CN110229497B - Bio-based polyurethane/polylactic acid alloy film blowing material and preparation method thereof - Google Patents
Bio-based polyurethane/polylactic acid alloy film blowing material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a bio-based polyurethane/polylactic acid alloy blown film material and a preparation method thereof. The obtained material has good toughness and high tearing strength. The method for preparing the material is simple to operate and easy to popularize.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a bio-based polyurethane/polylactic acid alloy film blowing material and a preparation method thereof.
Background
With the rapid development of Chinese economy, China will replace the United states as the largest global packaging market by 2020, and thus the demand for packaging films is becoming increasingly prominent. Traditional packaging film materials, such as polypropylene, polyethylene and the like, take petroleum as raw materials, so that resources cannot be regenerated, and the materials are not easy to degrade, thereby causing great harm to the environment. In order to relieve the energy crisis and reduce the environmental pressure, China is strongly advocating the research and development of bio-based and degradable materials, which is also the hottest field of high polymer materials.
Polylactic acid materials are biodegradable high polymer materials, have mechanical properties similar to those of traditional plastics, are often blended with materials such as poly (butylene adipate/terephthalate), poly (butylene succinate) and the like to prepare biological film materials, but the obtained film has unsatisfactory properties due to high brittleness, low tear strength and low elongation at break of the polylactic acid. In order to improve the properties of packaging films, blending polylactic acid with other materials, including bio-based polyurethane, is being attempted to obtain a packaging film that is both tear-resistant and environmentally friendly. However, it is known that polylactic acid is not well compatible with polyurethane, and direct blending does not give an ideal product.
The existing data for preparing other polymer materials show that the compatibility between various polymer raw materials can be improved by adding a compatilizer, such as: the printing wire disclosed in the chinese patent application CN 104592780 a is prepared by adding maleic anhydride for grafting to improve the compatibility of polyurethane and polylactic acid, and this method introduces other grafting structures to affect the product performance, and on the other hand, can only meet the requirement of the product with low compatibility requirement, and for the bio-based film, the method has insufficient degree of compatibility improvement and risk of performance improvement.
The following steps are repeated: discloses a method for grafting maleic anhydride by adding maleic anhydride grafted polylactic acid as compatilizer and directly using high molecular raw material as material in the prior art, for example, the chinese patent application CN 107698951 a uses maleic anhydride grafted polylactic acid as a compatibilizer to obtain a polylactic acid/cellulose biodegradable composite material, but the grafting aims to enhance the compatibility of polylactic acid and cellulose to strengthen the polylactic acid by the cellulose, and the polylactic acid is grafted by maleic anhydride, because the polylactic acid is sensitive to heat and acid and the maleic anhydride is a strong acid substance, the polylactic acid is easy to degrade in the grafting process, the melt index of the polylactic acid is greatly increased, and the melt strength of the material is required to be high because the film blowing material requires that a film bubble is stable during film blowing, and the melt index of each component is stable and cannot be too high. In conclusion, the maleic anhydride grafted polylactic acid is not suitable for preparing alloy blown film materials by polylactic acid and bio-based polyurethane.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a novel bio-based polyurethane/polylactic acid alloy film blowing material in the first aspect, the bio-based polyurethane and polylactic acid in the material have good compatibility, and a packaging film prepared by using the material has good toughness and high tearing strength.
The bio-based polyurethane/polylactic acid alloy blown film material is prepared by the following steps of firstly preparing 94-98 parts of bio-based polyurethane, 0.5-2 parts of maleic anhydride, 0.05-0.2 part of odorless initiator, 0.2-2 parts of lubricant and 0.2-2 parts of antioxidant according to weight percentage to obtain a maleic anhydride graft; then preparing 5-15 parts of maleic anhydride graft, 10-50 parts of polylactic acid, 30-70 parts of bio-based polyurethane, 0.2-2 parts of lubricant, 0.2-2 parts of antioxidant and 2-20 parts of filler to obtain a bio-based polyurethane/polylactic acid alloy blown film material;
wherein the weight-average molecular weight of the polylactic acid is 120000-180000;
the bio-based polyurethane is bio-based thermoplastic polyurethane elastomer rubber, and the weight-average molecular weight of the bio-based polyurethane elastomer rubber is 80000-200000;
the odorless initiator is dicumyl peroxide or benzoyl peroxide;
the filler is talcum powder, wollastonite, calcium carbonate or kaolin.
