Patent Application
20220363821
The present disclosure relates to the technical field of high molecular materials, and more particularly to a butenediol-based polyester elastomer and a method for preparing same.
As a class of degradable polymers, polyesters received extensive research and attention in the field of high molecular materials. At present, the annual output of the polyester industry has reached 10 million tons, but its application is still mainly limited to plastics, fibers and others. Polyester is rarely involved in the field of rubber. In view of this, since the concept of “bio-based engineering elastomer” was proposed in 2008, Beijing University of Chemical Technology was the first in proposing and preparing a variety of bio-based polyester elastomer materials, thus broadening the application of polyesters.
The design strategy of polyester elastomers is to destroy a crystallization behavior of a polyester molecular chain through multi-component copolymerization, and at the same time, introduce monomers containing carbon-carbon double-bonds to provide reaction sites for later crosslinking of polyester elastomers. However, in a polyester elastomer product that has been developed so far, monomers that provide double-bonds are still limited to dibasic acid, especially itaconic acid. For example, in “Polyester Bioengineering Rubber And A Method For The Same” disclosed in patent CN101450985B, a double-bond donor used for later chemical crosslinking is itaconic acid. However, the double-bond in the itaconic acid has extremely high activity, so that there is a risk of rapid gelation at a polycondensation stage, and a range/distribution of a sample's apparent molecular weights is wide. In addition, when peroxide is used for crosslinking, the crosslinking rate is relatively rapid, and the dosage of a crosslinking agent is relatively small, so that the controllability of crosslinking degree is poor.
Therefore, there is a need to develop a new polyester elastomer.
In order to solve the problems in the prior art, the present disclosure provides a butenediol-based polyester elastomer and a method for preparing same. In the present disclosure, 1,4-butenediol containing high-stability double-bond is selected to replace itaconic acid, and a series of butenediol-based polyester elastomers with high molecular weight and narrow distribution are synthesized, which have high relative molecular mass and narrow relative molecular mass distribution. The 1,4-butenediol is highly stable in the high-temperature polycondensation process, so that it is less likely to undergo side reactions like the itaconic acid (side reactions can easily lead to broadening of the molecular weight distribution of a product); the crosslinking is controllable in the subsequent processing process; and a dosage of a vulcanizing agent is equivalent to that of traditional rubber.
A first purpose of the present disclosure is to provide a butenediol-based polyester elastomer.
The butenediol-based polyester elastomer has a structure as shown below:
Rm1 and Rm2 may either be a branched or an unbranched chain alkyl group, and eRm1 and Rm2 may be the same or different to each other, wherein m1 and m2 represent the number of carbon atoms, 2≤m1≤14, preferably 2≤m1≤10; 2≤m2≤14, preferably 2≤m2≤10; m1 and m2 may be the same or different to each other;
Rn1 and Rn2 may be branched or unbranched chain alkyl group, and Rn1 and Rn2 may be the same or different to each other, wherein n1 and n2 represent the number of carbon atoms, 2≤n1≤12, preferably 2≤n1≤8; 2≤n2≤12, preferably 2≤n2≤8; n1 and n2 may be the same or different to each other;
Each of x and y is an integer ranged from 1 to 3; and x and y may be equal or unequal to each other.
a, b, c, d, e, f, g, h, i, j, k, l, m, n and o represent a polymerization degree;
wherein a, c, m and o are not 0 at the same time, and e and k are not 0 at the same time; and others can be 0 at the same time.
A second purpose of the present disclosure is to provide a method for preparing the butenediol-based polyester elastomer.
The method includes:
prepare a butenediol-based polyester elastomer, under the action of a catalyst, by carrying out an esterification reaction and a polymerization reaction in the presence of dihydric alcohol, binary acid and/or lactic acid, an antioxidant and a polymerization inhibitor;
said dihydric alcohol is 1,4-butenediol and other diols; other diols may be one or a combination of HO—Rm—OH, diglycol, triethylene glycol and tetraethylene glycol;
wherein Rm is either the branched or the unbranched chain alkyl group, wherein m represents the number of carbon atoms, 2≤m≤14; preferably 2≤m≤10;
the binary acid is one or a combination of HOOC—Rn—COOH;
wherein Rn is either the branched or the unbranched chain alkyl group, wherein n represents the number of carbon atoms, 2≤n≤12; preferably 2≤n≤8.
