CN111825965B - Foamable polylactic acid-containing plastic particles and preparation method and application thereof - Google Patents
Foamable polylactic acid-containing plastic particles and preparation method and application thereof Download PDFInfo
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- CN111825965B CN111825965B CN202010812562.1A CN202010812562A CN111825965B CN 111825965 B CN111825965 B CN 111825965B CN 202010812562 A CN202010812562 A CN 202010812562A CN 111825965 B CN111825965 B CN 111825965B
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Abstract
The invention discloses foamable polylactic acid-containing plastic particles, a preparation method and application thereof, wherein the foamable polylactic acid-containing plastic particles comprise the following components: 100 parts of a base resin; 8-15 parts of a load type foaming agent; 0.04-0.45 parts of an activator. According to the invention, polylactic acid alloy is formed as a matrix by mixing carboxyl-terminated polylactic acid, aliphatic polyester and styrene copolymer elastomer according to a specific proportion; porous or multi-layer inorganic powder loaded foaming agent is selected to form a loaded foaming agent, and then the loaded foaming agent is mixed with resin and other components to prepare foamable polylactic acid-containing plastic particles, so that the problems of pre-foaming and uneven dispersion of the traditional powdery chemical foaming agent in the mixing process are solved; the foamable polylactic acid-containing plastic particles have high foaming multiplying power, excellent dispersibility and no problem of volatilization of foaming agent, and can be stored for a long time.
Description
Technical Field
The invention belongs to the technical field of degradable plastic preparation, and particularly relates to foamable polylactic acid-containing plastic particles, and a preparation method and application thereof.
Background
Among all the commercial degradable plastics at present, polylactic acid is the material with the best physical and thermal properties, and is also the degradable plastic which has the highest hope of replacing polyolefin materials. However, the polylactic acid has a low crystallization rate and a high glass transition temperature, and the conventional molding process mainly obtains an amorphous product, so that the amorphous product still cannot replace the conventional polyolefin product in aspects of mechanical property, heat resistance and the like. In addition, the density of the polylactic acid is far higher than that of polyolefin, and for the same product, the weight of the product floats upwards by 30-40%, so that the polylactic acid is not beneficial to energy conservation and environmental protection, and the price is far higher than that of polyolefin. Therefore, the development of the light high-strength polylactic acid material has important practical significance. Foaming is an effective means of lightening the material.
At present, physical foaming methods are mainly utilized for foaming polylactic acid materials, and physical foaming agents are divided into organic matters and inorganic matters; the organic physical foaming agent is commonly used with low-boiling alkane and fluorocarbon; the inorganic physical foaming agent is generally nitrogen, carbon dioxide, argon, air or the like. The expandable polylactic acid particles containing the foaming agent are mainly obtained by injecting the foaming agent into the polylactic acid matrix under a certain pressure condition. The use of physical blowing agents, while capable of achieving a greater expansion ratio and a more complete cell morphology, is not suitable for long-term storage (where the blowing agent volatilizes), and is very disadvantageous for downstream manufacturers of polylactic acid foamed products, requiring as short a storage time as possible to ensure foaming efficiency. Patent application CN109312093a discloses a method for preparing expandable polylactic acid-containing particles, which can increase the storage life of expandable polylactic acid-containing particles, and is mainly achieved by the following two key points: (1) Semi-crystalline polylactic acid with 0.3-5% of D-lactic acid and amorphous polylactic acid with 10-18% of D-lactic acid are mixed according to a certain proportion to be used as a matrix component; (2) And pre-nucleation is performed by using a combination of an organic physical blowing agent (isopentane) and an inorganic physical blowing agent (nitrogen, carbon dioxide, argon or helium) to produce a pre-nucleated structure. However, this process is only carried out under specific process conditions and it actually increases the pot life of the expanded granules to a certain extent by reducing the loss of blowing agent; the problem of volatilization loss of the foaming agent is not really solved.
The foaming of the polylactic acid material can also adopt a chemical foaming method, and the chemical foaming agent is generally in a powder shape and is mainly used in extrusion foaming. The chemical foaming method does not have the problem of volatilization of the foaming agent, but the problems of pre-foaming and poor dispersion uniformity of the powdery foaming agent during the mixing process are obvious.
