CN111808343A

CN111808343A - Application of starch masterbatch in preparation of degradable material and/or product

Info

Publication number: CN111808343A
Application number: CN201910295847.XA
Authority: CN
Inventors: 常江
Original assignee: Beijing Yiside Logistics Technology Co Ltd
Current assignee: Beijing Yiside Logistics Technology Co Ltd
Priority date: 2019-04-12
Filing date: 2019-04-12
Publication date: 2020-10-23

Abstract

The invention relates to the field of biodegradable materials, and discloses a starch master batch, and a preparation method and application thereof. Based on the total weight of the starch concentrate, the starch concentrate contains: 30-70 wt% of starch, 5-20 wt% of plasticizer, 8-35 wt% of carrier, 2-15 wt% of compatilizer, 1-5 wt% of lubricant and 0.1-1 wt% of auxiliary agent. The starch master batch provided by the invention can further improve the addition amount of starch in a starch-based plastic product by optimizing the components and the proportion, saves the cost, ensures the excellent plastic performance of the prepared product and further improves the environmental protection performance of the product.

Description

Application of starch masterbatch in preparation of degradable material and/or product

Technical Field

The invention relates to the field of biodegradable materials, in particular to application of starch master batches in preparation of degradable materials and/or products.

Background

With the rapid development of Chinese economy and electronic commerce, the demand and the use amount of express packaging bags are increased rapidly. The existing express packaging bag is mainly used for conveying files, goods and the like in the express industry, but the disposable packaging bag is mainly a plastic packaging bag made of polyethylene and other materials, and has the characteristics of low cost, convenience in use and good waterproof performance.

Express delivery wrapping bag when having brought very big convenience for people's life, along with the increase of use amount, make this kind of disposable wrapping bag abandonment volume sharply increase, however, because the difficult decomposition of polyethylene is retrieved, its discarded object becomes harmful rubbish, the polluted environment, a large amount of abandonment plastic bags have become serious problem, simultaneously, along with the improvement of national environmental standard, also further improve to express delivery industry wrapping bag's environmental protection requirement, consequently, the urgent need provide a degradable plastics in order to solve a great deal of problems that current express delivery wrapping bag causes.

Therefore, in the prior art, a biodegradable material is mostly adopted to alleviate the problem, for example, CN108285622A discloses a biodegradable material and a preparation method thereof, which specifically discloses that the biodegradable material comprises the following raw materials in parts by weight: 20-50% of material A, 40-60% of material B and 20-40% of PBAT thermoplastic biodegradable plastic, wherein the material A comprises the following raw materials in parts by weight: 40-60% of PBAT thermoplastic biodegradable plastic, 78-50% of PLA30 and 8-15% of inorganic filler; the material B comprises the following raw materials in parts by weight: 40-60% of PBAT thermoplastic biodegradable plastic and 40-60% of starch master batch, wherein the starch master batch comprises the following raw materials in parts by weight: 60-70% of starch, 1-3% of coupling agent, 1-3% of paraffin, 25-30% of glycerol, 0.1-0.3% of citric acid and 2-5% of epoxidized soybean oil, the prepared biodegradable material has high degradation speed and good barrier property, and after being prepared into a film, the longitudinal elongation is 150.22%, the strength is 18.27MPa, the transverse elongation is 237.12%, and the strength is 12.49 MPa; CN104119647A discloses a full biodegradation with high starch content and a preparation method thereof, in particular to a full biodegradation prepared from 10-80 parts of full biodegradation thermoplastic starch master batch, 20-90 parts of biodegradable polyester and 0.3-5 parts of compatilizer, the provided full biodegradation has high starch content and good compatibility with a matrix, the mechanical property of the material in the long-time storage process is ensured, and the cost of a film product prepared by the method can be greatly reduced; CN101724178A discloses a biological potato starch degradable plastic master batch, a preparation method and an application thereof, wherein the plastic master batch comprises the following components by weight: 70-80% of refined potato starch, 7-10% of toughening agent, 0.5-2% of initiator, 4-7% of modifier, 1-3% of plasticizer and 3-6% of lubricating processing aid, wherein the prepared master batch product has certain strength and thermoplastic processing performance and can be used for processing various film products, blow molding products and injection molding products in different addition amounts; CN103342873A discloses an easily degradable environment-friendly plastic, which comprises the following components in parts by weight: 40-70 parts of ABS; 3-8 parts of an interface coupling agent; 3-10 parts of a toughening agent; 0.5-1.0 part by weight of dispersing lubricant; 5-10 parts of starch; 10-15 parts of polyethylene. The prepared easily degradable environment-friendly plastic has excellent easily degradable environment-friendly property and can be widely used in a plurality of industries; meanwhile, in the existing starch-based plastic, especially for preparing various plastic bag products, from the aspects of production cost, aging, processing convenience and the like, starch or starch master batches are usually directly used, and the starch master batches are already produced in large scale by manufacturers, but when the plastic bag is made, the addition amount of the starch master batches in the existing process cannot exceed 45% (the addition amount of the starch cannot exceed 25%), otherwise, the performance of the produced plastic is seriously attenuated.

