CN108164959B - Halogen-free flame-retardant polypropylene carbonate foam material and preparation method and application thereof - Google Patents
Halogen-free flame-retardant polypropylene carbonate foam material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a halogen-free flame-retardant polypropylene carbonate foam material, and a preparation method and application thereof, and belongs to the technical field of environment-friendly foam materials. The problem that the existing buffering packaging material is difficult to have buffering performance, flame retardant performance and environment-friendly performance is solved. The foam material of the present invention comprises: 100 parts of polypropylene carbonate, 10-200 parts of starch and/or modified starch, 1-16 parts of foaming agent, 0.5-5 parts of foaming nucleating agent, 10-60 parts of flame-retardant compound, 0-10 parts of flame-retardant synergist and 0-100 parts of degradable toughening resin. The foam material is obtained by an extrusion water foaming technology, the foaming multiplying power can reach 30 times, the halogen is not contained, the environment is protected, the safety is realized, the limit oxygen index can reach 35%, the UL-94 flame retardant grade can reach V-0 grade, the foam material has excellent flame retardant property and buffering property, and the foam material is suitable for being used as a packaging material.
Description
Technical Field
The invention belongs to the technical field of environment-friendly foam materials, and particularly relates to a halogen-free flame-retardant polypropylene carbonate foam material as well as a preparation method and application thereof.
Background
In recent years, with the improvement of environmental awareness, the use of halogen-free flame-retardant foam materials is receiving more and more attention and attention, with the rapid development of economy, the industrial scale of various products such as electronic and electric appliances is continuously increased, the sales volume of the products is rapidly increased, the required foam packaging materials are rapidly increased, and a large part of the foam packaging materials need to have flame retardant property. Therefore, the requirements for degradation property and flame retardance of the foam packaging material are higher and higher, so that the foam packaging material is required to have excellent buffering property, environmental protection property and certain flame retardance.
The polypropylene carbonate (PPC, also known as polypropylene carbonate or polymethyl ethylene carbonate) is a high molecular aliphatic polyester, is a carbon dioxide-propylene oxide copolymer, is one of the currently accepted green degradable plastic products, has certain rigidity and strength, is close to the mechanical properties of common plastics, needs to be degraded under specific conditions, can keep the performance for a long time unchanged under common daily conditions, is applied to the field of easily-consumed products of buffer packaging, and can solve the problem of increasing environmental pollution of buffer packaging garbage at present. However, PPC belongs to an amorphous polymer, and has large molecular chain flexibility and small intermolecular force, so that the PPC has low glass transition temperature and poor mechanical property, thereby limiting the application field of the PPC. Therefore, a large number of scholars have developed the work of modifying PPC to further expand its application range.
At present, the research on the application of PPC materials to the field of foam materials is less in China, and more recently, PPC foam packaging materials with flame retardant property are researched, wherein a lot of work is done on the aspect of water foaming technology by a subject group of Donthon researchers of the national institute of applied chemistry of Changchun, national academy of sciences, wherein the preparation technology of water foaming of PPC materials is described in detail in the doctor ' paper ' preparation technology and basic research on water foaming of high polymer foam materials ', and the density of the obtained PPC foam can be 0.031-0.872g/cm3The maximum expansion ratio can reach 40 times, and is similar to the expansion ratio of Expandable Polystyrene (EPS), but the flame retardant property of the material is not mentioned. The corresponding patent (application number CN201210284926) also defines the concrete technology of PPC water foaming, and the content does not relate to the resistance of foamAnd (4) combustion property. The research group of the Reddish researchers of the chemical research institute of the application of Changchun of China academy of sciences also does much work on the foaming work of the PPC material, and the patent (application No. 201310675554.7) mentions the chemical foaming of the PPC material and does not mention the flame retardant modification of the PPC foam material. The research on the foaming property of the PPC material is mentioned in a Master thesis 'preparation of polypropylene carbonate composite material and foaming property research thereof' by Master research of professor Pendulus of university of south China, wherein the research on the foaming property of a PPC composite material system by supercritical carbon dioxide is mainly researched, wherein the flame retardance of the PPC material is not mentioned, the subject group in Mechangshan university does much work on the application of the PPC material to a foam packaging material by the PPC material, and the research on the chemical foaming and processing modification of the PPC material is described in detail in a thesis 'chemical foaming and processing modification of polymethyl ethylene carbonate' and a patent publication No. CN1670086A by doctor research of Guangzao, wherein the flame retardance modification of the PPC material is not involved.
Disclosure of Invention
The invention aims to solve the technical problem that the existing buffer packaging material is difficult to have the buffer performance, the flame retardant performance and the environment-friendly performance, and provides a halogen-free flame retardant polypropylene carbonate foam material and a preparation method and application thereof.
In order to solve the technical problems, the invention provides the following technical solutions:
a halogen-free flame retardant polypropylene carbonate foam comprising:
the flame-retardant compound consists of a component A and a component B in a mass ratio of (0.2-0.8) to (0.8-0.2), wherein the component A is one or more of aluminum hydroxide, magnesium hydroxide and hydrotalcite, and the component B is one or more of coated ammonium polyphosphate, coated red phosphorus, melamine, tripolyphosphoric acid cyanurate, melamine phosphate and ammonium dihydrogen phosphate;
the flame-retardant synergist is one or two of zinc borate, expandable graphite, boric acid and molybdenum oxide.
