CN106589328A - Polyester elastomer and preparation method thereof - Google Patents
Polyester elastomer and preparation method thereof Download PDFInfo
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- CN106589328A CN106589328A CN201510683371.9A CN201510683371A CN106589328A CN 106589328 A CN106589328 A CN 106589328A CN 201510683371 A CN201510683371 A CN 201510683371A CN 106589328 A CN106589328 A CN 106589328A
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Abstract
The invention relates to the field of polyester elastomers, and discloses a polyester elastomer and a preparation method thereof. The method comprises the following steps: performing an esterification reaction and/or ester exchange reaction on a mixture containing first dicarboxylic acid (ester) and first dibasic alcohol to obtain a product after a first reaction; performing a second esterification reaction and/or ester exchange reaction on a mixture containing the product after the first reaction, second dicarboxylic acid (ester) and second dibasic alcohol to obtain a product after a second reaction; and in the presence of a condensation polymerization catalyst, performing a condensation polymerization reaction on the product after the second reaction, wherein the first dicarboxylic acid (ester) contains m-phthalic acid (ester), the second dicarboxylic acid (ester) contains oxalic acid (ester), and the first dibasic alcohol and the second dibasic alcohol contain ethylene glycol. The polyester elastomer disclosed by the invention has a greater molecular weight and a better chroma.
Description
Technical field
The present invention relates to a kind of polyester elastomer and preparation method thereof.
Background technology
Elastomer refers to vitrification point less than room temperature, elongation at break>50%, external force is restored after withdrawing from
The preferable macromolecular compound of property.Thermo-setting elastomer and thermoplasticity are divided into according to whether elastomer is plastic
Two big class of elastomer.
Polyethylene terephthalate (PET) is typically used as thermoplastic, in crystallinity, intensity etc.
The aspect excellent performance such as mechanical property, chemical resistance, thermostability, electrical property, transparency, thin film,
Used in the various uses such as fiber, bottle, extrusion molding article in a large number, China's polyethylene terephthalate
Up to 25,000,000 tons of ester production capacity.In the application scenario that some are not easily recycled, just because of poly- to benzene two
The above-mentioned excellent properties of formic acid glycol ester, cause some white pollutions to exist.In order to avoid this is asked
Topic, improves the biodegradability of polyester, is the developing direction of polyester material.
Therefore, be badly in need of a kind of biodegradability it is good, and with excellent tensile property and rebound performance
Polyester elastomer.In order to overcome the above-mentioned problems in the prior art, the applicant is in patent application
There is provided in CN201410573539.6 a kind of biodegradability it is good, and with excellent tensile property
And the polyester elastomer of rebound performance.But, the color of the polyester elastomer is deeper, and molecular weight needs
Further improve.
The content of the invention
It is an object of the invention to provide a kind of color is shallower, molecular weight is larger, and with excellent stretching
The biodegradability polyester elastomer of performance and rebound performance.
The present inventor is had found through in-depth study, directly by two kinds of dicarboxylic acids (ester) and two
First alcohol contact carries out ester exchange and esterification, then carries out polycondensation, and the usual color of resulting polymer is deeper,
Molecular weight is relatively low, and needs are processed further the modified molecular weight that improves and can just meet processing request.In consideration of it,
The present inventor is further studied to the reaction condition of polyester elastomer, it has surprisingly been found that will
The esterification and/or ester exchange reaction substep of dicarboxylic acids (ester) and dihydroxylic alcohols is carried out, and is obtained in that face
Color is shallower, molecular weight is larger, biodegradability is good, and with excellent tensile property and resilience
The polyester elastomer of energy, this completes the present invention.
That is, in a first aspect, the present invention provides a kind of preparation method of polyester elastomer, wherein, the party
Method includes：Under conditions of the first esterification and/or ester exchange reaction, make containing the first dicarboxylic acids
The mixture reaction of (ester) and the first dihydroxylic alcohols, after obtaining the first esterification and/or ester exchange reaction
Product；Under conditions of the second esterification and/or ester exchange reaction, make containing first esterification
And/or the mixture reaction of the product after ester exchange reaction, the second dicarboxylic acids (ester) and the second dihydroxylic alcohols,
Obtain the second esterification and/or the product after ester exchange reaction；Under the conditions of polycondensation reaction, urge in polycondensation
In the presence of agent, second esterification and/or the product after ester exchange reaction is made to carry out polycondensation reaction；
Wherein, first dicarboxylic acids (ester) are containing M-phthalic acid (ester), second dicarboxylic acids
(ester) contains ethylene glycol containing oxalic acid (ester), first dihydroxylic alcohols and second dihydroxylic alcohols.
Second aspect, the present invention provide a kind of preparation method of polyester elastomer, wherein, the method includes：
Under conditions of the first esterification and/or ester exchange reaction, make containing the first dicarboxylic acids (ester) and
The mixture reaction of one dihydroxylic alcohols, obtains the first esterification and/or the product after ester exchange reaction；
Under conditions of class reaction and/or ester exchange reaction, make containing the second dicarboxylic acids (ester) and the two or two
The mixture reaction of first alcohol, obtains the second esterification and/or the product after ester exchange reaction；It is anti-in polycondensation
Under the conditions of answering, in the presence of polycondensation catalyst, after making first esterification and/or ester exchange reaction
The mixture of product and second esterification and/or the product after ester exchange reaction carries out polycondensation reaction；
Wherein, first dicarboxylic acids (ester) are containing M-phthalic acid (ester), second dicarboxylic acids
(ester) contains ethylene glycol containing oxalic acid (ester), first dihydroxylic alcohols and second dihydroxylic alcohols.
The third aspect, the present invention also provide a kind of polyester elastomer obtained by said method.
