CN111875937A

CN111875937A - Function-adjusting master batch for biodegradation and preparation method thereof

Info

Publication number: CN111875937A
Application number: CN202010717251.7A
Authority: CN
Inventors: 陆海荣; 李智会; 杨梦梦
Original assignee: Ningxia Zhongyuan Plastic Industry Technology Co ltd
Current assignee: Ningxia Zhongyuan Plastic Industry Technology Co ltd
Priority date: 2020-07-23
Filing date: 2020-07-23
Publication date: 2020-11-03

Abstract

The invention belongs to the technical field of biological-based degradation, and relates to a function-adjusting master batch for biodegradation and a preparation method thereof. The functional adjusting master batch comprises 60-90 parts of carrier resin, 0.1-50 parts of degradation accelerator, 0.1-10 parts of heat stabilizer, 0.1-5 parts of light stabilizer, 0.1-5 parts of antioxidant, 0.1-20 parts of chain extender and 0.1-20 parts of other functional auxiliaries. The functional regulation master batch can effectively regulate degradation time and degradation speed, and has good ageing resistance.

Description

Function-adjusting master batch for biodegradation and preparation method thereof

Technical Field

The invention belongs to the technical field of biological-based degradation, and relates to a function-adjusting master batch for biodegradation and a preparation method thereof.

Background

With the rapid development of economy in China, the scale of the petroleum synthetic plastic industry is rapidly expanded, and plastic products are applied to more and more industries; specifically, the worldwide consumption of plastics is estimated to be 3.35 million tons, and the consumption of plastics in china is estimated to exceed 7000 million tons. Plastic products provide convenience for industry, agriculture and daily life, but also produce a large amount of waste. The wastes exist in a solid form, are mostly from disposable plastic products such as packaging bags, beverage bottles, agricultural mulching films and the like, and have the problems of large volume, long decomposition time, difficult degradation in natural environment and the like.

The existing treatment methods (such as landfill, incineration and recycling) aiming at plastic wastes are difficult to fundamentally solve the 'white pollution' caused by the plastic wastes and cannot meet the ever-increasing consciousness requirement of 'environment friendliness' of people; in addition, the plastic is a petroleum-based product, the price of the plastic product is unstable due to the fluctuation of petroleum price, and the limit of petroleum reserves and the unlimited consumption of human beings lead to the gradual reduction of petroleum resources and the explosion of oil prices in the international market, so that the long-term development of the plastic industry is limited.

The degradable plastic can be degraded into carbon dioxide and moisture under specific environment, and cannot pollute the environment. The degradable plastics are various, and the photodegradable plastics and the biodegradable plastics are common. Since the 90 s of the 20 th century, research on photodegradable plastics tends to be reduced because products thereof encounter obstacles in the process of popularization and application. The main expression is that when the photodegradable plastic is applied to manufacturing the mulching film, the part of the photodegradable mulching film embedded in soil can not be degraded due to no light irradiation; meanwhile, the degradation rate of the photodegradable plastic depends on the intensity of ultraviolet rays, and the degradability of the photodegradable plastic is greatly influenced by different geographical positions, climatic conditions and the like; in addition, the production cost of the photodegradable plastic is high, and the photodegradable plastic does not have competitive advantage in price.

Degradable plastics have been developed over decades and biodegradable plastics have become their major form, especially starch-based plastics, which have occupied a large proportion of biodegradable plastics. Although the development of degradable plastics is started later in China, the development is faster. From the reports of related data, the biodegradable plastics in China mainly focus on the researches on the aspects of grafting modification of starch, filling of modified starch in plastics and the like, and the related reports on the aspect of developing completely biodegradable plastics are less.

At present, the research on biodegradable plastics mainly focuses on starch-based biodegradable plastics and other bio-based resins PBS/PLAPLA/PBAT/PPC/PVA starch filled biodegradable plastics, all-starch plastics and some biochemical synthetic polymers taking starch as raw materials. Among them, foreign products are good in mechanical properties, biodegradability and other aspects, but expensive; some domestic products have a plurality of problems, such as reduced mechanical property, higher production cost and difficult control of degradation accuracy, starch-based degradable plastics use starch produced by grains as raw materials, conflict of industry and people for grains occurs, and the like.

Disclosure of Invention

The invention aims to provide a function-adjusting master batch for biodegradation, which can effectively adjust degradation time and degradation speed and has good ageing resistance.

