CN112646345A - High-impact carbon dioxide copolymer and preparation method thereof - Google Patents
High-impact carbon dioxide copolymer and preparation method thereof Download PDFInfo
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Abstract
The invention provides a high-impact carbon dioxide copolymer and a preparation method thereof. The high impact carbon dioxide copolymer provided by the invention is prepared from the following raw materials in parts by mass: 100 parts of carbon dioxide-epoxycyclohexane copolymer; 10-15 parts of a modified toughening agent; 1-2 parts of modified inorganic particles; the modified toughening agent is prepared from the following raw materials in parts by mass: 100 parts of thermoplastic styrene-butadiene rubber; 5-10 parts of a dispersing agent; 1-2 parts of 2- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane. The high-impact carbon dioxide copolymer provided by the invention can improve the impact resistance of PCHC and ensure that the material has good strength and hardness.
Description
Technical Field
The invention relates to the field of organic materials, in particular to a high-impact carbon dioxide copolymer and a preparation method thereof.
Background
Professor auscultatory in japan in 1969 reported for the first time that carbon dioxide can be copolymerized with an epoxy compound in the presence of an alkyl zinc catalyst to produce an aliphatic polycarbonate. Among copolymers of carbon dioxide and epoxide, cyclohexene oxide (CHO) is one of the most reactive monomers to copolymerize with carbon dioxide, and is one of the most studied copolymerization reactions in which carbon dioxide participates. The carbon dioxide-epoxycyclohexane copolymer (PCHC) has a rigid six-membered ring structure on the molecular main chain, limits the free movement of a molecular chain segment, increases the rigidity of the molecular chain, has higher glass transition temperature, and is a high-temperature-resistant biodegradable aliphatic polycarbonate, but the PCHC has high brittleness and poor impact resistance, and the development and application of downstream products of the PCHC are severely limited, so that the improvement of the impact resistance of the PCHC is the key for solving the development of high-quality products.
However, the materials commonly used for toughening at present are traditional materials such as styrene, polyvinyl chloride and the like, for example, methyl methacrylate-butadiene-styrene terpolymer (MBS), acrylonitrile-butadiene-styrene terpolymer (ABS), acrylate copolymer with core-shell structure (ACR), Chlorinated Polyethylene (CPE), rubber, elastomer and the like, and the toughening materials have compatibility and other problems with PCHC, and are difficult to be applied to PCHC, the toughening effect is not obvious when the addition amount of the toughening agent is small, and the toughening agent and the rubber are completely separated from each other when the addition amount of the toughening agent is increased, so that the expected toughening effect cannot be achieved. Moreover, the use of rubber or elastomer alone for toughening often results in too much loss in strength and hardness of the material even if impact toughness is improved.
Disclosure of Invention
In view of the above, the present invention aims to provide a high impact carbon dioxide copolymer and a preparation method thereof. The high-impact carbon dioxide copolymer provided by the invention can improve the impact resistance of PCHC and ensure that the material still has good strength and hardness.
The invention provides a high-impact carbon dioxide copolymer which is prepared from the following raw materials in parts by mass:
100 parts of carbon dioxide-epoxycyclohexane copolymer;
10-15 parts of a modified toughening agent;
1-2 parts of modified inorganic particles;
the modified toughening agent is prepared from the following raw materials in parts by mass:
100 parts of thermoplastic styrene-butadiene rubber;
5-10 parts of a dispersing agent;
1-2 parts of 2- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane.
Preferably, the dispersant is one or more selected from glyceryl triacetate, glyceryl tripropionate and glyceryl tributyrate.
Preferably, the modified toughening agent is obtained by the following method:
melting and blending thermoplastic styrene-butadiene rubber, a dispersing agent and 2- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane to obtain a modified toughening agent;
the temperature of the melt blending is 180-190 ℃, and the time is 5-10 min.
Preferably, the modified inorganic particles are rigid inorganic particles surface-treated with a coupling agent.
Preferably, the rigid inorganic particles are selected from one or more of silicon nitride, fumed silica, neutral alumina, carbon black and silicon carbide;
the coupling agent is selected from one or more of silane coupling agent, titanate coupling agent, aluminate coupling agent and borate coupling agent;
the mass ratio of the coupling agent to the rigid inorganic particles is 0.5-2%.
Preferably, the modified inorganic particles are obtained by:
mixing and heating rigid inorganic particles and a coupling agent to obtain modified inorganic particles;
the heating temperature is 110-120 ℃.