Preferably, the starch is one or a mixture of more of corn starch, wheat starch, potato starch, tapioca starch, mung bean starch, waxy corn starch and sweet potato starch.
Preferably, the modified starch is one or a mixture of more of pregelatinized starch, acidified starch, oxidized starch, etherified starch and esterified starch, and the starch in the modified starch is one of corn starch, wheat starch, potato starch, tapioca starch, mung bean starch, waxy corn starch and sweet potato starch.
Preferably, the blowing agent is water.
Preferably, the foaming nucleating agent is one or a mixture of more of calcium carbonate, talcum powder, boron nitride, silicon dioxide, zinc oxide, calcium oxide, magnesium oxide, kaolin, diatomite, citric acid, mica, sodium chloride, magnesium sulfate, sodium benzoate, aluminum oxide and titanium dioxide.
Preferably, the degradable toughening resin is one or a mixture of more of poly (butylene adipate terephthalate), poly (propylene carbonate) polyurethane elastomer, polyhydroxyalkanoate, polycaprolactone and polybutylene succinate.
The invention also provides a preparation method of the halogen-free flame-retardant polypropylene carbonate foam material, which comprises the following steps: according to the proportion, the polypropylene carbonate, the starch and/or the modified starch, the foaming agent, the foaming nucleating agent, the flame-retardant compound, the flame-retardant synergist and the degradable toughening resin are stirred and mixed uniformly, and then the mixture is added into continuous extrusion equipment to be extruded and foamed to obtain the foaming material.
Preferably, the stirring time is 1-8min, and the rotation speed is 500-.
Preferably, the continuous extrusion device is a single screw extruder or a twin screw extruder, and the length-diameter ratio of the continuous extrusion device is greater than 30.
The invention also provides application of the halogen-free flame-retardant polypropylene carbonate foam material as a packaging material.
Compared with the prior art, the invention has the beneficial effects that:
1. the halogen-free flame-retardant polypropylene carbonate foam material prepared by the invention has the advantages that the foaming multiplying power can reach 30 times, the limiting oxygen index can reach 35%, the UL94 can reach V-0 level, and the halogen-free flame-retardant polypropylene carbonate foam material has excellent flame retardant property, buffering property and environmental protection property, and is suitable for being used as a buffering packaging material.
2. The preparation method of the halogen-free flame-retardant polypropylene carbonate foam material does not use a halogen-containing flame-retardant compound, is environment-friendly, and emphasizes that the addition of the flame-retardant compound does not reduce the foaming ratio under the existence of foaming agent water by a specific flame-retardant compound compounding technology, the foaming ratio can reach more than 30, the foaming state of the whole mixture system is ensured, the final foam material can keep light weight, and the buffering performance is kept.
3. The preparation method of the halogen-free flame-retardant polypropylene carbonate foam material provided by the invention blends the PPC and starch, the starch is used as a carrier of a foaming agent and also forms a char forming agent in a flame-retardant system, the addition of the starch can improve the glass transition temperature of the PPC to a certain extent, and the PPC/starch material prepared by water-assisted processing has more excellent buffer performance, the application of the PPC is expanded, the improvement of the use performance is ensured, and the price is reduced.
4. The preparation method of the halogen-free flame-retardant polypropylene carbonate foam material uses water as a foaming agent, and has the advantages of simple technical production process, environmental protection, safety and strong operability.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention in conjunction with the following detailed description, but it is to be understood that the description is intended to further illustrate the nature and advantages of the invention rather than to limit the scope of the appended claims.
The invention provides a halogen-free flame-retardant polypropylene carbonate foam material, which comprises the following components: 100 parts of polypropylene carbonate, 10-200 parts of starch and/or modified starch, 1-16 parts of foaming agent, 0.5-5 parts of foaming nucleating agent, 10-60 parts of flame-retardant compound, 0-10 parts of flame-retardant synergist and 0-100 parts of degradable toughening resin. The foaming ratio is 12-35, the Limiting Oxygen Index (LOI) is 25-35%, and UL94 reaches V-0 level.
Wherein the starch is one or more of corn starch, wheat starch, potato starch, tapioca starch, mung bean starch, waxy corn starch and sweet potato starch. The modified starch is one or more of pregelatinized starch, acidified starch, oxidized starch, etherified starch and esterified starch, and the starch in the modified starch is one of corn starch, wheat starch, potato starch, tapioca starch, mung bean starch, waxy corn starch and sweet potato starch. In the invention, the starch is used as a carrier of the foaming agent and also constitutes a char forming agent in a flame retardant system, the addition of the starch can improve the glass transition temperature of the PPC to a certain extent, and the PPC/starch material prepared by water-assisted processing has more excellent slow performance, so that the application of the PPC is expanded, the improvement of the use performance is ensured, and the price is reduced. The starch and/or modified starch is preferably 30 to 180 parts by weight, more preferably 70 to 120 parts by weight.