The invention also aims to provide a preparation method of the functional regulation master batch for biodegradation, which has low production cost and simple and convenient operation and ensures the performance stability of products.

The technical scheme of the invention for solving the technical problems is as follows.

A functional regulation master batch for biodegradation comprises the following raw materials in parts by mass: carrier resin: 60-90 parts; degradation accelerator: 0.1-50 parts; thermal stabilizer: 0.1-10 parts; light stabilizer: 0.1-5 parts; antioxidant: 0.1-5 parts; chain extender: 0.1-20 parts; other functional auxiliary agents: 0.1-20 parts.

Further, the carrier resin of the function adjusting master batch is one or more of PP (polypropylene), PE (polyethylene), PLA (polylactic acid), PBAT (polybutylene adipate/terephthalate), PBS (polybutylene succinate), PVA (polyvinyl alcohol), PHA (polyhydroxyalkanoate), PPC (polypropylene carbonate) or plastic starch.

Further, the degradation promoter of the function adjusting master batch is one or more of a copper compound, an iron compound, a titanium compound, a cerium compound, a cobalt compound, a lanthanum compound, a praseodymium compound, titanium dioxide, ferric oxide, manganese dioxide, ferrocene, ferric stearate, manganese stearate, cobalt stearate, copper stearate, cerium stearate, lanthanum stearate, praseodymium stearate, iron dimethyldithiocarbamate or diethyldithiocarbamate; preferably, manganese stearate or cobalt stearate.

Further, the heat stabilizer of the function adjusting master batch is one or more of barium stearate, calcium stearate, zinc stearate, strontium stearate, magnesium stearate, barium laurate, calcium laurate, zinc laurate or magnesium laurate; preferably, zinc stearate.

Further, the light stabilizer of the function adjusting master batch is one or more of phenyl salicylate, 4-isopropylidene bis (phenol salicylate), p-tert-butyl benzoate salicylate, resorcinol monobenzoate, 2-hydroxy-4-methoxy benzophenone or 2-hydroxy-4-n-octoxy benzophenone; preferably, 4, 4-isopropylidene bis (phenol salicylate).

Furthermore, the antioxidant of the function adjusting master batch is one or more of 2, 6-di-tert-butyl-p-cresol, 2,4, 6-tri-tert-butylphenol, 4-hydroxymethyl-2, 6-di-tert-butylphenol, tert-butyl hydroxyanisole, pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 2, 2' -methylenebis (4-ethyl-6-tert-butylphenol) or triphenyl phosphite; preferably, the triphenyl phosphite and the 2, 6-ditertbutyl-p-cresol are compounded.

Furthermore, the function adjusting master batch and the chain extender are low molecular weight styrene ethylene acrylic acid copolymer and/or ethylene acrylic acid-glycidyl methacrylate terpolymer.

Furthermore, the function adjusting master batch and other functional additives are one or more of coupling agent, dispersing agent, plasticizer or degradation inhibitor.

Wherein the coupling agent is one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3- (methacryloyloxy) propyltrimethoxysilane; the dispersant is one or more of polyoxyethylene dodecyl ether, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether or propylene glycol phenyl ether; the plasticizer is one or more of glycerol, propylene glycol, polyethylene glycol, polypropylene glycol, pentaerythritol, 1, 4-butanediol, trimethylolpropane, dipropylene glycol dibenzoate, corn oil, citrate, monostearate or aliphatic diamide diol; the degradation inhibitor is one or more of barium sulfate, carbodiimide, p-phenylenediamine, di-fatty alkyl methyl tertiary amine, octadecyl dimethyl tertiary amine or 2, 6-di-tert-butyl-4 methylphenol.

A preparation method of a function-adjusting master batch for biodegradation comprises the following steps:

(1) weighing all raw materials required by the function adjusting master batch;

(2) stirring and mixing uniformly by adopting a high-speed mixer;

(3) and melting and extruding the stirred and mixed raw materials in a double-screw extruder, and granulating in a granulator to obtain the function regulating master batch.

