CN112143204B - Carbon dioxide-based copolymer foamed plastic and preparation method thereof - Google Patents
Carbon dioxide-based copolymer foamed plastic and preparation method thereof Download PDFInfo
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Abstract
The invention provides a carbon dioxide-based copolymer foam plastic which is prepared from the following raw materials: 100 parts by weight of a carbon dioxide-epoxycyclohexane copolymer; 5 to 30 parts by weight of a carbon dioxide-propylene oxide copolymer; 2-20 parts of toughening agent; 0.1 to 1 part by weight of ester exchanger. Compared with the prior art, the carbon dioxide-based copolymer foamed plastic provided by the invention takes the carbon dioxide-epoxy cyclohexane copolymer as a main foaming material, and is matched with other components with specific contents to realize better interaction, and the obtained carbon dioxide-based copolymer foamed plastic is semi-rigid or rigid foam and has good foaming performance, elastic modulus and compressive strength. Experimental results show that the foaming ratio of the carbon dioxide-based copolymer foamed plastic provided by the invention can reach 10 times, the elastic modulus can reach 804MPa, and the compression strength (50%) can reach 26 MPa.
Description
Technical Field
The invention relates to the technical field of biodegradable foamed plastics, in particular to a carbon dioxide-based copolymer foamed plastic and a preparation method thereof.
Background
In the prior art, foamed plastics such as polyolefin plastic foams and polyurethane plastic foams have been widely used as functional materials such as heat insulating materials and sound insulating materials because of their advantages such as light weight, heat insulation, sound absorption and vibration absorption, and also as housing materials for vehicles such as vehicles and ships. These plastic foams are light in weight and bulky when discarded, and therefore difficult to reuse. In addition, the plastic foam causes environmental pollution even if buried or burned.
In recent years, with global warming, carbon dioxide, a greenhouse gas, has attracted attention, and biodegradation of synthetic polymers using carbon dioxide as an inexpensive carbon resource has become a hot point of research. The carbon dioxide-epoxycyclohexane copolymer (PCHC) is another carbon dioxide-based biodegradable material, is expected to be used at 100 ℃ due to the higher glass transition temperature (106-110 ℃), is suitable for preparing hard biodegradable foam due to the high tensile strength of the PCHC, has wide application in the prior semi-hard and hard foams, is commonly used for heat insulation materials, sandwich materials, packaging materials, sound insulation and shock resistance materials, building materials and the like, is generally difficult to recycle in the application scenes, and is very suitable for being replaced by the biodegradable material; however, PCHC has the problems of large brittleness, poor thermal stability, narrow processing window and the like, a common chemical foaming method has high processing temperature and high requirement on the melt strength of a material, the PCHC cannot meet the process requirement, and the PCHC is physically foamed by using carbon dioxide alone and has the problems of low foaming ratio of only 2-4 times, brittle foam and insufficient strength. The carbon dioxide-propylene oxide copolymer (PPC) has low cost, good gas barrier property, proper mechanical property and good application potential, and because the PPC and the carbon dioxide have good affinity, when the carbon dioxide is used as a physical foaming agent for foaming, higher foaming multiplying power can be obtained, and the PPC has more advantages; chinese granted patents CN103665308B, CN103304977B, CN104140656B and CN105368028B all disclose a biodegradable foam prepared by PPC and a method thereof. However, the characteristics of PPC itself determine that foams produced using PPC as a main foaming material are flexible foams, and thus carbon dioxide-based copolymers are still limited in the production of semi-rigid and rigid foams.
Disclosure of Invention
In view of the above, the present invention provides a carbon dioxide-based copolymer foam and a preparation method thereof, wherein the carbon dioxide-based copolymer foam provided by the present invention uses a carbon dioxide-epoxycyclohexane copolymer as a main foaming material, can prepare semi-rigid and rigid foams, and has good foaming performance, elastic modulus and compressive strength.
The invention provides a carbon dioxide-based copolymer foam plastic which is prepared from the following raw materials:
100 parts by weight of a carbon dioxide-epoxycyclohexane copolymer;
5 to 30 parts by weight of a carbon dioxide-propylene oxide copolymer;
2-20 parts of toughening agent;
0.1 to 1 part by weight of ester exchanger.