The preparation method of polyester elastomer of the invention, with aforementioned patent applications
Mixture in CN201410573539.6 directly carries out reaction and compares, and the polymer molecular weight for obtaining is more
Greatly, color more preferably, polymer quality it is more preferable.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The preparation method of the polyester elastomer for providing according to the first aspect of the invention includes：In the first esterification
Under conditions of reaction and/or ester exchange reaction, make containing the first dicarboxylic acids (ester) and the first dihydroxylic alcohols
Mixture reaction, obtains the first esterification and/or the product after ester exchange reaction；In the second esterification
And/or under conditions of ester exchange reaction, make containing after first esterification and/or ester exchange reaction
The mixture reaction of product, the second dicarboxylic acids (ester) and the second dihydroxylic alcohols, obtains the second esterification
And/or the product after ester exchange reaction；Under the conditions of polycondensation reaction, in the presence of polycondensation catalyst, institute is made
Stating the second esterification and/or the product after ester exchange reaction carries out polycondensation reaction；Wherein, the described 1st
First carboxylic acid (ester) containing M-phthalic acid (ester), second dicarboxylic acids (ester) containing oxalic acid (ester),
First dihydroxylic alcohols and second dihydroxylic alcohols contain ethylene glycol.
The preparation method for providing according to the second aspect of the invention includes：In the first esterification and/or ester
Under conditions of exchange reaction, the mixture reaction containing the first dicarboxylic acids (ester) and the first dihydroxylic alcohols is made,
Obtain the first esterification and/or the product after ester exchange reaction；In the second esterification and/or ester exchange
Under conditions of reaction, the mixture reaction containing the second dicarboxylic acids (ester) and the second dihydroxylic alcohols is made, is obtained
Product to after the second esterification and/or ester exchange reaction；Under the conditions of polycondensation reaction, it is catalyzed in polycondensation
In the presence of agent, make first esterification and/or the product after ester exchange reaction and second esterification anti-
Should and/or ester exchange reaction after the mixture of product carry out polycondensation reaction；Wherein, the first binary carboxylic
Sour (ester) containing M-phthalic acid (ester), second dicarboxylic acids (ester) containing oxalic acid (ester),
First dihydroxylic alcohols and second dihydroxylic alcohols contain ethylene glycol.
In the present invention, dicarboxylic acids (ester) represent dicarboxylic acids and/or dicarboxylic esterss, similarly,
The oxalic acid (ester) represents oxalic acid and/or oxalate, and the M-phthalic acid (ester) represents isophthalic diformazan
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, first dicarboxylic acids (ester) contain M-phthalic acid as neccessary composition
(ester).
Preferably as the M-phthalic acid (ester) be M-phthalic acid, M-phthalic acid monoalkyl
One or more in ester and dialkyl isophthalate, and the M-phthalic acid monoalkyl ester and institute
State alkyl in dialkyl isophthalate to be carbon number (more preferably carbon is former for the straight chained alkyl of 1-4
Straight chained alkyl of the subnumber for 1-3)；It is highly preferred that the M-phthalic acid (ester) be M-phthalic acid,
One kind or many in dimethyl isophthalate, dimethyl isophthalate and M-phthalic acid dipropyl
Kind；It is further preferred that the M-phthalic acid (ester) is M-phthalic acid and/or M-phthalic acid two
Methyl ester.
Second dicarboxylic acids (ester) contain oxalic acid (ester) as neccessary composition.
Preferably as the oxalic acid (ester) be oxalic acid, in oxalic acid monoalkyl ester and dialkyl oxalate
One or more, and the oxalic acid monoalkyl ester and the alkyl in the dialkyl oxalate are carbon atom
Straight chained alkyl (more preferably carbon number straight chained alkyl for 1-3) of the number for 1-4；It is highly preferred that institute
State oxalic acid (ester) be oxalic acid, the one kind or many in dimethyl oxalate., ethyl oxalate and dipropyl oxalate
Kind；It is further preferred that the oxalic acid (ester) be oxalic acid, in dimethyl oxalate. and ethyl oxalate
One or more.
According to the present invention, in order to further improve the elastic performance of the elastomer for obtaining, it is preferable that with institute
The integral molar quantity for stating the first dicarboxylic acids (ester) and second dicarboxylic acids (ester) is 100 moles of %,
The mole of the oxalic acid (ester) is 9-90 mole of %, and the mole of the M-phthalic acid (ester) is
10-91 mole of %；It is highly preferred that with first dicarboxylic acids (ester) and second dicarboxylic acids
The integral molar quantity of (ester) is 100 moles of %, and the mole of the oxalic acid (ester) is 9-45 mole of %,
The mole of the M-phthalic acid (ester) is 55-91 mole of %.
According to the present invention, in order to improve the performance of the mechanics of the elastomer for obtaining, it is preferable that described first
Dicarboxylic acids (ester) and/or second dicarboxylic acids (ester) also containing remove the oxalic acid (ester) and
Dicarboxylic acids (ester) (hereinafter also referred to tricarboxylic acids (ester)) beyond M-phthalic acid (ester).Make
Can be p-phthalic acid, terephthalate, phthalic acid, neighbour for the tricarboxylic acids (ester)
Phthalic acid ester, 5- sodium sulfonates-p-phthalic acid (ester), 1,4- succinic acid (ester) and 1,6- adipic acids (ester),
One or more in decanedioic acid (ester)；Preferably 1,4- succinic acid (ester) and/or decanedioic acid (ester).
According to the present invention, in first dicarboxylic acids (ester) and/or second dicarboxylic acids (ester)
When also containing tricarboxylic acids (ester), with first dicarboxylic acids (ester) and second dicarboxylic acids
The integral molar quantity of (ester) is 100 moles of %, and the mole of the oxalic acid (ester) is 10-90 mole of %,
The mole of the M-phthalic acid (ester) be 9-80 mole of %, the tricarboxylic acids (ester) mole
Measure as 1-10 mole of %；Preferably, with first dicarboxylic acids (ester) and second dicarboxylic acids
The integral molar quantity of (ester) is 100 moles of %, and the mole of the oxalic acid (ester) is 9-45 mole of %,
The mole of the M-phthalic acid (ester) is 50-81 mole of %, and tricarboxylic acids (ester) rubs
Your amount is 5-10 mole of %.