Preferably, the rigid inorganic particles are heated and left to stand, and then the coupling agent is added and mixed to obtain the modified inorganic particles.
Preferably, the number average molecular weight of the carbon dioxide-epoxy cyclohexane copolymer is 40-60 kg/mol, and the molecular weight distribution is 1.8-3;
the thermoplastic styrene-butadiene rubber is linear styrene-butadiene rubber, and the melt flow rate is 0.1-5 g/10 min.
The invention also provides a preparation method of the high impact carbon dioxide copolymer in the technical scheme, which comprises the following steps:
and melting and blending the carbon dioxide-epoxy cyclohexane copolymer, the modified toughening agent and the modified inorganic particles to obtain the high-impact carbon dioxide copolymer.
Preferably, the temperature of the melt blending is 180-190 ℃ and the time is 3-8 min.
The invention adopts thermoplastic styrene-butadiene rubber, dispersant and 2- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane as raw materials to form a modified toughening agent, and combines the specific modified toughening agent, modified inorganic particles and carbon dioxide-epoxy cyclohexane copolymer to form the high-impact carbon dioxide copolymer. The modified toughening agent is thermoplastic styrene butadiene rubber modified according to the structural characteristics of PCHC, the toughness of the PCHC can be efficiently improved after modification, the modulus and the strength can be improved by adding modified rigid inorganic particles, and the modified toughening agent and the toughening agent have a synergistic toughening effect. Therefore, the high impact carbon dioxide copolymer provided by the invention has good impact strength.
Experimental results show that the high impact carbon dioxide-based copolymer provided by the invention has cantilever beam impact strength of 18.22KJ/m2Above, up to 22.91KJ/m2Meanwhile, the tensile strength can reach more than 31MPa, the elongation at break can reach more than 20%, and the Rockwell hardness can reach more than 106.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a graph showing mechanical properties of products obtained in example 1, comparative example 1 and comparative example 4.
Detailed Description
The invention provides a high-impact carbon dioxide copolymer which is prepared from the following raw materials in parts by mass:
100 parts of carbon dioxide-epoxycyclohexane copolymer;
10-15 parts of a modified toughening agent;
1-2 parts of modified inorganic particles;
the modified toughening agent is prepared from the following raw materials in parts by mass:
100 parts of thermoplastic styrene-butadiene rubber;
5-10 parts of a dispersing agent;
1-2 parts of 2- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane.
The invention adopts thermoplastic styrene-butadiene rubber, dispersant and 2- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane as raw materials to form a modified toughening agent, and combines the specific modified toughening agent, modified inorganic particles and carbon dioxide-epoxy cyclohexane copolymer to form the high-impact carbon dioxide copolymer. The modified toughening agent is thermoplastic styrene butadiene rubber modified according to the structural characteristics of PCHC, the toughness of the PCHC can be efficiently improved after modification, the modulus and the strength can be improved by adding modified rigid inorganic particles, and the modified toughening agent and the toughening agent have a synergistic toughening effect. Therefore, the high impact carbon dioxide copolymer provided by the invention has good impact resistance, and simultaneously maintains good strength and hardness.
In the invention, the carbon dioxide-epoxy cyclohexane copolymer (PCHC) is a main material, is copolymerized by carbon dioxide and epoxy cyclohexane, and is an amorphous biodegradable plastic. The carbon dioxide-epoxycyclohexane copolymer of the present invention can be prepared by a preparation method well known to those skilled in the art without any particular limitation on the source thereof.
In the invention, the number average molecular weight of the carbon dioxide-epoxy cyclohexane copolymer is preferably 40-60 kg/mol; the molecular weight distribution of the PCHC is preferably 1.8-3. In the present invention, the amount of the carbon dioxide-epoxycyclohexane copolymer is 100 parts by mass.
In the present invention, the raw material for forming the high impact carbon dioxide copolymer further comprises a modifying toughening agent. The amount of the modified toughening agent is 10-15 parts by weight based on 100 parts by weight of the carbon dioxide-epoxy cyclohexane copolymer.
According to the invention, the modified toughening agent is prepared from the following raw materials in parts by mass:
100 parts of thermoplastic styrene-butadiene rubber;
5-10 parts of a dispersing agent;
1-2 parts of 2- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane.
In the invention, the thermoplastic styrene-butadiene rubber is styrene-butadiene rubber with a linear structure, and the melt flow rate of the thermoplastic styrene-butadiene rubber is preferably 0.1-5 g/10min (190 ℃, 2.16 kg). The thermoplastic styrene-butadiene rubber of the present invention is not particularly limited in its source, and may be generally commercially available or prepared according to a conventional preparation method well known to those skilled in the art. In the invention, the amount of the thermoplastic styrene-butadiene rubber is 100 parts by mass.