In order to improve the compatibility of the bio-based polyurethane and the polylactic acid, a maleic anhydride functional group with strong reaction is introduced on the bio-based polyurethane molecule to prepare grafted bio-based polyurethane, the maleic anhydride graft has the same structure with the bio-based polyurethane, so the grafted bio-based polyurethane has good compatibility with the bio-based polyurethane, and meanwhile, the maleic anhydride graft contains a maleic anhydride group with strong reactivity and can react with the end group of the polylactic acid, so the interfacial tension between the bio-based polyurethane and the polylactic acid is reduced, and the compatibility of the two materials is good.
The bio-based polyurethane/polylactic acid alloy film blowing material has high tensile strength, high elongation at break and high right-angle tearing strength, and can be made into a packaging film by molding processing methods such as injection molding, film blowing and the like.
In one embodiment, the weight ratio of maleic anhydride to odorless initiator is 10: 1.
in another embodiment, the weight ratio of maleic anhydride graft to bio-based polyurethane is 1: 9.5-1: 6, the weight ratio of the polylactic acid to the bio-based polyurethane is 1: 1.8-1: 6.
in another embodiment, the antioxidant is tetra (β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoic acid) pentaerythritol ester and/or tris (2, 4-di-tert-butylphenol) phosphite.
In another embodiment, the lubricant is one or more of white oil, silicone oil, calcium stearate, silicone powder, oxidized polyethylene wax.
In yet another embodiment, the maleic anhydride graft is prepared from 98 parts of bio-based polyurethane, 2 parts maleic anhydride, 0.2 parts dicumyl peroxide initiator, 0.2 parts white oil, 0.1 parts tetra (β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 0.2 parts tris (2, 4-di-tert-butylphenol) phosphite, in weight percent.
The maleic anhydride graft prepared by the raw material ratio can enable the bio-based polyurethane and the polylactic acid to be blended in any proportion, and has no layering and good compatibility.
In another embodiment, the bio-based polyurethane/polylactic acid alloy blown film material is prepared from 7-10 parts by weight of maleic anhydride graft, 10-30 parts by weight of polylactic acid, 50-70 parts by weight of bio-based polyurethane, 0.2 part by weight of white oil, 0.2 part by weight of copper powder, 0.2 part by weight of polyethylene oxide wax, 0.1 part by weight of tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid) pentaerythritol ester, 0.2 part by weight of tris (2, 4-di-tert-butylphenol) phosphite and 5-20 parts by weight of talcum powder.
The invention leads polylactic acid and bio-polyurethane to form alloy blown film material under the action of maleic anhydride graft by melt extrusion technology, and the material has high strength and good toughness.
The invention also provides a preparation method of the bio-based polyurethane/polylactic acid alloy blown film material, which comprises the following steps
(1) Preparation of maleic anhydride graft: uniformly mixing bio-based polyurethane, maleic anhydride, an odorless initiator, an antioxidant and a lubricant, and extruding at 160-190 ℃ through a double-screw extruder;
(2) preparation of bio-based polyurethane/polylactic acid alloy blown film material: the maleic anhydride graft, the polylactic acid, the bio-based polyurethane, the lubricant, the antioxidant and the filler are uniformly mixed and then extruded at 160-190 ℃ through a double-screw extruder.
In one embodiment, in step (1), the twin-screw extruder is divided into six heating zones, and the temperatures of the zones are sequentially from head to tail: 175 ℃ in the first zone, 175 ℃ in the second zone, 180 ℃ in the third zone, 185 ℃ in the fourth zone, 185 ℃ in the fifth zone and 185 ℃ in the sixth zone.
In another embodiment, in step (1), the twin screw extruder has a screw length to diameter ratio of 40.
