阅读说明：本技术 具有高硫含量的弹性体三元共聚物及其制备方法 (Elastomeric terpolymers having high sulfur content and method of making same ) 是由 阿尔贝托·雷纳托·德·安吉利斯 乔瓦尼·瑞格蒂 恰拉·弗朗西斯卡·卡罗扎 于 2019-05-10 设计创作，主要内容包括：具有高硫含量的弹性体三元共聚物包含：-相对于所述弹性体三元共聚物的总重量高于或等于40重量％、优选在55重量％至90重量％的范围内的量的硫；-第一单体,其选自芳族乙烯基化合物,优选选自苯乙烯、二乙烯基苯、乙烯基甲苯、叔丁基苯乙烯、ρ-甲基苯乙烯、γ-甲基苯乙烯、α-甲基苯乙烯、乙烯基萘；-第二单体,其选自：-芳族乙烯基化合物,优选选自苯乙烯、二乙烯基苯、乙烯基甲苯、叔丁基苯乙烯、ρ-甲基苯乙烯、γ-甲基苯乙烯、α-甲基苯乙烯、乙烯基萘；-具有通式(I)的单体：CH_2＝CH-(CH_2)_y-(X)_n-(X)_m-(CH_2)_x-CH＝CH_2,其中：-X表示硫原子、硒原子、碲原子,优选硫原子、硒原子；-y和x彼此相同或不同,是在0至4的范围内的整数；-n和m彼此相同或不同,是在0至3的范围内的整数,n和m中的至少一个等于1；所述第一单体和所述第二单体以相对于所述弹性体三元共聚物的总重量低于或等于60重量％、优选在10重量％至45重量％的范围内的量存在；所述第一单体和所述第二单体彼此不同。所述具有高硫含量的弹性体三元共聚物可以有利地用于许多应用,诸如例如隔热、传送带、传动带、柔性软管并且特别是轮胎用弹性体组合物。(Elastomeric terpolymers having a high sulfur content comprise: -sulfur in an amount higher than or equal to 40% by weight, preferably in the range from 55% to 90% by weight, relative to the total weight of the elastomeric terpolymer; -a first monomer selected from aromatic vinyl compounds, preferably from styrene, divinylbenzene, vinyltoluene, tert-butylstyrene, p-methylstyrene, gamma-methylstyrene, alpha-methylstyrene, vinylnaphthalene; -a second monomer selected from: aromatic vinyl compounds, preferably selected from styrene, divinylPhenyl benzene, vinyl toluene, tert-butyl styrene, rho-methyl styrene, gamma-methyl styrene, alpha-methyl styrene, vinyl naphthalene; -monomers having general formula (I): CH (CH) 2 ＝CH‑(CH 2 ) y ‑(X) n ‑(X) m ‑(CH 2 ) x ‑CH＝CH 2 Wherein: -X represents a sulfur atom, a selenium atom, a tellurium atom, preferably a sulfur atom, a selenium atom; -y and x, equal to or different from each other, are integers ranging from 0 to 4; -n and m, equal to or different from each other, are integers ranging from 0 to 3, at least one of n and m being equal to 1; the first monomer and the second monomer are present in an amount lower than or equal to 60% by weight, preferably in the range from 10% to 45% by weight, relative to the total weight of the elastomeric terpolymer; the first monomer and the second monomer are different from each other. The elastomeric terpolymers having a high sulfur content may be advantageously used in many applications such as, for example, elastomeric compositions for thermal insulation, conveyor belts, power transmission belts, flexible hoses and, in particular, tires.)

1. An elastomeric terpolymer having a high sulfur content comprising:

-sulfur in an amount higher than or equal to 40% by weight, preferably in the range from 55% to 90% by weight, relative to the total weight of the elastomeric terpolymer;

-a first monomer selected from aromatic vinyl compounds, preferably from styrene, divinylbenzene, vinyltoluene, tert-butylstyrene, p-methylstyrene, gamma-methylstyrene, alpha-methylstyrene, vinylnaphthalene;

-a second monomer selected from:

-aromatic vinyl compounds, preferably selected from styrene, divinylbenzene, vinyltoluene, tert-butylstyrene, p-methylstyrene, gamma-methylstyrene, alpha-methylstyrene, vinylnaphthalene;

-monomers having general formula (I):

CH₂＝CH-(CH₂)_y-(X)_n-(X)_m-(CH₂)_x-CH＝CH₂ (I)

wherein:

-X represents a sulfur atom, a selenium atom, a tellurium atom, preferably a sulfur atom, a selenium atom;

-y and x, equal to or different from each other, are integers ranging from 0 to 4;

-n and m, equal to or different from each other, are integers ranging from 0 to 3, at least one of n and m being equal to 1;

the first monomer and the second monomer are present in an amount lower than or equal to 60% by weight, preferably in the range from 10% to 45% by weight, relative to the total weight of the elastomeric terpolymer; the first monomer and the second monomer are different from each other.