Considering that the use of starch masterbatch can improve the degradation performance of starch plastics, and the cost of starch masterbatch is relatively low, how to further increase the content of starch masterbatch in the raw material formulation and avoid the degradation of the plastic performance is still the primary problem that troubles the practical production and application.

Disclosure of Invention

The invention aims to overcome the problems in the prior art, and provides the application of the starch master batch in preparing the degradable material and/or the product.

In order to achieve the above object, the present invention provides an application of a starch concentrate in preparing a degradable material and/or a product, wherein the starch concentrate comprises, based on the total weight of the starch concentrate:

30-70 wt% of starch, 5-20 wt% of plasticizer, 8-35 wt% of carrier, 2-15 wt% of compatilizer, 1-5 wt% of lubricant and 0.1-1 wt% of auxiliary agent.

Preferably, the starch concentrate contains, based on the total weight of the starch concentrate:

45-70 wt% of starch, 8-16 wt% of plasticizer, 8-30 wt% of carrier, 3-12 wt% of compatilizer, 1-3 wt% of lubricant and 0.1-1 wt% of auxiliary agent.

50-65 wt% of starch, 10-14 wt% of plasticizer, 8-25 wt% of carrier, 6-10 wt% of compatilizer, 1-2 wt% of lubricant and 0.3-0.5 wt% of auxiliary agent.

Preferably, the starch is one or more of wheat starch, corn starch, tapioca starch and potato starch.

Preferably, the plasticizer is one or more of glycerol, glycerol monostearate, sorbitol, triethanolamine and urea.

Preferably, the carrier is one or a combination of LLDPE, EAA and EVA.

Preferably, the LLDPE, EAA and EVA have a melt index in the range of 10-100g/10 min.

Preferably, the LLDPE, EAA, EVA have melt indices in the range of 20-50g/10 min.

Preferably, the compatibilizer is a grafted combination of one or more selected from LDPE and MLLDPE and one or more selected from maleic anhydride, itaconic anhydride, and substituted maleic anhydride.

Preferably, the compatibilizer is of LDPE-g-MA and MLLDPE-g-MA, wherein the weight ratio of LDPE-g-MA to MLLDPE-g-MA is 1: 0.5-2.

Preferably, the LDPE-g-MA grafting rate is more than 0.5%.

Preferably, the MLLDPE-g-MA grafting rate is more than 0.5%.

Preferably, the lubricant is one or more of PE wax, oxidized PE wax, calcium stearate, and zinc stearate.

Preferably, the adjuvant is selected from the group consisting of antioxidants and antimicrobial modifiers.

Preferably, the particle size of the starch master batch is 10-30 μm.

Preferably, the water content of the starch concentrate is 0.1-0.5 wt%.