In the invention, the dispersant is preferably one or more of glyceryl triacetate, glyceryl tripropionate and glyceryl tributyrate; the dispersing agent plays an important role in modifying thermoplastic styrene butadiene rubber, can greatly improve the compatibility of PCHC and styrene butadiene rubber, is better compatible with 2- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane, and plays a favorable role in improving the impact resistance of a carbon dioxide copolymer. In the invention, the amount of the dispersing agent is 5-10 parts by mass based on 100 parts by mass of the thermoplastic styrene-butadiene rubber.
In the invention, the 2- (3, 4-epoxycyclohexane) ethyl trimethoxy silane contains an epoxycyclohexane structure and other specific molecular structures, and can synergistically play a role in increasing the compatibility of styrene butadiene rubber and PCHC and improving the impact resistance of the PCHC with a dispersant, and the specific 2- (3, 4-epoxycyclohexane) ethyl trimethoxy silane can effectively play a role, but other similar substances such as epoxycyclohexane cannot play a role in improving the impact resistance and can also generate negative effects. The source of the 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane is not particularly limited, and the 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane is a general commercial product, for example, a product with the brand name SCA-E86M, which is available from Nanjing Needer New Material technology Co. In the invention, the amount of the 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane is 1-2 parts based on 100 parts by mass of the thermoplastic styrene-butadiene rubber.
In the present invention, the modified toughening agent is preferably obtained by:
and (3) melting and blending the thermoplastic styrene-butadiene rubber, the dispersing agent and the 2- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane to obtain the modified toughening agent.
Wherein the melt blending may be carried out by means of an internal mixer. The rotating speed of the internal mixer is preferably 30-50 r/min. The temperature of the melt blending is preferably 180-190 ℃, and more preferably 180 ℃; the time for melt blending is preferably 5 to 10min, and more preferably 5 min. After the above melt blending, preferably cooling is further performed to obtain the solid modified toughening agent.
In the present invention, the raw material for forming the high impact carbon dioxide copolymer further includes modified inorganic particles. The amount of the modified inorganic particles is 1-2 parts by mass based on 100 parts by mass of the carbon dioxide-epoxycyclohexane copolymer.
In the present invention, the modified inorganic particles are preferably rigid inorganic particles surface-treated with a coupling agent.
Wherein:
the rigid inorganic particles are preferably one or more of silicon nitride, fumed silica, neutral alumina, carbon black and silicon carbide. The particle size of the rigid inorganic particles is preferably 5 to 50 μm. The coupling agent is preferably one or more of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent and a borate coupling agent. The mass ratio of the coupling agent to the rigid inorganic particles is preferably 0.5% to 2%.
In the present invention, the modified inorganic particles are preferably obtained by: and mixing and heating the rigid inorganic particles and the coupling agent to obtain the modified inorganic particles.
In the invention, the heating temperature is preferably 110-120 ℃, and more preferably 110 ℃.
In the present invention, the above preparation method is more preferably: firstly, rigid inorganic particles are heated and stood, and then a coupling agent is added for mixing to obtain modified inorganic particles. The rigid inorganic particles are heated to a target temperature and are kept warm for a period of time, then the coupling agent is added and uniformly mixed, through the treatment sequence, the moisture absorbed by the inorganic particles in the air can be removed, on the other hand, the active groups such as hydroxyl, carboxyl and the like on the surfaces of the inorganic particles can be heated and activated, the surface modification of the inorganic particles by the coupling agent is more facilitated, and if the rigid inorganic particles and the coupling agent are directly mixed and heated, the effective modification cannot be realized.
The above process can be carried out by means of a high-speed mixer, specifically, rigid inorganic particles are mixed and heated in the high-speed mixer, the mixture is kept stand and kept warm for a period of time after reaching the target temperature, and then, a coupling agent is added to continue stirring and mixing. Wherein the rotating speed of the high-speed mixer is preferably 1400-1500 rpm, and more preferably 1500 rpm. In the invention, the standing time is preferably 10-30 min. After the above treatment, modified inorganic particles are obtained. The modified inorganic particles are introduced, so that the effects of reinforcement and synergistic toughening can be generated in the material system.