For example, the mole percentage of the 1,4-butenediol in the diol is 2% to 60%, and more preferably 5% to 30%.
The catalyst can use a conventional catalyst in the prior art. In the present disclosure, one or a combination of selenium dioxide, antimony trioxide, ethylene glycol antimony, p-toluenesulfonic acid, acetate, alkyl aluminum having 1 to 12 carbon atoms, an organic tin compound and titanate is preferred. In view of the problem of heavy metal residues in a polyester product, a titanate catalyst without heavy metal elements is preferred, such as tetrabutyl titanate and titanate Tetraisopropyl ester. The catalyst can be added during the esterification reaction or a pre-polycondensation reaction. The dosage of the catalyst is 0.02-0.5% of the total mass of the diol, the binary acid and/or the lactic acid.
The antioxidant can be a conventional antioxidant in the prior art. In the present disclosure, the antioxidant may be preferably a phosphoric acid or phosphorous acid compound can be preferred, which is preferably one or two of phosphoric acid, phosphorous acid, phosphate, phosphite ester, phenyl phosphate and phenyl phosphite. The dosage of the antioxidant is 0.01-0.2% of the total mass of the diol, the binary acid and/or the lactic acid, preferably 0.04-0.08%.
The polymerization inhibitor can be a conventional polymerization inhibitor in the prior art. In the present disclosure, the polymerization inhibitor can be preferably a phenolic polymerization inhibitor, an ether polymerization inhibitor, a quinone polymerization inhibitor or an aromatic amine polymerization inhibitor, which is preferably one or two of benzenediol, p-tert-butylcatechol, p-hydroxyanisole, benzoquinone, diphenylamine and p-phenylenediamine. The dosage of the polymerization inhibitor is 0.01-0.5% of the total mass of the diol, the binary acid and/or the lactic acid, preferably 0.05-0.2%.
A molar ratio of alcohol to acid of the diol, the binary acid and/or the lactic acid is 1.05:1-1.8:1, preferably 1.1-1.5:1, wherein the molar ratio of alcohol to acid refers to a molar ratio of the number of functional groups —OH to the number of functional groups —COOH.
The esterification reaction is preferably provided as follows:
the esterification reaction is carried out by raising a temperature to 130-240° C. under the presence of a protective gas, and the esterification reaction lasts for 1-5 h. The protective gas is a gas that does not affect the reaction progress and may not react with raw materials. The protective gas is preferably inert gas or nitrogen.
The polymerization reaction is preferably provided as follows:
the polymerization reaction is carried out by performing the pre-polycondensation reaction at 190-250° C. and 3 kPa-10 kPa for 1-4 h; vacuuming at 200-250° C. to 500 Pa or below; and final polycondensation for 0.5-10 h.
The present disclosure may preferably use the following technical solution:
A method for preparing a butenediol-based polyester elastomer includes the following steps:
under the protection of the protective gas, adding diol (at least including 1,4-butenediol), binary acid and/or lactic acid into a reaction container according to an alcohol-to-acid ratio of 1.05:1-1.8:1, and adding the antioxidant which is 0.01-0.2% of the total mass of the monomer and the polymerization inhibitor that is 0.01-0.5% of the total mass of the monomer at the same time; then under the presence of the protective gas atmosphere, raising the temperature to 130-240° C. for the esterification reaction for 1-5 h; later, under the action of the catalyst, carrying out the pre-polycondensation reaction at 190-250° C. and 3 kPa-10 kPa for 1-4 h; vacuuming at 200-250° C. to 500 Pa or below; and a final polycondensation for 0.5-10 h to obtain the butenediol-based polyester elastomer.
In the present disclosure, a direct esterification pathway is adopted, so that its production procedure is simple, its implementation is easy, and its operability is high.
In the present disclosure, the butenediol-based polyester elastomer can be vulcanized by using the peroxide crosslinking agent commonly used in the rubber industry, preferably the most commonly used dicumyl peroxide.
In the present disclosure, the double-bond in the butenediol-based polyester elastomer has high stability, when the peroxide crosslinking agent is used for vulcanization, the dosage of the crosslinking agent is 0.2-3%, preferably 0.5-2%, of the total mass of the polyester elastomer.
