LOW COST BIO-BASED FULL DEGRADABLE FILM AND PREPARATION METHOD THEREOF

Abstract

The present invention discloses a low cost bio-based full degradable film and preparation method thereof, the ratio of each component in parts by mass of the film is as follows: 15-25 parts of a polyglycolic acid, 25-35 parts of corn starch, 35-55 parts of poly(butylene adipate-co-terephthalate), 5 parts of a compatilizer, 3.75-12.25 parts of a starch plasticizer, 0.5-0.7 part of citric acid, 0.75-1.25 parts of acetyl tributyl citrate, 0.3-0.5 part of maleic anhydride, 0.2 part of antioxidant 164, and 0.2 part of 2-(2-hydroxyl-5-methylphenyl)benzotriazole. The low cost bio-based full degradable film provided by the present invention has a bio-based content, which can reach 30% or more, a lower cost, and a tensile strength exceeding a traditional PE thin film, and has very important significance for solving the problem of white pollution and promoting the popularization and application of full biodegradable materials.

Claims

1. A low cost bio-based full degradable film, comprising the following materials in mass: 15-25 parts of a polyglycolic acid, 5-35 parts of corn starch, 35-55 parts of poly(butylene adipate-co-terephthalate), 5 parts of a compatilizer, 3.75-12.25 parts of a starch plasticizer, 0.5-0.7 part of citric acid, 0.75-1.25 parts of acetyl tributyl citrate, 0.3-0.5 part of maleic anhydride, 0.2 part of antioxidant 164, and 0.2 part of 2-(2 -hydroxyl-5-methylphenyl)benzotriazole.

2. The low cost bio-based full degradable film of claim 1, wherein the starch plasticizer is any one of or two of: glycerol, glycol, formamide, urea, an ethylene bisformamide.

3. The low cost bio-based full degradable film of claim 1, wherein the compatilizer is a graft copolymerization of butyl acrylate with glycidyl methacrylate , a ethylene-acrylic acid copolymer, or a ethylene-vinyl acetate copolymer.

4. A method for preparing the low cost bio-based full degradable film, the method comprising the steps of: a) put the polyglycolic acid, maleic anhydride and acetyl tributyl citrate into the parallel double screw extrusion machine, by fusing, cross blending, wind cooling and pelleting, obtain the plasticized and end capping modified polyglycolic acid master batch. b) put the corn starch and starch plasticizer into a high speed mixer, by heating and high speed agitating, obtain the thermoplastic starch. c) put the poly(butylene adipate-co-terephthalate), compatilizer, citric acid, antioxidant 164, 2-(2-hydroxyl-5-methylphenyl)benzotriazole, the modified polyglycolic acid master batch resulted from step a) into the thermoplastic starch resulted from step b), by heating in high speed mixer and slow speed agitating homogeneously obtain the compound master batch. d) put the compound master batch resulted from step c) into the parallel twin-screw extruder, by fusing, cross blending, wind cooling and pelleting, obtain the low cost bio-based full degradable blown film resin. e) put the bio-resin resulted from step d) into the common high pressure PE film blowing machine, obtain the low cost bio-based full degradable film with a thickness of 15 m and a width of 920 mm.

5. The method of claim 4, wherein the temperature of sections for 1-7 of the said double screw extrusion machine each is 160 C., 180 C., 230 C., 230 C., 230 C., 230 C., 230 C., and the extrusion head temperature is 220 C.

6. The method of claim 4, wherein the heating temperature of the high speed mixer is 100 C., with mixer rotating speed of 500 rpm, and blending material for 10 minutes.

7. The method of claim 4, wherein the heating temperature of the high speed mixer is 100 C., with mixer rotating speed of 200 rpm, and blending material for 4 minutes.

8. The method of claim 4, wherein the temperature of sections for 1-7 of the said double screw extrusion machine each is 150 , 170 C., 180 C., 180 C., 180 C., 180 C., 180 C., and the extrusion head temperature is 170 C. within step d).

9. The method of claim 4, wherein the temperature of sections for 1-4 of the said the common high pressure PE film blowing machine each is 150 C., 180 C., 180 C., 180 C. within step e).

Description

EXMPLES

[0021] The contents of the present invention are further explained by embodiments below, but shall not be construed as limiting the present invention. The modification and replacement of the method, step or condition of the invention without deviating from the spirit and essence of the invention belong to the scope of the invention. If not specified, the technical means used in the embodiments are the conventional means known to the technical personnel in the field.