Preferably, the number average molecular weight of the carbon dioxide-epoxy cyclohexane copolymer is 40kg/mol to 60kg/mol, and the molecular weight distribution is 1.8 to 3.
Preferably, the number average molecular weight of the carbon dioxide-propylene oxide copolymer is 80kg/mol to 150kg/mol, and the molecular weight distribution is 2.2 to 3.
Preferably, the toughening agent is selected from one or more of ethylene-octylene copolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer, methyl methacrylate-butadiene-styrene copolymer, and thermoplastic polyurethane elastomer synthesized by polyester polyol and isophorone diisocyanate.
Preferably, the transesterification agent is selected from tetra-n-butyl titanate and/or tetra-isopropyl titanate.
The invention also provides a preparation method of the carbon dioxide-based copolymer foam plastic, which comprises the following steps:
a) mixing and granulating a carbon dioxide-epoxy cyclohexane copolymer, a carbon dioxide-epoxy propane copolymer, a toughening agent and an ester exchange agent to obtain plastic particles;
b) putting the plastic particles obtained in the step a) into carbon dioxide of 3-8 MPa for reaction, then carrying out pressure relief treatment, and cooling to obtain the carbon dioxide-based copolymer plastic foam.
Preferably, the granulation process in step a) is carried out in a twin-screw granulator; the temperature of the granulation is 160-195 ℃.
Preferably, the foaming temperature in the step b) is 100-120 ℃, and the time is 60-240 min.
Preferably, the speed of the pressure relief treatment in the step b) is 5 MPa/s-20 MPa/s.
Preferably, the temperature of said cooling in step b) is between 20 ℃ and 30 ℃.
The invention provides a carbon dioxide-based copolymer foam plastic which is prepared from the following raw materials: 100 parts by weight of a carbon dioxide-epoxycyclohexane copolymer; 5 to 30 parts by weight of a carbon dioxide-propylene oxide copolymer; 2-20 parts of toughening agent; 0.1 to 1 part by weight of ester exchanger. Compared with the prior art, the carbon dioxide-based copolymer foamed plastic provided by the invention takes the carbon dioxide-epoxy cyclohexane copolymer as a main foaming material, and is matched with other components with specific contents to realize better interaction, and the obtained carbon dioxide-based copolymer foamed plastic is semi-rigid or rigid foam and has good foaming performance, elastic modulus and compressive strength. Experimental results show that the foaming ratio of the carbon dioxide-based copolymer foamed plastic provided by the invention can reach 10 times, the elastic modulus can reach 804MPa, and the compression strength (50%) can reach 26 MPa.
In addition, the preparation method provided by the invention has the advantages of simple process, mild conditions, easiness in operation control, lower cost, no toxicity, environmental friendliness and wide application prospect.
Drawings
FIG. 1 is a scanning electron microscope image of the carbon dioxide-based copolymer foam prepared in example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a carbon dioxide-based copolymer foam plastic which is prepared from the following raw materials:
100 parts by weight of a carbon dioxide-epoxycyclohexane copolymer;
5 to 30 parts by weight of a carbon dioxide-propylene oxide copolymer;
2-20 parts of toughening agent;
0.1 to 1 part by weight of ester exchanger.
In the present invention, the carbon dioxide-based copolymer foam is prepared from raw materials including a carbon dioxide-epoxycyclohexane copolymer (PCHC), a carbon dioxide-epoxypropane copolymer (PPC), a toughening agent and a transesterification agent, and preferably from a carbon dioxide-epoxycyclohexane copolymer (PCHC), a carbon dioxide-epoxypropane copolymer (PPC), a toughening agent and a transesterification agent.
In the invention, the carbon dioxide-epoxy cyclohexane copolymer (PCHC) is a main foaming material of the carbon dioxide-based copolymer foam plastic, is copolymerized by carbon dioxide and epoxy cyclohexane, and is an amorphous fully biodegradable plastic; the carbon dioxide-propylene oxide copolymer (PPC) is a key modified material of the carbon dioxide-based copolymer foamed plastic, can shorten the foaming time and improve the foaming multiplying power, is synthesized by carbon dioxide and propylene oxide in a copolymerization way, and is also an amorphous plastic which can be fully biodegraded; the carbon dioxide-based copolymer foam plastic prepared by using the carbon dioxide-based copolymer as the main raw material can be biodegraded, so that semi-rigid or rigid biodegradable foam can be prepared.