The modified carbon dioxide copolymer is prepared by taking PCHC as a main material and introducing a modified toughening agent and modified inorganic particles, wherein the modified toughening agent contains thermoplastic styrene-butadiene rubber, a dispersing agent and 2- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane, and the dispersing agent and the 2- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane can synergistically increase the compatibility and the bonding property of the styrene-butadiene rubber and the PCHC and effectively toughen the styrene-butadiene rubber and the PCHC, and meanwhile, the modified inorganic particles generate the effects of reinforcement and synergistic toughening in a system, so that the obtained carbon dioxide copolymer has improved impact strength and has good tensile strength and hardness.
In the invention, besides the raw materials, a person skilled in the art can select and add different types of additives according to actual conditions, so that the high impact carbon dioxide copolymer provided by the invention has the required performance; for example, in the present invention, the addition of an antioxidant can improve the thermal stability of the high impact carbon dioxide copolymer provided by the present invention; the addition of a lubricant can improve the processability of the high impact carbon dioxide copolymer provided by the invention; the addition of pigments can change the color of the high impact carbon dioxide copolymer provided by the present invention.
The invention also provides a preparation method of the high impact carbon dioxide copolymer in the technical scheme, which comprises the following steps:
and melting and blending the carbon dioxide-epoxy cyclohexane copolymer, the modified toughening agent and the modified inorganic particles to obtain the high-impact carbon dioxide copolymer.
The types, the amounts and the like of the carbon dioxide-epoxycyclohexane copolymer, the modified toughening agent and the modified inorganic particles are consistent with those in the technical scheme, and are not described in detail herein.
In the present invention, the above melt blending may be carried out by means of an internal mixer. The rotating speed of the internal mixer is preferably 30-50 r/min, and more preferably 50 r/min. The temperature of the melt blending is preferably 180-190 ℃, and more preferably 180 ℃; the time for melt blending is preferably 3 to 8min, and more preferably 5 min. The high impact carbon dioxide copolymer is obtained through the treatment.
The preparation method provided by the invention has the advantages of simple process, easiness in operation control, lower cost and good application and popularization prospects.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In the following examples and comparative examples, the PCHC used was made by the laboratory; the thermoplastic styrene-butadiene rubber is purchased from China petrochemical creel petrochemical company, and the melt flow rate is 1.8g/10min (190 ℃, 2.16 kg); the dispersant is provided by chemical reagent company of national drug group; 2- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane is a product of SCA-E86M purchased from Nanjing Needer New Material technology Co., Ltd; silicon nitride and silicon carbide inorganic particles are purchased from Andy metals, Inc.; neutral alumina was purchased from mclin reagent corporation; fumed silica was purchased from the German winning company; carbon black was purchased from cabot corporation, usa.
Example 1
S1, preparing modified toughening agent
5g of glyceryl triacetate and 50g of thermoplastic styrene-butadiene rubber are uniformly mixed in a mixer, then 1g of 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane is added to be mixed for 5min at 180 ℃ in an internal mixer at 50 r/min, and then the mixture is cooled to obtain the modified toughening agent.
S2 preparation of modified inorganic particles
500g of silicon nitride is placed in a high-speed mixer and heated to 110 ℃, kept stand for 30 minutes, then 2.5g of titanate coupling agent is added, stirred for 30 minutes at 1500 revolutions per minute at the temperature, and cooled to obtain modified silicon nitride particles.
S3 preparation of high impact carbon dioxide copolymer
50g of PCHC (number average molecular weight of 60kg/mol and molecular weight distribution of 2.8), 7.5g of modified toughening agent and 0.5g of modified silicon nitride are mixed in proportion and then melted and mixed for 5 minutes in an internal mixer at 180 ℃ at the rotating speed of 50 revolutions per minute to obtain the high impact carbon dioxide copolymer.
Example 2
S1, preparing modified toughening agent
5g of tripropionin and 50g of thermoplastic styrene-butadiene rubber are uniformly mixed in a mixer, then 1g of 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane is added to be mixed for 5min at 180 ℃ in an internal mixer at 50 r/min, and then the mixture is cooled to obtain the modified toughening agent.
S2 preparation of modified inorganic particles
500g of fumed silica is placed in a high-speed mixer and heated to 110 ℃, is kept stand for 30 minutes, then 2.5g of titanate coupling agent is added, and is stirred for 30 minutes at 1500 revolutions per minute at the temperature, and the modified silica particles are obtained after cooling.