Example 1

[0022] The low cost bio-based full degradable film comprises the following materials in mass: 15 parts of a polyglycolic acid, 25 parts of corn starch, 55 parts of poly(butylene adipate-co-terephthalate), 1.25 parts of glycerol, 2.5 parts of glycol, 5 parts of graft copolymerization of butyl acrylate with glycidyl methacrylate, 0.5 parts of citric acid, 0.75 parts of acetyl tributyl citrate, 0.3 parts of maleic anhydride, 0.2 parts of antioxidant 164, and 0.2 parts of 2-(2 -hydroxyl-5-methylphenyl)benzotriazole.

[0023] Preparation of the low cost bio-based full degradable film:

[0024] First, the polyglycolic acid, maleic anhydride and acetyl tributyl citrate are mixed evenly and then added to a parallel co-rotating twin-screw extruder for extrusion, set the temperature of sections for 1-7 of extruder to160 C., 180 C., 230 C., 230 C., 230 C., 230 C., 230 C. in turn, and the extrusion head temperature is 220 C., obtain the plasticized and end capping modified PGA master batch.

[0025] Then, the corn starch, glycerol and glycol are added to the high speed mixer, set the heating temperature of the high speed mixer at 100 C., rotating speed at 500 rpm and mixing time at 10 minutes, obtain the thermoplastic starch.

[0026] And then put the plasticized and end capping modified PGA master batch, poly(butylene adipate-co-terephthalate), graft copolymerization of butyl acrylate with glycidyl methacrylate citric acid, antioxidant 164 and 2-(2-hydroxyl-5-methylphenyl)benzotriazole into the prepared the thermoplastic starch, set the heating temperature of the high speed mixer at 100 C., rotating speed at 200 rpm and mixing time at 4 minutes, obtain the mixed master batch.

[0027] The mixed master batch is then added to a parallel co-rotating twin-screw extruder for blending extrusion, set the temperature of sections for 1-7 of extruder to150 C., 170 C., 180 C., 180 C., 180 C., 180 C., 180 C. in turn, and the extrusion head temperature is 170 C., obtain the bio-based low cost full degradation blowing film material.

[0028] And finally, the bio-based low cost full degradable blowing film material is passed through the common high pressure PE film blowing machine, set the temperature of sections for 1-4 of blowing machine to 150 C., 180 C., 180 C., 180 C. in turn.

[0029] Obtain the low cost bio-based full degradable film with a thickness of 15 m and a width of 920 mm.

Example 2

[0030] The low cost bio-based full degradable film comprises the following materials in mass: 20 parts of a polyglycolic acid, 30 parts of corn starch, 45 parts of poly(butylene adipate-co-terephthalate), 4 parts of formamide, 2 parts of urea, 5 parts of graft copolymerization of butyl acrylate with glycidyl methacrylate, 0.6 parts of citric acid, 1 parts of acetyl tributyl citrate, 0.4 parts of maleic anhydride, 0.2 parts of antioxidant 164, and 0.2 parts of 2-(2-hydroxyl-5-methylphenyl)benzotriazole.

[0031] Preparation of the low cost bio-based full degradable film:

[0032] First, the polyglycolic acid, maleic anhydride and acetyl tributyl citrate are mixed evenly and then added to a parallel co-rotating twin-screw extruder for extrusion, set the temperature of sections for 1-7 of extruder to160 C., 180 C., 230 C., 230 C., 230 C., 230 C., 230 C. in turn, and the extrusion head temperature is 220 C., obtain the plasticized and end capping modified PGA master batch.

[0033] Then, the corn starch, formamide and urea are added to the high speed mixer, set the heating temperature of the high speed mixer at 100 C., rotating speed at 500 rpm and mixing time at 10 minutes, obtain the thermoplastic starch.

[0034] And then put the plasticized and end capping modified PGA master batch, poly(butylene adipate-co-terephthalate), graft copolymerization of butyl acrylate with glycidyl methacrylate citric acid, antioxidant 164 and 2-(2-hydroxyl-5-methylphenyl)benzotriazole into the prepared the thermoplastic starch, set the heating temperature of the high speed mixer at 100 C., rotating speed at 200 rpm and mixing time at 4 minutes, obtain the mixed master batch.

[0035] The mixed master batch is then added to a parallel co-rotating twin-screw extruder for blending extrusion, set the temperature of sections for 1-7 of extruder to150 C., 170 C., 180 C., 180 C., 180 C., 180 C., 180 C. in turn, and the extrusion head temperature is 170 C., obtain the bio-based low cost full degradation blowing film material.