The foaming agent is water. The blowing agent is preferably 6 to 13 parts by weight, more preferably 8 to 12 parts by weight.
The foaming nucleating agent is one or a mixture of more of calcium carbonate, talcum powder, boron nitride, silicon dioxide, zinc oxide, calcium oxide, magnesium oxide, kaolin, diatomite, citric acid, mica, sodium chloride, magnesium sulfate, sodium benzoate, aluminum oxide and titanium dioxide. The foaming nucleating agent is preferably 1 to 4 parts by weight, more preferably 2 to 4 parts by weight.
The flame-retardant compound consists of a component A and a component B in a mass ratio of (0.2-0.8) to (0.8-0.2), wherein the component A is one or more of aluminum hydroxide, magnesium hydroxide and hydrotalcite, preferably the mixture of two or three of the aluminum hydroxide, the magnesium hydroxide and the hydrotalcite, and the component B is one or more of coated ammonium polyphosphate, coated red phosphorus, melamine, tripolyphosphoric acid cyanurate, melamine phosphate and ammonium dihydrogen phosphate. The flame-retardant formulation is preferably 20 to 50 parts by weight. It should be noted that the composition and proportion of the flame retardant compound must be within the limited range, and if the flame retardant compound exceeds the limited range or is replaced by other flame retardant compounds, the foaming ratio of the foam material is reduced in the presence of the foaming agent water, and the cushioning performance of the foam material cannot be realized.
The flame-retardant synergist is one or a mixture of more of zinc borate, expandable graphite, boric acid and molybdenum oxide. The flame retardant synergist the flame retardant formulation is preferably 2-8 parts by weight, more preferably 4-6 parts by weight.
The degradable toughening resin is preferably one or a mixture of more of polybutylene adipate terephthalate (PBAT), polypropylene carbonate polyurethane elastomer (PPC-TPU), Polyhydroxyalkanoates (PHAs), Polycaprolactone (PCL) and polybutylene succinate (PBS). The degradable toughening resin is preferably 10 to 80 parts by weight, more preferably 20 to 80 parts by weight.
According to the preparation method of the halogen-free flame-retardant polypropylene carbonate foam material, according to the formula, polypropylene carbonate, starch and/or modified starch, a foaming agent, a foaming nucleating agent, a flame-retardant compound, a flame-retardant synergist and degradable toughening resin are added into a high-speed stirrer to be uniformly mixed, and then continuous extrusion equipment is added to extrude and foam to prepare the foam material.
Wherein the high-speed stirring time is 1-8min, and the rotating speed is 500-. The continuous extrusion equipment can be a single screw extruder or a double screw extruder; in order to plasticize the mixture sufficiently in the screw, the screw length/diameter ratio used is preferably greater than 30. The extrusion temperature is preferably from 80 to 175 ℃.
The halogen-free flame-retardant polypropylene carbonate foam material can be used as a packaging material, and is particularly suitable for being used as a logistics buffering packaging material.
The present invention is further illustrated by the following examples. The substances listed in the examples are commercially available and readily available.
Example 1
The halogen-free flame-retardant polypropylene carbonate foam material is composed of 100 parts by weight of polypropylene carbonate, 10 parts by weight of corn starch, 3 parts by weight of foaming agent water, 0.5 part by weight of foaming nucleating agent talcum powder, 10 parts by weight of flame-retardant compound (wherein 2 parts by weight of magnesium hydroxide, 3 parts by weight of aluminum hydroxide, 3 parts by weight of coated ammonium polyphosphate and 2 parts by weight of cyanuric phosphate) and 5 parts by weight of flame-retardant synergist (wherein 2 parts by weight of zinc borate and 3 parts by weight of expandable graphite).
The preparation method of the halogen-free flame-retardant polypropylene carbonate foam material comprises the steps of weighing the components according to the proportion, adding the corn starch, the polypropylene carbonate, the foaming nucleating agent, the flame-retardant compound and the flame-retardant synergist into a high-speed stirrer, stirring at a high speed for 2min, adding the foaming agent, continuing stirring at a high speed for 3min, wherein the stirring speed is 1200 revolutions per minute all the time, adding the blended materials into a double-screw extruder, and directly extruding and foaming to obtain the halogen-free flame-retardant polypropylene carbonate foam material.
And (3) setting parameters of an extrusion foaming system:
the temperature is set to 80 ℃, 90 ℃, 140 ℃, 160 ℃, 175 ℃, 170 ℃ and 150 ℃ of a nose neck mold from the feeding port in sequence;
the screw rotating speed of the extruder is 150 r/min, the feeding rotating speed is 15 r/min, and the length-diameter ratio of the screw is 40.
The obtained foam material was tested, and the results were: the foaming ratio was 6, the Limiting Oxygen Index (LOI) was 26.5%, and UL94 was V-1 grade.
Example 2
The halogen-free flame-retardant polypropylene carbonate foam material is composed of 100 parts by weight of polypropylene carbonate, 30 parts by weight of PPC-TPU, 20 parts by weight of wheat starch, 30 parts by weight of corn starch, 5 parts by weight of foaming agent water, 2 parts by weight of foaming nucleating agent calcium carbonate, 20 parts by weight of flame-retardant compound (wherein 5 parts by weight of magnesium hydroxide, 5 parts by weight of aluminum hydroxide, 8 parts by weight of coated ammonium polyphosphate and 2 parts by weight of tripolyphosphoric acid cyanuric acid salt) and 6 parts by weight of flame-retardant synergist (wherein 3 parts by weight of zinc borate and 3 parts by weight of expandable graphite).
