阅读说明：本技术 用于高度可崩解薄膜的聚合物组合物 (Polymer compositions for highly disintegrable films ) 是由 S·吉思加西亚 G·泰顿尼 于 2018-02-27 设计创作，主要内容包括：本发明涉及一种聚合物组合物,它特别适用于制造具有很高崩解能力的薄膜,优选在低温下,可用于覆盖薄膜领域。(The invention relates to a polymer composition which is particularly suitable for producing films having a high disintegration capacity, preferably at low temperatures, and which can be used in the field of covering films.)

1. A film comprising a composition comprising:

i) 40-80% by weight, relative to the total weight of the composition, of at least one aliphatic polyester (i) comprising:

a) a dicarboxylic acid component comprising, relative to the total dicarboxylic acid component:

a1) from 70 to 100 mol% of units derived from succinic acid, and

a2) from 0 to 30 mol% of units derived from at least one saturated dicarboxylic acid different from succinic acid, and

b) a diol component comprising, relative to the total diol component:

b1)95 to 100 mol% of units derived from 1, 4-butanediol, and

b2)0 to 5 mole% of a saturated aliphatic group derived from at least one other than 1, 4-butanediol

Units of a diol;

ii) 5 to 40% by weight, relative to the total weight of the composition, of at least one aliphatic-aromatic polyester (ii) comprising:

a) a dicarboxylic acid component comprising, relative to the total dicarboxylic acid component:

a1) from 30 to 70 mol% of units derived from at least one aromatic dicarboxylic acid, and

a2) from 70 to 30 mol% of units derived from at least one saturated aliphatic dicarboxylic acid,

b) a diol component comprising, relative to the total diol component:

b1)95 to 100 mole% of units derived from at least one saturated aliphatic diol, and

b2)0 to 5 mole% of units derived from at least one unsaturated aliphatic diol;

iii) 1 to 25% by weight, relative to the total weight of the composition, of at least one polyhydroxyalkanoate,

the film has an impact strength index of at least 2 mJ/(g/m) measured according to the standard ASTM D3420-08a²)。

2. The film according to claim 1, wherein the composition comprises:

i) 60-80% by weight, relative to the total weight of the composition, of at least one aliphatic polyester (i),

ii) 5 to 30% by weight, relative to the total weight of the composition, of at least one aliphatic-aromatic polyester (ii), and

iii) 1 to 25% by weight, relative to the total weight of the composition, of at least one polyhydroxyalkanoate (iii).

3. A film according to claim 1 or 2, wherein the composition comprises:

i) 60-80% by weight, relative to the total weight of the composition, of at least one aliphatic polyester (i),

ii) 16-30% by weight, relative to the total weight of the composition, of at least one aliphatic-aromatic polyester (ii), and

iii) 1 to 20% by weight, relative to the total weight of the composition, of at least one polyhydroxyalkanoate (iii).

4. The film according to any one of claims 1 to 3, wherein the dicarboxylic acid-based component a2) of the aliphatic polyester (i) is selected from adipic acid, azelaic acid, sebacic acid and mixtures thereof.

5. A film according to any of claims 1 to 4 wherein the diol component of the aliphatic polyester (i) is 1, 4-butanediol.

6. The film according to any of claims 1 to 5, wherein the aromatic dicarboxylic acid a1) of the aliphatic-aromatic polyester (ii) is selected from aromatic dicarboxylic acids of the phthalic acid and heterocyclic dicarboxylic acid aromatic compound types, their esters, salts and mixtures.

7. The film according to any of claims 1 to 6, wherein the aromatic dicarboxylic acid a1) of the aliphatic-aromatic polyester (ii) is selected from terephthalic acid and its esters and salts, 2, 5-furandicarboxylic acid and its esters and salts, and mixtures thereof.

8. The film according to any of claims 1 to 7, wherein the aliphatic dicarboxylic acid a2) of the aliphatic-aromatic polyester (ii) is selected from the group consisting of succinic acid, adipic acid, azelaic acid, sebacic acid, brassylic acid and mixtures thereof.

9. The film according to any of claims 1 to 8, wherein the aliphatic dicarboxylic acid a2) of the aliphatic-aromatic polyester (ii) is selected from adipic acid and azelaic acid.

10. The film according to any one of claims 1 to 9, wherein the polyhydroxyalkanoate (iii) is selected from the group consisting of polyesters of lactic acid, poly-e-caprolactone, polyhydroxybutyrate-valerate, polyhydroxybutyrate propionate, polyhydroxybutyrate-hexanoate, polyhydroxybutyrate-decanoate, polyhydroxybutyrate-dodecanoate, polyhydroxybutyrate-hexadecanoate, polyhydroxybutyrate-octadecanoate, poly-3-hydroxybutyrate 4-hydroxybutyrate, and mixtures thereof.

