are also added in esterification and ester exchange reaction
The dosage of lemon acid is 1 mole of % of dosage of the dicarboxylic acids (ester) in embodiment 1, obtains polyester elastomer A6.A6 is surveyed
Fixed, glass transition temperature, tensile strength, elongation at break, intrinsic viscosity, color and biodegradability are as shown in table 1.
Embodiment 7
Unlike carrying out according to the method for embodiment 1, fumaric acid diformazan is also added in esterification and ester exchange reaction
Ester, and the dosage of dimethyl fumarate is 10 moles of % of dosage of the dicarboxylic acids (ester) in embodiment 1, obtains polyester elastomer
A7.A7 is measured, glass transition temperature, tensile strength, elongation at break, intrinsic viscosity, color and biodegradability
As shown in table 1.
Embodiment 8
The diethy-aceto oxalate of 146g (1.0mol), the ethylene glycol and acetic acid of 93g (1.5mol) are added in batch reactor
Magnesium (on the basis of the weight of above-mentioned dicarboxylic acids (ester), dosage be 0.01 weight %), under 160~220 DEG C, normal pressure esterification and
Terminate esterification after transesterification 1 hour, in an other reaction kettle, the M-phthalic acid and 93g of 198.2g (1.2mol) is added
(1.5mol) ethylene glycol terminates esterification after being esterified 4 hours at 220~250 DEG C, pressure 0.25MPa and obtains prepolymer.Esterification knot
The prepolymer for being esterified two kinds after beam mixes, and phosphoric acid is added and (to be esterified on the basis of the weight of the product after ester exchange reaction, uses
Amount is 0.5 weight %), (on the basis of the weight of above-mentioned dicarboxylic acids (ester), dosage is 0.03 weight %) to antimony glycol and stirs
Mix uniformly after, gradually decompression heating, 200 DEG C, pressure be 30kPa under conditions of polycondensation 0.5 hour, then, continue heating simultaneously
Decompression, reaction kettle vacuum reaches 600Pa after 15 minutes, and reaction temperature is maintained 240-250 DEG C, ties after polymerizeing using 90 minutes
Beam polymerization reaction eliminates vacuum with nitrogen, and water cooled, pelletizing can obtain polyester elastomer A8.A8 is measured, vitrifying temperature
Degree, tensile strength, elongation at break, intrinsic viscosity, color and biodegradability are as shown in table 1.
Embodiment 9
The diethy-aceto oxalate of 146g (1.0mol), the ethylene glycol and acetic acid of 93g (1.5mol) are added in batch reactor
Magnesium (on the basis of the weight of above-mentioned dicarboxylic acids (ester), dosage be 0.01 weight %), under 160~220 DEG C, normal pressure esterification and
Terminate esterification after transesterification 1 hour, in an other reaction kettle, the M-phthalic acid and 12.4g of 16.6g (0.1mol) is added
(0.2mol) ethylene glycol terminates esterification after being esterified 4 hours at 220~250 DEG C, pressure 0.25MPa and obtains prepolymer.Esterification knot
The prepolymer for being esterified two kinds after beam mixes, and phosphoric acid is added and (to be esterified on the basis of the weight of the product after ester exchange reaction, uses
Amount is 0.5 weight %), (on the basis of the weight of above-mentioned dicarboxylic acids (ester), dosage is 0.03 weight %) to antimony glycol and stirs
Mix uniformly after, gradually decompression heating, 200 DEG C, pressure be 30kPa under conditions of polycondensation 0.5 hour, then, continue heating simultaneously
Decompression, reaction kettle vacuum reaches 600Pa after 15 minutes, and reaction temperature is maintained 240-250 DEG C, ties after polymerizeing using 90 minutes
Beam polymerization reaction eliminates vacuum with nitrogen, and water cooled, pelletizing can obtain polyester elastomer A9.A9 is measured, vitrifying temperature
Degree, tensile strength, elongation at break, intrinsic viscosity, color and biodegradability are as shown in table 1.