In the present invention, the tricarboxylic acids (ester) if consumption meet above-mentioned consumption, which can
To be included in first dicarboxylic acids (ester), it is also possible to be included in second dicarboxylic acids (ester)
In, it is further included in first dicarboxylic acids (ester) and second dicarboxylic acids (ester).
According to the present invention, first dihydroxylic alcohols and/or the second dihydroxylic alcohols can be ethylene glycol.It but is
On the basis of biodegradability is kept, the fusing point of copolymer further reduced, preferably described first
Dihydroxylic alcohols and/or the second dihydroxylic alcohols are ethylene glycol and the dihydroxylic alcohols in addition to ethylene glycol.
In the present invention, when first dihydroxylic alcohols and/or the second dihydroxylic alcohols also containing except ethylene glycol with
During outer dihydroxylic alcohols, as the dihydroxylic alcohols in addition to ethylene glycol be preferably 1,2-PD, 1,3-
Propylene Glycol, 2- methyl-1,3-propanediols, 2,2- dimethyl -1,3- Propylene Glycol, 2- ethyl -2- butyl -1,3- the third two
One kind in alcohol, 1,3 butylene glycol, 1,4- butanediols, 1,4 cyclohexane dimethanol, diethylene glycol and 2,2'-ethylenedioxybis(ethanol).
Or it is various；One or more more preferably in 1,3- Propylene Glycol, 1,4- butanediols and diethylene glycol.
In the present invention, when first dihydroxylic alcohols and/or second dihydroxylic alcohols are also containing except second two
During dihydroxylic alcohols beyond alcohol, the integral molar quantity with first dihydroxylic alcohols and second dihydroxylic alcohols is as 100
Mole %, the mole of the ethylene glycol is 90-99.9 mole of %, the binary beyond the removing ethylene glycol
The mole of alcohol is 0.1-10 mole of %.
In the present invention, as long as the consumption of the dihydroxylic alcohols beyond the removing ethylene glycol meets above-mentioned consumption i.e.
Can, which is may be embodied in first dihydroxylic alcohols, it is also possible to be included in second dihydroxylic alcohols, also
May be embodied in first dihydroxylic alcohols and second dihydroxylic alcohols.
According to the present invention, the amount ratio of first dicarboxylic acids (ester) and first dihydroxylic alcohols can be with
Change in wider scope, it is preferable that first dicarboxylic acids (ester) and first dihydroxylic alcohols
Mol ratio be 1：0.8-4, more preferably 1：0.8-1.5.
According to the present invention, the amount ratio of second dicarboxylic acids (ester) and second dihydroxylic alcohols can be with
Change in wider scope, it is preferable that second dicarboxylic acids (ester) and second dihydroxylic alcohols
Mol ratio be 1：0.8-4, more preferably 1：0.8-1.5.
According to the present invention, in order to further improve stability, resilience and the mechanics of the elastomer for obtaining
Performance, it is preferable that first esterification and/or ester exchange reaction, in polyhydric alcohol, polyprotic acid, no
Carry out in the presence of one or more in saturated acid and unsaturated alcohol.
According to the present invention, described polyprotic acid and polyhydric alcohol refer to that carboxyl and the functional group number of hydroxyl are more than 2
Compound, including but not limited to citric acid, glycerol, gluconic acid, trimethylolpropane, 1,3,5-
Trimesic acid, 1,2,4- trimellitic acids, 1,2,4- inclined benzene three anhydride, tetramethylolmethanes, double Ji Wusi
Alcohol etc., one or more in preferred trimethylolpropane, citric acid, 1,3,5- trimesic acids.
According to the present invention, the unsaturated acids (ester) or unsaturated alcohol refer to the alcohol with olefinic double bonds or
Sour (ester) compound, including but not limited to epoxy soybean oil, fumaric acid, fumarate, itaconic acid or
Itaconate.Preferably fumaric acid and/or dimethyl fumarate.
As the consumption of the polyhydric alcohol, polyprotic acid, unsaturated acids (ester) or unsaturated alcohol, preferably with
On the basis of the integral molar quantity of first dicarboxylic acids (ester) and second dicarboxylic acids (ester), institute
The consumption for stating polyhydric alcohol, polyprotic acid, unsaturated acids (ester) or unsaturated alcohol is 0.1-10 mole of %, more
Preferably 0.5-5 mole %, more preferably 2-5 mole %.
According to the present invention, for first esterification and/or ester exchange reaction and described
There is no particular limitation for the condition of class reaction and/or ester exchange reaction, can be bar commonly used in the art
Part.Such as described first esterification and/or ester exchange reaction and it is described the second esterification and/
Or ester exchange reaction can be carried out under catalyst, it is also possible to do not carry out under catalyst.Whether in catalysis
Carry out under agent, those skilled in the art suitably can be selected according to the raw material of reaction.In addition, institute
State the first esterification and/or ester exchange reaction and described anti-in the second esterification and/or ester exchange
The actual conditions answered for example includes：Reaction temperature is 100-280 DEG C, and reaction absolute pressure is 0-0.5MPa,
Response time is 1-10 hours；Preferably, reaction temperature is 140-250 DEG C, and reaction absolute pressure is
0.1-0.4MPa, response time are 2-6 hours.
According to the present invention, first esterification and/or ester exchange reaction and described in the second ester
Changing reaction and/or ester exchange reaction can be carried out in the presence of a catalyst, it is also possible to not have the feelings of catalyst
Carry out under condition.It is preferred that first esterification and/or ester exchange reaction and described anti-in the second esterification
Answer and/or ester exchange reaction is carried out in the presence of a catalyst, ester exchange catalyst is selected from metal hydroxide
One or more in thing, metal-oxide, slaine or titanate compound, preferred metal acetate
Salt or titanate esters.More preferably described catalyst is manganese acetate, magnesium acetate, antimony oxide and titanate esters
In one or more.