11. The film according to any one of claims 1 to 10, wherein the composition comprises from 0 to 5% by weight, relative to the total weight of the composition, of at least one crosslinking and/or chain extender comprising at least one compound having two and/or more functional groups selected from the group of isocyanates, peroxides, carbodiimides, isocyanurates, oxazolines, epoxides, anhydrides, divinyl ethers and mixtures thereof.

12. A film according to claim 11, wherein the cross-linking and/or chain extender comprises a compound having epoxy groups of the styrene-glycidyl ether-methyl methacrylate type.

13. The film according to any one of claims 1 to 12, wherein the composition comprises from 0 to 30% by weight of at least one filler, relative to the total weight of the composition.

14. Use of a film according to any one of claims 1 to 13 for the manufacture of a cover film.

15. A cover film comprising a film according to any one of claims 1 to 13.

Examples

Component i

Poly (1, 4-butylene succinate) ("PBS") prepared according to the following procedure: an 80 wt% ethanol solution of 17150g succinic acid, 14000g 1, 4-butanediol, 26.75g glycerol and 2.0g diisopropy-triethanolamine titanate (Tyzor TE containing 8.2 wt% titanium) was charged at a diol to dicarboxylic acid molar ratio (MGR) of 1.07 to a 60 liter steel reactor geometry equipped with a mechanical stirring system, nitrogen inlet, distillation column, high boiling distillate separation system and interface to a high vacuum system. The temperature of the mass was gradually increased to 230 ℃ over 120 minutes. When 95% of the theoretical amount of water had distilled off, 21.25g of tetra-n-butyl titanate were added (corresponding to 119ppm of metal relative to the amount of poly-1, 4-butanediol succinate theoretically obtainable if all the succinic acid fed to the reactor had been converted). The temperature of the reactor was then raised to 235-240 ℃ and the pressure was gradually reduced over a period of 60 minutes to reach a value of less than 2 mbar. The reaction was allowed to proceed for the time necessary to obtain poly (1, 4-butylene succinate) having an MFR of about 7g/10 min, measured at about 190 ℃ and 2.16 kg. The material was then discharged in the form of strands into a water bath and pelletized.

Poly (1, 4-butanediol succinate-co-1, 4-butanediol azelate) prepared according to the following procedure ("PBSAz"): 14830g of succinic acid, 2625g of azelaic acid, 13450g of 1, 4-butanediol, 25.7g of glycerol and 2.0g of an 80% by weight ethanol solution of diiso-triethanol-amine titanate (Tyzor TE containing 8.2% by weight of titanium) were charged with a molar ratio diol/dicarboxylic acid (MGR) of 1.07 to a steel reactor fitted with a mechanical stirring system, nitrogen inlet, distillation column, high-boiling distillate separation system and a geometric capacity of 60 litres connected to a high vacuum system interface. The temperature of the mass was gradually increased to 230 ℃ over a period of 120 minutes. When 95% of the theoretical amount of water had been distilled off, 21.25g of tetra-n-butyl titanate (corresponding to 119ppm of metal relative to the amount of poly (1, 4-butanediol succinate-co-1, 4-butanediol azelate) theoretically obtainable by conversion of all the succinic and azelaic acids fed to the reactor) were added. The temperature of the reactor was then raised to 235-240 ℃ and the pressure was gradually reduced in order to reach a value of less than 2mbar within 60 minutes. The reaction was allowed to proceed for the time necessary to obtain poly (1, 4-butanediol succinate-co-1, 4-butanediol azelate) having an MFR of about 7g/10 min, measured at 190 ℃ and 2.16 kg. The material was then discharged in the form of strands into a water bath and pelletized.

Component ii

ii-1 ═ poly (1, 4-butanediol adipate-co-1, 4-butanediol terephthalate) ("PBAT") prepared according to the following procedure: 7453g of terephthalic acid, 7388g of adipic acid, 12033g of 1, 4-butanediol, 4.4g of glycerol and 3.4g of an 80% by weight ethanol solution of diiso-propyl triethanolamine titanate (Tyzor TE containing 8.2% by weight of titanium) were charged, in a molar diol/dicarboxylic acid ratio (MGR) of 1.40, into a steel reactor with a geometric capacity of 60 litres fitted with a mechanical stirring system, a nitrogen inlet, a distillation column, a high-boiling distillate separation system and a connection to a high-vacuum system. The temperature of the mass was gradually increased to 230 ℃ over a period of 120 minutes. When 95% of the theoretical amount of water had been distilled off, 17.0g of tetra-n-butyl titanate (corresponding to 119ppm of metal relative to the amount of poly (1, 4-butanediol adipate-co-1, 4-butanediol terephthalate) theoretically obtainable by conversion of all the adipic and terephthalic acids fed to the reactor) were added. The temperature of the reactor was then raised to 235-240 ℃ and the pressure was gradually reduced over a period of 60 minutes to reach a value of less than 2 mbar. The reaction was allowed to proceed for the time necessary to obtain poly (1, 4-butylene adipate-co-terephthalate 1, 4-butylene) having an MFR of about 6g/10 min, measured at 190 ℃ and 2.16 kg. The material was then discharged in the form of strands into a water bath and pelletized.

