CN105524261B - 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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- CN105524261B CN105524261B CN201410573539.6A CN201410573539A CN105524261B CN 105524261 B CN105524261 B CN 105524261B CN 201410573539 A CN201410573539 A CN 201410573539A CN 105524261 B CN105524261 B CN 105524261B
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Abstract
The invention discloses a kind of polyester elastomer and preparation method thereof, it is characterised in that this method includes：Under conditions of esterification and/or ester exchange reaction, make to react containing the mixture of dicarboxylic acids (ester) and dihydric alcohol；Under the conditions of polycondensation reaction, in the presence of polycondensation catalyst, the product after esterification and/or ester exchange reaction is set to carry out polycondensation reaction；Wherein, the dicarboxylic acids (ester) contains ethylene glycol containing oxalic acid (ester) and M-phthalic acid (ester), the dihydric alcohol.The polyester elastomer of the present invention, its biodegradability is good and has excellent tensile property and resilience performance.
Description
Technical field
The present invention relates to a kind of polyester elastomer and preparation method thereof.
Background technology
Elastomer refers to that glass transition temperature is less than room temperature, elongation at break>50%, it is preferably high that external force withdraws from rear restoration
Molecular compound.Two major class of thermo-setting elastomer and thermoplastic elastomer (TPE) is divided into according to whether elastomer is plastic.
Polyethylene terephthalate (PET) is typically used as thermoplastic, the mechanical properties such as crystallinity, intensity,
Chemical resistance, heat resistance, electrical property, the transparency etc. excellent performance, it is various in film, fiber, bottle, extrusion molding article etc.
Largely used in purposes, China's polyethylene terephthalate production capacity is up to 25,000,000 tons.It is some be not easily recycled should
With occasion, just because of the above-mentioned excellent properties of polyethylene terephthalate, some white pollutions are caused to exist.In order to keep away
Exempt from this problem, improve the biodegradability of polyester, be the developing direction of polyester material.
Therefore, it is badly in need of a kind of biodegradability well and there is the polyester bullet of excellent tensile property and resilience performance
Property body.
The content of the invention
The purpose of the present invention is overcoming the above-mentioned problems in the prior art, there is provided a kind of biodegradability is good,
And the polyester elastomer with excellent tensile property and resilience performance.
To solve the above-mentioned problems, the present inventor conducts in-depth research discovery, by making the present invention specific
Dicarboxylic acids (ester) and specific dihydric alcohol mixture reaction；Under the conditions of polycondensation reaction, in the presence of polycondensation catalyst,
The product after esterification and/or ester exchange reaction is set to carry out the copolymer that polycondensation reaction obtains, it does not have clear and definite fusing point, table
Reveal elastomer performance, embody excellent tensile property, resilience, and can be biodegradable, have thus completed the present invention.
That is, the present invention provides a kind of preparation method of polyester elastomer, it is characterised in that this method includes：It is being esterified
Under conditions of reaction and/or ester exchange reaction, make to react containing the mixture of dicarboxylic acids (ester) and dihydric alcohol；In polycondensation reaction
Under the conditions of, in the presence of polycondensation catalyst, the product after esterification and/or ester exchange reaction is carried out polycondensation reaction；Wherein,
The dicarboxylic acids (ester) contains ethylene glycol containing oxalic acid (ester) and M-phthalic acid (ester), the dihydric alcohol.
The present invention also provides a kind of polyester elastomer obtained by the above method.
The preparation method of polyester elastomer according to the present invention, due to the use of having the oxalic acid (ester) of biological degradability,
So that the polyester elastomer that the present invention obtains has biological degradability；Due to using specific dicarboxylic acids (ester) and specific two
First alcohol so that obtained copolymer demonstrates flexibility body performance, and embodies excellent tensile property, resilience.
Polyester elastomer according to the present invention, has the advantages of glass transition temperature is low, and mechanical property is good, and resilience is good.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The preparation method of polyester elastomer provided by the invention includes：In esterification and/or the condition of ester exchange reaction
Under, make to react containing the mixture of dicarboxylic acids (ester) and dihydric alcohol；Under the conditions of polycondensation reaction, exist in polycondensation catalyst
Under, the product after esterification and/or ester exchange reaction is carried out polycondensation reaction；Wherein, the dicarboxylic acids (ester) contains grass
Sour (ester) and M-phthalic acid (ester), the dihydric alcohol contain ethylene glycol.