Comparative example 1
Be added in batch reactor the M-phthalic acid of 182.6g (1.1mol), 100.6g (1.62mol) ethylene glycol,
(on the basis of the weight of above-mentioned dicarboxylic acids (ester), dosage is 0.01 weight to the oxalic acid and antimony glycol of 10g (0.11mol)
Measure %), at 220~250 DEG C, pressure 0.25MPa esterification and after transesterification 1 hour terminate esterification, by reactor pressure let out to
Trimethyl phosphate is added in normal pressure (to be esterified on the basis of the weight of the product after ester exchange reaction, dosage is 0.1 weight %)
Afterwards, gradually decompression heating, 200 DEG C, pressure be 30kPa under conditions of polycondensation 0.5 hour, then, continue to heat up and depressurize, 45
Reaction kettle vacuum reaches 1500Pa after minute, and reaction temperature is maintained 250~260 DEG C, poly- using terminating after polymerization in 110 minutes
Reaction is closed, eliminates vacuum with nitrogen, water cooled, pelletizing can obtain polyester elastomer B1.B1 is measured, glass transition temperature,
Tensile strength, elongation at break, intrinsic viscosity, color and biodegradability are as shown in table 1.
Comparative example 2
Be added in batch reactor the M-phthalic acid of 182.6g (1.1mol), 100.6g (1.62mol) ethylene glycol,
(on the basis of the weight of above-mentioned dicarboxylic acids (ester), dosage is 0.01 weight to the oxalic acid and antimony glycol of 10g (0.11mol)
Measure %), it is esterified under 160-220 degree under normal pressure, esterification and ester are handed at 220~250 DEG C, pressure 0.25MPa again after 2 hours
Terminate esterification after changing 1 hour, reactor pressure is let out to normal pressure, trimethyl phosphate is added (after esterification and ester exchange reaction
On the basis of the weight of product, dosage be 0.1 weight %) after, gradually decompression heating, 200 DEG C, pressure be 30kPa under conditions of
Polycondensation 0.5 hour, then, continue to heat up and depressurize, reaction kettle vacuum reaches 1500Pa after 45 minutes, and reaction temperature is maintained
250~260 DEG C, using polymerization reaction is terminated after polymerization in 110 minutes, vacuum is eliminated with nitrogen, water cooled, pelletizing can obtain polyester
Elastomer B2.B2 is measured, glass transition temperature, tensile strength, elongation at break, intrinsic viscosity, color and biology drop
It is as shown in table 1 to solve performance.
Comparative example 3
Be added in batch reactor the M-phthalic acid of 16.6g (0.1mol), 105.4g (1.7mol) ethylene glycol,
The diethy-aceto oxalate and magnesium acetate (on the basis of the weight of above-mentioned dicarboxylic acids, dosage is 0.1 weight %) of 146g (1.0mol),
Three times with nitrogen displacement, it is esterified under 160-220 degree under normal pressure, after 1 hour again at 220~250 DEG C, pressure 0.25MPa
Esterification and end esterification after transesterification 4 hours,.Then phosphoric acid is added (is with esterification and the weight of the product after ester exchange reaction
Benchmark, dosage is 0.5 weight %), (on the basis of the weight of above-mentioned dicarboxylic acids (ester), dosage is 0.03 weight to antimony glycol
Measure %) and after mixing evenly, polycondensation 4 hours under conditions of 240 DEG C, pressure is 30kPa, then, continues to heat up and depressurize, 15
Reaction kettle vacuum reaches 90Pa after minute, and reaction temperature is maintained 250~260 DEG C, using terminating polymerization reaction after 80 minutes
Vacuum is eliminated with nitrogen, water cooled, pelletizing can obtain polyester elastomer B3.B3 is measured, glass transition temperature stretches by force
Degree, elongation at break, intrinsic viscosity, color and biodegradability are as shown in table 1.