The source of the PCHC and the PPC is not particularly limited in the invention, and the PCHC and the PPC can be prepared by the carbon dioxide-based copolymer which is well known to those skilled in the art and is of the above kind, can be purchased from the market, and can also be prepared by the preparation method of the carbon dioxide-based copolymer which is well known to those skilled in the art; PPC can be prepared, for example, according to the methods disclosed in Chinese patent publication Nos. CN1257885A, CN1436803A or CN 1257753A.
In the present invention, the number average molecular weight of the carbon dioxide-epoxycyclohexane copolymer is preferably 40kg/mol to 60 kg/mol; the molecular weight distribution of the carbon dioxide-epoxycyclohexane copolymer is preferably 1.8-3. In the present invention, the carbon dioxide-based copolymer foam includes 100 parts by weight of a carbon dioxide-epoxycyclohexane copolymer.
In the present invention, the number average molecular weight of the carbon dioxide-propylene oxide copolymer is preferably 80kg/mol to 150 kg/mol; the molecular weight distribution of the carbon dioxide-propylene oxide copolymer is preferably 2.2-3. In the present invention, the carbon dioxide-based copolymer foam includes 5 to 30 parts by weight of a carbon dioxide-propylene oxide copolymer.
In the present invention, the toughening agent is preferably selected from one or more of ethylene-octylene copolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer, methyl methacrylate-butadiene-styrene copolymer, and thermoplastic polyurethane elastomer synthesized from polyester polyol and isophorone diisocyanate, and more preferably ethylene-octene copolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer, or thermoplastic polyurethane elastomer synthesized from polyester polyol and isophorone diisocyanate. The source of the toughening agent is not particularly limited in the present invention, and any toughening agent of the above kind known to those skilled in the art can be used and is commercially available, for example, an ethylene-methyl acrylate-glycidyl methacrylate copolymer available from akoma corporation under the trade name AX 8900.
In the invention, the toughening agent can improve the toughness of the carbon dioxide-based copolymer foam plastic provided by the invention, so that the carbon dioxide-based copolymer foam plastic provided by the invention has better mechanical properties. In the present invention, the carbon dioxide-based copolymer foam includes 2 to 20 parts by weight of a toughening agent.
In the present invention, the transesterification agent is preferably selected from tetra-n-butyl titanate and/or tetra-isopropyl titanate, more preferably tetra-n-butyl titanate or tetra-isopropyl titanate. The present invention is not particularly limited with respect to the source of the transesterification agent, and is commercially available.
In the invention, the ester exchanger can enable the carbon dioxide-epoxycyclohexane copolymer and the carbon dioxide-epoxypropane copolymer to react, thereby improving the compatibility of the two. In the present invention, the carbon dioxide-based copolymer foam includes 0.1 to 1 part by weight of a transesterification agent.
In addition, the technicians in the field can select and add different types of auxiliary agents according to the actual conditions, so that the carbon dioxide-based copolymer foam plastic provided by the invention has the required performance; for example, in the present invention, the addition of an antioxidant can improve the aging properties of the carbon dioxide-based copolymer foam provided by the present invention; the double-screw processability of the carbon dioxide-based copolymer foam plastic provided by the invention can be improved by adding the lubricant; the addition of pigments can change the color of the carbon dioxide based copolymer foam provided by the present invention.
The carbon dioxide-based copolymer foamed plastic provided by the invention takes the carbon dioxide-epoxycyclohexane copolymer as a main foaming material, has biodegradability as a whole, realizes better interaction by matching with other components with specific contents due to high strength of PCHC, has higher elastic modulus and better compression strength, and can be used for preparing semi-rigid and rigid foams.
