阅读说明：本技术 一种高淀粉含量的全生物降解吹膜料及其制备方法 (Full-biodegradable film blowing material with high starch content and preparation method thereof ) 是由 曾勤 王继鑫 任超 白娟 于 2020-12-29 设计创作，主要内容包括：本发明属于生物基复合材料领域,具体涉及一种高淀粉含量的全生物降解吹膜料,包括按质量百分含量计的如下组分：淀粉50-80％、生物降解聚酯5-30％、相熔剂3-10％、增塑剂3-10％、淀粉改性剂3-10％、无机填料5-20％；其制备方法为：先将淀粉和淀粉改性剂、增塑剂加入到高混机中加热并高速搅拌均匀,制得改性淀粉；再将生物降解聚酯、相熔剂、无机填料加入改性淀粉中,通过高混机加热低速搅拌均匀,制得混合母料；最后将混合母料加入拉伸流变机中塑化挤出,再进行造粒。本发明通过增塑剂、淀粉改性剂对淀粉进行改性后,与生物降解聚酯、相熔剂、无机填料混合进行造粒制得高淀粉含量的全生物降解吹膜料,可以将淀粉含量提高至50-80％,降低成本,同时还能保证其加工性能和材料强度。(The invention belongs to the field of bio-based composite materials, and particularly relates to a full-biodegradable film blowing material with high starch content, which comprises the following components in percentage by mass: 50-80% of starch, 5-30% of biodegradable polyester, 3-10% of phase flux, 3-10% of plasticizer, 3-10% of starch modifier and 5-20% of inorganic filler; the preparation method comprises the following steps: adding starch, a starch modifier and a plasticizer into a high-speed mixer, heating and uniformly stirring at a high speed to prepare modified starch; adding the biodegradable polyester, the phase flux and the inorganic filler into the modified starch, and heating and uniformly stirring at a low speed by a high-speed mixer to prepare a mixed master batch; and finally adding the mixed master batch into a stretching rheometer for plasticizing and extruding, and then granulating. The invention modifies starch by plasticizer and starch modifier, then mixes with biodegradable polyester, phase flux and inorganic filler for granulation to prepare the full-biodegradable blown film material with high starch content, which can improve the starch content to 50-80%, reduce cost and ensure the processing performance and material strength.)

1. The full-biodegradable film blowing material with high starch content is characterized by comprising the following components in percentage by mass: 50-80% of starch, 5-30% of biodegradable polyester, 3-10% of phase flux, 3-10% of plasticizer, 3-10% of starch modifier and 5-20% of inorganic filler; the plasticizer is one or more of glycerol, glycol, formamide, urea and ethylene glycol dimethyl formamide; the starch modifier is one or more of oleic acid, maleic anhydride and liquid paraffin.

2. The fully biodegradable blown film material with high starch content according to claim 1, wherein: the starch is one or more of corn starch, potato starch, sweet potato starch and cassava starch.

3. The fully biodegradable blown film material with high starch content according to claim 1, wherein: the biodegradable polyester is one or more of polylactic acid, polybutylene adipate/terephthalate and polybutylene succinate.

4. The fully biodegradable blown film material with high starch content according to claim 1, wherein: the phase fusing agent is any one of ethylene butyl acrylate grafted glycidyl methacrylate, ethylene-acrylic acid copolymer and ethylene-vinyl acetate copolymer.

5. The fully biodegradable blown film material with high starch content according to claim 1, wherein: the inorganic filler is one of calcium carbonate, talcum powder and montmorillonite.

6. The fully biodegradable blown film material with high starch content according to claim 1, wherein: comprises the following components in percentage by mass: 70% of corn starch, 10% of polylactic acid, 5% of ethylene-vinyl acetate copolymer, 5% of glycerol, 5% of maleic anhydride and 5% of calcium carbonate.

7. The fully biodegradable blown film material with high starch content according to claim 1, wherein: comprises the following components in percentage by mass: 40% of cassava starch, 40% of potato starch, 5% of poly (butylene adipate)/terephthalate, 3% of ethylene butyl acrylate grafted glycidyl methacrylate, 1% of ethylene glycol, 2% of formamide, 3% of oleic acid and 6% of talcum powder.