Table 1
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (23)
1. a kind of preparation method of polyester elastomer, which is characterized in that this method includes：It is handed in the first esterification and/or ester
It changes under conditions of reaction, makes to react containing the mixture of the first dicarboxylic acids (ester) and the first dihydric alcohol, it is anti-to obtain the first esterification
Answer and/or ester exchange reaction after product；Under conditions of the second esterification and/or ester exchange reaction, make containing described
The mixture of product, the second dicarboxylic acids (ester) and the second dihydric alcohol after one esterification and/or ester exchange reaction reacts, and obtains
Product to after the second esterification and/or ester exchange reaction；Under the conditions of polycondensation reaction, in the presence of polycondensation catalyst, make
Product after second esterification and/or ester exchange reaction carries out polycondensation reaction；Wherein, first dicarboxylic acids (ester)
Containing M-phthalic acid (ester), second dicarboxylic acids (ester) contains oxalic acid (ester), first dihydric alcohol and described second
Dihydric alcohol contains ethylene glycol.
2. a kind of preparation method of polyester elastomer, which is characterized in that this method includes：It is handed in the first esterification and/or ester
It changes under conditions of reaction, makes to react containing the mixture of the first dicarboxylic acids (ester) and the first dihydric alcohol, it is anti-to obtain the first esterification
Answer and/or ester exchange reaction after product；Under conditions of the second esterification and/or ester exchange reaction, make containing the two or two
The reaction of the mixture of first carboxylic acid (ester) and the second dihydric alcohol, the product after obtaining the second esterification and/or ester exchange reaction；?
Under the conditions of polycondensation reaction, in the presence of polycondensation catalyst, product after making first esterification and/or ester exchange reaction and
The mixture of product after second esterification and/or ester exchange reaction carries out polycondensation reaction；Wherein, first binary
Carboxylic acid (ester) contain M-phthalic acid (ester), second dicarboxylic acids (ester) contain oxalic acid (ester), first dihydric alcohol and
Second dihydric alcohol contains ethylene glycol.
3. method according to claim 1 or 2, wherein first dicarboxylic acids (ester) and first dihydric alcohol
Molar ratio is 1：0.8-4.
4. according to the method described in claim 3, wherein, mole of first dicarboxylic acids (ester) and first dihydric alcohol
Than being 1：0.8-1.5.
5. method according to claim 1 or 2, wherein second dicarboxylic acids (ester) and second dihydric alcohol
Molar ratio is 1：0.8-4.
6. according to the method described in claim 5, wherein, mole of second dicarboxylic acids (ester) and second dihydric alcohol
Than being 1：0.8-1.5.
7. the method according to claim 1 or claim 2, wherein with first dicarboxylic acids (ester) and the described 2nd 2
The integral molar quantity of first carboxylic acid (ester) is 100 moles of %, and the mole of the oxalic acid (ester) is 9-90 moles of %, the isophthalic diformazan
The mole of sour (ester) is 10-91 moles of %.
8. the method according to claim 1 or claim 2, wherein first dicarboxylic acids (ester) and/or the described 2nd 2
First carboxylic acid (ester) is also containing the dicarboxylic acids (ester) removed other than the oxalic acid (ester) and M-phthalic acid (ester), with described first
The integral molar quantity of dicarboxylic acids (ester) and second dicarboxylic acids (ester) is 100 moles of %, the mole of the oxalic acid (ester)
For 9-90 moles of %, the mole of the M-phthalic acid (ester) is 9-81 moles of %, it is described remove the oxalic acid (ester) and
The mole of dicarboxylic acids (ester) other than phthalic acid (ester) is 1-10 moles of %.
9. described to remove other than the oxalic acid (ester) and M-phthalic acid (ester) according to the method described in claim 8, wherein
Dicarboxylic acids (ester) is terephthalic acid (TPA), terephthalate, phthalic acid, phthalic acid ester, 5- sodium sulfonate-to benzene two
One of formic acid (ester), 1,4- succinic acid (ester), adipic acid (ester) and decanedioic acid (ester) are a variety of.
10. method according to claim 1 or 2, wherein first dihydric alcohol and the second dihydric alcohol are ethylene glycol.
11. the method according to claim 1 or claim 2, wherein first dihydric alcohol and/or second dihydric alcohol
Also containing the dihydric alcohol removed other than ethylene glycol, with the integral molar quantity of first dihydric alcohol and second dihydric alcohol for 100
Mole %, the mole of the ethylene glycol are 90-99.9 moles of %, and the mole for removing the dihydric alcohol other than ethylene glycol is
0.1-10 moles of %.