Can be the conventional amount used of this area as the consumption of above-mentioned catalyst, for example, in first ester
Change in reaction and/or ester exchange reaction, it is on the basis of the weight of first dicarboxylic acids (ester), described
The consumption of catalyst is 0.01-1 weight %, preferably 0.03-0.2 weight %, more preferably 0.03-0.1
Weight %.In second esterification and/or ester exchange reaction, with second dicarboxylic acids (ester)
Weight on the basis of, the consumption of the catalyst is 0.01-1 weight %, preferably 0.03-0.2 weight %,
More preferably 0.03-0.1 weight %.
According to the present invention, the polymerizing condition is less than 45kPa for reaction absolute pressure, and polymerization temperature is
200-300 DEG C, polymerization time is 0.5-10 hours.
In order to preferably control polymer quality, the polycondensation can be divided into prepolymerization and poly- two ranks of final minification
Section.Esterification products, under the vacuum condition of 45kPa～5kPa, are carried out precondensation by the precondensation stage
Reaction.Preferably, described precondensation condition includes reaction temperature for 200-240 DEG C, reacts absolute pressure
Power is that, between 30kPa-5kPa, the response time is 0.5-4 hours
In order to preferably carry out polycondensation reaction, increase polymer molecular weight, through precondensation polymer also
Further reduction pressure is needed, temperature is improved, is carried out melt polycondensation.Preferably, the melt polycondensation
The condition of reaction includes：Reaction temperature is 220-300 DEG C, and reaction absolute pressure is below 1500Pa, instead
It is 0.5-6 hours between seasonable.
The polycondensation catalyst can be the various catalyst for ester polycondensation commonly used in the art, such as institute
State polycondensation catalyst and can be selected from metal hydroxidess, metal-oxide, slaine or titanate esters chemical combination
One or more in thing, preferably antimony glycol, antimony oxide, selenium dioxide, carbon number are
One kind in the alkyl aluminum of 1-12, acetate, titanate esters, fluoroform sulphonate and organic tin compound
Or it is various；One or more more preferably in antimony glycol, butyl titanate and selenium dioxide.
As the polycondensation catalyst consumption can be this area conventional amount used, for example, with described the
On the basis of the gross weight of one dicarboxylic acids (ester) and second dicarboxylic acids (ester), the catalyst
Consumption be 0.005-1 weight %, preferably 0.03-0.2 weight %, more preferably 0.03-0.1 weight %.
According to the present invention, the present invention is not specially required to the feed postition of polycondensation catalyst, polycondensation catalysis
Agent once can be added, it is also possible to be continuously added in batches.In addition, for the addition opportunity of polycondensation catalyst
Also it is special to require, can add in first esterification and/or ester exchange reaction or
Add in the second esterification and/or ester exchange reaction described, or add in polycondensation reaction.
, according to the invention it is preferred in the case of, the polycondensation reaction is deposited in heat stabilizer and/or antioxidant
Under carry out.The stabilizer and antioxidant can be various stabilizers commonly used in the art and antioxidant.
The stabilizer is preferably phosphorus compound, the phosphorus compound be preferably phosphoric acid, phosphorous acid, hypophosphorous acid,
Polyphosphoric acids, phosphate n-butyl, p isopropylbenzoic acid ester, triethyl phosphate, trimethyl phosphate, phosphoric acid triphen
One or more of ester etc..The antioxidant can be hindered phenol, thio-2 acid dibasic acid esters and aromatic amine
Antioxidant one or more, 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) propanoic acid) pentaerythritol ester,
One or more in antioxidant 1222 and antioxidant 1010.
In the present invention, it is (poly- as a first aspect of the present invention on the basis of the weight of polycondensation reaction raw material
During the preparation method of ester elastomer, in this way in after the second esterification for obtaining and/or ester exchange reaction
Product weight on the basis of；During the preparation method of the polyester elastomer of a second aspect of the present invention, with this
Product and the second esterification after the first esterification obtained in method and/or ester exchange reaction and/or
On the basis of the weight of the mixture of the product after ester exchange reaction), the consumption of the heat stabilizer is 0.1-10
Weight %, preferably 0.3-8 weight %, more preferably 0.5-5 weight %；The use of the antioxidant
Measure as 0.1-5 weight %, preferably 0.3-3 weight %, more preferably 0.5-2.5 weight %.
In accordance with the present invention it is preferred that, the method is additionally included in first esterification and/or ester exchange
In course of reaction or it is described in the second esterification and/or ester exchange reaction during, or contracting
In collecting process, add chain extender to increase the reaction rate of end group, improve the molecular weight of product.Preferably,
The chain extender is selected from comprising two or more epoxide groups, compound of isocyanate groups, double
One or more in oxazoline or organic acid anhydride.Further preferably the chain extender is two Carbimide .s
At least one in ester, phthalic anhydride, pyromellitic dianhydride, double oxazolines and epoxy resin.Separately
Outward, the consumption of chain extender can be the conventional amount used of this area, such as with first dicarboxylic acids (ester)
On the basis of the gross weight of second dicarboxylic acids (ester), it is 0.1-3 weight %.
According to the present invention, other a small amount of functional additive, such as ultraviolet can also be contained as needed
Absorbent, fire retardant, fluorescent whitening agent, delustering agent, antistatic additive, antibacterial, opening agent etc..It is right
In the consumption of above-mentioned additive, there is no particular limitation, can be the conventional amount used of this area, and here not exist
It is tired to state.
, according to the invention it is preferred in the case of, the method also includes：After polycondensation reaction terminates, it is passed through
Pressure is risen to 0.1-1MPa by noble gases, is then cooled down and pelletizing.The cooling and pelletizing are this
Well known to field, here is not repeated.
The present invention also provides a kind of polyester elastomer being prepared by said method.
Polyester elastomer of the invention, at -60～-8 DEG C, tensile strength is its vitrification point
More than 0.3MPa, elongation at break be more than 390%, intrinsic viscosity in more than 0.1dl/L, with glass
Glass temperature is low, mechanical property is good, color is good and the advantages of good resilience.
Hereinafter will be described the present invention by embodiment.