The present disclosure will be specifically described below in conjunction with the accompanying drawings and specific embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present disclosure, and should not be construed as limiting the protection scope of the present disclosure. Some non-essential improvements and adjustments made by those skilled in the art according to the Summary to the present disclosure still fall within the protection scope of the present disclosure.
Raw materials used in the embodiments are all commercially available.
Gel permeation chromatography (GPC) test (conventional, common in the prior art): Polystyrene was used as a standard substance, and tetrahydrofuran was used as a mobile phase, so as to measure a relative molecular mass and distribution of an obtained polyester elastomer. Experimental test results were shown in Table 1.
Differential scanning calorimetry (DSC) test (conventional, common in the prior art): Under a nitrogen atmosphere, a sample was heated from 25° C. to 200° C. at a rate of 10° C./min for 5 min; then the sample was cooled from 200° C. to −100° C. at the rate of 10° C./min for 10 min; and the sample was then heated from −100° C. to 200° C. at the rate of 10° C./min. Values of Tg and Tm of an obtained polyester elastomer were read, and experimental test results were shown in Table 1.
565 g of (7.43 mol) 1,3-propanediol, 669 g of (7.43 mol) 1,4-butanediol, 145 g of (1.65 mol) 1,4-butenediol, 1050 g of (8.89 mol) succinic acid, 770 g of (3.81 mol) sebacic acid, 0.32 g of phosphorous acid and 1.28 g of hydroquinone were added into a reaction kettle with mechanical stirring, a heating device, a temperature measurement device, a nitrogen system and a vacuum system; under a nitrogen atmosphere, the temperature was raised to 180° C. under a normal pressure esterification for 2 h; tetrabutyl titanate that was 0.1% of the total mass of the monomer was added and used as the catalyst; the temperature was raised to 220° C. for pre-polycondensation at 3 kPa for 1 h; and finally at 220° C., vacuumizing was carried out to be 500 Pa or below, and final polycondensation was carried out for 9 h to obtain the butenediol-based polyester elastomer.
The structure of the prepared butenediol-based polyester elastomer is as follows:
where m1=3, m2=4; n1=2, n2=8;
in addition, (a+c+e):(k+m+o)≈9.52: 4.08.
598 g of (6.63 mol) 1,4-butanediol, 212 g of (2.41 mol) 1,4-butenediol, 931 g of (10.33 mol) lactic acid, 153 g of (1.29 mol) succinic acid, 1,306 g of (6.46 mol) sebacic acid, 3.2 g of tri-(2,4-di-tert-butylphenyl)-phosphite ester and 12.8 g of p-hydroxyanisole were added into a reaction kettle with the mechanical stirring, the heating device, the temperature measurement device, the nitrogen system and the vacuum system; under the nitrogen atmosphere, the temperature was raised to 130° C. under normal pressure esterification for 2 h; the temperature was then raised to 190° C. for continuous normal pressure esterification for 2 h; tetraisopropyl titanate that was 0.05% of the total mass of the monomer was added and used as the catalyst; the temperature was raised to 190° C. for pre-polycondensation at 10 kPa for 4 h; and finally at 210° C., vacuumizing was carried out to be 500 Pa or below, and final polycondensation was carried out for 6 h to obtain the butenediol-based polyester elastomer.
The structure of the prepared butenediol-based polyester elastomer is as follows:
where m1=4, m2=0 (equivalent to m1=m2=4); n1=2, n2=8;
in addition, (b+d+f): (a+e): (k+m)≈10.33: 1.29: 6.46.
709 g of (7.86 mol) 1,4-butanediol, 277 g of (3.15 mol) 1,4-butenediol, 501 g of (4.72 mol) diglycol, 851 g of (7.21 mol) succinic acid, 862 g of (5.90 mol) adipic acid, 1.6 g of triphenyl phosphite and 8 g of hydroquinone were added into a reaction kettle with the mechanical stirring, the heating device, the temperature measurement device, the nitrogen system and the vacuum system; under the nitrogen atmosphere, the temperature was raised to 185° C. under the normal pressure esterification for 3 h; p-toluenesulfonic acid that was 0.40% of the total mass of the monomer was added and used as the catalyst; the temperature was raised to 210° C. for pre-polycondensation at 5 kPa for 2 h; and finally at 230° C., vacuumizing was carried out to be 500 Pa or below, and final polycondensation was carried out for 7 h to obtain the butenediol-based polyester elastomer.