In the preparation of the degradable material and/or the product, the components and the proportion of the starch master batch are optimized, so that the addition amount of the starch in the degradable material and/or the product can be increased, and the production cost is further saved;

the starch-based plastic product prepared from the starch master batch provided by the invention has excellent plastic performance; the packaging bag is suitable for packaging products, is particularly suitable for various packaging bags and/or sealing bags, and is particularly suitable for express bags, hand bags, vest bags, rope-penetrating bags, flat bags, buckle bags, zipper bags, edge sealing bags, hand bags, rope drawing bags and the like.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Drawings

FIG. 1 is an SEM photograph of a stretched cross-section of sample S1 in the example;

FIG. 2 is a SEM photograph of a plane where the sample S2 is stretched in the example;

FIG. 3 is an SEM photograph of a stretched cross-section of sample S3 in example.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

The invention provides an application of starch master batch in preparing degradable materials and/or products, wherein the total weight of the starch master batch is taken as a reference, and the starch master batch contains:

The addition amount of the starch in the degradable material and/or the product is increased through the optimized components and the proportion of the starch master batch, so that the production cost and the environmental protection performance are further saved.

In the present invention, in order to further increase the addition amount of starch in the subsequent product, preferably, the starch masterbatch comprises, based on the total weight of the starch masterbatch:

In the present invention, in order to further increase the addition amount of starch in the subsequent product, preferably, the starch concentrate contains, based on the total weight of the starch concentrate:

50-65 wt%, plasticizer 10-14 wt%, carrier 8-25 wt%, compatilizer 6-10 wt%, lubricant 1-2 wt%, and auxiliary agent 0.3-0.5 wt%.

In the present invention, the kind of the above starch is not particularly limited, and may be various commercially available starches, and in the present invention, it is preferable that the starch is one or more of wheat starch, corn starch, tapioca starch and potato starch. The source of the starch used in the present invention is not particularly limited, and may be deposited grain or industrial grain, or may be industrial grade or food grade, and those skilled in the art can determine the kind of the starch to be used according to market and industry requirements, and in the method of the present invention, industrial grade deposited grain is preferably selected.

The plasticizer is not particularly limited, and may be various plasticizers commonly used in the art, and may be determined by those skilled in the art according to actual use requirements, such as alcohols, esters, and the like, and in the present invention, in order to increase the addition amount of starch in subsequent products and ensure excellent performance of the products, preferably, the plasticizer is one or more of glycerol, glycerol monostearate, sorbitol, triethanolamine, and urea.

The carrier is not particularly limited, and may be various carriers commonly used in the art, and in the present invention, in order to ensure the fluidity of the final starch concentrate, it is preferable that the carrier is one or a combination of more of LLDPE, EAA and EVA.

In order to further increase the addition amount of starch in subsequent products and ensure the excellent performance of the products, in the invention, the LLDPE, EAA and EVA preferably have a melt index range of 10-100g/10 min.

In order to further increase the addition amount of starch in subsequent products and ensure excellent performance of the products, in the invention, the LLDPE, EAA and EVA preferably have a melt index in the range of 20-50g/10 min.

In order to improve the dispersibility of the starch in the starch masterbatch, in the present invention, preferably, the compatibilizer is a graft combination of one or more selected from LDPE and MLLDPE and one or more selected from maleic anhydride, itaconic anhydride, and substituted maleic anhydride.

In order to further increase the adding amount of starch in subsequent products and ensure the excellent performance of the products, in the invention, the compatilizer is LDDE-g-MA and MLLDPE-g-MA, wherein the weight ratio of the LDPE-g-MA to the MLLDPE-g-MA is 1: 0.5-2.

In the present invention, preferably, the compatibilizer is LDPE-g-MA, and the graft ratio is 0.5% or more, and in the embodiment of the present invention, the graft ratio is 0.6 to 1.0%.

In the present invention, the MLLDPE-g-MA grafting ratio is preferably 0.5% or more, and in the present embodiment, the grafting ratio is 0.6 to 1.0%.

In order to improve the processing performance of the starch masterbatch during granulation, the lubricant is preferably one or more of PE wax, oxidized PE wax, calcium stearate and zinc stearate.

The above-mentioned auxiliary agents are not particularly limited, and may be selected to be compounded according to specific use requirements, in order to increase the addition amount of starch in subsequent products and ensure the excellent performance of the products, preferably, the auxiliary agents are selected from antioxidants and antibacterial modifiers, in one embodiment of the present invention, a combination of a compounded antioxidant comprising an antioxidant 1076 and an antioxidant 168 and an antibacterial modifier comprising vanillin is selected, and the amount ratio of the antioxidant to the antibacterial modifier in the combination can be determined by those skilled in the art according to actual needs.