In following examples and comparative example, the vitrification point of polyester elastomer is tested using DSC method；
Using the tensile strength and elongation at break of the method test polyester elastomer of GB/T 528-2009；Using
The biodegradability of 14855 compost measuring polyester of standard ISO.
The measure of colourity is carried out by color difference meter., take after 110 DEG C of dryings 4 hours by by sample
Go out after being cooled to 25 DEG C, take the granule of 350～833um, sample granule is put into into specimen cup and piles up tight
It is close, specimen cup is placed on measured hole, the colourity (L, a, b) of sample is determined, 120 degree of surveys are often rotated
Amount once, is surveyed altogether at 3 points, takes 3 points of meansigma methodss.
Molecular weight of polyesters is represented with intrinsic viscosity.
In following examples and comparative example, pressure is absolute pressure.
Embodiment 1
M-phthalic acid, the 93g (1.5mol) of 182.6g (1.1mol) are added in batch reactor
(on the basis of the weight of above-mentioned dicarboxylic acids (ester), consumption is 0.01 weight for ethylene glycol and antimony glycol
Amount %), terminate esterification after esterification and ester exchange 1 hour under 220～250 DEG C, pressure 0.25MPa,
Reactor pressure is let out to normal pressure, the oxalic acid and 7.6g (0.12mol) of 10g (0.11mol) is added
Ethylene glycol, antimony glycol (on the basis of the weight of above-mentioned oxalic acid, consumption is 0.01 weight %), normal pressure
It is esterified under lower 160-200 degree, esterification adds trimethyl phosphate (anti-with ester exchange to be esterified after terminating
Should after product weight on the basis of, consumption be 0.1 weight %) after, gradually decompression heat up, 200 DEG C,
Pressure is polycondensation under conditions of 30kPa 0.5 hour, then, continues to heat up and reduces pressure, anti-after 45 minutes
Answer kettle vacuum up to 1500Pa, reaction temperature is maintained into 250～260 DEG C, then be polymerized through 110 minutes
After terminate polyreaction, with nitrogen eliminate vacuum, water cooled, pelletizing can obtain polyester elastomer A1.It is right
A1 is measured, its vitrification point, tensile strength, elongation at break, intrinsic viscosity, color and luster and
Biodegradability is as shown in table 1.
Embodiment 2
M-phthalic acid, the 93g (1.5mol) of 182.6g (1.1mol) are added in batch reactor
Ethylene glycol and magnesium acetate (on the basis of the weight of above-mentioned dicarboxylic acids (ester), consumption is 0.01 weight %),
Terminate esterification after esterification and ester exchange 1 hour under 220～250 DEG C, pressure 0.25MPa, will reaction
Kettle pressure is let out to normal pressure, adds the oxalic acid and 62g (1.0mol) ethylene glycol normal pressure of 81g (0.9mol)
It is esterified under lower 160-200 degree, esterification is subsequently adding phosphoric acid (with esterification and ester exchange reaction after terminating
On the basis of the weight of product afterwards, consumption is 0.5 weight %), antimony glycol is (with above-mentioned dicarboxylic acids
On the basis of the weight of (ester), consumption is 0.03 weight %) and after stirring, in 240 DEG C, pressure
For polycondensation under conditions of 30kPa 4 hours, then, continue to heat up and reduce pressure, reactor is true after 15 minutes
It is empty to reach 90Pa, reaction temperature is maintained into 250～260 DEG C, then terminates polyreaction after 80 minutes
Vacuum is eliminated with nitrogen, water cooled, pelletizing can obtain polyester elastomer A2.A2 is measured, its glass
Glass temperature, tensile strength, elongation at break, intrinsic viscosity, color and luster and biodegradability such as table 1
It is shown.
Embodiment 3
Ethyl oxalate, the 93g (1.5mol) of 146g (1.0mol) are added in batch reactor
Ethylene glycol and magnesium acetate (on the basis of the weight of above-mentioned dicarboxylic acids (ester), consumption is 0.01 weight %),
Terminate esterification after esterification and ester exchange 1 hour under 160～220 DEG C, normal pressure, add 198.2g
(1.2mol) M-phthalic acid and 62g (1.0mol) ethylene glycol are in 220～250 DEG C, pressure 0.25MPa
Terminate esterification after lower esterification and ester exchange 4 hours, esterification is subsequently adding phosphoric acid (to be esterified and ester after terminating
On the basis of the weight of the product after exchange reaction, consumption is 0.5 weight %), antimony glycol is (with above-mentioned
On the basis of the weight of dicarboxylic acids (ester), consumption is 0.03 weight %) and after stirring, gradually subtract
Pressure heats up, polycondensation 0.5 hour under conditions of being 30kPa in 200 DEG C, pressure, then, continues to heat up
And reduce pressure, after 15 minutes, reactor vacuum reaches 600Pa, and reaction temperature is maintained 240-250 DEG C, then
Terminating polyreaction after polymerization in 90 minutes, vacuum being eliminated with nitrogen, water cooled, pelletizing can gather
Ester elastomer A3.A3 is measured, its vitrification point, tensile strength, elongation at break, spy
The viscosity number, color and luster of property and biodegradability are as shown in table 1.
Embodiment 4
Method according to embodiment 1 is carried out, except for the difference that：Replace the isophthalic two of part with p-phthalic acid
Formic acid, and the consumption of p-phthalic acid is 10 moles of % of consumption of the dicarboxylic acids (ester) in embodiment 1；
Replace the ethylene glycol of part with BDO, and the consumption of BDO is the binary in embodiment 1
10 moles of % of consumption of alcohol, obtain polyester elastomer A4.A4 is measured, its vitrification point,
Tensile strength, elongation at break, intrinsic viscosity, color and luster and biodegradability are as shown in table 1.