The invention also provides a preparation method of the carbon dioxide-based copolymer foam plastic, which comprises the following steps:
a) mixing and granulating a carbon dioxide-epoxy cyclohexane copolymer, a carbon dioxide-epoxy propane copolymer, a toughening agent and an ester exchange agent to obtain plastic particles;
b) putting the plastic particles obtained in the step a) into carbon dioxide of 3-8 MPa for reaction, then carrying out pressure relief treatment, and cooling to obtain the carbon dioxide-based copolymer plastic foam.
Firstly, mixing and granulating a carbon dioxide-epoxy cyclohexane copolymer, a carbon dioxide-epoxy propane copolymer, a toughening agent and an ester exchange agent to obtain plastic particles. In the present invention, the carbon dioxide-epoxycyclohexane copolymer, the carbon dioxide-epoxypropane copolymer, the toughening agent and the ester exchange agent are the same as those in the above technical solution, and are not described herein again.
In the present invention, the mixing is preferably performed by stirring, so as to uniformly mix the raw materials; any mixer or blender known to those skilled in the art may be used. In the invention, the rotating speed of the stirring is preferably 600 r/min-800 r/min, and more preferably 700 r/min; the stirring time is preferably 3 to 5min, and more preferably 4 min.
In the present invention, the granulation process is preferably carried out in a twin-screw granulator; the temperature of the granulation is preferably 160-195 ℃; the specific setting mode is as follows:
the temperature of the first zone of the double-screw granulator is preferably 160-165 ℃, the temperature of the second zone is preferably 170-175 ℃, the temperature of the third zone is preferably 180-185 ℃, the temperature of the fourth zone is preferably 180-185 ℃, the temperature of the fifth zone is preferably 185-195 ℃, the temperature of the sixth zone is preferably 180-195 ℃, the temperature of the seventh zone is preferably 165-175 ℃, and the temperature of the die head is preferably 160-165 ℃.
After the plastic particles are obtained, the obtained plastic particles are placed in carbon dioxide of 3 MPa-8 MPa for reaction, and then the carbon dioxide-based copolymer plastic foam is obtained after pressure relief treatment and cooling.
In the invention, the plastic particles are placed in carbon dioxide of 3 MPa-8 MPa, preferably 5MPa, so that the plastic particles absorb the carbon dioxide.
In the present invention, the foaming process is preferably specifically:
and placing the obtained plastic particles in a high-pressure resistant container, filling carbon dioxide into the high-pressure resistant container, heating the high-pressure resistant container to a foaming temperature, and maintaining the constant temperature and the pressure for a certain time to enable the plastic particles to absorb the carbon dioxide. In the present invention, the high pressure resistant vessel is preferably a high pressure reaction vessel.
In the present invention, the charging pressure of the carbon dioxide is the same as the pressure of the carbon dioxide environment in the above technical solution, and is not described herein again. In the present invention, the temperature at which the high pressure resistant container is heated, i.e. the temperature at which the reaction is carried out, is not described herein again. In the present invention, the time for maintaining the constant temperature and pressure of the high pressure resistant container is the time for performing the reaction, and is not described herein again.
In the present invention, the reaction temperature is preferably 100 to 120 ℃; the reaction time is preferably 60min to 240 min; on this basis, the carbon dioxide in the plastic granules is preferably in a saturated state.
After the plastic particles absorb carbon dioxide, the invention carries out pressure relief treatment on the plastic particles, and the carbon dioxide-propylene oxide copolymer foamed plastic is obtained after cooling. In the present invention, the rate of the pressure relief treatment is preferably 5MPa/s to 20MPa/s, more preferably 5 MPa/s. According to the invention, through pressure relief treatment, the carbon dioxide in the plastic particles is driven by the internal and external pressure difference to spontaneously nucleate and grow, so that the plastic particles are foamed, and the carbon dioxide-based copolymer foamed plastic is obtained.
The carbon dioxide-based copolymer foam provided by the invention utilizes carbon dioxide as a foaming agent, the foam is prepared in a physical foaming mode, the foaming is not required to be carried out under the condition of carbon dioxide in a supercritical state, the foaming multiplying power is in the range of 4-10 times, semi-rigid and rigid foams can be prepared, and the product has higher compression strength.
In the present invention, the temperature of the cooling is preferably 20 to 30 ℃, more preferably 25 ℃.