The invention has the beneficial effects that:
the bio-based polyurethane/polylactic acid alloy film blowing material is prepared from degradable bio-based polyurethane and polylactic acid, wherein the bio-based polyurethane is renewable in source and does not influence the renewability and degradability of the polylactic acid matrix. The maleic anhydride graft compatilizer has obvious effect, the elongation at break of the alloy is obviously improved by adding a small amount of compatilizer, the tear resistance of polyurethane is also kept, and the prepared alloy material can form various packaging films by an extrusion film blowing technology.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited to these examples, and the examples are only illustrative.
Example 1
(1) Polylactic acid (4032D) is dried for 6h in a 65 ℃ blast oven, and bio-based thermoplastic polyurethane elastomer rubber (12T80) is dried for 6h at 90 ℃ in a blast oven.
(2) Weighing 20 parts of polylactic acid, 75 parts of bio-based thermoplastic polyurethane elastomer rubber, 0.2 part of white oil, 0.2 part of silicone powder, 0.2 part of oxidized polyethylene wax, 0.1 part of antioxidant 1010, 0.2 part of antioxidant 168 and 5 parts of talcum powder, mixing for 10min at normal temperature in a high-speed mixer, and enabling the melt temperature of extrusion granulation to be 180 ℃, wherein the phenomenon that an extrusion die orifice is seriously expanded, unstable in flowing and incapable of drawing wires and granulating is found in an experiment. This is due to the poor compatibility of the bio-based thermoplastic polyurethane elastomer rubber with the polylactic acid.
Example 2
(1) Polylactic acid (4032D) is dried for 6h in a 65 ℃ blast oven, and bio-based thermoplastic polyurethane elastomer rubber (12T80) is dried for 6h at 90 ℃ in a blast oven.
(2) Then, mixing 98 parts of bio-based thermoplastic polyurethane elastomer rubber, 2 parts of maleic anhydride, 0.2 part of dicumyl peroxide initiator, 0.2 part of white oil and 0.1 part of antioxidant 1010/0.2 part of antioxidant 168 in a high-speed mixer at normal temperature for 10 min;
(3) adding the obtained blend into a double-screw extruder for extrusion granulation, wherein the double-screw extruder is divided into six heating zones, and the temperature of each zone is as follows from head to tail: 175 ℃ in the first zone, 175 ℃ in the second zone, 180 ℃ in the third zone, 185 ℃ in the fourth zone, 185 ℃ in the fifth zone, 185 ℃ in the sixth zone, 185 ℃ in the head, 130rpm in the rotation speed of the screw, 30mm in the diameter of the screw and 40 in the length-diameter ratio of the screw;
(4) drying the granules prepared in the last step in a forced air oven at 90 ℃ for 6 hours;
(5) weighing 7 parts of dried maleic anhydride graft, 20 parts of polylactic acid, 66 parts of bio-based thermoplastic polyurethane elastomer rubber, 0.2 part of white oil, 0.2 part of silicone powder, 0.2 part of oxidized polyethylene wax, 0.1 part of antioxidant 1010, 0.2 part of antioxidant 168 and 5 parts of talcum powder, mixing for 10min at normal temperature in a high-speed mixer, and controlling the melt temperature of extrusion granulation to be 180 ℃ to obtain the bio-based polyurethane/polylactic acid alloy blown film material.
The material has a melt index of 0.5g/10min, a tensile strength of 42.5MP, an elongation at break of 557% and a right-angle tear strength of 5.7N.
Example 3
(1) Polylactic acid (4032D) is dried for 6h in a 65 ℃ blast oven, and bio-based thermoplastic polyurethane elastomer rubber (12T80) is dried for 6h at 90 ℃ in a blast oven.