The structure of the prepared butenediol-based polyester elastomer is as follows:
where m1=4, m2=0 (equivalent to m1 =m2=4); n1=2, n2=1; x=y=1;
in addition, (a+e+g): (i+k+o)≈7.21: 5.90.
687 g of (11.07 mol) ethanediol, 321 g of (1.84 mol) decamethylene glycol, 488 g of (5.53 mol) 1,4-butenediol, 934 g of (7.91 mol) succinic acid, 770 g of (5.27 mol) adipic acid, 2.56 g of trimethyl phosphate and 6.4 g of benzoquinone were added into a reaction kettle with the mechanical stirring, the heating device, the temperature measurement device, the nitrogen system and the vacuum system; under the nitrogen atmosphere, the temperature was raised to 180° C. under the normal pressure esterification for 3 h; tetrabutyl titanate that was 0.20% of the total mass of the monomer was added and used as the catalyst; the temperature was raised to 200° C. for pre-polycondensation at 5 kPa for 2 h; and finally at 225° C., vacuumizing was carried out to be 500 Pa or below, and final polycondensation was carried out for 4 h to obtain the butenediol-based polyester elastomer.
The structure of the prepared butenediol-based polyester elastomer is as follows:
where m1=2, m2=10; n1=2, n2=4;
in addition, (a+c+e): (k+m+o)≈7.91: 5.27.
550 g of (7.22 mol) 1,3-propanediol, 163 g of (1.81 mol) 2,3-butanediol, 796 g of (9.03 mol) 1,4-butenediol, 1,137 g of (9.63 mol) succinic acid, 555 g of (2.41 mol) dodecanedioic acid, 4.8 g of phosphorous acid and 16 g of p-hydroxyanisole were added into a reaction kettle with the mechanical stirring, the heating device, the temperature measurement device, the nitrogen system and the vacuum system; under the nitrogen atmosphere, the temperature was raised to 160° C. under the normal pressure esterification for 1 h; the temperature was then raised to 180° C. for continuous esterification for 3 h; ethylene glycol antimony that was 0.50% of the total mass of the monomer was added and used as the catalyst; the temperature was raised to 200° C. for pre-polycondensation at 10 kPa for 2 h; and finally at 230° C., vacuumizing was carried out to be 500 Pa or below, and final polycondensation was carried out for 3 h to obtain the butenediol-based polyester elastomer.
The structure of the prepared butenediol-based polyester elastomer is as follows:
where m1=3, m2=4 (branched chain alkyl with 4 carbon atoms); n1=2, n2=10;
in addition, (a+c+e):(k+m+o)≈9.63: 2.41.
543 g of (6.02 mol) 1,4-butanediol, 1,086 g of (12.05 mol) 2,3-butanediol, 177 g of (2.01 mol) 1,4-butenediol, 1,395 g of (11.81 mol) succinic acid, 3.2 g of trimethyl phosphate and 12.8 g of p-hydroxyanisole were added into a reaction kettle with the mechanical stirring, the heating device, the temperature measurement device, the nitrogen system and the vacuum system; under the nitrogen atmosphere, the temperature was raised to 170° C. under the normal pressure esterification for 2 h; the temperature was then raised to 210° C. for esterification for 1 h; the temperature was then raised to 240° C. for continuous esterification for 0.5 h; ethylene glycol antimony that was 0.25% of the total mass of the monomer was added and used as the catalyst; the temperature was raised to 250° C. for pre-polycondensation at 10 kPa for 1 h; and finally at 250° C., vacuumizing was carried out to be 500 Pa or below, and final polycondensation was carried out for 0.5 h to obtain the butenediol-based polyester elastomer.
The structure of the prepared butenediol-based polyester elastomer is as follows:
where m1=4, m2=4 (branched chain alkyl with 4 carbon atoms); n1=2, n2=0 (equivalent to n1=n2=2);
in addition, a: c: e≈6.02: 12.05: 2.01.