The preparation method of the halogen-free flame-retardant polypropylene carbonate foam material comprises the steps of weighing the components according to the proportion, adding the wheat starch, the corn starch, the polypropylene carbonate, the PPC-TPU, the foaming nucleating agent, the flame-retardant compound and the flame-retardant synergist into a high-speed stirrer, stirring at a high speed for 2min, adding the foaming agent, continuing stirring at a high speed for 5min, wherein the stirring speed is 500 revolutions per minute, adding the blended materials into a double-screw extruder, and directly extruding and foaming to obtain the halogen-free flame-retardant polypropylene carbonate foam material.
And (3) setting parameters of an extrusion foaming system:
the temperature is set to 80 ℃, 90 ℃, 140 ℃, 160 ℃, 175 ℃, 170 ℃ and 150 ℃ of a nose neck mold from the feeding port in sequence;
the screw rotating speed of the extruder is 200 r/min, the feeding rotating speed is 20 r/min, and the length-diameter ratio of the screw is 40.
The obtained foam material was tested, and the results were: the foaming ratio was 8, the Limiting Oxygen Index (LOI) was 28%, and UL94 was V-1 grade.
Example 3
The halogen-free flame-retardant polypropylene carbonate foam material is composed of 100 parts by weight of polypropylene carbonate, 80 parts by weight of tapioca starch, 10 parts by weight of foaming agent water, 3 parts by weight of foaming nucleating agent talcum powder, 40 parts by weight of flame-retardant compound (wherein 15 parts by weight of magnesium hydroxide, 15 parts by weight of hydrotalcite and 10 parts by weight of coated ammonium polyphosphate), 5 parts by weight of flame-retardant synergist (wherein 2 parts by weight of zinc borate and 3 parts by weight of expandable graphite) and 50 parts by weight of degradable toughening resin (wherein 10 parts by weight of polycaprolactone and 40 parts by weight of poly (butylene adipate terephthalate)).
The preparation method of the halogen-free flame-retardant polypropylene carbonate foam material comprises the steps of weighing the components according to the proportion, adding the cassava starch, the polypropylene carbonate, the foaming nucleating agent and the degradable toughening resin into a high-speed stirrer, stirring at a high speed for 2min, adding the foaming agent, the flame-retardant compound and the flame-retardant synergist, continuing stirring at a high speed for 3min, wherein the stirring speed is 1200 r/min, adding the blended materials into a double-screw extruder, and directly extruding and foaming to obtain the halogen-free flame-retardant polypropylene carbonate foam material.
And (3) setting parameters of an extrusion foaming system:
the temperature is set to be 100 ℃, 120 ℃, 140 ℃, 160 ℃, 190 ℃, 175 ℃, 170 ℃ and 170 ℃ from the feeding port in turn;
the screw rotating speed of the extruder is 150 r/min, the feeding rotating speed is 15 r/min, and the length-diameter ratio of the screw is 40.
The obtained foam material was tested, and the results were: the foaming ratio was 12, the Limiting Oxygen Index (LOI) was 26%, and UL94 was V-0 grade.
Example 4
The halogen-free flame-retardant polypropylene carbonate foam material is composed of 100 parts by weight of polypropylene carbonate, 50 parts by weight of waxy corn starch, 5 parts by weight of foaming agent water, 2 parts by weight of foaming nucleating agent talcum powder, 20 parts by weight of flame-retardant compound (wherein 2 parts by weight of hydrotalcite, 2 parts by weight of aluminum hydroxide and 16 parts by weight of cyanuric phosphate) and 5 parts by weight of flame-retardant synergist (wherein 2 parts by weight of zinc borate and 3 parts by weight of expandable graphite).
The preparation method of the halogen-free flame-retardant polypropylene carbonate foam material comprises the steps of weighing the components according to the proportion, adding the waxy corn starch, the polypropylene carbonate, the foaming nucleating agent, the flame-retardant compound and the flame-retardant synergist into a high-speed stirrer, stirring at a high speed for 2min, adding the foaming agent, continuing stirring at a high speed for 3min, wherein the stirring speed is 1200 revolutions per minute, adding the blended materials into a double-screw extruder, and directly extruding and foaming to obtain the halogen-free flame-retardant polypropylene carbonate foam material.
And (3) setting parameters of an extrusion foaming system:
the temperature is set to 70 ℃, 100 ℃, 140 ℃, 160 ℃, 175 ℃, 170 ℃ and 140 ℃ of a nose neck mold from the feeding port in sequence;
the screw rotation speed of the extruder is 200 r/min, and the feeding rotation speed is 15 r/min.
The obtained foam material was tested, and the results were: the foaming ratio was 15, the Limiting Oxygen Index (LOI) was 27%, and UL94 was V-1 grade.