Embodiment 5
Method according to embodiment 3 is carried out, except for the difference that：Replace the oxalic acid of part, and oneself with adipic acid
The 5 moles of % of consumption of the consumption of diacid for the dicarboxylic acids (ester) in embodiment 1；Replaced with diethylene glycol
Partial ethylene glycol, and the consumption of diethylene glycol is 5 moles of % of consumption of the dihydroxylic alcohols in embodiment 1, is obtained
To polyester elastomer A5.A5 is measured, its vitrification point, tensile strength, elongation at break,
Intrinsic viscosity, color and luster and biodegradability are as shown in table 1.
Embodiment 6
Unlike method according to embodiment 1 is carried out, lemon is also added with esterification and ester exchange reaction
Lemon acid, and the consumption of citric acid is 1 mole of % of consumption of the dicarboxylic acids (ester) in embodiment 1, is obtained
To polyester elastomer A6.A6 is measured, its vitrification point, tensile strength, elongation at break,
Intrinsic viscosity, color and luster and biodegradability are as shown in table 1.
Embodiment 7
Unlike method according to embodiment 1 is carried out, richness is also added with esterification and ester exchange reaction
Horse dimethyl phthalate, and the consumption of dimethyl fumarate is the consumption of the dicarboxylic acids (ester) in embodiment 1
10 moles of %, obtain polyester elastomer A7.A7 is measured, its vitrification point, tensile strength,
Elongation at break, intrinsic viscosity, color and luster and biodegradability are as shown in table 1.
Embodiment 8
Ethyl oxalate, the 93g (1.5mol) of 146g (1.0mol) are added in batch reactor
Ethylene glycol and magnesium acetate (on the basis of the weight of above-mentioned dicarboxylic acids (ester), consumption is 0.01 weight %),
Terminate esterification after esterification and ester exchange 1 hour under 160～220 DEG C, normal pressure, in an other reactor
It is interior, add the M-phthalic acid and 93g (1.5mol) ethylene glycol of 198.2g (1.2mol) 220～
250 DEG C, under pressure 0.25MPa esterification terminate esterification after 4 hours and obtain prepolymer.Esterification will after terminating
The prepolymer of two kinds of esterifications mixes, and addition phosphoric acid (with the weight being esterified with the product after ester exchange reaction is
Benchmark, consumption be 0.5 weight %), (weight with above-mentioned dicarboxylic acids (ester) is as base for antimony glycol
Standard, consumption are 0.03 weight %) and after stirring, gradually decompression heats up, and in 200 DEG C, pressure is
Polycondensation 0.5 hour under conditions of 30kPa, then, continues to heat up and reduces pressure, and after 15 minutes, reactor is true
It is empty to reach 600Pa, reaction temperature is maintained into 240-250 DEG C, then terminates polymerization after polymerization in 90 minutes
Reaction, eliminates vacuum with nitrogen, and water cooled, pelletizing can obtain polyester elastomer A8.A8 is measured,
Its vitrification point, tensile strength, elongation at break, intrinsic viscosity, color and luster and biodegradability are such as
Shown in table 1.
Embodiment 9
Ethyl oxalate, the 93g (1.5mol) of 146g (1.0mol) are added in batch reactor
Ethylene glycol and magnesium acetate (on the basis of the weight of above-mentioned dicarboxylic acids (ester), consumption is 0.01 weight %),
Terminate esterification after esterification and ester exchange 1 hour under 160～220 DEG C, normal pressure, in an other reactor
It is interior, add the M-phthalic acid and 12.4g (0.2mol) ethylene glycol of 16.6g (0.1mol) 220～
250 DEG C, under pressure 0.25MPa esterification terminate esterification after 4 hours and obtain prepolymer.Esterification will after terminating
The prepolymer of two kinds of esterifications mixes, and addition phosphoric acid (with the weight being esterified with the product after ester exchange reaction is
Benchmark, consumption be 0.5 weight %), (weight with above-mentioned dicarboxylic acids (ester) is as base for antimony glycol
Standard, consumption are 0.03 weight %) and after stirring, gradually decompression heats up, and in 200 DEG C, pressure is
Polycondensation 0.5 hour under conditions of 30kPa, then, continues to heat up and reduces pressure, and after 15 minutes, reactor is true
It is empty to reach 600Pa, reaction temperature is maintained into 240-250 DEG C, then terminates polymerization after polymerization in 90 minutes
Reaction, eliminates vacuum with nitrogen, and water cooled, pelletizing can obtain polyester elastomer A9.A9 is measured,
Its vitrification point, tensile strength, elongation at break, intrinsic viscosity, color and luster and biodegradability are such as
Shown in table 1.
Comparative example 1
M-phthalic acid, the 100.6g (1.62mol) of 182.6g (1.1mol) are added in batch reactor
Ethylene glycol, the oxalic acid of 10g (0.11mol) and antimony glycol be (with the weight of above-mentioned dicarboxylic acids (ester)
On the basis of amount, consumption be 0.01 weight %), under 220～250 DEG C, pressure 0.25MPa esterification and
Ester exchange terminated esterification after 1 hour, and reactor pressure is let out to normal pressure, added trimethyl phosphate (with ester
On the basis of changing the weight with the product after ester exchange reaction, consumption is 0.1 weight %) after, gradually reduce pressure
Heat up, then polycondensation 0.5 hour under conditions of being 30kPa in 200 DEG C, pressure, continues to heat up simultaneously
Decompression, after 45 minutes, reactor vacuum reaches 1500Pa, and reaction temperature is maintained 250～260 DEG C, then
Terminating polyreaction after polymerization in 110 minutes, vacuum being eliminated with nitrogen, water cooled, pelletizing can gather
Ester elastomer B1.B1 is measured, its vitrification point, tensile strength, elongation at break, spy
The viscosity number, color and luster of property and biodegradability are as shown in table 1.