In the present invention, the dicarboxylic acids (ester) represents dicarboxylic acids and/or dicarboxylic esters, similarly, the grass
Sour (ester) represents oxalic acid and/or oxalate, and the M-phthalic acid (ester) represents M-phthalic acid and/or isophthalic acid ester.
In addition, in the present invention, expression similar to the above also illustrates that identical implication.
According to the present invention, the dicarboxylic acids (ester) contains oxalic acid (ester) and M-phthalic acid (ester).
It is oxalic acid, oxalic acid dihydrate, oxalic acid monoalkyl ester and dialkyl oxalate preferably as the oxalic acid (ester)
In one or more, and the alkyl in the oxalic acid monoalkyl ester and the dialkyl oxalate is that carbon number is 1-4's
Straight chained alkyl (straight chained alkyl that more preferably carbon number is 1-3)；It is highly preferred that the oxalic acid (ester) is oxalic acid, oxalic acid two
One or more in methyl esters, diethy-aceto oxalate and dipropyl oxalate；It is further preferred that the oxalic acid (ester) is oxalic acid, grass
One or more in dimethyl phthalate and diethy-aceto oxalate.
It is M-phthalic acid, M-phthalic acid monoalkyl ester and isophthalic two preferably as the M-phthalic acid (ester)
One or more in formic acid dialkyl ester, and in the M-phthalic acid monoalkyl ester and the dialkyl isophthalate
Alkyl is the straight chained alkyl (straight chained alkyl that more preferably carbon number is 1-3) that carbon number is 1-4；It is it is highly preferred that described
M-phthalic acid (ester) is M-phthalic acid, dimethyl isophthalate, dimethyl isophthalate and M-phthalic acid dipropyl
One or more in ester；It is further preferred that the M-phthalic acid (ester) is M-phthalic acid and/or M-phthalic acid two
Methyl esters.
According to the present invention, for the elastic performance of elastomer further improved, it is preferable that with the dicarboxylic acids
The integral molar quantity of (ester) is 100 moles of %, and the mole of the oxalic acid (ester) is 9-90 moles of %, the M-phthalic acid (ester)
Mole be 10-91 moles of %；In addition, in order on the basis of the elastic performance for keeping obtaining, further improve
The biodegradability of elastomer, it is highly preferred that using the integral molar quantity of the dicarboxylic acids (ester) as 100 moles of %, the grass
The mole of sour (ester) is 9-45 moles of %, 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 elastomer improved, it is preferable that the dicarboxylic acids (ester) is also
Contain dicarboxylic acids (ester) (hereinafter also referred to second carboxylic acid removed beyond the oxalic acid (ester) and M-phthalic acid (ester)
(ester)).Can be terephthalic acid (TPA), terephthalate, phthalic acid, phthalic acid as second carboxylic acid (ester)
One kind or more in ester, 5- sodium sulfonates-terephthalic acid (TPA) (ester), 1,4- succinic acid (ester), adipic acid (ester), decanedioic acid (ester)
Kind；Preferably decanedioic acid (ester) and/or adipic acid (ester).
According to the present invention, when the dicarboxylic acids (ester) also contains the second carboxylic acid (ester), with the dicarboxylic acids (ester)
Integral molar quantity be 100 moles of %, the mole of the oxalic acid (ester) is 9-90 moles of %, and M-phthalic acid (ester) rubs
Your amount is 9-81 moles of %, and the mole of dicarboxylic acids (ester) is 1-10 moles of %；Preferably, with the dicarboxylic acids (ester)
Integral molar quantity be 100 moles of %, the mole of the oxalic acid (ester) is 9-45 moles of %, and M-phthalic acid (ester) rubs
Your amount is 50-81 moles of %, and the mole of the dicarboxylic acids (ester) is 5-10 moles of %.