Example 5
The halogen-free flame-retardant polypropylene carbonate foam material is composed of 100 parts by weight of polypropylene carbonate, 50 parts by weight of waxy corn starch, 5 parts by weight of foaming agent water, 2 parts by weight of foaming nucleating agent talcum powder, 20 parts by weight of flame-retardant compound (wherein 2 parts by weight of hydrotalcite, 2 parts by weight of aluminum hydroxide and 16 parts by weight of cyanuric phosphate) and 5 parts by weight of flame-retardant synergist (wherein 2 parts by weight of zinc borate and 3 parts by weight of expandable graphite).
The preparation method of the halogen-free flame-retardant polypropylene carbonate foam material comprises the steps of weighing the components according to the proportion, adding the waxy corn starch, the polypropylene carbonate, the foaming nucleating agent, the flame-retardant compound and the flame-retardant synergist into a high-speed stirrer, stirring at a high speed for 2min, adding the foaming agent, continuing stirring at a high speed for 3min, wherein the stirring speed is 1200 revolutions per minute, adding the blended materials into a double-screw extruder, and directly extruding and foaming to obtain the halogen-free flame-retardant polypropylene carbonate foam material.
And (3) setting parameters of an extrusion foaming system:
the temperature is set to 70 ℃, 100 ℃, 140 ℃, 160 ℃, 175 ℃, 170 ℃ and 140 ℃ of a nose neck mold from the feeding port in sequence;
the screw rotation speed of the extruder is 200 r/min, and the feeding rotation speed is 15 r/min.
The obtained foam material was tested, and the results were: the foaming ratio was 16, the Limiting Oxygen Index (LOI) was 29%, and UL94 was V-0 grade.
Example 6
The halogen-free flame-retardant polypropylene carbonate foam material is composed of 100 parts by weight of polypropylene carbonate, 100 parts by weight of corn starch, 50 parts by weight of pregelatinized starch, 10 parts by weight of foaming agent water, 1 part by weight of foaming nucleating agent talcum powder, 25 parts by weight of flame-retardant compound (10 parts by weight of magnesium hydroxide, 10 parts by weight of aluminum hydroxide, 3 parts by weight of coated ammonium polyphosphate and 2 parts by weight of tripolyphosphate cyanurate), 10 parts by weight of flame-retardant synergist (5 parts by weight of zinc borate and 5 parts by weight of expandable graphite) and 30 parts by weight of degradable toughening resin (15 parts by weight of polypropylene carbonate polyurethane elastomer and 15 parts by weight of poly adipate-butylene terephthalate).
The preparation method of the halogen-free flame-retardant polypropylene carbonate foam material comprises the steps of weighing the components according to the proportion, adding the corn starch, the pregelatinized starch, the polypropylene carbonate, the foaming nucleating agent and the degradable toughening resin into a high-speed stirrer, stirring for 2min at a high speed, adding the foaming agent, the flame-retardant compound and the flame-retardant synergist, continuing stirring for 3min at a high speed, wherein the stirring speed is 800 revolutions per minute all the time, adding the blended material into a single-screw extruder, and directly extruding and foaming to obtain the halogen-free flame-retardant polypropylene carbonate foam material.
And (3) setting parameters of an extrusion foaming system:
the temperature setting is 60 ℃, 110 ℃, 160 ℃, 175 ℃, 160 ℃ and 145 ℃ from the feeding port in turn;
the screw rotating speed of the extruder is 180 r/min, the feeding rotating speed is 20 r/min, and the length-diameter ratio of the screw is 40.
The obtained foam material was tested, and the results were: the foaming ratio was 20, the Limiting Oxygen Index (LOI) was 29%, and UL94 was V-0 grade.
Example 7
The halogen-free flame-retardant polypropylene carbonate foam material is composed of 100 parts by weight of polypropylene carbonate, 50 parts by weight of tapioca starch, 50 parts by weight of corn starch, 10 parts by weight of foaming agent, 5 parts by weight of foaming nucleating agent talcum powder, 20 parts by weight of flame-retardant compound (wherein 8 parts by weight of magnesium hydroxide, 6 parts by weight of aluminum hydroxide, 3 parts by weight of coated ammonium polyphosphate and 3 parts by weight of ammonium dihydrogen phosphate) and 40 parts by weight of degradable toughening resin (wherein 20 parts by weight of polycaprolactone and 20 parts by weight of poly (adipic acid-co-butylene terephthalate)).
The preparation method of the halogen-free flame-retardant polypropylene carbonate foam material comprises the steps of weighing the components according to the proportion, adding the cassava starch, the corn starch, the polypropylene carbonate, the foaming nucleating agent, the flame-retardant compound and the degradable toughening resin into a high-speed stirrer, stirring at a high speed for 3min, adding the foaming agent, continuing stirring at a high speed for 3min, wherein the stirring speed is 1000 revolutions per minute, adding the blended material into a double-screw extruder, and directly extruding and foaming to obtain the halogen-free flame-retardant polypropylene carbonate foam material.
And (3) setting parameters of an extrusion foaming system:
the temperature is set to 80 ℃, 90 ℃, 140 ℃, 160 ℃, 185 ℃, 175 ℃, 170 ℃ and 150 ℃ of a nose neck mold from the feeding port in sequence;
the screw rotating speed of the extruder is 150 r/min, the feeding rotating speed is 15 r/min, and the length-diameter ratio of the screw is 40.