On the other hand, polylactic acid is easy to generate oxidative fracture in the processing process, so that the melt strength of the polylactic acid is very low, and the problems of cell distortion, fracture, uneven foaming and the like are easy to generate in the foaming process, so that the foaming particles with high foaming multiplying power are difficult to obtain. The technical scheme for improving the melt strength in the prior art comprises the following steps: 1. the melt strength is improved by adopting the reverse spiral chain coupling synthesis nucleus of the left-handed polylactic acid during extrusion; 2. branching and grafting reaction are adopted to form a cross-linking structure so as to improve the melt strength; 3. using polylactic acid alloy as a matrix; 4. fillers are employed to increase melt strength, etc.
Disclosure of Invention
In order to overcome the defects in the prior art, the primary aim of the invention is to provide the foamable polylactic acid-containing plastic particles, which have high foaming multiplying power and excellent dispersibility; and the foaming agent is free from volatilization, and can be stored for a long time.
Another object of the present invention is to provide a method for producing the above-mentioned foamable polylactic acid-containing plastic particles.
The invention is realized by the following technical scheme:
the foamable polylactic acid-containing plastic particles comprise the following components in parts by weight:
100 parts of a base resin;
8-15 parts of a load type foaming agent;
0.04-0.45 part of activator.
Wherein the base resin is carboxyl-terminated polylactic acid, aliphatic polyester and styrene copolymer elastomer according to the mass ratio of (40-70): (30-60): (0-5) mixing.
The invention selects carboxyl-terminated polylactic acid, has good coating property on the foaming agent and good foamability; the glass transition temperature of the carboxyl-terminated polylactic acid is 60-65 ℃, the melting point is 170-180 ℃, and the weight average molecular weight is 360000 ～ 1020000.
The aliphatic polyester is selected from any one or more of polybutylene succinate, polybutylene succinate-co-adipate or polybutylene succinate-co-sebacate; the styrene copolymer elastomer is selected from any one or more of styrene-isoprene-styrene, styrene-pentadiene-styrene, styrene-ethylene-propylene-styrene, styrene-ethylene-propylene-styrene or styrene-ethylene-butylene-styrene.
The supported foaming agent is functional inorganic powder formed by supporting the foaming agent with the thermal decomposition temperature of more than 160 ℃ on the inorganic powder. The use of a supported blowing agent helps control foaming, and can reduce cell size and homogenize cell size.
Wherein, the inorganic powder is porous or multi-layer inorganic powder. The D50 of the inorganic powder is 0.8 μm to 5. Mu.m, preferably 0.8 μm to 2. Mu.m. The inorganic powder has small particle size, is easy to agglomerate, has insufficient loading capacity on the foaming agent and cannot achieve the required foaming effect; too large particle size affects the crystallization nucleation and foaming nucleation of polylactic acid.
The inorganic powder is selected from any one or more of zirconium phosphate, montmorillonite, talcum powder, porous silicon dioxide, zeolite or alumina molecular sieve.
The foaming agent is selected from any one or more of azodicarbonamide, barium azodicarbonate, p-toluenesulfonyl semicarbazide, 4' -oxo-bis (benzenesulfonyl semicarbazide) or trihydrazinotriazine, and is preferably azodicarbonamide. Wherein, the azodicarbonamide is selected from the group consisting of AC-2000, AC-1600, AC-1601, AC-2001, AC-2002, AC-2300W, and AC-4000.
The preparation method of the supported foaming agent comprises the following steps:
(1) Mixing a foaming agent and a solvent to form a foaming agent solution, wherein the mixing temperature is 60-100 ℃; the solvent is at least one of dimethyl sulfoxide or dimethylformamide; wherein the volume ratio of the mass of the foaming agent to the solvent is (20-60) g: (300-500) mL;
(2) Mixing inorganic powder with the foaming agent solution obtained in the step (1), and filtering to obtain a load type foaming agent, wherein the mixing temperature is 60-100 ℃; wherein the mass ratio of the foaming agent to the inorganic powder is (0.25-2): 1.
the invention requires the mass of the activator to be 0.5-3% of the mass of the supported foaming agent. The activator can promote the decomposition of the foaming agent and reduce the decomposition temperature; too little amount results in low foaming efficiency of the foaming agent. The activator is selected from any one or more of zinc oxide, zinc stearate and zinc benzene sulfinate.