According to the present invention, the dihydric alcohol can be ethylene glycol.But in order on the basis of biodegradability is kept,
The fusing point of copolymer is further reduced, preferably described dihydric alcohol can also be ethylene glycol and the others two in addition to ethylene glycol
First alcohol.
In the present invention, it is preferred as other dihydric alcohols when the dihydric alcohol is also containing other dihydric alcohols
For 1,2- propane diols, 1,3- propane diols, 2- methyl-1,3-propanediols, 2,2- dimethyl -1,3- propane diols, 2- ethyl -2- fourths
Base -1,3- propane diols, 1,3 butylene glycol, 1,4- butanediols, 1,4 cyclohexane dimethanol, diethylene glycol (DEG) and one kind in triethylene glycol or
It is a variety of；One or more more preferably in 1,4- butanediols and diethylene glycol (DEG).
In the present invention, when the dihydric alcohol is also containing other dihydric alcohols, preferably with the total moles of the dihydric alcohol
Measure as 100 moles of %, the mole of the ethylene glycol is 90-99.9 moles of %, removes other dihydric alcohols beyond ethylene glycol
Mole be 0.1-10 moles of %；More preferably rub by 100 moles of %, the ethylene glycol of the integral molar quantity of the dihydric alcohol
Your amount is 90-95 moles of %, and the mole for removing other dihydric alcohols beyond ethylene glycol is 5-10 moles of %.
According to the present invention, the dicarboxylic acids (ester) and the amount ratio of dihydric alcohol can change in a wider scope, excellent
The molar ratio of selection of land, the dicarboxylic acids (ester) and dihydric alcohol is 1：0.8-4, more preferably 1：0.8-1.5, more preferably 1：
1.0-1.5。
According to the present invention, for stability, resilience and the mechanical property of the elastomer that further improve, preferably
Ground, also containing the one or more in polyalcohol, polyacid, unsaturated acids and unsaturated alcohol in the mixture.
According to the present invention, the polyacid and polyalcohol refer to compound of the functional group number more than 2 of carboxyl and hydroxyl,
The including but not limited to inclined benzene front three of citric acid, glycerine, gluconic acid, trimethylolpropane, 1,3,5- trimesic acids, 1,2,4-
Acid, preferably 1,2,4- inclined benzene three acid anhydrides, pentaerythrites, bipentaerythrite etc., trimethylolpropane, citric acid, 1,3,5- is equal
One or more in benzenetricarboxylic acid.
According to the present invention, the unsaturated acids (ester) or unsaturated alcohol refer to the alcohol with olefinic double bonds or acid (ester) chemical combination
Thing, includes 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 the dicarboxylic acids
On the basis of the mole of (ester), the polyalcohol, polyacid, the dosage of unsaturated acids (ester) or unsaturated alcohol are rubbed for 0.1-10
You are %, more preferably 0.5-5 moles of %, more preferably 2-5 moles of %.
According to the present invention, for the condition of the esterification and/or ester exchange reaction, there is no particular limitation, Ke Yiwei
Condition commonly used in the art., can not also be such as the esterification and/or ester exchange reaction can carry out under catalyst
Carried out under catalyst.Whether carried out under catalyst, those skilled in the art can suitably be selected according to the raw material of reaction
Select.In addition, the actual conditions of the esterification and/or ester exchange reaction for example including：Reaction temperature is 120-280 DEG C, instead
It is 0-0.5MPa to answer absolute pressure, when the reaction time is 0.5-10 small；Preferably, reaction temperature is 180-250 DEG C, and reaction is absolute
Pressure is 0.1-0.4MPa, when the reaction time is 1-4 small.
According to the present invention, the esterification and/or ester exchange reaction can carry out in the presence of a catalyst, can also
Do not have to carry out in the case of catalyst.It is preferred that the esterification and/or ester exchange reaction carry out in the presence of a catalyst, ester
The one kind or more of exchange process catalyst in metal hydroxides, metal oxide, metal salt or titanate compound
Kind, preferably metal acetate salt or titanate esters.More preferably described catalyst is manganese acetate, magnesium acetate, antimony oxide and metatitanic acid
One or more in ester.