8. The fully biodegradable blown film material with high starch content according to claim 1, wherein: comprises the following components in percentage by mass: 50% of sweet potato starch, 10% of polybutylene succinate, 5% of poly adipic acid/butylene terephthalate, 10% of ethylene-vinyl acetate copolymer, 7% of ethylene-diethylene diamine, 4% of oleic acid, 4% of maleic anhydride, 4% of calcium carbonate and 6% of talcum powder.

9. The preparation method of the full-biodegradable film blowing material with high starch content according to any one of claims 1 to 8, characterized by comprising the following steps:

1) adding starch, plasticizer and starch modifier into a high-speed mixer, heating at 100 deg.C, rotating at 500rpm, and mixing for 15-30min to obtain modified starch;

2) adding biodegradable polyester, a phase flux and an inorganic filler into the modified starch, heating by a high-speed mixer at 100 ℃, rotating at 200rpm, and mixing for 1-5min to prepare a mixed master batch;

3) and adding the mixed master batch into a stretching rheometer for plasticizing and extruding, and then granulating to obtain the full-biodegradable film blowing material with high starch content.

10. The method for preparing the full-biodegradable blown film material with high starch content according to claim 9, wherein the method comprises the following steps: the processing temperature for plasticizing in the drawing rheometer in the step 3) is 150-190 ℃.

Technical Field

The invention belongs to the technical field of film blowing materials, and particularly relates to a full-biodegradable film blowing material with high starch content and a preparation method thereof.

Background

With the development of the plastic industry and the development of plastic varieties, more and more plastic products become indispensable materials in human lives. Plastic film bags are widely applied to the fields of food packaging, medical packaging, industrial packaging and the like, and particularly, disposable shopping bags, disposable garbage bags and other products have wide application markets, but the traditional plastics are difficult to biodegrade, and the environment is seriously polluted by the large stacking of plastic wastes. Therefore, the research on the fully biodegradable materials, especially the fully biodegradable blown film materials, is a hot topic at present. Due to the change of foreign situation, the raw material price of the biodegradable material is high, even the market supply can not be met, so the starch-based fully biodegradable material is produced at the same time. Starch, as an agricultural product with low price and rich sources, becomes a main raw material for developing biodegradable materials, but the starch content in the fully-degradable film blowing materials in the current market is generally lower than 50%, and the effect of reducing the cost cannot be achieved. The starch content exceeding 50 percent has a series of problems of poor processing performance, reduced material strength and the like.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention aims to provide the full-biodegradable film blowing material with high starch content, which can reduce the cost and ensure the processing performance and the material strength.

In order to achieve the aim, the technical scheme of the invention is that the full-biodegradable film blowing material with high starch content comprises the following components in percentage by mass: 50-80% of starch, 5-30% of biodegradable polyester, 3-10% of phase flux, 3-10% of plasticizer, 3-10% of starch modifier and 5-20% of inorganic filler; the plasticizer is one or more of glycerol, glycol, formamide, urea and ethylene glycol dimethyl formamide; the starch modifier is one or more of oleic acid, maleic anhydride and liquid paraffin.

Further, the starch is one or more of corn starch, potato starch, sweet potato starch and cassava starch.

Further, the biodegradable polyester is one or more of polylactic acid, polybutylene adipate/terephthalate and polybutylene succinate.

Further, the phase fusing agent is any one of ethylene butyl acrylate grafted glycidyl methacrylate, ethylene-acrylic acid copolymer and ethylene-vinyl acetate copolymer.

Further, the inorganic filler is one of calcium carbonate, talcum powder and montmorillonite.

Preferably, the high-starch-content full-biodegradable blown film material comprises the following components in percentage by mass: 70% of corn starch, 10% of polylactic acid, 5% of ethylene-vinyl acetate copolymer, 5% of glycerol, 5% of maleic anhydride and 5% of calcium carbonate.