The function-adjusting master batch for biodegradation and the preparation method thereof have the beneficial effects that:

(1) because the degradation of the bio-based resin is influenced by various conditions such as environmental temperature, humidity and climate, the degradation speed is greatly changed, especially the premature degradation of the mulching film can influence the growth and water retention of crops, the master batch is blended with various functional additives by utilizing carrier resin, and meanwhile, the bidirectional degradation is realized by the combination of a degradation inhibitor and a degradation accelerator, the adjustment of the addition amount and the delayed degradation of an antioxidant, so that the degradation time and the degradation speed are effectively regulated and controlled, the bio-based resin is completely biodegradable and has no pollution to the environment;

(2) the master batch has good compatibility with a high molecular biodegradable copolymer, a plasticizer, other auxiliary fillers and the like, can increase the strength and the film forming property of a product, has the characteristics of water resistance and oil resistance, can adapt to the adjustment of the degradation time of various bio-based resins, overcomes the bad effects of uncertain degradation time and the like caused by different environmental temperatures and humidity of the product made of the bio-based resins, can be widely applied to the injection molding and film blowing of plastic products, has positive effects on the pressure brought by white pollution and the shortage of petroleum resources, and has good economic benefit and social benefit;

(3) the master batch has stronger specificity, effectively improves the practicability of the material, effectively controls the degradation time according to the addition amount of the master batch, integrates light/heat/oxygen/growth/inhibition composite degradation, effectively enlarges the application range of the master batch, and overcomes the defect of incomplete single degradation;

(4) the master batch has low production cost, simple and convenient operation and stable performance, and is superior to domestic similar products in the aspects of service performance, biodegradation performance, price and the like.

Drawings

FIG. 1 is an FTIR spectrum (full) of a degraded film after 15 days of thermal oxidation in example 4;

FIG. 2 is an FTIR spectrum (partial) of a degraded film after thermal oxidation for 15 days in example 4.

Detailed Description

Example 1

A preparation method of a function-adjusting master batch for biodegradation comprises the following process steps:

(1) weighing the following raw materials in proportion, placing into a mixer, heating and stirring at 60 deg.C for 30min to mix them uniformly, cooling, and placing into a barrel for use; raw materials to be weighed comprise a degradation promoter, a heat stabilizer, a light stabilizer, an antioxidant, a coupling agent, a dispersant and a plasticizer; wherein the degradation promoter is 5 parts of copper compound, 5 parts of manganese stearate and 3 parts of anatase titanium dioxide, the heat stabilizer is 5 parts of magnesium stearate, the light stabilizer is 3 parts of 4, 4-isopropylidene bis (phenol salicylate), the antioxidant is 2 parts of 4-hydroxymethyl-2, 6-di-tert-butylphenol, the coupling agent is 5 parts of 3-aminopropyltriethoxysilane, the dispersing agent is 2 parts of polyoxyethylene dodecyl ether, the plasticizer is 5 parts of glycerol and 5 parts of polyethylene glycol 400;

(2) weighing 65 parts of PBAT, 10 parts of chain extender ethylene acrylic acid-glycidyl methacrylate terpolymer (France arkema AX-8900), 5 parts of chain extender ethylene acrylic acid-glycidyl methacrylate terpolymer (KL-4370) and 20 parts of the mixture obtained in the step (1), uniformly mixing, putting into a double-screw extruder for extrusion and granulation by a granulator, and finishing the processing of the functional regulation master batch.

Example 2

(1) weighing the following raw materials in proportion, placing into a mixer, heating and stirring at 60 deg.C for 30min to mix them uniformly, cooling, and placing into a barrel for use; raw materials to be weighed comprise a degradation promoter, a heat stabilizer, a light stabilizer, an antioxidant, a degradation inhibitor, a coupling agent and a plasticizer; wherein the degradation accelerator is 5 parts of cobalt stearate, the heat stabilizer is 5 parts of zinc stearate, the light stabilizer is 5 parts of 2-hydroxy-4-n-octoxy benzophenone, the antioxidant is 3 parts of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, the degradation inhibitor is 5 parts of barium sulfate, 2 parts of carbodiimide and 3 parts of octadecyl dimethyl tertiary amine, the coupling agent is 5 parts of 3-glycidyl ether oxypropyltrimethoxysilane, and the plasticizer is 5 parts of dipropylene glycol dibenzoate and 5 parts of trimethylolpropane;