The particle size of the starch concentrate is not particularly limited, and in the method of the present invention, the particle size of the starch concentrate is preferably 10 to 30 μm, in consideration of the actual conditions of the starch concentrate production equipment and convenience in the subsequent use of the starch concentrate.

The particle size of the starch concentrate is not particularly limited, and the moisture content of the starch concentrate is preferably 0.1-0.5 wt% in the method of the present invention, in consideration of the actual conditions of the starch concentrate production equipment and convenience in the subsequent use of the starch concentrate.

In the specific embodiment of the present invention, the preparation method of the starch concentrate is not particularly limited, and may be various preparation methods conventionally adopted by those skilled in the art, and will not be described herein again. In a specific embodiment of the invention, the preparation is carried out according to the following steps:

1) adding the starch and the plasticizer into a high-speed mixer, and stirring for 15-30 minutes at normal temperature;

2) adding the rest components, stirring at normal temperature for 10-15 min, and discharging;

3) and extruding and granulating by using a parallel double-screw granulator unit to obtain the starch master batch.

In the specific embodiment of the invention, the temperature of each section of the double-screw granulator unit is 90-175 ℃, and the screw rotating speed is 250-400 rpm.

The article may be a blow molded article, an injection molded article, an extrusion molded article or a foamed article.

The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples.

All the starting materials used in the examples are commercially available, except where otherwise indicated.

The performance test method comprises the following steps:

tensile strength, tearing strength, pendulum impact resistance and puncture strength test: and testing according to a corresponding national standard testing method.

And (3) testing tensile property: according to the test of GB/T1040.3-2006, the sample adopts type 2, the length is 150mm, the width is 15mm, and the test speed is 200 mm/min. Detecting data of the sample in the longitudinal direction and the transverse direction;

and (3) testing the tearing strength: the method is carried out according to the regulation of GB/T16578.2-2009. Detecting data of the sample in the longitudinal direction and the transverse direction;

pendulum impact resistance: testing according to GB/T8809-2015 standard;

puncture strength: testing according to GB/T10004-2008 standard;

the unit of tensile strength is N, the unit of tensile strength is MPa, the unit of elongation at break is%, the unit of pendulum impact resistance is J, and the unit of puncture strength is N.

Example 1

50 wt% of corn starch, 10 wt% of glycerol, 26 wt% of LLDPE, 1 wt% of PE wax, 8 wt% of LDPE-g-MA + 4 wt% of MLLDPE-g-MA and 1 wt% of auxiliary agent.

Example 2

50 wt% of corn starch, 10 wt% of glycerol, 26 wt% of LLDPE, 1 wt% of PE wax, 6 wt% of LDPE-g-MA + 6 wt% of MLLDPE-g-MA and 1 wt% of auxiliary agent.

Example 3

50 wt% of corn starch, 10 wt% of glycerol, 26 wt% of LLDPE, 1 wt% of PE wax, 4 wt% of LDPE-g-MA + 8 wt% of MLLDPE-g-MA and 1 wt% of auxiliary agent.

Example 4

60 wt% of corn starch, 7 wt% of glycerol, 7 wt% of sorbitol, 16 wt% of EAA, 2 wt% of PE wax, 3.5 wt% of LDPE-g-MA3.5wt%, 3.5 wt% of MLLDPE-g-MA and 1 wt% of auxiliary agent.

Example 5

60 wt% of corn starch, 7 wt% of glycerin, 7 wt% of sorbitol, 16 wt% of EAA, 2 wt% of oxidized PE wax, 3.5 wt% of LDPE-g-MA, 3.5 wt% of MLLDPE-g-MA and 1 wt% of auxiliary agent.

Example 6

60 wt% of corn starch, 14 wt% of glycerol, 16 wt% of EAA, 2 wt% of oxidized PE wax, 3.5 wt% of LDPE-g-MA + 3.5 wt% of MLLDPE-g-MA and 1 wt% of auxiliary agent.