(2) Then, mixing 98 parts of bio-based thermoplastic polyurethane elastomer rubber, 2 parts of maleic anhydride, 0.2 part of dicumyl peroxide initiator, 0.2 part of white oil and 0.1 part of antioxidant 1010/0.2 part of antioxidant 168 in a high-speed mixer at normal temperature for 10 min;
(3) adding the obtained blend into a double-screw extruder for extrusion granulation, wherein the double-screw extruder is divided into six heating zones, and the temperature of each zone is as follows from head to tail: 175 ℃ in the first zone, 175 ℃ in the second zone, 180 ℃ in the third zone, 185 ℃ in the fourth zone, 185 ℃ in the fifth zone, 185 ℃ in the sixth zone, 185 ℃ in the head, 130rpm in the rotation speed of the screw, 30mm in the diameter of the screw and 40 in the length-diameter ratio of the screw;
(4) drying the granules prepared in the last step in a forced air oven at 90 ℃ for 6 hours;
(5) weighing 7 parts of dried maleic anhydride graft, 25 parts of polylactic acid, 61 parts of bio-based thermoplastic polyurethane elastomer rubber, 0.2 part of white oil, 0.2 part of silicone powder, 0.2 part of oxidized polyethylene wax, 0.1 part of antioxidant 1010, 0.2 part of antioxidant 168 and 5 parts of talcum powder, mixing for 10min at normal temperature in a high-speed mixer, and controlling the temperature of extruded and granulated melt to be 180 ℃ to obtain the bio-based polyurethane/polylactic acid alloy blown film material.
The melt index of the material is 0.63g/10min, the tensile strength is 43MP, the elongation at break is 523%, and the right-angle tear strength is 5.3N.
Example 4
(1) Polylactic acid (4032D) is dried for 6h in a 65 ℃ blast oven, and bio-based thermoplastic polyurethane elastomer rubber (12T80) is dried for 6h at 90 ℃ in a blast oven.
(2) Then, mixing 98 parts of bio-based thermoplastic polyurethane elastomer rubber, 2 parts of maleic anhydride, 0.2 part of dicumyl peroxide initiator, 0.2 part of white oil and 0.1 part of antioxidant 1010/0.2 part of antioxidant 168 in a high-speed mixer at normal temperature for 10 min;
(3) adding the obtained blend into a double-screw extruder for extrusion granulation, wherein the double-screw extruder is divided into six heating zones, and the temperature of each zone is as follows from head to tail: 175 ℃ in the first zone, 175 ℃ in the second zone, 180 ℃ in the third zone, 185 ℃ in the fourth zone, 185 ℃ in the fifth zone, 185 ℃ in the sixth zone, 185 ℃ in the head, 130rpm in the rotation speed of the screw, 30mm in the diameter of the screw and 40 in the length-diameter ratio of the screw;
(4) drying the granules prepared in the last step in a forced air oven at 90 ℃ for 6 hours;
(5) weighing 7 parts of dried maleic anhydride graft, 30 parts of polylactic acid, 56 parts of bio-based thermoplastic polyurethane elastomer rubber, 0.2 part of white oil, 0.2 part of silicone powder, 0.2 part of oxidized polyethylene wax, 0.1 part of antioxidant 1010, 0.2 part of antioxidant 168 and 5 parts of talcum powder, mixing for 10min at normal temperature in a high-speed mixer, and controlling the melt temperature of extrusion granulation to be 180 ℃ to obtain the bio-based polyurethane/polylactic acid alloy blown film material.
The melt index of the material is 0.73g/10min, the tensile strength is 39MP, the elongation at break is 480%, and the right-angle tear strength is 4.3N.
Example 5
(1) Polylactic acid (4032D) is dried for 6h in a 65 ℃ blast oven, and bio-based thermoplastic polyurethane elastomer rubber (12T80) is dried for 6h at 90 ℃ in a blast oven.