633 g of (8.32 mol) 1,3-propanediol, 750 g of (8.32 mol) 1,4-butanediol, 952 g of (8.06 mol) succinic acid, 699 g of (3.46 mol) sebacic acid, 166 g of (1.28 mol) itaconic acid, 0.32 g of phosphorous acid and 1.28 g of hydroquinone were added into a reaction kettle with mechanical stirring, a heating device, a temperature measurement device, a nitrogen system and a vacuum system; under a nitrogen atmosphere, the temperature was raised to 180° C. for normal pressure esterification for 2 h; tetrabutyl titanate that was 0.1% of the total mass of a monomer was added and used as a catalyst; the temperature was raised to 220° C. for pre-polycondensation at 3 kPa for 1 h; and finally at 220° C., vacuumizing was carried out to be 500 Pa or below, and final polycondensation was carried out for 6 h to obtain an itaconic acid-based polyester elastomer.
The structure of the prepared itaconic acid-based polyester elastomer is as follows:
where m1=3, m2=4; n1=2, n2=8;
in addition, (a+c): (m+o): (e′+k′)≈8.06: 3.46: 1.28.
a: the alcohol-to-acid ratio of the present disclosure, that is, during feeding, a molar ratio of —OH to —COOH in the monomer. For a lactic acid-containing system, during calculation of the molar ratio, —OH and —COOH contained in lactic acid also need to be counted.
b: BeDO % mol refers to the mole percentage of 1,4-butenediol in diol. The diol is conventionally defined, including saturated diol, glycol and 1,4-butenediol.
c: In the secondary heating curve, zero Tc and Tm prove that the obtained polyester material has a glass transition temperature that is less than the room temperature, without crystallization and melting, so the obtained polyester material is an elastomer material.
d: “10% mol IA” means that the mole fraction of itaconic acid in the total amount of binary acid is 10%. Since each mole of itaconic acid and each mole of butenediol both contain 1 mole of double-bonds, the number of double-bonds contained in the system of “10% mol IA” is theoretically equivalent to that of “10% mol BeDO”.
It can be seen from the data in Table 1 that the butenediol-based polyester elastomer prepared in the present disclosure generally has higher relative molecular mass and narrower relative molecular mass distribution than the itaconic acid-based polyester elastomer. When the dosage of the butenediol is low, the relative molecular mass distribution is around 2.0, which is close to that of saturated polyester plastic, such as PBS and PBA, which can prove that the butenediol has extremely high stability. When the dosage of the butenediol increases, the relative molecular mass distribution gradually broadens, but the butenediol system still has the advantages of “high molecular weight and narrow distribution” compared with the itaconic acid system. The main reason is that compared with the double-bond in the itaconic acid, the double-bond in the butenediol is more stable, so in high-temperature melting and polycondensation processes, side reactions are not easy to occur, thereby ensuring a narrower relative molecular mass distribution.
In the present disclosure, due to a high molecular weight of the butenediol-based polyester elastomer and a similar crosslinking mechanism to that of traditional rubber, it can be reinforced by carbon black and/or white carbon black and vulcanized by the peroxide crosslinking agent, thus preparing a polyester elastomer/white carbon black (and/or carbon black) rubber composite material with high performance. The butenediol-based polyester elastomer has the potential to be used in the fields of low-temperature- and oil-resistant rubber, degradable tires and the like.
Compared with the prior art, the present disclosure has the following advantages. First, the 1,4-butenediol is introduced into a polyester elastomer for the first time, and a novel polyester elastomer production procedure is developed. Second, the double-bond in the butenediol is highly stable in the polymerization process and is not easy to undergo side reactions, so that a polyester elastomer product with a high molecular weight and narrow distribution can be obtained. Finally, the method for preparing the butanediol-based polyester elastomer product is simple, feasible and easy to implement, and there are a variety of products prepared from optional monomers in a large scale, which is expected to achieve large-scale preparation and has a wide application prospect.
| Number | Date | Country | Kind |
|---|---|---|---|
| CN202010045414.1 | Jan 2020 | CN | national |
This application is a continuation of PCT patent application No. PCT/CN2020/137013 filed on Dec. 17, 2020 which claims priority to the Chinese patent application No. CN202010045414.1 filed on Jan. 16, 2020, the entire disclosures of which are hereby incorporated by reference herein for all purposes.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/CN2020/137013 | Dec 2020 | US |
| Child | 17866424 | US |