The preparation method provided by the invention has the advantages of simple process, mild condition, easy control of operation and lower cost; the preparation method of the carbon dioxide-based copolymer foamed plastic provided by the invention is non-toxic and environment-friendly, and has a wide application prospect.
The invention provides a carbon dioxide-based copolymer foam plastic which is prepared from the following raw materials: 100 parts by weight of a carbon dioxide-epoxycyclohexane copolymer; 5 to 30 parts by weight of a carbon dioxide-propylene oxide copolymer; 2-20 parts of toughening agent; 0.1 to 1 part by weight of ester exchanger. Compared with the prior art, the carbon dioxide-based copolymer foamed plastic provided by the invention takes the carbon dioxide-epoxy cyclohexane copolymer as a main foaming material, and is matched with other components with specific contents to realize better interaction, and the obtained carbon dioxide-based copolymer foamed plastic is semi-rigid or rigid foam and has good foaming performance, elastic modulus and compressive strength. Experimental results show that the foaming ratio of the carbon dioxide-based copolymer foamed plastic provided by the invention can reach 10 times, the elastic modulus can reach 804MPa, and the compression strength (50%) can reach 26 MPa.
In addition, the preparation method provided by the invention has the advantages of simple process, mild conditions, easiness in operation control, lower cost, no toxicity, environmental friendliness and wide application prospect.
To further illustrate the present invention, the following examples are provided for illustration. The PCHC used in the following examples of the present invention was self-made by the laboratory; the PPC used is purchased from Jilin Boda New materials Co; the ethylene-octene copolymer (POE) and methyl methacrylate-butadiene-styrene copolymer (MBS) are provided by Dow chemical company of America; the ethylene-methyl acrylate-glycidyl methacrylate copolymer is an Akema brand AX8900 product; the thermoplastic polyurethane elastomer synthesized by polyester polyol and isophorone diisocyanate is self-made by laboratories.
Example 1
(1) 1kg of PCHC having a number average molecular weight of 60kg/mol and a molecular weight distribution of 2.8, 0.05kg of PPC having a number average molecular weight of 150kg/mol and a molecular weight distribution of 2.6, 0.1kg of an ethylene-octene copolymer and 10g of tetra-n-butyl titanate were uniformly mixed in a mixer, and the resulting mixture was fed into a twin-screw pelletizer to be pelletized, thereby obtaining plastic pellets.
(2) And (2) placing the plastic particles obtained in the step (1) in a high-pressure reaction kettle, filling 5MPa of carbon dioxide into the high-pressure reaction kettle, heating the high-pressure reaction kettle to 110 ℃, keeping the temperature and the pressure for 60min, then relieving the pressure in the high-pressure reaction kettle at the speed of 5MPa/s, and finally cooling the high-pressure reaction kettle to 25 ℃ to obtain the carbon dioxide-based copolymer plastic foam.
Scanning electron microscope test is carried out on the carbon dioxide-based copolymer foamed plastic obtained in the embodiment 1 of the invention, and the test result is shown in figure 1; FIG. 1 is a scanning electron microscope image of the carbon dioxide-based copolymer foam prepared in example 1 of the present invention. As can be seen from FIG. 1, the carbon dioxide-based copolymer foam prepared in example 1 of the present invention has a uniform cell structure.
Through detection, the foaming ratio, the elastic modulus and the compressive strength data of the carbon dioxide-based copolymer foam prepared in example 1 of the present invention are shown in table 1.
Example 2
(1) 1kg of PCHC having a number average molecular weight of 40kg/mol and a molecular weight distribution of 3, 0.3kg of PPC having a number average molecular weight of 80kg/mol and a molecular weight distribution of 2.2, 0.2kg of an ethylene-octene copolymer and 10g of tetra-n-butyl titanate were uniformly mixed in a mixer, and then the obtained mixture was fed into a twin-screw pelletizer to be pelletized, thereby obtaining plastic pellets.