The obtained foam material was tested, and the results were: the foaming ratio was 25, the Limiting Oxygen Index (LOI) was 27%, and UL94 was V-1 grade.
Example 8
The halogen-free flame-retardant polypropylene carbonate foam material is composed of 100 parts by weight of polypropylene carbonate, 150 parts by weight of waxy corn starch, 12 parts by weight of foaming agent water, 2 parts by weight of foaming nucleating agent talcum powder, 40 parts by weight of flame-retardant compound (wherein 3 parts by weight of magnesium hydroxide, 4 parts by weight of aluminum hydroxide, 3 parts by weight of hydrotalcite, 20 parts by weight of coated ammonium polyphosphate, 5 parts by weight of coated red phosphorus and 5 parts by weight of cyanuric cyanurate), 4 parts by weight of flame-retardant synergist (wherein 2 parts by weight of boric acid and 2 parts by weight of expandable graphite) and 20 parts by weight of degradable toughening resin (wherein 10 parts by weight of polycaprolactone and 10 parts by weight of polybutylene adipate terephthalate).
The preparation method of the halogen-free flame-retardant polypropylene carbonate foam material comprises the steps of weighing the components according to the proportion, adding the waxy corn starch, the polypropylene carbonate, the foaming nucleating agent and the degradable toughening resin into a high-speed stirrer, stirring at a high speed for 3min, adding the foaming agent, the flame-retardant compound and the flame-retardant synergist, continuing stirring at a high speed for 2min, wherein the stirring speed is 1000 revolutions per minute, adding the blended material into a double-screw extruder, and directly extruding and foaming to obtain the halogen-free flame-retardant polypropylene carbonate foam material.
And (3) setting parameters of an extrusion foaming system:
the temperature setting is 60 ℃, 80 ℃, 140 ℃, 160 ℃, 185 ℃, 175 ℃, 170 ℃ and 150 ℃ of a nose neck mold from the feeding port in sequence;
the screw rotating speed of the extruder is 150 r/min, the feeding rotating speed is 18 r/min, and the length-diameter ratio of the screw is 40.
The obtained foam material was tested, and the results were: the foaming ratio was 30, the Limiting Oxygen Index (LOI) was 28%, and UL94 was V-0 grade.
Example 9
The halogen-free flame-retardant polypropylene carbonate foam material is prepared from 100 parts by weight of polypropylene carbonate, 200 parts by weight of waxy corn starch, 15 parts by weight of foaming agent water, 3 parts by weight of foaming nucleating agent talcum powder, 30 parts by weight of flame-retardant compound (wherein 10 parts by weight of magnesium hydroxide, 10 parts by weight of aluminum hydroxide and 10 parts by weight of coated red phosphorus) and 5 parts by weight of flame-retardant synergist (wherein 2 parts by weight of zinc borate and 3 parts by weight of expandable graphite).
The preparation method of the halogen-free flame-retardant polypropylene carbonate foam material comprises the steps of weighing the components according to the proportion, adding the waxy corn starch, the polypropylene carbonate, the foaming nucleating agent, the flame-retardant compound and the flame-retardant synergist into a high-speed stirrer, stirring at a high speed for 2min, adding the foaming agent, continuing stirring at a high speed for 3min, wherein the stirring speed is 1000 revolutions per minute all the time, adding the blended material into a single-screw extruder, and directly extruding and foaming to obtain the halogen-free flame-retardant polypropylene carbonate foam material.
And (3) setting parameters of an extrusion foaming system:
the temperature is set to 80 ℃, 110 ℃, 180 ℃, 175 ℃, 170 ℃ and 170 ℃ from the feeding port in turn;
the screw rotating speed of the extruder is 150 r/min, the feeding rotating speed is 18 r/min, and the length-diameter ratio of the screw is 38.
The obtained foam material was tested, and the results were: the foaming ratio was 30, the Limiting Oxygen Index (LOI) was 31%, and UL94 was V-0 grade.
Example 10
The halogen-free flame-retardant polypropylene carbonate foam material is composed of 100 parts by weight of polypropylene carbonate, 100 parts by weight of corn starch, 50 parts by weight of pregelatinized starch, 12 parts by weight of foaming agent water, 4 parts by weight of foaming nucleating agent talcum powder, 60 parts by weight of flame-retardant compound (wherein 20 parts by weight of magnesium hydroxide, 10 parts by weight of aluminum hydroxide, 20 parts by weight of coated ammonium polyphosphate and 10 parts by weight of tripolyphosphate cyanurate), 6 parts by weight of flame-retardant synergist (wherein 5 parts by weight of zinc borate and 1 part by weight of expandable graphite) and 30 parts by weight of degradable toughening resin (wherein 15 parts by weight of polypropylene carbonate polyurethane elastomer and 15 parts by weight of poly adipate-butylene terephthalate).