Example 3

(1) weighing the following raw materials in proportion, placing into a mixer, heating and stirring at 60 deg.C for 30min to mix them uniformly, cooling, and placing into a barrel for use; raw materials to be weighed comprise a degradation promoter, a heat stabilizer, a light stabilizer, an antioxidant, a coupling agent, a dispersant and a plasticizer; wherein the degradation promoter is 5 parts of copper compound, 5 parts of manganese stearate and 3 parts of anatase titanium dioxide, the heat stabilizer is 5 parts of magnesium stearate, the light stabilizer is 3 parts of 4, 4-isopropylidene bis (phenol salicylate), the antioxidant is 2 parts of 4-hydroxymethyl-2, 6-di-tert-butylphenol, the coupling agent is 3 parts of 3-aminopropyltriethoxysilane, the dispersing agent is 2 parts of polyoxyethylene dodecyl ether, the plasticizer is 3 parts of glycerol 5 parts, and the polyethylene glycol 400 is 2 parts;

(2) weighing 65 parts of PE, 10 parts of chain extender ethylene acrylic acid-glycidyl methacrylate terpolymer (France arkema AX-8900), 5 parts of chain extender ethylene acrylic acid-glycidyl methacrylate terpolymer (KL-4370) and 20 parts of the mixture obtained in the step (1), uniformly mixing, putting into a double-screw extruder for extrusion and granulation by a granulator, and finishing the processing of the functional regulation master batch.

Example 4

An application of a function adjusting master batch for biodegradation is that 3% of the function adjusting master batch in embodiment 2 is added into polyethylene plastic resin, and a film with the width of 35cm and the thickness of 0.025mm is blown by a film blowing machine, and related performances are tested.

(1) Mechanical properties before and after degradation

The thermal oxidation degradation degree and the elongation rate of the environmental biodegradable plastic have close relationship; the elongation of the sample is measured according to the national standard GB/T1040.1-2006 "determination of the tensile properties of plastics: part 1 general rule "; definition of the thermal oxidative degradation end-point the end-point of degradation of polyethylene and polypropylene is determined by tensile testing with reference to the US standard ASTM D3826-98 ".

In this example, the relationship between the thermo-oxidative degradation time and the elongation of the degraded polyethylene film is shown in the following table.

Thermal oxidation time (day)	0	5	10	15
					Elongation at Break (%)	283	147	81	<5

As can be seen from the above table, the elongation at break of the thin film is greatly reduced with the increase of the thermal oxidation time; when the thermal oxidation degradation time is 15 days, the elongation at break is less than 5%, and the test film reaches the degradation endpoint.

(2) Infrared spectra before and after degradation

The infrared spectrum detection refers to international standard ISO10640:2011 'plastic-method for evaluating polymer aging by Fourier transform infrared spectrum and ultraviolet/visible light spectrum'; when infrared light with wave number continuously converted passes through the sample, the intensity of the infrared light of some wave numbers is not changed, and the intensity of the infrared light of some wave numbers is obviously weakened.

In this example, the relationship between the thermal oxidative degradation time and the increase in absorbance for the degraded polyethylene film is shown in the following table.

Thermal oxidation time (day)	0	5	10	15
					Absorbance of the solution	0	0.0044	0.0132	0.0458

FIG. 1 shows the wave number of 4000cm after 15 days of thermal oxidation of degraded polyethylene film^-1And 400cm^-1A Fourier Transform Infrared (FTIR) spectrogram of the infrared band within the range; the figure uses the thermal oxidation time of the film as the abscissa and the absorbance as the ordinate. After thermal oxidation, the polyethylene film can generate carbonyl-containing organic matters such as ester, aldehyde, ketone, acid and the like; the stretching vibration frequency of the organic characteristic group C-O is 1760cm at the wave number^-1To 1660cm^-1Wherein the range of the ester is 1770-1750 cm^-1Aldehyde 1735-1715 cm^-1Ketone 1720-1710 cm^-1The acid is 1770-1750 cm^-1。

FIG. 2 shows the degraded polyethylene film at a wave number of 1800cm^-1And 1400cm^-1A Fourier Transform Infrared (FTIR) spectrogram of the mid-infrared band; at a wavenumber of 1760cm^-1To 1660cm^-1In the range, an organic characteristic group C-O is found, which indicates that after thermal oxidation degradation, organic matters such as ester, aldehyde, ketone, acid and the like are generated in the film.

(3) Molecular weight before and after degradation

Molecular weight measurement reference is made to the U.S. Standard ASTM D6474-1999(2006) "test method for determining polyolefin molecular weight distribution and molecular weight average by high temperature gel permeation chromatography". The degraded film undergoes the well-known Norrish type I and type II reactions under the action of heat, and organic substances such as ester, aldehyde, ketone, acid and the like are generated, so that the molecular weight is changed. The following table shows the relationship between the thermal degradation time and the weight average molecular weight.