Example 7

65 wt% of corn starch, 15 wt% of glycerol, 11.7 wt% of EAA, 2 wt% of oxidized PE wax, 3 wt% of LDPE-g-MA + 3 wt% of MLLDPE-g-MA and 0.3 wt% of auxiliary agent.

Example 8

70 wt% of corn starch, 16 wt% of glycerol, 8 wt% of LLDPE, 2 wt% of oxidized PE wax, 1.5 wt% of LDPE-g-MA + 1.5 wt% of MLLDPE-g-MA and 1 wt% of auxiliary agent.

Example 9

30 wt% of corn starch, 7 wt% of glycerol, 16 wt% of EAA, 16 wt% of EVA, 16 wt% of LLDPE, 1 wt% of PE wax, 6.5 wt% of LDPE-g-MA, 6.5 wt% of MLLDPE-g-MA and 1 wt% of auxiliary agent.

Example 10

55 wt% of wheat starch, 12 wt% of glycerol, 27 wt% of LLDPE, 2 wt% of PE wax, 1.5 wt% of LDPE-g-MA, 1.5 wt% of MLLDPE-g-MA and 1 wt% of auxiliary agent.

Example 11

55 wt% of potato starch, 6 wt% of glycerol, 6 wt% of sorbitol, 13.5 wt% of EAA, 13.5 wt% of EVA, 2 wt% of oxidized PE wax, 1.5 wt% of LDPE-g-MA, 1.5 wt% of MLLDPE-g-MA and 1 wt% of auxiliary agent.

Example 12

40 wt% of potato starch, 8 wt% of glycerol, 15 wt% of EAA, 10 wt% of EVA, 22 wt% of LLDPE, 1 wt% of PE wax, 1.5 wt% of LDPE-g-MA, 1.5 wt% of MLLDPE-g-MA and 1 wt% of auxiliary agent.

Comparative example 1

55 wt% of corn starch, 12 wt% of glycerol, 30 wt% of LLDPE, 2 wt% of PE wax and 1 wt% of auxiliary agent.

Comparative example 2

60 wt% of corn starch, 8 wt% of glycerol, 8 wt% of sorbitol, 20 wt% of EAA, 2 wt% of oxidized PE wax, 0.5 wt% of LDPE-g-MA, 0.5 wt% of MLLDPE-g-MA and 1 wt% of auxiliary agent.

Comparative example 3

60 wt% of corn starch, 8 wt% of glycerol, 8 wt% of sorbitol, 16 wt% of EAA, 3.5 wt% of LDPE-g-MA, 3.5 wt% of MLLDPE-g-MA and 1 wt% of auxiliary agent.

Preparation of starch concentrate

According to a specific implementation mode, firstly, starch and plasticizer are added into a high-speed mixer according to the proportion shown in examples 1-12 and comparative examples 1-3 and are stirred for 15 minutes at normal temperature; then adding the carrier, the compatilizer, the lubricant and the auxiliary agent according to the proportion, continuously stirring for 10 minutes at normal temperature, and discharging for later use;

extruding and granulating by using a parallel double-screw granulator set, and setting the temperature of each area of the double-screw extruder as follows: first zone 90 deg.C, second zone 140 deg.C, third zone 145 deg.C, fourth zone 150 deg.C, fifth zone 150 deg.C, sixth zone 150 deg.C, seventh zone 150 deg.C, eighth zone 150 deg.C, ninth zone 150 deg.C, tenth zone 150 deg.C, eleventh zone 150 deg.C, twelfth zone 140 deg.C, thirteenth zone 120 deg.C, and head 120 deg.C; setting the rotation speed of the screw at 380rpm to obtain starch master batches M1-12 and D1-3 with the grain diameter of 10-30 mu M.