S3 preparation of high impact carbon dioxide copolymer
After 50g of PCHC (number average molecular weight of 40kg/mol, molecular weight distribution of 3), 5g of modified toughening agent and 0.5g of modified silica are mixed in proportion, the mixture is melted and mixed for 5 minutes in an internal mixer at 180 ℃ at the rotating speed of 50 revolutions per minute, and the high impact carbon dioxide copolymer is obtained.
Example 3
S1, preparing modified toughening agent
2.5g of glyceryl triacetate and 50g of thermoplastic styrene-butadiene rubber are uniformly mixed in a mixer, then 1g of 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane is added to be mixed for 5min at 180 ℃ in an internal mixer at 50 r/min, and then the mixture is cooled to obtain the modified toughening agent.
S2 preparation of modified inorganic particles
500g of carbon black was placed in a high-speed mixer and heated to 110 ℃ and left to stand for 30 minutes, and then 2.5g of a silane coupling agent was added thereto, and stirred at 1500 rpm for 30 minutes at that temperature, and cooled to obtain modified carbon black particles.
S3 preparation of high impact carbon dioxide copolymer
After 50g of PCHC (number average molecular weight 60kg/mol, molecular weight distribution 2.8), 7.5g of modified toughening agent and 0.5g of modified carbon black are mixed in proportion, the mixture is melted and mixed for 5 minutes in an internal mixer at 180 ℃ at the rotating speed of 50 revolutions per minute, and the high impact carbon dioxide copolymer is obtained.
Comparative example 1
50g of PCHC having a number-average molecular weight of 60kg/mol and a molecular weight distribution of 2.8 were melt-mixed in an internal mixer at a rotational speed of 50 revolutions per minute at 180 ℃ for 5 minutes to give pure PCHC.
Comparative example 2
A high impact carbon dioxide copolymer was prepared according to the procedure of example 1 except that no modifying toughener was added.
Comparative example 3
After 50g of PCHC with the number average molecular weight of 60kg/mol and the molecular weight distribution of 2.8 and 7.5g of styrene-butadiene rubber are mixed in proportion, the mixture is melted and mixed for 5 minutes in an internal mixer at the rotating speed of 50 revolutions per minute and at the temperature of 180 ℃, and the styrene-butadiene rubber modified PCHC is prepared.
Comparative example 4
After 50g of PCHC with the number average molecular weight of 60kg/mol and the molecular weight distribution of 2.8 and 15g of styrene-butadiene rubber are mixed in proportion, the mixture is melted and mixed for 5 minutes in an internal mixer at 180 ℃ at the rotating speed of 50 revolutions per minute to prepare the styrene-butadiene rubber modified PCHC.
Comparative example 5
A high impact carbon dioxide copolymer was prepared according to the preparation process of example 1, except that the modified inorganic particles were not added.
Comparative example 6
S1, preparing modified toughening agent
The procedure is as in example 1, except that 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane is replaced by the same amount of epoxycyclohexane.
S2, preparing modified inorganic particles: the same as in example 1.
S3 preparation of high impact carbon dioxide copolymer
Proceeding as in example 1, the modified toughening agent was replaced with the modified toughening agent prepared in step S1 of this comparative example.
Example 4
The products obtained in examples 1-3 and comparative examples 1-6 were subjected to performance tests, specifically, the products were prepared into test specimens on a Process model 11 mini-injection molding machine of Thermo Scientific corporation, and the test results are shown in table 1. The mechanical properties of the products obtained in example 1, comparative example 1 and comparative example 4 are shown in fig. 1, and fig. 1 is a mechanical property test chart of the products obtained in example 1, comparative example 1 and comparative example 4.
The impact strength is tested according to GB/T1843-2008 standard, the cantilever beam has no notch impact, the test humidity is 50%, the model of the testing machine is JJ-20, the number of the testing machine is MM12-003, and the impact speed is 3.5 m/s. The tensile strength and the elongation at break are tested according to the GB/T1040.1-2006 standard, the model of the testing machine is a ZWick/Z010 type multifunctional electronic tensile testing machine, and the tensile speed is 50 mm/min. The Rockwell hardness testing apparatus is an epoch TH320 Rockwell hardness tester.