[0036] And finally, the bio-based low cost full degradable blowing film material is passed through the common high pressure PE film blowing machine, set the temperature of sections for 1-4 of blowing machine to 150 C., 180 C., 180 C., 180 C. in turn.

[0037] Obtain the low cost bio-based full degradable film with a thickness of 15 m and a width of 920 mm.

Example 3

[0038] The low cost bio-based full degradable film comprises the following materials in mass: 25 parts of a polyglycolic acid, 35 parts of corn starch, 35 parts of poly(butylene adipate-co-terephthalate), 12.25 parts of ethylene bisformamide, 5 parts of graft copolymerization of butyl acrylate with glycidyl methacrylate, 0.7 parts of citric acid, 1.25 parts of acetyl tributyl citrate, 0.5 parts of maleic anhydride, 0.2 parts of antioxidant 164, and 0.2 parts of 2-(2-hydroxyl-5-methylphenyl)benzotriazole.

[0039] Preparation of the low cost bio-based full degradable film:

[0040] First, the polyglycolic acid, maleic anhydride and acetyl tributyl citrate are mixed evenly and then added to a parallel co-rotating twin-screw extruder for extrusion, set the temperature of sections for 1-7 of extruder to160 C., 180 C., 230 C., 230 C., 230 C., 230 C., 230 C. in turn, and the extrusion head temperature is 220 C., obtain the plasticized and end capping modified PGA master batch.

[0041] Then, the corn starch and ethylene bisformamide are added to the high speed mixer, set the heating temperature of the high speed mixer at 100 C., rotating speed at 500 rpm and mixing time at 10 minutes, obtain the thermoplastic starch.

[0042] And then put the plasticized and end capping modified PGA master batch, poly(butylene adipate-co-terephthalate), graft copolymerization of butyl acrylate with glycidyl methacrylate citric acid, antioxidant 164 and 2-(2-hydroxyl-5-methylphenyl)benzotriazole into the prepared the thermoplastic starch, set the heating temperature of the high speed mixer at 100 C., rotating speed at 200 rpm and mixing time at 4 minutes, obtain the mixed master batch.

[0043] The mixed master batch is then added to a parallel co-rotating twin-screw extruder for blending extrusion, set the temperature of sections for 1-7 of extruder to150 C., 170 C., 180 C., 180 C., 180 C., 180 C., 180 C. in turn, and the extrusion head temperature is 170 C., obtain the bio-based low cost full degradable blowing film material.

[0044] And finally, the bio-based low cost full degradable blowing film material is passed through the common high pressure PE film blowing machine, set the temperature of sections for 1-4 of blowing machine to 150 C., 180 C., 180 C., 180 C. in turn.

[0045] Obtain the low cost bio-based full degradable film with a thickness of 15 m and a width of 920 mm.

Example 4

[0046] The low cost bio-based full degradable film comprises the following materials in mass: 25 parts of a polyglycolic acid, 35 parts of corn starch, 35 parts of poly(butylene adipate-co-terephthalate), 12.25 parts of ethylene bisformamide, 5 parts of a ethylene-acrylic acid copolymer,0.7 parts of citric acid, 1.25 parts of acetyl tributyl citrate, 0.5 parts of maleic anhydride, 0.2 parts of antioxidant 164, and 0.2 parts of 2-(2-hydroxyl-5-methylphenyl)benzotriazole.

[0047] Preparation of the low cost bio-based full degradable film:

[0048] First, the polyglycolic acid, maleic anhydride and acetyl tributyl citrate are mixed evenly and then added to a parallel co-rotating twin-screw extruder for extrusion, set the temperature of sections for 1-7 of extruder to160 C., 180 C., 230 C., 230 C., 230 C., 230 C., 230 C. in turn, and the extrusion head temperature is 220 C., obtain the plasticized and end capping modified PGA master batch.

[0049] Then, the corn starch and a ethylene bisformamide are added to the high speed mixer, set the heating temperature of the high speed mixer at 100 C., rotating speed at 500 rpm and mixing time at 10 minutes, obtain the thermoplastic starch.

[0050] And then put the plasticized and end capping modified PGA master batch, poly(butylene adipate-co-terephthalate), ethylene-acrylic acid copolymer, citric acid, antioxidant 164 and 2-(2-hydroxyl-5-methylphenyl)benzotriazole into the prepared the thermoplastic starch, set the heating temperature of the high speed mixer at 100 C., rotating speed at 200 rpm and mixing time at 4 minutes, obtain the mixed master batch.