Preferably, the high-starch-content full-biodegradable blown film material comprises the following components in percentage by mass: 40% of cassava starch, 40% of potato starch, 5% of poly (butylene adipate)/terephthalate, 3% of ethylene butyl acrylate grafted glycidyl methacrylate, 1% of ethylene glycol, 2% of formamide, 3% of oleic acid and 6% of talcum powder.

Preferably, the high-starch-content full-biodegradable blown film material comprises the following components in percentage by mass: 50% of sweet potato starch, 10% of polybutylene succinate, 5% of poly adipic acid/butylene terephthalate, 10% of ethylene-vinyl acetate copolymer, 7% of ethylene-diethylene diamine, 4% of oleic acid, 4% of maleic anhydride, 4% of calcium carbonate and 6% of talcum powder.

The invention also provides a preparation method of the full-biodegradable film blowing material with high starch content, which comprises the following steps:

1) adding starch, plasticizer and starch modifier into a high-speed mixer, heating at 100 deg.C, rotating at 500rpm, and mixing for 15-30min to obtain modified starch;

2) adding biodegradable polyester, a phase flux and an inorganic filler into the modified starch, heating by a high-speed mixer at 100 ℃, rotating at 200rpm, and mixing for 1-5min to prepare a mixed master batch;

3) and adding the mixed master batch into a stretching rheometer for plasticizing and extruding, and then granulating to obtain the full-biodegradable film blowing material with high starch content.

Further, the processing temperature for plasticizing in the draw-out rheometer in step 3) is 150-190 ℃.

Compared with the prior art, the invention has the following beneficial effects:

after the starch is modified by the plasticizer and the starch modifier, the modified starch is mixed with the biodegradable polyester, the phase flux and the inorganic filler for granulation to prepare the full-biodegradable film blowing material with high starch content, so that the starch content can be increased to 50-80%, the cost is reduced, and the processing performance and the material strength of the full-biodegradable film blowing material can be ensured; the starch modifier not only can change the hydrophilicity of the starch into hydrophobicity, improve the processing performance of the starch, but also can improve the compatibility with the biodegradable polyester; the proper addition of inorganic filler can improve the processing performance of the biodegradable polyester and can be used as a nucleating agent of polyester crystallization to improve the performance of the whole material.

Detailed Description

The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention provides a full-biodegradable film blowing material with high starch content, which comprises the following components in percentage by mass: 50-80% of starch, 5-30% of biodegradable polyester, 3-10% of phase flux, 3-10% of plasticizer, 3-10% of starch modifier and 5-20% of inorganic filler.

Wherein the starch is one or more of corn starch, potato starch, sweet potato starch and cassava starch; the biodegradable polyester is one or more of polylactic acid, polybutylene adipate/terephthalate and polybutylene succinate; the phase fusing agent is any one of ethylene butyl acrylate grafted glycidyl methacrylate, ethylene-acrylic acid copolymer and ethylene-vinyl acetate copolymer; the plasticizer is one or more of glycerol, glycol, formamide, urea and ethylene glycol dimethyl formamide; the starch modifier is one or more of oleic acid, maleic anhydride and liquid paraffin; the inorganic filler is one of calcium carbonate, talcum powder and montmorillonite.

The technical effect of the inventive fully biodegradable blown film material with high starch content is illustrated by the following specific examples.

Example 1

The embodiment provides a full-biodegradable film blowing material with high starch content, which comprises the following components in percentage by mass: 70% of corn starch, 10% of polylactic acid, 5% of ethylene-vinyl acetate copolymer, 5% of glycerol, 5% of maleic anhydride and 5% of calcium carbonate.

The preparation method of the full-biodegradable blown film material with high starch content comprises the following steps:

1) adding corn starch, glycerol and maleic anhydride into a high-speed mixer, heating, and uniformly stirring at a high speed, wherein the heating temperature of the high-speed mixer is 100 ℃, the rotating speed is 500rpm, and the mixing time is 30min, so as to prepare modified starch;

2) adding polylactic acid, ethylene-vinyl acetate copolymer and calcium carbonate into the modified starch, heating by a high-speed mixer at 100 ℃, rotating at 200rpm, and mixing for 5min to prepare a mixed master batch;

3) and adding the mixed master batch into a stretching rheometer for plasticizing and extruding, and then granulating to obtain the full-biodegradable film blowing material with high starch content.