ii-2 ═ poly (1, 4-butanediol adipate-co-1, 4-butanediol azelate-co-1, 4-butanediol terephthalate) ("PBATAz") prepared according to the following procedure: an 80% by weight ethanol solution of 7335g of terephthalic acid, 6185g of adipic acid, 1406g of azelaic acid, 11848g of 1, 4-butanediol, 4.4g of glycerol and 3.4g of diiso-propyl triethanolamine titanate (Tyzor TE containing 8.2% by weight of titanium) was charged at a molar diol/dicarboxylic acid ratio (MGR) of 1.40 to a steel reactor with a geometric capacity of 60 liters equipped with a mechanical stirring system, nitrogen inlet, distillation column, high-boiling-point distillate separation system and an interface to a high-vacuum system, and the temperature of the contents was gradually raised to 230 ℃ over a period of 120 minutes. When 95% of the theoretical water had distilled off, 17.0g of tetra-n-butyl titanate (corresponding to 119ppm of metal relative to the amount of poly (1, 4-butanediol adipate-co-azelaic acid 1, 4-butanediol-co-terephthalic acid 1, 4-butanediol) theoretically obtainable by conversion of all adipic acid, azelaic acid and terephthalic acid fed to the reactor) were added. The temperature of the reactor was then raised to 235-240 ℃ and the pressure was gradually reduced over a period of 60 minutes to reach a value of less than 2 mbar. The reaction was allowed to proceed for the time necessary to obtain poly (1, 4-butanediol adipate-co-azelaic acid 1, 4-butanediol-co-terephthalic acid 1, 4-butanediol) having an MFR of about 6g/10 min, measured at 190 ℃ and 2.16 kg. The material was then discharged in the form of strands into a water bath and pelletized.

Component iii

iii & gt polylactic acid ("PLA") Ingeo 4043D, MFR 3.5/10min (190 ℃, 2.16 kg).

Component iv

iv-a masterbatch comprising 10 wt.% of Joncryl ADR368CS (styrene-glycidyl ether-methyl methacrylate copolymer) and 90 wt.% of component iii.

The compositions shown in Table 1 were fed into an APC 2030 co-rotating twin-screw extruder (L/D40; diameter 30mm) operating under the following conditions:

-rpm：170，

-capacity: 10kg/h of the reaction mixture is added,

-temperature profile: 30-90-140-150-200X 9-160X 3 ℃,

open degassing.

The composition thus obtained was fed to a Ghioldi bubble film former having a 40mm diameter screw and L/D30, operating at 64rpm, a temperature profile of 120-. Film formation was performed at a blow-up ratio of 3 and a stretch ratio of 14X to obtain a film having a thickness of 20 μm.

The mechanical properties of films comprising the composition of the invention at a thickness of 20 μm were determined by measuring the tensile strength of the films according to ASTM D882(23 ℃, 50% Relative Humidity (RH) -Vo 50 mm/min).

The energy of impact strength [ J ] of a film of 20 μm thickness comprising a composition according to the invention was determined by measuring the impact-puncture penetration resistance of the film according to ASMT D3420-08a (procedure A, 23 ℃, 50% RH, pendulum force: 2J)]The value of (c). By applying the impact strength energy [ J ] according to the following equation]Is divided by the grammage of the film [ g/m [)²]To calculate an impact strength index [ mJ/(g/m) of the film (see Table 2)²)]：

The level of disintegration in soil of a film comprising a composition of the invention was determined by inserting a film sample having dimensions of 5 x 5cm into a slide holder. Insert slide holder into soil: specifically, a first layer of approximately 4cm of soil was placed into the reactor (a 20X 30X 10cm plastic box with a lid), and then a slide holder was placed over the first layer of soil and covered with a second layer of approximately 2 cm. The slide holders were periodically observed and photographed to check their degree of disintegration. The test was carried out at a temperature of 28 ℃. + -. 2.

TABLE 1 compositions

TABLE 2 characterization of the films

TABLE 3 disintegration of the film in soil