(2) And (2) placing the plastic particles obtained in the step (1) in a high-pressure reaction kettle, filling 5MPa of carbon dioxide into the high-pressure reaction kettle, heating the high-pressure reaction kettle to 100 ℃, keeping the temperature and the pressure for 180min, then relieving the pressure in the high-pressure reaction kettle at the speed of 5MPa/s, and finally cooling the high-pressure reaction kettle to 25 ℃ to obtain the carbon dioxide-based copolymer plastic foam.
Through detection, the foaming ratio, the elastic modulus and the compressive strength data of the carbon dioxide-based copolymer foam prepared in example 2 of the present invention are shown in table 1.
Example 3
(1) 1kg of PCHC having a number average molecular weight of 60kg/mol and a molecular weight distribution of 2.8, 0.2kg of PPC having a number average molecular weight of 150kg/mol and a molecular weight distribution of 2.6, 0.02kg of an ethylene-methyl acrylate-glycidyl methacrylate copolymer and 10g of tetra-n-butyl titanate were uniformly mixed in a mixer, and then the resulting mixture was fed into a twin-screw pelletizer to be pelletized, thereby obtaining plastic pellets.
(2) And (2) placing the plastic particles obtained in the step (1) in a high-pressure reaction kettle, filling 5MPa of carbon dioxide into the high-pressure reaction kettle, heating the high-pressure reaction kettle to 100 ℃, keeping the temperature and the pressure for 200min, then relieving the pressure in the high-pressure reaction kettle at the speed of 5MPa/s, and finally cooling the high-pressure reaction kettle to 25 ℃ to obtain the carbon dioxide-based copolymer plastic foam.
Through detection, the foaming ratio, the elastic modulus and the compressive strength data of the carbon dioxide-based copolymer foam prepared in example 3 of the present invention are shown in table 1.
Example 4
(1) 1kg of PCHC with the number average molecular weight of 40kg/mol and the molecular weight distribution of 3, 0.1kg of PPC with the number average molecular weight of 150kg/mol and the molecular weight distribution of 2.6, 0.2kg of thermoplastic polyurethane elastomer synthesized by polyester polyol and isophorone diisocyanate, and 10g of tetra-n-butyl titanate were uniformly mixed in a mixer, and then the obtained mixture was added into a twin-screw granulator to granulate, thereby obtaining plastic granules.
(2) And (2) placing the plastic particles obtained in the step (1) in a high-pressure reaction kettle, filling 5MPa of carbon dioxide into the high-pressure reaction kettle, heating the high-pressure reaction kettle to 100 ℃, keeping the temperature and the pressure for 240min, relieving the pressure in the high-pressure reaction kettle at the speed of 5MPa/s, and finally cooling the high-pressure reaction kettle to 25 ℃ to obtain the carbon dioxide-based copolymer plastic foam.
Through detection, the foaming ratio, the elastic modulus and the compressive strength data of the carbon dioxide-based copolymer foam prepared in example 4 of the present invention are shown in table 1.
Example 5
(1) 1kg of PCHC having a number average molecular weight of 60kg/mol and a molecular weight distribution of 2.8, 0.1kg of PPC having a number average molecular weight of 150kg/mol and a molecular weight distribution of 2.6, 0.1kg of an ethylene-octene copolymer and 5g of tetraisopropyl titanate were uniformly mixed in a mixer, and the resulting mixture was fed into a twin-screw pelletizer to be pelletized, thereby obtaining plastic pellets.
(2) And (2) placing the plastic particles obtained in the step (1) in a high-pressure reaction kettle, filling 5MPa of carbon dioxide into the high-pressure reaction kettle, heating the high-pressure reaction kettle to 110 ℃, keeping the temperature and the pressure for 60min, then relieving the pressure in the high-pressure reaction kettle at the speed of 5MPa/s, and finally cooling the high-pressure reaction kettle to 25 ℃ to obtain the carbon dioxide-based copolymer plastic foam.
Through detection, the foaming ratio, the elastic modulus and the compressive strength data of the carbon dioxide-based copolymer foam prepared in example 4 of the present invention are shown in table 1.
Comparative example 1
(1) 1kg of PCHC having a number average molecular weight of 60kg/mol and a molecular weight distribution of 2.8, 0.1kg of an ethylene-octene copolymer and 10g of tetra-n-butyl titanate were uniformly mixed in a mixer, and the resulting mixture was fed into a twin-screw pelletizer to be pelletized, thereby obtaining plastic pellets.