12. according to the method for claim 11, wherein it is described remove ethylene glycol other than dihydric alcohol be 1,2-PD,
1,3- propylene glycol, 2- methyl-1,3-propanediol, 2,2- dimethyl -1,3- propylene glycol, 2- ethyl -2- butyl -1,3- propylene glycol,
One of 1,3 butylene glycol, 1,4- butanediol, 1,4 cyclohexane dimethanol, diethylene glycol (DEG) and triethylene glycol are a variety of.
13. method according to claim 1 or 2, wherein the oxalic acid (ester) is oxalic acid, oxalic acid monoalkyl ester and oxalic acid
One of dialkyl ester is a variety of, and the alkyl in the oxalic acid monoalkyl ester and the dialkyl oxalate is carbon atom number
For the straight chained alkyl of 1-4；The M-phthalic acid (ester) is M-phthalic acid, M-phthalic acid monoalkyl ester and M-phthalic acid
One of dialkyl ester is a variety of, and alkyl in the M-phthalic acid monoalkyl ester and the dialkyl isophthalate
The straight chained alkyl for being 1-4 for carbon atom number.
14. according to the method for claim 13, wherein the oxalic acid (ester) is oxalic acid, dimethyl oxalate, diethy-aceto oxalate
With one of dipropyl oxalate or a variety of；The M-phthalic acid (ester) be M-phthalic acid, dimethyl isophthalate,
One of diethyl phthalate and M-phthalic acid dipropyl are a variety of.
15. method according to claim 1 or 2, wherein first esterification and/or ester exchange reaction, polynary
One of alcohol, polyacid, unsaturated acids and unsaturated alcohol or it is a variety of in the presence of carry out, with first dicarboxylic acids (ester)
On the basis of the integral molar quantity of second dicarboxylic acids (ester), the polyalcohol, polyacid, unsaturated acids (ester) or unsaturation
The dosage of alcohol is 0.1-10 moles of %.
16. method according to claim 1 or 2, wherein first esterification and/or ester exchange reaction, Yi Jisuo
It states the second esterification and/or ester exchange reaction to carry out in the presence of a catalyst, the catalyst is selected from metal hydroxides, gold
Belong to one of oxide, metal salt or titanate compound or a variety of.
17. according to the method for claim 16, wherein the catalyst is manganese acetate, magnesium acetate, antimony oxide and titanium
One of acid esters is a variety of.
18. according to the method for claim 16, wherein in first esterification and/or ester exchange reaction, with institute
On the basis of the weight for stating the first dicarboxylic acids (ester), the dosage of the catalyst is 0.01-1 weight %；
In second esterification and/or ester exchange reaction, on the basis of the weight of second dicarboxylic acids (ester), institute
The dosage for stating catalyst is 0.01-1 weight %.
19. according to the method for claim 16, wherein first esterification and/or ester exchange reaction and described
The condition of second esterification and/or ester exchange reaction includes：Reaction temperature is 120-280 DEG C, and reaction absolute pressure is 0-
0.5MPa, reaction time are 0.5-10 hours.
20. method according to claim 1 or 2, wherein the polycondensation catalyst is antimony glycol, antimony oxide, two
In selenium oxide, the alkyl aluminum that carbon atom number is 1-12, acetate, titanate esters, fluoroform sulphonate and organic tin compound
It is one or more；It is described to urge on the basis of the total weight of first dicarboxylic acids (ester) and second dicarboxylic acids (ester)
The dosage of agent is 0.005-1 weight %.
21. according to the method for claim 20, wherein the condition of the polycondensation reaction includes：Reaction absolute pressure is less than
45kPa, polymerization temperature are 200-300 DEG C, and polymerization time is 0.5-10 hours.
22. a kind of polyester elastomer of the preparation of the method as described in any one of claim 1-21.
23. polyester elastomer according to claim 22, wherein the glass transition temperature of the polyester elastomer be -60~-
8℃。
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