Dosage as above-mentioned catalyst can be the conventional amount used of this area, for example, with the dicarboxylic acids (ester)
On the basis of weight, the dosage of the catalyst is 0.01-1 weight %, is preferably 0.03-0.2 weight %, more preferably 0.03-
0.1 weight %.
According to the present invention, after the mixture reaction of dicarboxylic acids (ester) and dihydric alcohol is made；Under the conditions of polycondensation reaction,
Under vacuum condition, in the presence of polycondensation catalyst, the product after esterification and/or ester exchange reaction is set to carry out polycondensation reaction.
The polymerizing condition is in the presence of polycondensation catalyst, and reaction absolute pressure is less than 45kPa, 200-300 DEG C of polymerization temperature, polymerization
When time is 0.5-10 small.
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 under the vacuum condition of 45kPa~5kPa, are carried out prepolymerization reaction by the poly- stage.Preferably, the precondensation
It is 200-240 DEG C that condition, which includes reaction temperature, and reaction absolute pressure is between 30kPa-5kPa, when the reaction time is 0.5-4 small.
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
For 220-300 DEG C, reaction absolute pressure is below 1500Pa, when the reaction time is 0.5-6 small.
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 the one or more in metal hydroxides, metal oxide, metal salt or titanate compound, preferably
The alkyl aluminum for being 1-12 for antimony glycol, antimony oxide, selenium dioxide, carbon number, acetate, titanate esters, fluoroform sulphur
One or more in hydrochlorate and organic tin compound；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 area, for example, with the dicarboxylic acids
On the basis of the weight of (ester), the dosage of the catalyst is 0.005-1 weight %, is preferably 0.03-0.2 weight %, more preferably
For 0.03-0.1 weight %.
According to the present invention, the present invention does not specially require the feed postition of polycondensation catalyst, and polycondensation catalyst can be with one
Secondary addition, can also be continuously added in batches., can be with addition, the addition opportunity for polycondensation catalyst does not also require particularly
Add, can also be added in polycondensation reaction in esterification and/or ester exchange reaction.
In the case of, 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
Thing, the phosphorus compound are preferably phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acids, phosphate n-butyl, p isopropylbenzoic acid ester, tricresyl phosphate
The one or more of ethyl ester, trimethyl phosphate, triphenyl phosphate etc..The antioxidant can be hindered phenol, thio-2 acid pair
The one or more of ester and aromatic amine antioxidant, are preferably 2,6- three-level butyl -4- methylphenols, double (3,5- three-level fourths
Base -4- hydroxy phenyls) thioether, four (β-(3,5- three-level butyl -4- hydroxy phenyls) propionic acid) pentaerythritol esters, 1222 and of antioxidant
One or more in antioxidant 1010.
In the present invention, on the basis of the weight of the product after the esterification and/or ester exchange reaction, the heat is steady
The dosage for determining agent is 0.1-10 weight %, is preferably 0.3-8 weight %, more preferably 0.5-5 weight %；The antioxidant
Dosage be 0.1-5 weight %, be preferably 0.3-3 weight %, more preferably 0.5-2.5 weight %.
In accordance with the present invention it is preferred that this method is additionally included in esterification and/or ester-exchange reaction, Huo Zhe
In polycondensation process, chain extender is added to increase the reaction rate of end group, improves the molecular weight of product.Kind of the present invention to chain extender
Class does not specially require, and can only react with difunctional with oxalate prepolymer.Preferably, the chain extender
In comprising two or more epoxide groups, the compound of isocyanate groups, double oxazolines or organic acid acid anhydrides
It is one or more.The further preferred chain extender is diisocyanate, phthalic anhydride, pyromellitic dianhydride, double oxazoles
At least one of quinoline and epoxy resin.In addition, the dosage of chain extender can be the conventional amount used of this area, such as with binary carboxylic
It is 0.1-3 weight % on the basis of sour (ester).
According to the present invention it is possible to it is conditioning agent and/or red system's conditioning agent to add as the indigo plant of color tone adjustment agents.Tone is adjusted
Agent can be dyestuff or cobalt salt.According to purpose, one or more can be used.