(2) And (2) placing the plastic particles obtained in the step (1) in a high-pressure reaction kettle, filling 5MPa of carbon dioxide into the high-pressure reaction kettle, heating the high-pressure reaction kettle to 110 ℃, keeping the temperature and the pressure for 60min, then relieving the pressure in the high-pressure reaction kettle at the speed of 5MPa/s, and finally cooling the high-pressure reaction kettle to 25 ℃ to obtain the carbon dioxide-based copolymer plastic foam.
The data of the expansion ratio, the elastic modulus and the compressive strength of the carbon dioxide-based copolymer foam prepared in comparative example 1 are shown in Table 1.
Comparative example 2
(1) 1kg of PCHC with a number average molecular weight of 40kg/mol and a molecular weight distribution of 3, 0.3kg of PPC with a number average molecular weight of 80kg/mol and a molecular weight distribution of 2.2 and 10g of tetra-n-butyl titanate were uniformly mixed in a mixer, and then the obtained mixture was added to a twin-screw granulator to granulate, thereby obtaining plastic granules.
(2) And (2) placing the plastic particles obtained in the step (1) in a high-pressure reaction kettle, filling 5MPa of carbon dioxide into the high-pressure reaction kettle, heating the high-pressure reaction kettle to 100 ℃, keeping the temperature and the pressure for 180min, then relieving the pressure in the high-pressure reaction kettle at the speed of 5MPa/s, and cooling the high-pressure reaction kettle to 25 ℃ to obtain the carbon dioxide-based copolymer plastic foam.
The data of the expansion ratio, the elastic modulus and the compressive strength of the carbon dioxide-based copolymer foam prepared in comparative example 2 are shown in Table 1.
TABLE 1 data on the properties of the carbon dioxide-based copolymer foams prepared in examples 1 to 5 and comparative examples 1 to 2
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. The carbon dioxide-based copolymer foam plastic is prepared from the following raw materials:
100 parts by weight of a carbon dioxide-epoxycyclohexane copolymer;
5 to 30 parts by weight of a carbon dioxide-propylene oxide copolymer;
2-20 parts of toughening agent;
0.1 to 1 part by weight of ester exchanger; the ester exchanger is selected from tetra-n-butyl titanate and/or tetra-isopropyl titanate.
2. The carbon dioxide-based copolymer foam according to claim 1, wherein the carbon dioxide-epoxycyclohexane copolymer has a number average molecular weight of 40 to 60kg/mol and a molecular weight distribution of 1.8 to 3.
3. The carbon dioxide-based copolymer foam according to claim 1, wherein the carbon dioxide-propylene oxide copolymer has a number average molecular weight of 80kg/mol to 150kg/mol and a molecular weight distribution of 2.2 to 3.
4. The carbon dioxide based copolymer foam according to claim 1, wherein the toughening agent is selected from one or more of ethylene-octylene copolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer, methyl methacrylate-butadiene-styrene copolymer, thermoplastic polyurethane elastomer synthesized from polyester polyol and isophorone diisocyanate.
5. A method for preparing the carbon dioxide-based copolymer foam according to any one of claims 1 to 4, comprising the steps of:
a) mixing and granulating a carbon dioxide-epoxy cyclohexane copolymer, a carbon dioxide-epoxy propane copolymer, a toughening agent and an ester exchange agent to obtain plastic particles;
b) putting the plastic particles obtained in the step a) into carbon dioxide of 3-8 MPa for reaction, then carrying out pressure relief treatment, and cooling to obtain the carbon dioxide-based copolymer plastic foam.
6. The process according to claim 5, wherein the granulation in step a) is carried out in a twin-screw granulator; the temperature of the granulation is 160-195 ℃.
7. The method according to claim 5, wherein the foaming temperature in step b) is 100-120 ℃ and the time is 60-240 min.
8. The method according to claim 5, wherein the pressure relief treatment speed in step b) is 5 to 20 MPa/s.
9. The method according to claim 5, wherein the temperature of the cooling in the step b) is 20 to 30 ℃.
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