The preparation method of the halogen-free flame-retardant polypropylene carbonate foam material comprises the steps of weighing the components according to the proportion, adding the corn starch, the pregelatinized starch, the polypropylene carbonate, the foaming nucleating agent and the degradable toughening resin into a high-speed stirrer, stirring for 2min at a high speed, adding the foaming agent, the flame-retardant compound and the flame-retardant synergist, continuing stirring for 3min at a high speed, wherein the stirring speed is 800 revolutions per minute all the time, adding the blended material into a single-screw extruder, and directly extruding and foaming to obtain the halogen-free flame-retardant polypropylene carbonate foam material.
And (3) setting parameters of an extrusion foaming system:
the temperature setting is 60 ℃, 110 ℃, 160 ℃, 175 ℃, 160 ℃ and 145 ℃ from the feeding port in turn;
the screw rotating speed of the extruder is 180 r/min, the feeding rotating speed is 20 r/min, and the length-diameter ratio of the screw is 40.
The obtained foam material was tested, and the results were: the foaming ratio was 19, the Limiting Oxygen Index (LOI) was 35%, and UL94 was V-0 grade.
Example 11
The halogen-free flame-retardant polypropylene carbonate foam material is composed of 100 parts by weight of polypropylene carbonate, 100 parts by weight of waxy corn starch, 50 parts by weight of cassava starch, 50 parts by weight of corn starch, 15 parts by weight of foaming agent water, 2 parts by weight of foaming nucleating agent talcum powder, 60 parts by weight of flame-retardant compound (wherein 20 parts by weight of magnesium hydroxide, 20 parts by weight of aluminum hydroxide, 10 parts by weight of coated ammonium polyphosphate, 5 parts by weight of coated red phosphorus, 5 parts by weight of tripolyphosphate cyanurate), 4 parts by weight of flame-retardant synergist (wherein 2 parts by weight of molybdenum oxide and 2 parts by weight of expandable graphite) and 100 parts by weight of degradable toughening resin (wherein 20 parts by weight of Polyhydroxyalkanoates (PHAs), 20 parts by weight of polybutylene adipate terephthalate (PBAT) and 60 parts by weight of polybutylene succinate (PBS).
The preparation method of the halogen-free flame-retardant polypropylene carbonate foam material comprises the steps of weighing the components according to the proportion, adding waxy corn starch, tapioca starch, corn starch, polypropylene carbonate, a foaming nucleating agent, a flame-retardant compound, a flame-retardant synergist and degradable toughening resin into a high-speed stirrer, stirring at a high speed for 4min, adding a foaming agent, continuing stirring at a high speed for 4min, wherein the stirring speed is 500 revolutions per minute, adding the blended material into a double-screw extruder, and directly extruding and foaming to obtain the halogen-free flame-retardant polypropylene carbonate foam material.
And (3) setting parameters of an extrusion foaming system:
the temperature is set to 80 ℃, 90 ℃, 140 ℃, 170 ℃, 180 ℃, 175 ℃, 170 ℃ and 150 ℃ of a nose neck mold from the feeding port in sequence;
the screw rotating speed of the extruder is 150 r/min, the feeding rotating speed is 18 r/min, and the length-diameter ratio of the screw is 38.
The obtained foam material was tested, and the results were: the expansion ratio was 15, the Limiting Oxygen Index (LOI) was 35%, and UL94 was V-0 grade.
Comparative example 1
The halogen-free flame-retardant polypropylene carbonate foam material is composed of 100 parts by weight of polypropylene carbonate, 100 parts by weight of waxy corn starch, 50 parts by weight of cassava starch, 50 parts by weight of corn starch, 15 parts by weight of foaming agent water, 2 parts by weight of foaming nucleating agent talcum powder, 60 parts by weight of magnesium hydroxide, 4 parts by weight of flame-retardant synergistic agent (molybdenum oxide 2 parts by weight and expandable graphite 2 parts by weight) and 100 parts by weight of degradable toughening resin (polyhydroxyalkanoates (PHAs)20 parts by weight, polybutylene adipate terephthalate (PBAT)20 parts by weight and polybutylene succinate (PBS)60 parts by weight.
The preparation method of the halogen-free flame-retardant polypropylene carbonate foam material comprises the steps of weighing the components according to the proportion, adding waxy corn starch, tapioca starch, corn starch, polypropylene carbonate, a foaming nucleating agent, magnesium hydroxide, a flame-retardant synergist and degradable toughening resin into a high-speed stirrer, stirring at a high speed for 4min, adding a foaming agent, continuing stirring at a high speed for 4min, wherein the stirring speed is 500 revolutions per minute, adding the blended material into a double-screw extruder, and directly extruding and foaming to obtain the halogen-free flame-retardant polypropylene carbonate foam material.
And (3) setting parameters of an extrusion foaming system:
the temperature is set to 80 ℃, 90 ℃, 140 ℃, 170 ℃, 180 ℃, 175 ℃, 170 ℃ and 150 ℃ of a nose neck mold from the feeding port in sequence;
the screw rotating speed of the extruder is 150 r/min, the feeding rotating speed is 18 r/min, and the length-diameter ratio of the screw is 38.
The obtained foam material was tested, and the results were: the foaming ratio was 15, the Limiting Oxygen Index (LOI) was 25%, and UL94 was V-2 grade.