[0051] The mixed master batch is then added to a parallel co-rotating twin-screw extruder for blending extrusion, set the temperature of sections for 1-7 of extruder to150 C., 170 C., 180 C., 180 C., 180 C., 180 C., 180 C. in turn, and the extrusion head temperature is 170 C., obtain the bio-based low cost full degradable blowing film material.

[0052] And finally, the bio-based low cost full degradable blowing film material is passed through the common high pressure PE film blowing machine, set the temperature of sections for 1-4 of blowing machine to 150 C., 180 C., 180 C., 180 C. in turn.

[0053] Obtain the low cost bio-based full degradable film with a thickness of 15 m and a width of 920 mm.

Example 5

[0054] The low cost bio-based full degradable film comprises the following materials in mass: 25 parts of a polyglycolic acid, 35 parts of corn starch, 35 parts of poly(butylene adipate-co-terephthalate), 12.25 parts of ethylene bisformamide, 5 parts of ethylene-vinyl acetate copolymer,0.7 parts of citric acid, 1.25 parts of acetyl tributyl citrate, 0.5 parts of maleic anhydride, 0.2 parts of antioxidant 164, and 0.2 parts of 2-(2-hydroxyl-5-methylphenyl)benzotriazole.

[0055] Preparation of the low cost bio-based full degradable film:

[0056] First, the polyglycolic acid, maleic anhydride and acetyl tributyl citrate are mixed evenly and then added to a parallel co-rotating twin-screw extruder for extrusion, set the temperature of sections for 1-7 of extruder to160 C., 180 C., 230 C., 230 C., 230 C., 230 C., 230 C. in turn, and the extrusion head temperature is 220 C., obtain the plasticized and end capping modified PGA master batch.

[0057] Then, the corn starch and a ethylene bisformamide are added to the high speed mixer, set the heating temperature of the high speed mixer at 100 C., rotating speed at 500 rpm and mixing time at 10 minutes, obtain the thermoplastic starch.

[0058] And then put the plasticized and end capping modified PGA master batch, poly(butylene adipate-co-terephthalate), ethylene-acrylic acid copolymer, citric acid, antioxidant 164 and 2-(2-hydroxyl-5-methylphenyl)benzotriazole into the prepared the thermoplastic starch, set the heating temperature of the high speed mixer at 100 C., rotating speed at 200 rpm and mixing time at 4 minutes, obtain the mixed master batch.

[0059] The mixed master batch is then added to a parallel co-rotating twin-screw extruder for blending extrusion, set the temperature of sections for 1-7 of extruder to 150 C., 170 C., 180 C., 180 C., 180 C., 180 C., 180 C. in turn, and the extrusion head temperature is 170 C., obtain the bio-based low cost full degradation blowing film material.

[0060] And finally, the bio-based low-cost full degradable blowing film material is passed through the common high pressure PE film blowing machine, set the temperature of sections for 1-4 of blowing machine to 150 C., 180 C., 180 C., 180 C. in turn.

[0061] Obtain the low cost bio-based full degradable film with a thickness of 15 m and a width of 920 mm.

Comparative Example 1

[0062] The full biodegradable film comprises the following materials in mass: 25 parts of corn starch, 75 parts of poly(butylene adipate-co-terephthalate), 1.25 parts of glycerol, 2.5 parts of glycol, 5 parts of graft copolymerization of butyl acrylate with glycidyl methacrylate, 0.5 parts of citric acid, 0.2 parts of antioxidant 164, and 0.2 parts of 2-(2-hydroxyl-5-methylphenyl)benzotriazole.

[0063] Preparation of the full biodegradable film:

[0064] First, the corn starch, glycerol and glycol are added to the high speed mixer, set the heating temperature of the high speed mixer at 100 C., rotating speed at 500 rpm and mixing time at 10 minutes, obtain the thermoplastic starch.

[0065] And then put the poly(butylene adipate-co-terephthalate), graft copolymerization of butyl acrylate with glycidyl methacrylate, citric acid, antioxidant 164 and 2-(2-hydroxyl-5-methylphenyl)benzotriazole into the prepared the thermoplastic starch, set the heating temperature of the high speed mixer at 100 C., rotating speed at 200 rpm and mixing time at 4 minutes, obtain the mixed master batch.

