Butenediol-based Polyester Elastomer and Method for Preparing Same

Abstract

The present disclosure discloses a butenediol-based polyester elastomer and a method for preparing same. In the present disclosure, 1,4-butenediol containing high-stability double-bond is used 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 weight and narrow relative molecular weight distribution. The crosslinking in subsequent processing is more controllable, and the dosage of a vulcanizing agent is equivalent to that of traditional rubber.

Claims

1. A butenediol-based polyester elastomer, comprising a structure as shown below: ##STR00009## R.sub.m1 and R.sub.m2 are branched or unbranched chain alkyl groups, and R.sub.m1 and R.sub.m2 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; R.sub.n1 and R.sub.n2 are branched or unbranched chain alkyl groups, and R.sub.n1 and R.sub.n2 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≤12m preferably 2≤n2≤8; n1 and n2 may be the same or different; wherein a, c, m and o are not 0 at the same time, and e and k are not 0 at the same time; 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.

2. The method for preparing the butenediol-based polyester elastomer according to claim 1, further comprising: under the action of a catalyst, 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 to prepare a butenediol-based polyester elastomer; the dihydric alcohol is 1,4-butenediol and other diols; other diols is one or a combination of HO—R.sub.m—OH, diglycol, triethylene glycol and tetraethylene glycol; wherein R.sub.m is either a branched or unbranched chain alkyl group, and m represents the number of carbon atoms, 2≤m≤14; preferably 2≤m≤10; the binary acid is one or a combination of HOOC—R.sub.n—COOH; wherein R.sub.n is either the branched or unbranched chain alkyl group, and n represents the number of carbon atoms, 2≤n≤12; preferably 2≤n≤8.

3. The method for preparing the butenediol-based polyester elastomer according to claim 2, wherein a mole percentage of 1,4-butenediol in the diol is 2% to 60%.

4. The method for preparing the butenediol-based polyester elastomer according to claim 3, wherein the mole percentage of the 1,4-butenediol in the diol is 5% to 30%.

5. The method for preparing the butenediol-based polyester elastomer according to claim 2, wherein the catalyst is 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; wherein the antioxidant is one or a combination of phosphoric acid or a phosphorous acid compound; and wherein the polymerization inhibitor is one or a combination of a phenol polymerization inhibitor, an ether polymerization inhibitor, a quinone polymerization inhibitor or an aromatic amine polymerization inhibitor.

6. The method for preparing the butenediol-based polyester elastomer according to claim 2, wherein a molar ratio of a number of functional groups —OH to the number of functional groups —COOH in the diol, binary acid and/or lactic acid is 1.05:1-1.8:1; wherein a dosage of the antioxidant is 0.01-0.2% of a total mass of the diol, the binary acid and/or the lactic acid; and wherein a 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.

7. The method for preparing the butenediol-based polyester elastomer according to claim 6, wherein the molar ratio of the number of functional groups —OH to the number of functional groups —COOH in the diol, binary acid and/or lactic acid is 1.1-1.5:1; wherein the dosage of the antioxidant is 0.04-0.08% of the total mass of the diol, the binary acid and/or the lactic acid; and wherein the dosage of the polymerization inhibitor is 0.05-0.2% of the total mass of the diol, the binary acid and/or the lactic acid.

8. The method for preparing the butenediol-based polyester elastomer according to claim 2, wherein a dosage of the catalyst is 0.02-0.5% of a total mass of the diol, the binary acid and/or the lactic acid.

9. The method for preparing the butenediol-based polyester elastomer according to claim 2, wherein 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.

10. The method for preparing the butenediol-based polyester elastomer according to claim 2, wherein the polymerization reaction is carried out by performing a 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.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0036] FIG. 1 is an FTIR spectrogram of a prepared butenediol-based polyester elastomer in Embodiment 1;

[0037] FIG. 2 is an H-NMR spectrogram of the prepared butenediol-based polyester elastomer in Embodiment 1; and

[0038] FIG. 3 is a DSC secondary heating curve of the prepared butenediol-based polyester elastomer in Embodiment 1.

DETAILED DESCRIPTION OF THE DISCLOSURE

[0039] 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.

[0040] Raw materials used in the embodiments are all commercially available.

[0041] 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.

[0042] 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.

Embodiment 1

[0043] FIG. 1 is an FTIR spectrogram of a prepared butenediol-based polyester elastomer. The FTIR spectrogram and the H-NMR spectrogram verify the structure of the obtained butenediol-based polyester. In the FTIR spectrogram, the presence of peaks —C═O and —C—O—C═O proves that a large number of ester groups are contained, and peak —CH2- corresponds to a large number of aliphatic chains; and the presence of peaks —C═C— and —CH═CH— proves the successful introduction of butenediol, that is, the obtained material is a butenediol-based polyester.