According to the present invention, a small amount of other functional additives, such as ultra-violet absorber, resistance can also be contained as needed
Fire agent, fluorescent whitening agent, delustering agent, antistatic additive, antiseptic, opening agent etc..It is not special for the dosage of above-mentioned additive
Restriction, can be this area conventional amount used, do not stated herein tired.
In the case of, 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, is then cooled down and pelletizing.The cooling and pelletizing are well known in the art, no longer tired herein
State.
The present invention also provides a kind of polyester elastomer being prepared by the above method.
Polyester elastomer according to the present invention, for its glass transition temperature at -60~-8 DEG C, tensile strength is more than 0.1MPa,
Elongation at break is more than 420%, has the advantages of glass transition temperature is low, and mechanical property is good, and resilience is good.
The present invention will be described in detail by way of examples below.
In following embodiments 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；Tested using 14855 compost of standard ISO
Measure the biodegradability of polyester.
In following embodiments and comparative example, pressure is absolute pressure.
Embodiment 1
M-phthalic acid, the ethylene glycol of 93g (1.5mol), the 10g of 182.6g (1.1mol) is added in batch reactor
The oxalic acid and antimony glycol (on the basis of the weight of above-mentioned dicarboxylic acids (ester), dosage is 0.01 weight %) of (0.11mol),
220~250 DEG C, when esterification and ester exchange 1 are small under pressure 0.25MPa after terminate esterification, reactor pressure is let out to normal pressure, is added
After trimethyl phosphate (to be esterified with the basis of the weight of the product after ester exchange reaction, dosage is 0.1 weight %), gradually decompression
Heating, when polycondensation 0.5 is small under conditions of being 30kPa in 200 DEG C, pressure, then, continues to heat up and depressurizes, reacted after 45 minutes
Kettle vacuum reaches 1500Pa, and reaction temperature is maintained 250~260 DEG C, then terminates polymerisation after polymerization in 110 minutes, uses
Nitrogen eliminates vacuum, and water cooled, pelletizing can obtain polyester elastomer A1.A1 is measured, its glass transition temperature, tensile strength,
Elongation at break and biodegradability are as shown in table 1.
Embodiment 2
M-phthalic acid, the ethylene glycol of 62.0g (1.0mol), the 81g of 16.6g (0.1mol) is added in batch reactor
The oxalic acid and magnesium acetate (on the basis of the weight of above-mentioned dicarboxylic acids, dosage is 0.1 weight %) of (0.9mol), use nitrogen displacement
Three times, esterification is terminated after when ester exchange 10 is small under 160~240 DEG C of normal pressures.Then phosphoric acid is added (with esterification and ester exchange reaction
On the basis of the weight of product afterwards, dosage is 0.5 weight %), antimony glycol is (using the weight of above-mentioned dicarboxylic acids (ester) as base
Standard, dosage are 0.03 weight %) and after stirring evenly, when polycondensation 4 is small under conditions of being 30kPa in 240 DEG C, pressure, then, after
Temperature of continuing rising simultaneously depressurizes, and reaction kettle vacuum reaches 90Pa after 15 minutes, and reaction temperature is maintained 250~260 DEG C, then by 80 minutes
After terminate polymerisation nitrogen eliminate vacuum, water cooled, pelletizing can obtain polyester elastomer A2.A2 is measured, its glass
It is as shown in table 1 to change temperature, tensile strength, elongation at break and biodegradability.
Embodiment 3
In batch reactor add 198.2g (1.2mol) M-phthalic acid, 155g (2.4mol) ethylene glycol,
The diethy-aceto oxalate and 1.5g antimony glycols of 146g (1.0mol), esterification and ester exchange under 220~250 DEG C, pressure 0.25MPa
4 it is small when after terminate esterification, reactor pressure is let out to normal pressure, add trimethyl phosphate (be esterified and ester exchange reaction after production
On the basis of the weight of thing, dosage is 0.5 weight %) after, gradually decompression heating, contracts under conditions of being 30kPa in 200 DEG C, pressure
It is poly- 0.5 it is small when, then, continue to heat up and depressurize, reaction kettle vacuum reaches 600Pa after 15 minutes, and reaction temperature is maintained 240-
250 DEG C, then terminate polymerisation after polymerization in 90 minutes, vacuum is eliminated with nitrogen, water cooled, pelletizing can obtain polyester elastomer
A3.A3 is measured, its glass transition temperature, tensile strength, elongation at break and biodegradability are as shown in table 1.