Thermal oxidation time (day)	0	5	10	15
					Molecular weight (Mw)	1.7×10⁵	7.6×10⁴	2.7×10⁴	8.8×10³

As can be seen from the above table, the molecular weight of the degraded plastic film decreased from the first 17 tens thousands to around 9000 through 15 days of thermal oxidative degradation.

In summary, the degradable film of the present example:

1) the elongation of the degradable film is reduced from 283% to less than 5% through thermal oxidation for 15 days, and the degradation end point of polyolefin is reached;

2) the degraded film is subjected to thermal oxidation to generate organic matters containing carbonyl groups such as ester, aldehyde, ketone, acid and the like. After 15 days, the absorbance of the film was 0.0458;

3) the film undergoes thermal oxidation and the molecular weight is reduced from 17 ten thousand to 8800.

Claims

1. A functional regulation master batch for biodegradation is characterized by comprising the following raw materials in parts by mass:

carrier resin: 60-90 parts;

degradation accelerator: 0.1-50 parts;

thermal stabilizer: 0.1-10 parts;

light stabilizer: 0.1-5 parts;

antioxidant: 0.1-5 parts;

chain extender: 0.1-20 parts;

other functional auxiliary agents: 0.1-20 parts.

2. The functional conditioning masterbatch of claim 1, wherein the carrier resin is one or more of PP, PE, PLA, PBAT, PBS, PVA, PHA, PPC, or a plastic starch.

3. The functional conditioning masterbatch of claim 1, wherein the degradation promoter is one or more of a copper compound, an iron compound, a titanium compound, a cerium compound, a cobalt compound, a lanthanum compound, a praseodymium compound, titanium dioxide, ferric oxide, manganese dioxide, ferrocene, ferric stearate, manganese stearate, cobalt stearate, copper stearate, cerium stearate, lanthanum stearate, praseodymium stearate, iron dimethyldithiocarbamate, or diethyldithiocarbamate.

4. The functional conditioning masterbatch of claim 1, wherein the thermal stabilizer is one or more of barium stearate, calcium stearate, zinc stearate, strontium stearate, magnesium stearate, barium laurate, calcium laurate, zinc laurate, or magnesium laurate.

5. The conditioning masterbatch of claim 1, wherein the light stabilizer is one or more of phenyl salicylate, 4-isopropylidene bis (phenol salicylate), p-tert-butyl salicylate, resorcinol monobenzoate, 2-hydroxy-4-methoxybenzophenone, or 2-hydroxy-4-n-octoxybenzophenone.

6. The conditioning masterbatch of claim 1, wherein said antioxidant is one or more of 2, 6-di-tert-butyl-p-cresol, 2,4, 6-tri-tert-butylphenol, 4-hydroxymethyl-2, 6-di-tert-butylphenol, tert-butyl hydroxyanisole, pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 2, 2' -methylenebis (4-ethyl-6-tert-butylphenol) or triphenyl phosphite.

7. The functional conditioning masterbatch of claim 1, wherein the chain extender is a low molecular weight styrene ethylene acrylic acid copolymer and/or an ethylene acrylic acid-glycidyl methacrylate terpolymer.

8. The function-adjusting masterbatch according to claim 1, wherein the other functional additives are one or more of coupling agent, dispersant, plasticizer or degradation inhibitor.

9. The function-adjusting masterbatch according to claim 8,

the coupling agent is one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and 3- (methacryloyloxy) propyltrimethoxysilane;

the dispersing agent is one or more of polyoxyethylene dodecyl ether, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether or propylene glycol phenyl ether;

the plasticizer is one or more of glycerol, propylene glycol, polyethylene glycol, polypropylene glycol, pentaerythritol, 1, 4-butanediol, trimethylolpropane, dipropylene glycol dibenzoate, corn oil, citrate, monostearate and aliphatic diamide diol;

the degradation inhibitor is one or more of barium sulfate, carbodiimide, p-phenylenediamine, di-fatty alkyl methyl tertiary amine, octadecyl dimethyl tertiary amine or 2, 6-di-tert-butyl-4 methylphenol.

10. The method for preparing a function-adjusting masterbatch according to any one of claims 1 to 9, comprising the steps of:

(1) weighing all raw materials required by the function adjusting master batch;

(2) stirring and mixing uniformly by adopting a high-speed mixer;