According to performance requirements, the foamable polylactic acid-containing plastic particles also comprise 0.5-4 parts of lubricant and 3-8 parts of plasticizer according to parts by weight.
The lubricant is selected from any one or more of polyethylene wax, oxidized polyethylene wax or paraffin wax;
the plasticizer is selected from any one or more of citric acid ester, glyceride or polyethylene glycol; preferably, the citrate is acetyl tributyl citrate; the glyceride is triacetin; the molecular weight of the polyethylene glycol is 4000-10000.
The invention also provides a preparation method of the foamable polylactic acid-containing plastic particles, which comprises the following steps:
(1) Pre-drying the components before processing;
(2) Mixing the components according to the proportion under high-speed stirring, and adding the mixture into a double-screw extruder for extrusion granulation to obtain foamable polylactic acid-containing plastic particles; wherein the stirring speed is 500-800 rpm; the length-diameter ratio of the double screw extruder is not more than 48, and the extrusion temperature is 110-135 ℃.
The invention also provides application of the foamable polylactic acid-containing plastic particles in degradable plastics; the method is particularly applicable to polylactic acid extrusion foaming products.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the polylactic acid alloy is formed by mixing carboxyl-terminated polylactic acid, aliphatic polyester and styrene copolymer elastomer according to a specific proportion to serve as a matrix, so that the melt strength of the resin is improved, and the foaming is stable and uniform; porous or multi-layer inorganic powder is selected to load the foaming agent to form the load foaming agent, and then the load foaming agent is mixed with resin and other components, so that the problems of pre-foaming and uneven dispersion of the traditional powdery chemical foaming agent in the mixing process are solved, the obtained foamable polylactic acid-containing plastic particles have high foaming multiplying power (up to 6-15 times), and the foaming agent is free from volatilization, and can be stored for a long time.
(2) The foamable polylactic acid-containing plastic particles can realize full degradation, can be used for various degradable plastics, and have stable foaming effect and excellent dispersibility.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
The raw materials used in the examples and comparative examples of the present invention are all commercially available, but are not limited to these materials:
preparation of a supported foaming agent:
(1) Weighing the components according to the proportion of the table 1; mixing a foaming agent and a solvent to form a foaming agent solution, wherein the mixing temperature is 60-100 ℃;
(2) Mixing inorganic powder with the foaming agent solution obtained in the step (1), and filtering to obtain the load type foaming agent, wherein the mixing temperature is 60-100 ℃.
Preparation of Expandable polylactic acid-containing Plastic particles of examples 1 to 9 and comparative examples 1 to 5:
(1) Pre-drying the components before processing;
(2) According to the proportions of the table 2 and the table 3, the components are mixed in a high-speed stirrer with the rotating speed of 500-800 r/min, and extrusion granulation is carried out by using a double-screw extruder, so that the foamable polylactic acid-containing plastic particles are obtained; wherein the length-diameter ratio of the twin-screw extruder is not more than 48, the heating temperature of 6 sections is 110 ℃, 115 ℃, 120 ℃, 135 ℃, 130 ℃ and the die head temperature is 130 ℃ respectively.
The preparation method of comparative example 5:
the difference from example 4 is that 4,4' -oxybis (benzenesulfonyl semicarbazide) is first mixed with porous silica to obtain a mixed blowing agent, and the rest steps are the same.
After preparing a foamed plastic using the foamable polylactic acid-containing plastic particles prepared in examples and comparative examples, the foaming ratio and cell dispersibility thereof were tested. The preparation method of the foaming plastic comprises the following steps: adding the foamable polylactic acid-containing plastic particles into an autoclave, setting the temperature to 180 ℃, heating and foaming while stirring, and cooling to room temperature to obtain the foamed plastic. The test method of the correlation performance is as follows:
1. foaming ratio: measuring the apparent density of the foamed plastic by using an Archimedes method, and calculating the foaming multiplying power according to the ratio of the apparent density to the initial density; the test data are shown in tables 2 and 3.
2. Cell dispersibility: the dispersibility of the cells is judged by means of observation conditions of a slicing rear-body microscope, and root mean square error of average sizes of the cells in a view field is calculated; the smaller the value of the root mean square error of the cell size, the better the dispersibility; the test data are shown in tables 2 and 3.