TABLE 1 Performance test data for the products obtained in examples 1-3 and comparative examples 1-6
The test results show that the impact property of the high impact carbon dioxide copolymer provided by the invention is obviously improved, and the impact strength of pure PCHC is only 10.41KJ/m2(see comparative example 1), whereas the impact strength of the high impact carbon dioxide copolymer prepared by the present invention can be improved to 18.22KJ/m2Above, up to 22.91KJ/m2The impact strength is multiplied. In addition, as can be seen from comparative example 3 and comparative example 4, although the impact strength is improved by only adding the styrene-butadiene rubber, the tensile strength of the material is obviously reduced, the impact strength cannot be obviously further increased by simply increasing the content of the styrene-butadiene rubber, and the mechanical properties, particularly the elongation at break, are reduced in comparative example 4 because the styrene-butadiene rubber and the PCHC cannot be well compatible. As can be seen from the comparison of the effects of the example 1, the comparative example 2 and the comparative example 5, the modified toughening agent and the modified inorganic particles are added simultaneously, and the modified toughening agent and the modified inorganic particles play a role in synergistic toughening, so that the impact resistance of the PCHC is remarkably improved. As can be seen from comparative example 6, the impact resistance can not be improved by using cyclohexene oxide with a similar structure, and the tensile property of the material can be influenced, so that the specific 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane can be used for effectively improving the impact resistance of the PCHC and ensuring good tensile strength and hardness.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. 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 (10)
1. The high-impact carbon dioxide copolymer is characterized by being prepared from the following raw materials in parts by mass:
100 parts of carbon dioxide-epoxycyclohexane copolymer;
10-15 parts of a modified toughening agent;
1-2 parts of modified inorganic particles;
the modified toughening agent is prepared from the following raw materials in parts by mass:
100 parts of thermoplastic styrene-butadiene rubber;
5-10 parts of a dispersing agent;
1-2 parts of 2- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane.
2. The high impact carbon dioxide copolymer according to claim 1, wherein the dispersant is selected from one or more of triacetin, tripropionin and tributyrin.
3. The high impact carbon dioxide copolymer of claim 1, wherein the modified toughening agent is obtained by:
melting and blending thermoplastic styrene-butadiene rubber, a dispersing agent and 2- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane to obtain a modified toughening agent;
the temperature of the melt blending is 180-190 ℃, and the time is 5-10 min.
4. The high impact carbon dioxide copolymer of claim 1, wherein the modified inorganic particles are rigid inorganic particles surface treated with a coupling agent.
5. The high impact carbon dioxide copolymer according to claim 4, wherein the rigid inorganic particles are selected from one or more of silicon nitride, fumed silica, neutral alumina, carbon black, and silicon carbide;
the coupling agent is selected from one or more of silane coupling agent, titanate coupling agent, aluminate coupling agent and borate coupling agent;
the mass ratio of the coupling agent to the rigid inorganic particles is 0.5-2%.
6. The high impact carbon dioxide copolymer according to claim 4 or 5, characterized in that the modified inorganic particles are obtained by:
mixing and heating rigid inorganic particles and a coupling agent to obtain modified inorganic particles;
the heating temperature is 110-120 ℃.
7. The high impact carbon dioxide copolymer of claim 6, wherein the rigid inorganic particles are heated and allowed to stand, and then the coupling agent is added and mixed to obtain the modified inorganic particles.
8. The high impact carbon dioxide copolymer of 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;
the thermoplastic styrene-butadiene rubber is linear styrene-butadiene rubber, and the melt flow rate is 0.1-5 g/10 min.
9. A method for preparing a high impact carbon dioxide copolymer according to any one of claims 1 to 8, comprising:
and melting and blending the carbon dioxide-epoxy cyclohexane copolymer, the modified toughening agent and the modified inorganic particles to obtain the high-impact carbon dioxide copolymer.
10. The preparation method according to claim 9, wherein the melt blending temperature is 180-190 ℃ and the time is 3-8 min.
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| CN115160760A (en) * | 2022-08-24 | 2022-10-11 | 岳阳昌德新材料有限公司 | Modified polycarbonate cyclohexene ester material and preparation method and application thereof |
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| JIN-KAI ZHAO ET AL.: "Highly elastic and degradable thermoset elastomers from CO2-based polycarbonatesand bioderived polyesters", 《POLYMER CHEMISTRY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114479043A (en) * | 2022-01-18 | 2022-05-13 | 上海华峰新材料研发科技有限公司 | High-impact carbon dioxide random copolymer and preparation method and application thereof |
| CN115160760A (en) * | 2022-08-24 | 2022-10-11 | 岳阳昌德新材料有限公司 | Modified polycarbonate cyclohexene ester material and preparation method and application thereof |
| CN115160760B (en) * | 2022-08-24 | 2023-10-27 | 岳阳昌德新材料有限公司 | Modified polycyclohexenyl carbonate material and preparation method and application thereof |
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