Embodiment 4
Carried out according to the method for embodiment 1, unlike：The M-phthalic acid of part, and decanedioic acid are replaced with decanedioic acid
Dosage be embodiment 1 in dicarboxylic acids (ester) 10 moles of % of dosage；The ethylene glycol of part is replaced with 1,4-butanediol, 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 surveyed
Fixed, its glass transition temperature, tensile strength, elongation at break and biodegradability are as shown in table 1.
Embodiment 5
Carried out according to the method for embodiment 3, unlike：The M-phthalic acid of part, and adipic acid are replaced with adipic acid
Dosage be embodiment 1 in dicarboxylic acids (ester) 5 moles of % of dosage；The ethylene glycol of part is replaced with diethylene glycol (DEG), and two is sweet
The dosage of alcohol is 5 moles of % of dosage of the dihydric alcohol in embodiment 1, obtains polyester elastomer A5.A5 is measured, its glass
It is as shown in table 1 to change temperature, tensile strength, elongation at break and biodegradability.
Embodiment 6
Unlike method according to embodiment 1 carries out, it is being esterified and is also being added with citric acid, and lemon in 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, its glass transition temperature, tensile strength, elongation at break and biodegradability are as shown in table 1.
Embodiment 7
Unlike method according to embodiment 1 carries out, it is being esterified and is also being added with fumaric acid diformazan in ester exchange reaction
Ester, and 10 moles of % of dosage that the dosage of dimethyl fumarate is the dicarboxylic acids (ester) in embodiment 1, obtain polyester elastomer
A7.A7 is measured, its glass transition temperature, tensile strength, elongation at break and biodegradability are as shown in table 1.
Comparative example 1
Carried out according to the method for embodiment 1, unlike, replace isophthalic diformazan with the terephthalic acid (TPA) of same molar
Acid, obtains polymer D1.D1 is measured, its glass transition temperature, tensile strength, elongation at break and biodegradability are such as
Shown in table 1.
Comparative example 2
Carried out according to the method for embodiment 1, unlike, binary acid (ester) is replaced with the oxalic acid of same molar, is obtained
Polymer D2.D2 is measured, its glass transition temperature, tensile strength, elongation at break and the biodegradability such as institute of table 1
Show.
Table 1
"-" represents to degrade.
As it can be seen from table 1 excellent biodegradability is shown with polymer provided by the invention, it is biodegradable
Rate can reach 98%.Do not possess polymer crystallization ability at the same time, this avoid influence of the crystallization to elasticity.It is prior
It is elastomer tensile strength provided by the invention, elongation at break, degradation property can be modified by the form of copolymerization,
Meet the requirement of the product of shaping class.Polymer provided by the invention can be used in preparing the material products such as rubber, film.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
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 equally be considered as content disclosed in this invention.
Claims (18)
1. a kind of preparation method of polyester elastomer, it is characterised in that this method includes：It is anti-in esterification and/or ester exchange
Under conditions of answering, react the mixture of dicarboxylic acids (ester) and dihydric alcohol；Under the conditions of polycondensation reaction, deposited in polycondensation catalyst
Under, the product after esterification and/or ester exchange reaction is set to carry out polycondensation reaction；Wherein, the dicarboxylic acids (ester) is grass
Sour (ester) and M-phthalic acid (ester), the dihydric alcohol contain ethylene glycol.
2. according to the method described in claim 1, wherein, the molar ratio of the dicarboxylic acids (ester) and dihydric alcohol is 1：0.8-4.
3. according to the method described in claim 2, wherein, the molar ratio of the dicarboxylic acids (ester) and dihydric alcohol is 1：0.8-
1.5。
4. according to the method described in claim 2, wherein, using the integral molar quantity of the dicarboxylic acids (ester) as 100 moles of %, institute
The mole for stating oxalic acid (ester) is 9-90 moles of %, and the mole of the M-phthalic acid (ester) is 10-91 moles of %.
5. according to the method described in any one in claim 1-4, wherein, the dihydric alcohol is ethylene glycol.