Example 2

The embodiment provides a full-biodegradable film blowing material with high starch content, which comprises the following components in percentage by mass: 40% of cassava starch, 40% of potato starch, 5% of poly (butylene adipate)/terephthalate, 3% of ethylene butyl acrylate grafted glycidyl methacrylate, 1% of ethylene glycol, 2% of formamide, 3% of oleic acid and 6% of talcum powder.

The preparation method of the full-biodegradable blown film material with high starch content comprises the following steps:

1) adding cassava starch, potato starch, ethylene glycol, formamide and oleic acid into a high-speed mixer, heating and uniformly stirring at a high speed, wherein the heating temperature of the high-speed mixer is 100 ℃, the rotating speed is 500rpm, and the mixing time is 15min, so as to prepare modified starch;

2) adding polybutylene adipate/terephthalate, ethylene butyl acrylate grafted glycidyl methacrylate and talcum powder into the modified starch, heating by a high-speed mixer at 100 ℃, rotating at 200rpm, and mixing for 3min to prepare a mixed master batch;

3) and adding the mixed master batch into a stretching rheometer for plasticizing and extruding, and then granulating to obtain the full-biodegradable film blowing material with high starch content.

Example 3

The embodiment provides a full-biodegradable film blowing material with high starch content, which comprises the following components in percentage by mass: 50% of sweet potato starch, 10% of polybutylene succinate, 5% of poly adipic acid/butylene terephthalate, 10% of ethylene-vinyl acetate copolymer, 7% of ethylene-diethylene diamine, 4% of oleic acid, 4% of maleic anhydride, 4% of calcium carbonate and 6% of talcum powder.

The preparation method of the full-biodegradable blown film material with high starch content comprises the following steps:

1) adding sweet potato starch, ethylene glycol dimethyl formamide, oleic acid and maleic anhydride into a high-speed mixer, heating and uniformly stirring at a high speed, wherein the heating temperature of the high-speed mixer is 100 ℃, the rotating speed is 500rpm, and the mixing time is 20min, so as to prepare modified starch;

2) adding polybutylene succinate, poly (butylene adipate/terephthalate), ethylene-vinyl acetate copolymer, calcium carbonate and talcum powder into the modified starch, heating by a high-speed mixer at 100 ℃, rotating at 200rpm, and mixing for 1min to prepare a mixed master batch;

3) and adding the mixed master batch into a stretching rheometer for plasticizing and extruding, and then granulating to obtain the full-biodegradable film blowing material with high starch content.

Comparative example 1

The comparative example provides a full-biodegradable film blowing material, which comprises the following components in percentage by mass: 70% of corn starch, 10% of polylactic acid, 5% of ethylene-vinyl acetate copolymer, 10% of glycerol and 5% of calcium carbonate; the preparation was substantially the same as in example 1, except that the maleic anhydride in example 1 was replaced with glycerin.

Comparative example 2

The comparative example provides a full-biodegradable film blowing material, which comprises the following components in percentage by mass: 50% of sweet potato starch, 10% of polybutylene succinate, 5% of poly adipic acid/butylene terephthalate, 10% of ethylene-vinyl acetate copolymer, 15% of ethylene-dimethylene diamine, 4% of calcium carbonate and 6% of talcum powder; the preparation was substantially the same as in example 3, except that oleic acid and maleic anhydride were replaced with ethylenebisdimethylamide in example 3.

The performance of the plastic film bag products prepared from the fully biodegradable blown film materials prepared in the above examples 1 to 3 and comparative examples 1 to 2 was tested, and the results are shown in table 1.

TABLE 1 Properties of the Plastic film bag products

As can be seen from Table 1, the plasticizer and the starch modifier are adopted to modify the starch, compared with the method that the plasticizer is only adopted to modify the starch, the mechanical property of the prepared plastic film bag is more excellent, the content of the starch can be increased to 50-80%, and the cost is greatly reduced.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.