2. The elastomeric terpolymer having high sulfur content of claim 1 wherein the first monomer is selected from styrene, divinylbenzene.

3. The elastomeric terpolymer with high sulfur content of claim 1 or 2 wherein the second monomer is selected from styrene, divinylbenzene, allyl disulfide, diallyl trisulfide, divinyl disulfide.

4. The elastomeric terpolymer having high sulfur content of any of the preceding claims, wherein the elastomeric terpolymer having high sulfur content comprises:

-sulfur in an amount equal to 60% by weight relative to the total weight of the elastomeric terpolymer;

-styrene in an amount equal to 30% by weight relative to the total weight of the elastomeric terpolymer;

-allyl disulfide in an amount equal to 10% by weight relative to the total weight of the elastomeric terpolymer.

5. The elastomeric terpolymer having high sulfur content of any one of claims 1 to 3, wherein the elastomeric terpolymer having high sulfur content comprises:

-sulfur in an amount equal to 60% by weight relative to the total weight of the elastomeric terpolymer;

-styrene in an amount equal to 10% by weight relative to the total weight of the elastomeric terpolymer;

-divinylbenzene in an amount equal to 30% by weight relative to the total weight of the elastomeric terpolymer.

6. The elastomeric terpolymer with high sulfur content of any of the preceding claims, wherein the elastomeric terpolymer with high sulfur content has a glass transition temperature (T) less than or equal to +1 ℃_g)。

7. The elastomeric terpolymer having high sulfur content of any of the preceding claims, wherein the elastomeric terpolymer having high sulfur content has an elongation at break greater than or equal to 500%.

8. A process for preparing an elastomeric terpolymer having a high sulfur content comprising:

(i) melting the sulphur at a temperature in the range of 110 ℃ to 190 ℃, preferably in the range of 120 ℃ to 170 ℃, for a time in the range of 1 minute to 15 minutes, preferably in the range of 2 minutes to 10 minutes, obtaining sulphur in liquid form;

(ii) (ii) reacting the sulphur obtained in liquid form in stage (i) with a first monomer selected from aromatic vinyl compounds, preferably selected from styrene, divinylbenzene, vinyltoluene, tert-butylstyrene, p-methylstyrene, gamma-methylstyrene, alpha-methylstyrene, vinylnaphthalene, at a temperature in the range of from 110 ℃ to 190 ℃, preferably in the range of from 120 ℃ to 170 ℃, for a time in the range of from 1 minute to 15 minutes, preferably in the range of from 2 minutes to 10 minutes, and subsequently adding a second monomer selected from aromatic vinyl compounds, at a temperature in the range of from 110 ℃ to 190 ℃, preferably in the range of from 120 ℃ to 170 ℃, for a time in the range of from 1 minute to 15 minutes, preferably in the range of from 2 minutes to 10 minutes, to obtain a liquid prepolymer, preferably selected from styrene, divinylbenzene, vinyltoluene, tert-butylstyrene, p-methylstyrene, gamma-methylstyrene, alpha-methylstyrene, vinylnaphthalene, or from monomers having general formula (I), preferably selected from allyl disulfide, diallyl trisulfide, divinyl disulfide, the first and second monomers being different from each other;

(iii) (iii) pouring the liquid prepolymer obtained in stage (ii) into a mould and holding the mould at a temperature in the range of from 100 ℃ to 150 ℃, preferably in the range of from 110 ℃ to 130 ℃, for a time in the range of from 1 hour to 20 hours, preferably in the range of from 2 hours to 15 hours, obtaining an elastomeric terpolymer having a high sulphur content.

9. The process for the preparation of elastomeric terpolymers with high sulfur content according to claim 8, wherein the sulfur used in said stage (i) is elemental sulfur.

10. Use of the elastomeric terpolymer with high sulfur content according to any of claims 1 to 9 in elastomeric compositions for thermal insulation, conveyor belts, power transmission belts, flexible hoses and in particular tires.

Examples

Analysis and characterization method

The analysis and characterization methods reported below were used.