[0066] The mixed master batch is then added to a parallel co-rotating twin-screw extruder for blending extrusion, set the temperature of sections for 1-7 of extruder to150 C., 170 C., 180 C., 180 C., 180 C., 180 C., 180 C. in turn, and the extrusion head temperature is 170 C., obtain the full biodegradable blowing film material.

[0067] And finally, the bio-based blowing film material is passed through the common high pressure PE film blowing machine, set the temperature of sections for 1-4 of blowing machine to 150 C., 180 C., 180 C., 180 C. in turn.

[0068] Obtain the full biodegradable film with a thickness of 15 m and a width of 920 mm.

Comparative Example 2

[0069] The low density polyethylene (LDPE) film grade FB 3000 made by LG Company is passed through the common PE film blowing machine, set the temperature of each section of blowing machine to 150 C.

[0070] Obtain the thin film with a thickness of 15 p.m and a width of 920 mm.

Example 6

[0071] The purpose of this embodiment is to evaluate the mechanical properties of the films prepared in embodiments 1-5 and in comparative example 1 and 2, according to GB/T1040.3-2006, the relevant tests are carried out on the universal tensile testing machine (CMT-4304, Shenzhen Xinsansi Co., Ltd.). The test speed is 50 mm/Min. The test results are detailed in Table 1.

TABLE-US-00001 TABLE 1 Mechanical properties of different films Angle Tensile Elongation tear strength/ Film type strength/MPa at break/% (N .Math. mm1) Example 1 longitudinal 25.55 2.11 297.48 19.31 123.46 8.77 lateral 23.49 1.02 248.96 33.47 128.55 6.82 Example 2 longitudinal 30.06 4.98 233.21 28.94 108.89 13.99 lateral 24.92 2.06 227.46 12.31 100.31 9.66 Example 3 longitudinal 38.87 4.66 159.71 17.88 114.41 3.22 lateral 32.94 5.72 144.36 27.55 98.66 6.36 Example 4 longitudinal 30.27 1.78 106.74 18.84 92.31 11.29 lateral 28.86 6.87 96.55 25.67 88.66 7.82 Example 5 longitudinal 28.71 3.66 135.39 17.79 108.75 21.15 lateral 26.54 3.76 129.96 15.83 94.00 3.32 Compar- longitudinal 19.57 1.99 357.21 37.87 127.26 12.17 ative lateral 17.87 4.87 377.26 23.68 119.83 3.42 Example 1 Compar- longitudinal 22.37 1.76 223.76 12.21 101.28 6.32 ative lateral 20.58 3.19 207.19 21.18 96.43 3.33 Example 2

[0072] From the test data of Examples 13, it is observed that along with the increase of PGA content of in the formulation system, the tensile strength of film increase continually, and elongation at break is decrease gradually. According to the test data of Examples 35, the graft copolymerization of butyl acrylate with glycidyl methacrylate has the best compatibilization effect on PGA, TPS and PBAT within three compatiblizing agents.

[0073] Compared with the biodegradable film without addition of PGA and the conventional PE film, it can be seen from the test data of the embodiment 15 and the comparative examples of 12, the low cost bio-based full degradable film has greater tensile strength.

[0074] In conclusion the invention takes PGA, starch and PBAT as base materials, reduces the melting temperature of the PGA through plasticizing modification, and avoids the serious slication of the starch when it is mixed at high temperature, the invention takes PGA, starch and PBAT as substrate, reduces the melting temperature of the PGA through plasticizing modification, so as to avoid the serious gelatinization of the starch during high temperature blending; reactive additives are used to solve the problem of interface compatibility between PGA, PBAT and thermoplastic starch (TPS), low cost full biodegradable film materials are prepared by blending modification technology, and furthermore, the bio-base content of the low cost bio-base full degraded film provided by the present invention can reach more than 30%, the cost is lower, and the tensile strength is higher than that of the traditional PE film, it is of great significance to solve the problem of white pollution and promote the popularization and application of all biodegradable materials.

[0075] The PGA used in the invention is produced by our company, other ingredients such as PBAT, maleic anhydride, corn starch, starch plasticizer, compatilizer, citric acid, acetyl tributyl citrate, antioxidant 164, 2-(2-hydroxyl-5-methylphenyl)benzotriazole, etc. are purchased directly from the market.

[0076] The above description is only a description of a better embodiment of the invention and is not any limitation of the scope of the invention. Any alteration or modification made by an ordinary technician who is familiar with the field in accordance with the technical content disclosed above shall be deemed to be an equivalent effective embodiment and shall fall under the protection of the technical scheme of the present invention.