(2) Then, mixing 98 parts of bio-based thermoplastic polyurethane elastomer rubber, 2 parts of maleic anhydride, 0.2 part of dicumyl peroxide initiator, 0.2 part of white oil and 0.1 part of antioxidant 1010/0.2 part of antioxidant 168 in a high-speed mixer at normal temperature for 10 min;
(3) adding the obtained blend into a double-screw extruder for extrusion granulation, wherein the double-screw extruder is divided into six heating zones, and the temperature of each zone is as follows from head to tail: 175 ℃ in the first zone, 175 ℃ in the second zone, 180 ℃ in the third zone, 185 ℃ in the fourth zone, 185 ℃ in the fifth zone, 185 ℃ in the sixth zone, 185 ℃ in the head, 130rpm in the rotation speed of the screw, 30mm in the diameter of the screw and 40 in the length-diameter ratio of the screw;
(4) drying the granules prepared in the last step in a forced air oven at 90 ℃ for 6 hours;
(5) weighing 10 parts of dried maleic anhydride graft, 10 parts of polylactic acid, 60 parts of bio-based thermoplastic polyurethane elastomer rubber, 0.2 part of white oil, 0.2 part of silicone powder, 0.2 part of oxidized polyethylene wax, 0.1 part of antioxidant 1010, 0.2 part of antioxidant 168 and 20 parts of talcum powder, mixing for 10min at normal temperature in a high-speed mixer, and controlling the melt temperature of extrusion granulation to be 180 ℃ to obtain the bio-based polyurethane/polylactic acid alloy blown film material.
The melt index of the material is 2g/10min, the tensile strength is 26.7MP, the elongation at break is 550%, and the right-angle tear strength is 5.1N.
Example 6
(1) Polylactic acid (4032D) is dried for 6h in a 65 ℃ blast oven, and bio-based thermoplastic polyurethane elastomer rubber (12T80) is dried for 6h at 90 ℃ in a blast oven.
(2) Then, mixing 98 parts of bio-based thermoplastic polyurethane elastomer rubber, 2 parts of maleic anhydride, 0.2 part of dicumyl peroxide initiator, 0.2 part of white oil and 0.1 part of antioxidant 1010/0.2 part of antioxidant 168 in a high-speed mixer at normal temperature for 10 min;
(3) adding the obtained blend into a double-screw extruder for extrusion granulation, wherein the double-screw extruder is divided into six heating zones, and the temperature of each zone is as follows from head to tail: 175 ℃ in the first zone, 175 ℃ in the second zone, 180 ℃ in the third zone, 185 ℃ in the fourth zone, 185 ℃ in the fifth zone, 185 ℃ in the sixth zone, 185 ℃ in the head, 130rpm in the rotation speed of the screw, 30mm in the diameter of the screw and 40 in the length-diameter ratio of the screw;
(4) drying the granules prepared in the last step in a forced air oven at 90 ℃ for 6 hours;
(5) weighing 10 parts of dried maleic anhydride graft, 10 parts of polylactic acid, 60 parts of bio-based thermoplastic polyurethane elastomer rubber, 0.2 part of white oil, 0.2 part of silicone powder, 0.2 part of oxidized polyethylene wax, 0.1 part of antioxidant 1010, 0.2 part of antioxidant 168, 10 parts of talcum powder and 10 parts of calcium carbonate, mixing for 10min at normal temperature in a high-speed mixer, and controlling the temperature of extruded and granulated melt to be 180 ℃ to obtain the bio-based polyurethane/polylactic acid alloy blown film material.
The melt index of the material is 3.2g/10min, the tensile strength is 25MP, the elongation at break is 575%, and the right-angle tear strength is 5N.
Example 7
The alloy film blowing material prepared in the embodiment 2-6 is made into an express packaging film by film blowing molding, standard samples are prepared on a sampling machine, and then the melt index, the tensile strength elongation at break and the right-angle tear test are respectively carried out according to the standards GB/T9643, GB 13022-91 and QB/T1130-91, and the comparison is the commercial PBAT TH801T of the Lanshan Tun river film blowing grade. Specific performance data are shown in table 1:
from table 1, it can be seen that the modified blend not only has higher tensile strength, but also has very high elongation at break, and also has excellent tear resistance of polyurethane. The reason is that the maleic anhydride grafted bio-based thermoplastic polyurethane elastomer rubber can reduce the interfacial tension among the components of the material, so that the compatibility of the components is good, and the alloy material has excellent performance of the components. The modified alloy material can be directly used in the fields of express packaging films and the like.
Details not described in this specification are within the skill of the art that are well known to those skilled in the art.