Thermal analysis (DSC)

For determining the glass transition temperature (T) of the elastomeric terpolymers obtained_g) For the purposes of DSC (differential scanning calorimetry) thermal analysis with the aid of a Perkin Elmer Pyris differential scanning calorimeter, using the following thermal program:

-cooling from ambient temperature (T ═ 25 ℃) to-60 ℃ at a rate of-5 ℃/min;

-heating from-60 ℃ to +150 ℃ at a rate of +10 ℃/min (first scan);

-cooling from +150 ℃ to-60 ℃ at a rate of-5 ℃/min;

-heating from-60 ℃ to +150 ℃ at a rate of +10 ℃/min (second scan);

under nitrogen (N) at 70 ml/min₂) The flow was down operated.

Example 1 (invention)

Elastomeric terpolymer with sulfur (60 wt%), styrene (30 wt%) and allyl disulfide (10 wt%) Synthesis of copolymer

6g of pure sulfur [ Sigma-Aldrich in orthorhombic crystal form (S)₈) Of elemental sulfur]Into a 60ml glass autoclave equipped with a magnetic stirrer: the autoclave was heated to 160 ℃ and held at said temperature for 10 minutes, obtaining melting of the sulphur, which turned into a yellow liquid. Then 3g of liquid styrene (Sigma-Aldrich) were added dropwise to the liquid: the whole was kept at 160 ℃ for 3 minutes under stirring to obtain a solution. To the solution was then added dropwise 1g of liquid allyl disulfide (Sigma-Aldrich): the whole was kept at 160 ℃ for a further 3 minutes with stirring, obtaining a solution which remained fluid and exhibited an intense red colour. Pouring the fluid solution thus obtained into a Teflon mould, sealing the mouldClosed and heated in an oven to 120 ℃: the fluid solution was held at the temperature for 12 hours to obtain an elastomeric terpolymer that was black in color and had a translucent appearance.

To measure the glass transition temperature (T)_g) The elastomeric terpolymer was subjected to DSC (differential scanning calorimetry) thermal analysis operating as described above and found to have a glass transition temperature equal to-0.3 ℃.

The elastomeric terpolymer was also subjected to an elongation at break determined according to standard ISO 37:2017, finding an elongation at break equal to 520%.

Example 2 (invention)

Elastomer terpolymer with sulfur (60 wt%), styrene (10 wt%) and divinylbenzene (30 wt%) Synthesis of Polymer

6g of pure sulfur [ Sigma-Aldrich in orthorhombic crystal form (S)₈) Of elemental sulfur]Into a 60ml glass autoclave equipped with a magnetic stirrer: the autoclave was heated to 160 ℃ and held at said temperature for 10 minutes, obtaining melting of the sulphur, which turned into a yellow liquid. Then 1g of liquid styrene (Sigma-Aldrich) was added dropwise to the liquid: the whole was kept at 160 ℃ for 3 minutes under stirring to obtain a solution. Then 3g of liquid divinylbenzene (Sigma-Aldrich) were added dropwise to the solution: the whole was kept at 160 ℃ for a further 3 minutes with stirring, obtaining a solution which remained fluid and exhibited an intense red colour. The fluid solution thus obtained is poured into a teflon mould, which is closed and heated in an oven to 120 ℃: the fluid solution was held at the temperature for 12 hours to obtain an elastomeric terpolymer that was black in color and had a translucent appearance.

For measuring glass transition temperature (T)_g) Subject said elastomeric terpolymer to DSC (differential scanning calorimetry) thermal analysis operating as described above, finding a glass transition temperature equal to +0.96 ℃.

The elastomeric terpolymer was also subjected to an elongation at break determined according to standard ISO 37:2017, finding an elongation at break equal to 630%.

Example 3 (comparative)

Synthesis of an elastomeric copolymer with Sulfur (70 wt.%) and Diallyldisulfide (30 wt.%)

7g of pure sulfur [ Sigma-Aldrich in orthorhombic crystal form (S)₈) Of elemental sulfur]Into a 60ml glass autoclave equipped with a magnetic stirrer: the autoclave was heated to 160 ℃ and held at said temperature for 10 minutes, obtaining melting of the sulphur, which turned into a yellow liquid. Then 3g of liquid diallyl disulfide (Sigma-Aldrich) were added dropwise to the liquid: the whole was kept at 160 ℃ for 3 minutes with stirring, obtaining a solution that remained fluid and exhibited an intense red colour. The fluid solution thus obtained is poured into a teflon mould, which is closed and heated in an oven to 120 ℃: the fluid solution was kept at the temperature for 12 hours, obtaining an elastomeric copolymer that was black in color and had a translucent appearance.

For measuring glass transition temperature (T)_g) Subject said elastomeric copolymer to DSC (differential scanning calorimetry) thermal analysis operating as described above, finding a glass transition temperature equal to-15 ℃.

The elastomeric copolymer is also subjected to an elongation at break determined according to standard ISO 37:2017, finding an elongation at break equal to 56%.