[0044] FIG. 2 is an H-NMR spectrogram of the prepared butenediol-based polyester elastomer in Embodiment 1. In the H-NMR spectrum, peaks k and j correspond to two hydrogen atoms in a butenediol structure, which can prove the successful introduction of butenediol, and this peak position can be analogized to all the embodiments. As far as Embodiment 1 is concerned: peaks a and b correspond to two kinds of hydrogens in 1,3-propanediol; peaks c and d correspond to two kinds of hydrogens in 1,4-butanediol; e corresponds to one kind of hydrogen of succinic acid; f, g, h and i correspond to four kinds of hydrogens in sebacic acid; and therefore, it can be proved that the structure of the obtained butenediol-based polyester is consistent with an expected structure.

[0045] FIG. 3 is a DSC secondary heating curve of the prepared butenediol-based polyester elastomer in Embodiment 1. The DSC curve proves that the obtained butenediol-based polyester is an elastomer. It can be seen from FIG. 3 that there is only one glass transition in the curve, and there is no crystallization and melting behaviors. Therefore, it can be proved that the butenediol-based polyester obtained in Embodiment 1 has an amorphous structure, which is a new polyester elastomer with a glass transition temperature (Tg) of −51° C.

[0046] 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.

[0047] The structure of the prepared butenediol-based polyester elastomer is as follows:

##STR00002##

[0048] where m1=3, m2=4; n1=2, n2=8;

[0049] in addition, (a+c+e):(k+m+o)≈9.52: 4.08.

Embodiment 2

[0050] 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.

[0051] The structure of the prepared butenediol-based polyester elastomer is as follows:

##STR00003##

[0052] where m1=4, m2=0 (equivalent to m1=m2=4); n1=2, n2=8;

[0053] in addition, (b+d+f): (a+e): (k+m)≈10.33: 1.29: 6.46.

Embodiment 3

[0054] 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.

[0055] The structure of the prepared butenediol-based polyester elastomer is as follows:

##STR00004##

[0056] where m1=4, m2=0 (equivalent to m1 =m2=4); n1=2, n2=1; x=y=1;

[0057] in addition, (a+e+g): (i+k+o)≈7.21: 5.90.

Embodiment 4

[0058] 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.

[0059] The structure of the prepared butenediol-based polyester elastomer is as follows:

##STR00005##

[0060] where m1=2, m2=10; n1=2, n2=4;

[0061] in addition, (a+c+e): (k+m+o)≈7.91: 5.27.

Embodiment 5

[0062] 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.

[0063] The structure of the prepared butenediol-based polyester elastomer is as follows:

##STR00006##

[0064] where m1=3, m2=4 (branched chain alkyl with 4 carbon atoms); n1=2, n2=10;

[0065] in addition, (a+c+e):(k+m+o)≈9.63: 2.41.

Embodiment 6

[0066] 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.

[0067] The structure of the prepared butenediol-based polyester elastomer is as follows:

##STR00007##

[0068] where m1=4, m2=4 (branched chain alkyl with 4 carbon atoms); n1=2, n2=0 (equivalent to n1=n2=2);

[0069] in addition, a: c: e≈6.02: 12.05: 2.01.

COMPARATIVE EXAMPLE 1

[0070] 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.

[0071] The structure of the prepared itaconic acid-based polyester elastomer is as follows:

##STR00008##

[0072] where m1=3, m2=4; n1=2, n2=8;

[0073] in addition, (a+c): (m+o): (e′+k′)≈8.06: 3.46: 1.28.

TABLE-US-00001 TABLE 1 Test results of polyester elastomers in the embodiments and the comparative example in the present disclosure Alcohol-to- BeDO % Tg Tc, acid ratio .sup.a mol .sup.b (° C.) Tm Mn PDI Comparative 1.3:1 10% mol −51 None 37,200 3.77 example 1 IA .sup.d Embodiment 1.3:1 10% −52 None .sup.c 76,800 1.99 1 Embodiment 1.1:1 27% −45 None 65,300 2.21 2 Embodiment 1.2:1 20% −47 None 70,300 2.15 3 Embodiment 1.4:1 30% −44 None 67,700 2.25 4 Embodiment 1.5:1 50% −50 None 45,000 3.33 5 Embodiment 1.7:1 10% −17 None 39,000 2.17 6

[0074] 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.

[0075] 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.

[0076] 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.

[0077] 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”.

[0078] 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.

[0079] 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.

[0080] 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.