TABLE 1 Effect of different lubricants on the processability of the granulation Process

	Lubricant agent	Pressure of granulation die head
			Example 1	2% PE wax	6.0-7.0/12
Example 2	2% oxidized PE wax	4.0-5.0/12
			Comparative example 3	Without addition of PE wax	Blocking the die head and not granulating stably

Preparation of Plastic products S1-S12 and SD1-SD3

Respectively taking the prepared light powder master batches M1-M12 and D1-D3(60 parts by weight) and PE (40 parts by weight) to prepare plastics according to the following modes:

after mixing the raw materials, putting the raw materials into a film blowing machine for film blowing, and setting the temperature of each area of the film blowing machine as follows: the first zone is 160 ℃, the second zone is 165 ℃, the third zone is 170 ℃, the fourth zone is 170 ℃, the fifth zone is 170 ℃, the upper die head is 170 ℃ and the lower die head is 170 ℃ to obtain plastic products S1-S12 and SD1-SD 3. FIG. 1 is an SEM photograph of a cross section of S1 stretched film, wherein starch particles have small particle size, are uniformly dispersed, have no obvious agglomeration and have excellent film stretching performance;

FIG. 2 is a SEM photograph of a plane at the stretching position of S2, wherein the starch particles have small particle size, are uniformly dispersed, have no obvious agglomeration and have excellent film stretching performance;

FIG. 3 is an SEM photograph of a cross section of the stretched S3 film, wherein the starch particles have small particle size, are uniformly dispersed, have no obvious agglomeration and have excellent tensile properties;

the above-mentioned tests S1-S12 and SD1-SD3 were carried out, and the test results are shown in Table 2 below.

TABLE 2

As can be seen from the above Table 2, the film products prepared by using the starch concentrate of the present invention have excellent plastic properties, and the properties of the products are not reduced by the increase of the starch concentrate.

The starch used in the above examples was a commercially available conventional product, the plasticizer was a plasticizer of whole plant origin, the melt index of LLDPE was 20g/10min, the melt index of EVA was 50g/10min, the melt index of EAA was 20g/10min, the graft ratio of LDPE-g-MA was 0.6% (purchased from Chinese Korea, model KHPE-2311), and the graft ratio of MLLDPE-g-MA was 0.6% (purchased from southern Selaginella Foshanensis, model AD-70A).

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims

1. The application of the starch master batch in preparing degradable materials and/or products is characterized in that the starch master batch contains the following components by taking the total weight of the starch master batch as a reference:

2. The use of claim 1, wherein the starch concentrate comprises, based on the total weight of the starch concentrate:

3. The use according to claim 2, wherein the starch concentrate comprises, based on the total weight of the starch concentrate:

4. Use according to any one of claims 1-3, wherein the starch is one or more of wheat starch, corn starch, tapioca starch and potato starch.

5. Use according to any one of claims 1 to 3, wherein the plasticizer is one or more of glycerol, glycerol monostearate, sorbitol, triethanolamine and urea.

6. Use according to any one of claims 1 to 3, wherein the carrier is a combination of one or more of LLDPE, EAA, EVA;

preferably, the LLDPE, EAA and EVA have a melt index in the range of 10-100g/10 min;

more preferably, the LLDPE, EAA, EVA have melt indices in the range of 20-50g/10 min.

7. Use according to any one of claims 1 to 3 wherein the compatibiliser is a grafted combination of one or more selected from LDPE and MLLDPE and one or more selected from maleic anhydride, itaconic anhydride and substituted maleic anhydride.

8. Use according to claim 7, wherein the compatibiliser is of LDPE-g-MA and MLLDPE-g-MA, wherein the weight ratio of LDPE-g-MA to MLLDPE-g-MA is 1: 0.5 to 2;

preferably, the LDPE-g-MA has a grafting rate of more than 0.5 percent;

preferably, the MLLDPE-g-MA grafting rate is more than 0.5%.

9. Use according to any one of claims 1 to 3, wherein the lubricant is one or more of PE wax, oxidized PE wax, calcium stearate and zinc stearate.

10. Use according to any one of claims 1 to 3, wherein the adjuvant is selected from antioxidants and antibacterial modifiers.

11. Use according to any one of claims 1 to 3, wherein the starch concentrate has a particle size of 10 to 30 μm;

preferably, the water content of the starch concentrate is 0.1-0.5 wt%.