Comparative example 2
M-phthalic acid, the 100.6g (1.62mol) of 182.6g (1.1mol) are added in batch reactor
Ethylene glycol, the oxalic acid of 10g (0.11mol) and antimony glycol be (with the weight of above-mentioned dicarboxylic acids (ester)
On the basis of amount, consumption is 0.01 weight %), it is esterified under 160-220 degree under normal pressure, after 2 hours
Terminate esterification after esterification and ester exchange 1 hour under 220～250 DEG C, pressure 0.25MPa again, will be anti-
Answer kettle pressure to let out to normal pressure, trimethyl phosphate is added (to be esterified the weight with the product after ester exchange reaction
On the basis of, consumption is 0.1 weight %) after, gradually decompression heats up, and is 30kPa in 200 DEG C, pressure
Under conditions of polycondensation 0.5 hour, then, continue to heat up and reduce pressure, after 45 minutes, reactor vacuum reaches
Reaction temperature is maintained 250～260 DEG C by 1500Pa, then after polymerization in 110 minutes terminates polymerization
Reaction, eliminates vacuum with nitrogen, and water cooled, pelletizing can obtain polyester elastomer B2.B2 is measured,
Its vitrification point, tensile strength, elongation at break, intrinsic viscosity, color and luster and biodegradability are such as
Shown in table 1.
Comparative example 3
M-phthalic acid, the 105.4g (1.7mol) of 16.6g (0.1mol) are added in batch reactor
Ethylene glycol, the ethyl oxalate of 146g (1.0mol) and magnesium acetate be (with the weight of above-mentioned dicarboxylic acids
On the basis of, consumption is 0.1 weight %), with nitrogen displacement three times, carry out under 160-220 degree under normal pressure
Esterification, is tied after esterification and ester exchange 4 hours under 220～250 DEG C, pressure 0.25MPa after 1 hour again
Beam is esterified,.It is subsequently adding phosphoric acid (on the basis of being esterified the weight with the product after ester exchange reaction, to use
Measure as 0.5 weight %), antimony glycol (on the basis of the weight of above-mentioned dicarboxylic acids (ester), consumption
For 0.03 weight %) and after stirring, under conditions of being 30kPa in 240 DEG C, pressure, polycondensation 4 is little
When, then, continue to heat up and reduce pressure, after 15 minutes, reactor vacuum reaches 90Pa, and reaction temperature is tieed up
Hold at 250～260 DEG C, then terminate polyreaction nitrogen after 80 minutes and eliminate vacuum, it is water cooled,
Pelletizing can obtain polyester elastomer B3.B3 is measured, its vitrification point, tensile strength, fracture
Percentage elongation, intrinsic viscosity, color and luster and biodegradability are as shown in table 1.
Table 1
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the present invention, can be to the technical side of the present invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, the present invention are no longer separately illustrated to various possible compound modes.
Additionally, combination in any between a variety of embodiments of the present invention, can also be carried out, as long as its
Without prejudice to the thought of the present invention, which 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 the method includes：In the first ester
Under conditions of changing reaction and/or ester exchange reaction, make containing the first dicarboxylic acids (ester) and the first dihydroxylic alcohols
Mixture reaction, obtain the first esterification and/or the product after ester exchange reaction；It is anti-in the second esterification
Should and/or ester exchange reaction under conditions of, make containing after first esterification and/or ester exchange reaction
Product, the second dicarboxylic acids (ester) and the second dihydroxylic alcohols mixture reaction, obtain the second esterification anti-
Should and/or ester exchange reaction after product；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, described first
Dicarboxylic acids (ester) contain oxalic acid containing M-phthalic acid (ester), second dicarboxylic acids (ester)
(ester), first dihydroxylic alcohols and second dihydroxylic alcohols contain ethylene glycol.
2. a kind of preparation method of polyester elastomer, it is characterised in that the method includes：In the first ester
Under conditions of changing reaction and/or ester exchange reaction, make containing the first dicarboxylic acids (ester) and the first dihydroxylic alcohols
Mixture reaction, obtain the first esterification and/or the product after ester exchange reaction；It is anti-in the second esterification
Should and/or ester exchange reaction under conditions of, make mixing containing the second dicarboxylic acids (ester) and the second dihydroxylic alcohols
Compound reacts, and obtains the second esterification and/or the product after ester exchange reaction；Under the conditions of polycondensation reaction,
In the presence of polycondensation catalyst, first esterification and/or the product after ester exchange reaction and described are made
The mixture of the product after the second esterification and/or ester exchange reaction carries out polycondensation reaction；Wherein, it is described
First dicarboxylic acids (ester) contain containing M-phthalic acid (ester), second dicarboxylic acids (ester)
Oxalic acid (ester), first dihydroxylic alcohols and second dihydroxylic alcohols contain ethylene glycol.
3. method according to claim 1 and 2, wherein, first dicarboxylic acids (ester)
Mol ratio with first dihydroxylic alcohols is 1：0.8-4, preferably 1：0.8-1.5.
4. method according to claim 1 and 2, wherein, second dicarboxylic acids (ester)
Mol ratio with second dihydroxylic alcohols is 1：0.8-4, preferably 1：0.8-1.5.
5. described method according to claim 1 or claim 2, wherein, with first dicarboxylic acids
The integral molar quantity of (ester) and second dicarboxylic acids (ester) be 100 moles of %, the oxalic acid (ester)
Mole be 9-90 mole of %, the mole of the M-phthalic acid (ester) is 10-91 mole of %.
6. described method according to claim 1 or claim 2, wherein, first dicarboxylic acids (ester)
And/or second dicarboxylic acids (ester) are also containing the removing oxalic acid (ester) and M-phthalic acid (ester)
Dicarboxylic acids (ester) in addition, with first dicarboxylic acids (ester) and second dicarboxylic acids (ester)
Integral molar quantity be 100 moles of %, the mole of the oxalic acid (ester) is 9-90 mole of %, it is described between
The mole of phthalic acid (ester) is 9-81 mole of %, the removing oxalic acid (ester) and isophthalic two
The mole of the dicarboxylic acids (ester) beyond formic acid (ester) is 1-10 mole of %.
7. method according to claim 6, wherein, it is described remove the oxalic acid (ester) and
Dicarboxylic acids (ester) beyond phthalic acid (ester) are p-phthalic acid, terephthalate, adjacent benzene
Dioctyl phthalate, phthalic acid ester, 5- sodium sulfonates-p-phthalic acid (ester), 1,4- succinic acid (ester), oneself
One or more in diacid (ester) and decanedioic acid (ester).