Table 1: the proportion of the components of the load-type foaming agent
Table 2: examples 1 to 9 the ratio of the amounts of the respective components (in parts by weight) and the results of the performance test
Table 3: comparative examples 1 to 5 the ratio of the amounts of the respective components (in parts by weight) and the results of the performance test
Claims (8)
1. The foamable polylactic acid-containing plastic particles are characterized by comprising the following components in parts by weight:
100 parts of a base resin;
8-15 parts of a load type foaming agent;
0.04-0.45 parts of an activating agent;
0.5-4 parts of lubricant;
3-8 parts of plasticizer;
the base resin is prepared from carboxyl-terminated polylactic acid, aliphatic polyester and styrene copolymer elastomer according to the mass ratio of (40-70): (30-60): (2-5) mixing; wherein the glass transition temperature of the carboxyl-terminated polylactic acid is 60-65 ℃, the melting point is 170-180 ℃, and the weight average molecular weight is 360000-102000; the aliphatic polyester is selected from any one or more of polybutylene succinate-co-adipic acid butanediol ester or polybutylene succinate-co-sebacic acid butanediol ester;
the load type foaming agent is a functional inorganic powder formed by loading the foaming agent with the thermal decomposition temperature of more than 160 ℃ on the inorganic powder; the D50 of the inorganic powder is 0.8-5 mu m; the inorganic powder is selected from any one or more of talcum powder, porous silicon dioxide, zeolite or alumina molecular sieve;
the foaming agent is selected from any one or more of azodicarbonamide, barium azodicarbonate, p-toluenesulfonyl semicarbazide, 4' -oxo-bis (benzenesulfonyl semicarbazide) or trihydrazino triazine;
the mass of the activator is 0.5% -3% of that of the supported foaming agent.
2. The expandable polylactic acid-containing plastic particles according to claim 1, wherein the styrene copolymer elastomer is selected from any one or more of styrene-isoprene-styrene, styrene-pentadiene-styrene, styrene-ethylene-propylene-styrene, styrene-ethylene-propylene-styrene, or styrene-ethylene-butylene-styrene.
3. The foamable polylactic acid-containing plastic particles according to claim 1, wherein the inorganic powder has a D50 of 0.8 μm to 2 μm; the foaming agent is azodicarbonamide.
4. The foamable polylactic acid-containing plastic particle according to claim 1, wherein the preparation method of the supported foaming agent comprises the following steps:
(1) Mixing a foaming agent and a solvent to form a foaming agent solution, wherein the mixing temperature is 60-100 ℃; the solvent is at least one of dimethyl sulfoxide or dimethylformamide; the volume ratio of the mass of the foaming agent to the solvent is (20-60) g: (300-500) mL;
(2) Mixing inorganic powder with the foaming agent solution obtained in the step (1), and filtering to obtain a load type foaming agent, wherein the mixing temperature is 60-100 ℃; wherein the mass ratio of the foaming agent to the inorganic powder is (0.25-2): 1.
5. the expandable polylactic acid-containing plastic particle according to claim 1, wherein the activator is selected from any one or more of zinc oxide, zinc stearate and zinc benzene sulfinate.
6. The expandable polylactic acid-containing plastic particles according to claim 1, wherein the lubricant is selected from any one or more of polyethylene wax, oxidized polyethylene wax, and paraffin wax; the plasticizer is selected from any one or more of citric acid ester, glyceride or polyethylene glycol; wherein the citrate is acetyl tributyl citrate; the glyceride is triacetin; the weight average molecular weight of the polyethylene glycol is 4000-10000.
7. The method for preparing the foamable polylactic acid-containing plastic particles according to any one of claims 1 to 6, comprising the steps of:
(1) Pre-drying the components before processing;
(2) Mixing the components according to the proportion under high-speed stirring, and adding the mixture into a double-screw extruder for extrusion granulation to obtain foamable polylactic acid-containing plastic particles; wherein the stirring speed is 500-800 rpm; the length-diameter ratio of the double-screw extruder is not more than 48, and the extrusion temperature is 110-135 ℃.
8. The use of the foamable polylactic acid-containing plastic particles according to any one of claims 1 to 6 in degradable plastics.
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