Comparative example 2
The halogen-free flame-retardant polypropylene carbonate foam material is composed of 100 parts by weight of polypropylene carbonate, 100 parts by weight of waxy corn starch, 50 parts by weight of cassava starch, 50 parts by weight of corn starch, 15 parts by weight of foaming agent water, 2 parts by weight of foaming nucleating agent talcum powder, 60 parts by weight of coated ammonium polyphosphate, 4 parts by weight of flame-retardant synergist (wherein 2 parts by weight of molybdenum oxide and 2 parts by weight of expandable graphite) and 100 parts by weight of degradable toughening resin (wherein 20 parts by weight of Polyhydroxyalkanoates (PHAs), 20 parts by weight of polybutylene adipate terephthalate (PBAT) and 60 parts by weight of polybutylene succinate (PBS).
The preparation method of the halogen-free flame-retardant polypropylene carbonate foam material comprises the steps of weighing the components according to the proportion, adding waxy corn starch, tapioca starch, corn starch, polypropylene carbonate, a foaming nucleating agent, coated ammonium polyphosphate, a flame-retardant synergist and degradable toughening resin into a high-speed stirrer, stirring at a high speed for 4min, adding a foaming agent, continuing stirring at a high speed for 4min, wherein the stirring speed is 500 revolutions per minute, adding the blended material into a double-screw extruder, and directly extruding and foaming to obtain the halogen-free flame-retardant polypropylene carbonate foam material.
And (3) setting parameters of an extrusion foaming system:
the temperature is set to 80 ℃, 90 ℃, 140 ℃, 170 ℃, 180 ℃, 175 ℃, 170 ℃ and 150 ℃ of a nose neck mold from the feeding port in sequence;
the screw rotating speed of the extruder is 150 r/min, the feeding rotating speed is 18 r/min, and the length-diameter ratio of the screw is 38.
The obtained foam material was tested, and the results were: the foaming ratio was 3, the Limiting Oxygen Index (LOI) was 28%, and UL94 was V-0 grade.
It is obvious that the above description of the embodiments is only intended to assist understanding of the method and the core idea of the present invention. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. A halogen-free flame-retardant polypropylene carbonate foam material is characterized by comprising the following components:
the flame-retardant compound consists of a component A and a component B in a mass ratio of (0.2-0.8) to (0.8-0.2), wherein the component A is one or more of aluminum hydroxide, magnesium hydroxide and hydrotalcite, and the component B is one or more of coated ammonium polyphosphate, coated red phosphorus, melamine, tripolyphosphoric acid cyanurate, melamine phosphate and ammonium dihydrogen phosphate;
the flame-retardant synergist is one or two of zinc borate, expandable graphite, boric acid and molybdenum oxide.
2. The halogen-free flame retardant polypropylene carbonate foam material of claim 1, wherein the starch is one or a mixture of corn starch, wheat starch, potato starch, tapioca starch, mung bean starch, waxy corn starch, and sweet potato starch.
3. The halogen-free flame retardant polypropylene carbonate foam material of claim 1, wherein the modified starch is one or a mixture of more of pregelatinized starch, acidified starch, oxidized starch, etherified starch and esterified starch, and the starch in the modified starch is one of corn starch, wheat starch, potato starch, tapioca starch, mung bean starch, waxy corn starch and sweet potato starch.
4. The halogen-free, flame retardant polypropylene carbonate foam of claim 1 wherein the blowing agent is water.
5. The halogen-free flame retardant polypropylene carbonate foam material as claimed in claim 1, wherein the foaming nucleating agent is one or a mixture of calcium carbonate, talcum powder, boron nitride, silicon dioxide, zinc oxide, calcium oxide, magnesium oxide, kaolin, diatomite, citric acid, mica, sodium chloride, magnesium sulfate, sodium benzoate, aluminum oxide and titanium dioxide.
6. The halogen-free flame retardant polypropylene carbonate foam material of claim 1, wherein the degradable toughening resin is one or a mixture of polybutylene adipate-co-terephthalate, polypropylene carbonate polyurethane elastomer, polyhydroxyalkanoate, polycaprolactone and polybutylene succinate.
7. The preparation method of the halogen-free flame-retardant polypropylene carbonate foam material according to any one of claims 1 to 6, characterized in that polypropylene carbonate, starch and/or modified starch, foaming agent, foaming nucleating agent, flame-retardant compound, flame-retardant synergist and degradable toughening resin are mixed uniformly according to the mixture ratio, added into continuous extrusion equipment, extruded and foamed to obtain the foam material.
8. The method as claimed in claim 7, wherein the stirring time is 1-8min, and the rotation speed is 500-2000 rpm.
9. The method for preparing halogen-free flame retardant polypropylene carbonate foam material according to claim 7, wherein the continuous extrusion device is a single screw extruder or a twin screw extruder, and the length-diameter ratio of the continuous extrusion device is more than 30.
10. Use of the halogen free flame retardant polypropylene carbonate foam according to any of claims 1 to 6 as packaging material.
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| CN102276971A (en) * | 2011-07-21 | 2011-12-14 | 中山大学 | Fully-degradable polymethyl methacrylate ethylene carbonic ester foaming material and preparation method thereof |
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