8. the method according to any one in claim 1-7, wherein, first dihydroxylic alcohols
It is ethylene glycol with the second dihydroxylic alcohols.
9. described method according to claim 1 or claim 2, wherein, first dihydroxylic alcohols and/or
Second dihydroxylic alcohols also containing the dihydroxylic alcohols removed beyond ethylene glycol, with first dihydroxylic alcohols and described
The integral molar quantity of the second dihydroxylic alcohols is 100 moles of %, and the mole of the ethylene glycol is 90-99.9 mole of %,
The mole of the dihydroxylic alcohols beyond the removing ethylene glycol is 0.1-10 mole of %.
10. method according to claim 9, wherein, the dihydroxylic alcohols removed beyond ethylene glycol
For 1,2- Propylene Glycol, 1,3- Propylene Glycol, 2- methyl-1,3-propanediols, 2,2- dimethyl -1,3- Propylene Glycol, 2-
It is ethyl -2- butyl -1,3- Propylene Glycol, 1,3 butylene glycol, 1,4- butanediols, 1,4 cyclohexane dimethanol, two sweet
One or more in alcohol and 2,2'-ethylenedioxybis(ethanol)..
11. methods according to claim 1 and 2, wherein, the oxalic acid (ester) be oxalic acid,
One or more in oxalic acid monoalkyl ester and dialkyl oxalate, and the oxalic acid monoalkyl ester and described
Alkyl in dialkyl oxalate is the straight chained alkyl that carbon number is 1-4；The M-phthalic acid (ester)
For the one kind or many in M-phthalic acid, M-phthalic acid monoalkyl ester and dialkyl isophthalate
Kind, and alkyl is carbon atom in the M-phthalic acid monoalkyl ester and the dialkyl isophthalate
Straight chained alkyl of the number for 1-4；
Preferably, the oxalic acid (ester) be oxalic acid, dimethyl oxalate., ethyl oxalate and oxalic acid dipropyl
One or more in ester；The M-phthalic acid (ester) is M-phthalic acid, M-phthalic acid diformazan
One or more in ester, dimethyl isophthalate and M-phthalic acid dipropyl.
12. methods according to claim 1 and 2, wherein, first esterification and/or
Ester exchange reaction, one or more in polyhydric alcohol, polyprotic acid, unsaturated acids and unsaturated alcohol are deposited
Carry out under, with first dicarboxylic acids (ester) and the total moles of second dicarboxylic acids (ester)
On the basis of amount, the consumption of the polyhydric alcohol, polyprotic acid, unsaturated acids (ester) or unsaturated alcohol is 0.1-10
Mole %.
13. methods according to claim 1 and 2, wherein, first esterification and/or
Ester exchange reaction and second esterification and/or ester exchange reaction are carried out in the presence of a catalyst,
The catalyst is in metal hydroxidess, metal-oxide, slaine or titanate compound
One or more；
Preferably, the catalyst is the one kind in manganese acetate, magnesium acetate, antimony oxide and titanate esters
Or it is various；
It is highly preferred that in first esterification and/or ester exchange reaction, with first binary
On the basis of the weight of carboxylic acid (ester), the consumption of the catalyst is 0.01-1 weight %；
In second esterification and/or ester exchange reaction, with second dicarboxylic acids (ester)
Weight on the basis of, the consumption of the catalyst is 0.01-1 weight %.
14. methods according to claim 13, wherein, first esterification and/or ester are handed over
Change reaction, and the condition of second esterification and/or ester exchange reaction include：Reaction temperature is
120-280 DEG C, reaction absolute pressure is 0-0.5MPa, and the response time is 0.5-10 hours.
15. methods according to claim 1 and 2, wherein, the polycondensation catalyst is ethylene glycol
Antimony, antimony oxide, selenium dioxide, carbon number are the alkyl aluminum of 1-12, acetate, titanate esters,
One or more in fluoroform sulphonate and organic tin compound；With first dicarboxylic acids (ester)
On the basis of the gross weight of second dicarboxylic acids (ester), the consumption of the catalyst is 0.005-1
Weight %.
16. methods according to claim 15, wherein, the condition of the polycondensation reaction includes：
Reaction absolute pressure is less than 45kPa, and polymerization temperature is 200-300 DEG C, and polymerization time is 0.5-10 hours.
Polyester elastomer prepared by a kind of 17. methods by described in any one in claim 1-16.
18. polyester elastomers according to claim 17, wherein, the glass of the polyester elastomer
Glass temperature is -60～-8 DEG C.
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| CN111393617A (en) * | 2019-11-29 | 2020-07-10 | 开滦（集团）有限责任公司 | Performance-adjustable thermoplastic polyester elastomer and preparation method thereof |
| CN114561000A (en) * | 2022-02-28 | 2022-05-31 | 辽宁东盛塑业有限公司 | Preparation method of 1, 4-cyclohexanedicarboxylic acid molecular structure modified polybutylene terephthalate-adipate |
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| CN103087305A (en) * | 2011-11-07 | 2013-05-08 | 上海杰事杰新材料(集团)股份有限公司 | Biodegradable aromatic-aliphatic copolyester and preparation method thereof |
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| CN103087305A (en) * | 2011-11-07 | 2013-05-08 | 上海杰事杰新材料(集团)股份有限公司 | Biodegradable aromatic-aliphatic copolyester and preparation method thereof |
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|---|---|---|---|---|
| CN111393617A (en) * | 2019-11-29 | 2020-07-10 | 开滦（集团）有限责任公司 | Performance-adjustable thermoplastic polyester elastomer and preparation method thereof |
| CN114561000A (en) * | 2022-02-28 | 2022-05-31 | 辽宁东盛塑业有限公司 | Preparation method of 1, 4-cyclohexanedicarboxylic acid molecular structure modified polybutylene terephthalate-adipate |
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