Claims (7)
1. The bio-based polyurethane/polylactic acid alloy film blowing material is characterized in that: according to weight percentage, firstly preparing 94-98 parts of bio-based polyurethane, 0.5-2 parts of maleic anhydride, 0.05-0.2 part of odorless initiator, 0.2-2 parts of lubricant and 0.2-2 parts of antioxidant to obtain maleic anhydride graft; then preparing 5-15 parts of maleic anhydride graft, 10-50 parts of polylactic acid, 30-70 parts of bio-based polyurethane, 0.2-2 parts of lubricant, 0.2-2 parts of antioxidant and 2-20 parts of filler to obtain a bio-based polyurethane/polylactic acid alloy blown film material;
the preparation method of the bio-based polyurethane/polylactic acid alloy blown film material comprises the following steps:
(1) preparation of maleic anhydride graft: uniformly mixing bio-based polyurethane, maleic anhydride, an odorless initiator, an antioxidant and a lubricant, and extruding at 160-190 ℃ through a double-screw extruder; the length-diameter ratio of a screw of the double-screw extruder is 40, the double-screw extruder is divided into six heating zones, and the temperature of each zone is from head to tail: 175 ℃ in the first zone, 175 ℃ in the second zone, 180 ℃ in the third zone, 185 ℃ in the fourth zone, 185 ℃ in the fifth zone and 185 ℃ in the sixth zone;
(2) preparation of bio-based polyurethane/polylactic acid alloy blown film material: uniformly mixing the maleic anhydride graft, the polylactic acid, the bio-based polyurethane, the lubricant, the antioxidant and the filler, and extruding the mixture at 160-190 ℃ through a double-screw extruder;
wherein the weight-average molecular weight of the polylactic acid is 120000-180000;
the bio-based polyurethane is bio-based thermoplastic polyurethane elastomer rubber, and the weight-average molecular weight of the bio-based polyurethane elastomer rubber is 80000-200000;
the odorless initiator is dicumyl peroxide or benzoyl peroxide;
the filler is talcum powder, wollastonite, calcium carbonate or kaolin.
2. The bio-based polyurethane/polylactic acid alloy blown film material according to claim 1, wherein: the weight ratio of the maleic anhydride to the odorless initiator is 10: 1.
3. the bio-based polyurethane/polylactic acid alloy blown film material according to claim 2, wherein: the weight ratio of the maleic anhydride graft to the bio-based polyurethane is 1: 9.5-1: 6, the weight ratio of the polylactic acid to the bio-based polyurethane is 1: 1.8-1: 6.
4. the bio-based polyurethane/polylactic acid alloy blown film material according to claim 3, wherein: the antioxidant is tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid) pentaerythritol ester and/or tri (2, 4-di-tert-butylphenol) phosphite ester.
5. The bio-based polyurethane/polylactic acid alloy blown film material according to claim 4, wherein: the lubricant is one or more of white oil, silicone oil, calcium stearate, silicone powder and oxidized polyethylene wax.
6. The bio-based polyurethane/polylactic acid alloy blown film material according to claim 5, wherein: the maleic anhydride graft is prepared from 98 parts by weight of bio-based polyurethane, 2 parts by weight of maleic anhydride, 0.2 part by weight of dicumyl peroxide initiator, 0.2 part by weight of white oil, 0.1 part by weight of tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid) pentaerythritol ester and 0.2 part by weight of tris (2, 4-di-tert-butylphenol) phosphite.
7. The bio-based polyurethane/polylactic acid alloy blown film material according to claim 6, wherein: according to the weight percentage, 7-10 parts of maleic anhydride graft, 10-30 parts of polylactic acid, 50-70 parts of bio-based polyurethane, 0.2 part of white oil, 0.2 part of copper powder, 0.2 part of oxidized polyethylene wax, 0.1 part of tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid) pentaerythritol ester, 0.2 part of tri (2, 4-di-tert-butylphenol) phosphite ester and 5-20 parts of talcum powder are used for preparing the bio-based polyurethane/polylactic acid alloy film blowing material.
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