6. according to the method described in any one in claim 1-4, wherein, beyond the dihydric alcohol is also containing removing ethylene glycol
Other dihydric alcohols, using the integral molar quantity of the dihydric alcohol as 100 moles of %, the mole of the ethylene glycol is 90-99.9
Mole %, the mole for removing other dihydric alcohols beyond ethylene glycol is 0.1-10 moles of %.
7. according to the method described in claim 6, wherein, the dihydric alcohol removed beyond ethylene glycol is 1,2-PD, 1,3- third
Glycol, 2- methyl-1,3-propanediols, 2,2- dimethyl -1,3- propane diols, 2- ethyl -2- butyl -1,3- propane diols, 1,3- fourths
One or more in glycol, 1,4- butanediols, 1,4 cyclohexane dimethanol, diethylene glycol (DEG) and triethylene glycol.
8. according to the method described in any one in claim 1-4, wherein, the oxalic acid (ester) is oxalic acid, oxalic acid monoalkyl
One or more in ester and dialkyl oxalate, and the alkyl in the oxalic acid monoalkyl ester and the dialkyl oxalate is
Carbon number is the straight chained alkyl of 1-4；The M-phthalic acid (ester) for M-phthalic acid, M-phthalic acid monoalkyl ester and
One or more in dialkyl, and the M-phthalic acid monoalkyl ester and the M-phthalic acid dialkyl group
Alkyl is the straight chained alkyl that carbon number is 1-4 in ester.
9. according to the method described in claim 8, wherein, the oxalic acid (ester) is oxalic acid, dimethyl oxalate, diethy-aceto oxalate and
One or more in dipropyl oxalate；The M-phthalic acid (ester) is M-phthalic acid, dimethyl isophthalate, isophthalic
One or more in dicarboxylate and M-phthalic acid dipropyl.
10. according to the method described in any one in claim 1-4, wherein, polyalcohol, polynary is also contained in the mixture
One or more in acid, unsaturated acids (ester) and unsaturated alcohol, it is described polynary on the basis of the mole of the dicarboxylic acids
Alcohol, polyacid, the dosage of unsaturated acids (ester) or unsaturated alcohol are 0.1-10 moles of %.
11. according to the method described in any one in claim 1-4, wherein, the esterification and/or ester exchange reaction exist
Carried out in the presence of catalyst, the catalyst is in metal hydroxides, metal oxide, metal salt or titanate compound
One or more.
12. according to the method for claim 11, wherein, the catalyst is manganese acetate, magnesium acetate, antimony oxide and titanium
One or more in acid esters；On the basis of the weight of the dicarboxylic acids (ester), the dosage of the catalyst is 0.01-1 weights
Measure %.
13. according to the method for claim 12, wherein, the condition of the esterification and/or ester exchange reaction includes：Instead
It is 120-280 DEG C to answer temperature, and reaction absolute pressure is 0-0.5MPa, when the reaction time is 0.5-10 small.
14. according to the method described in any one in claim 1-4, wherein, the polycondensation catalyst is antimony glycol, three oxygen
Change two antimony, selenium dioxide, alkyl aluminum, acetate, titanate esters, fluoroform sulphonate and the organic tin that carbon number is 1-12
One or more in compound；On the basis of the weight of the dicarboxylic acids (ester), the dosage of the catalyst is 0.005-1 weights
Measure %.
15. according to the method for claim 14, wherein, the condition of the polycondensation reaction includes：Reaction absolute pressure is less than
45kPa, 200-300 DEG C of polymerization temperature, when polymerization time is 0.5-10 small.
16. according to the method described in any one in claim 1-4, wherein, the polycondensation reaction is in heat stabilizer and/or resists
Carried out in the presence of oxygen agent, on the basis of the weight of the product after the esterification and/or ester exchange reaction, the heat stabilizer
Dosage be 0.1-10 weight %, the dosage of the antioxidant is 0.1-5 weight %.
17. polyester elastomer prepared by a kind of method in 1-16 as claim described in any one.
18. polyester elastomer according to claim 17, wherein, the glass transition temperature of the polyester elastomer for -60~-
8℃。
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