Chlorinated poly(propylene carbonate) and preparation method thereof

Abstract

This invention provides a chlorinated poly(propylene carbonate) and the preparation method thereof, the chlorinated poly(propylene carbonate) is as represented by formula (I). Compared to the prior poly(propylene carbonate)s, the chlorinated poly(propylene carbonate) has relatively stronger electronegativity due to the presence of chlorine atoms and the interaction of the chlorinated poly(propylene carbonate) with other polar materials can be enhanced, so that it can be widely used as a compatilizer, a binder, a paint, an ink, and the like. After the introduction of chlorine atoms, hydrogen bond interaction is generated within the chlorinated poly(propylene carbonate), so that its processability and mechanical properties are both improved. Furthermore, the chlorine atom may improve the flame retardancy of chlorinated poly(propylene carbonate) materials. ##STR00001##

Claims

1. A preparation method of a chlorinated poly(propylene carbonate), comprising: mixing a poly(propylene carbonate) with a first dispersant and a first initiator, wherein the first initiator is one or more selected from a peroxide, an azo compound, tert-butyl perbenzoate, potassium persulfate, sodium sulfite, N,N-dimethylaniline, N,N-dimethyl-p-toluidine, and N,N-di(2-hydroxyethyl) p-toluidine, and introducing chlorine for performing reaction to obtain a chlorinated poly(propylene carbonate) represented by formula (I): ##STR00007## wherein x is an integer of 0-3; y is an integer of 0-2; and n is degree of polymerization.

2. The preparation method according to claim 1, wherein the mass ratio of the poly(propylene carbonate) to the dispersant is 100:(0.1-10).

3. The preparation method of claim 1, wherein the first dispersant comprises an organic solvent.

4. A preparation method of a chlorinated poly(propylene carbonate), comprising: mixing a poly(propylene carbonate), an emulsion accelerator, and a second dispersant with water, and introducing chlorine for performing reaction to obtain a chlorinated poly(propylene carbonate) represented by formula (I): ##STR00008## wherein x is an integer of 0-3; y is an integer of 0-2; and n is degree of polymerization.

5. The preparation method according to claim 4, wherein the preparation method further makes use of a second initiator, wherein the second initiator is one or more selected from a hydrogen peroxide-sodium nitrite system, a hydrogen peroxide-ferrous nitrate system, a hydrogen peroxide-silver nitrate system, a hydrogen peroxide-sodium bisulfite system, a hydrogen peroxide-ferrous ammonium sulfate system, a persulfate-sulfite system, a persulfate-mercaptan system, a dibenzoyl peroxide-ferrous sulfate system, a dibenzoyl peroxide-formic acid system, a dibenzoyl peroxide-mercaptan system, a dibenzoyl peroxide-thiophenol system, a lauroyl peroxide-ferrous sulfate system, a lauroyl peroxide-formic acid system, a lauroyl peroxide-mercaptan system, a lauroyl peroxide-thiophenol system, a cumene hydroperoxide-ferrous salt system, a cumene hydroperoxide-dihydroxyacetone system, a cumene hydroperoxide derivative-ferrous salt system, a cumene hydroperoxide derivative-dihydroxyacetone system, a furan hydroperoxide-ferrous salt system, a furan hydroperoxide-dihydroxyacetone system, a tert-butyl hydroperoxide-ferrous salt system, and a tert-butyl hydroperoxide-dihydroxyacetone system.

6. The preparation method according to claim 4, wherein the emulsion accelerator is one or more selected from a polyoxyethylene fatty alcohol, a polyoxyethylene alkylphenol, and a polyoxyethylene fatty alcohol ether.

7. The preparation method according to claim 4, wherein the mass ratio between the poly(propylene carbonate), the emulsion accelerator, and the second dispersant is 100:(0.1-10):(0.1-10).

Description

BRIEF DESCRIPTION OF THE DRAWING

(1) FIG. 1 is a process flow chart of a solid phase method for preparing the chlorinated poly(propylene carbonate) represented by formula (I) of this invention;

(2) FIG. 2 is a process flow chart of a solution method for preparing the chlorinated poly(propylene carbonate) represented by formula (I) of this invention;

(3) FIG. 3 is a process flow chart of a water phase suspension method for preparing the chlorinated poly(propylene carbonate) represented by formula (I) of this invention;

(4) FIG. 4 is a spectrogram of the scanning electron microscope-energy dispersive spectrometry analysis of the poly(propylene carbonate) used in Example 1 of this invention;

(5) FIG. 5 is a spectrogram of the scanning electron microscope-energy dispersive spectrometry analysis of the chlorinated poly(propylene carbonate) prepared in Example 1 of this invention.

DETAILED DESCRIPTION OF THE INVENTION

(6) This invention provides a chlorinated poly(propylene carbonate) represented by formula (I):

(7) ##STR00006##

(8) wherein x is an integer of 0-3, preferably an integer of 1-2; y is an integer of 0-2, preferably an integer of 1-2; and n is degree of polymerization, preferably 50-5000.

(9) This invention further provides a solid phase preparation method of the chlorinated poly(propylene carbonate) represented by the above formula (I), comprising: mixing a poly(propylene carbonate) with a first dispersant, and introducing chlorine for performing reaction to obtain a chlorinated poly(propylene carbonate) represented by formula (I).

(10) Wherein, the sources of all raw materials in this invention are not particularly limited, and those commercially available may be used.

(11) The first dispersant is not particularly limited, as long as it is one that is well known by the person skilled in the art, and it is preferably white carbon black in the present invention. The poly(propylene carbonate) and the first dispersant are mixed in a mass ratio of preferably 100:(0.1-10) and more preferably 100:(0.5-6).

(12) After the poly(propylene carbonate) is mixed with the first dispersant, chlorine is introduced for performing reaction to obtain a chlorinated poly(propylene carbonate) represented by formula (I). The process flow chart of this solid phase method is as shown in FIG. 1, and the auxiliaries include a first dispersant and a first initiator. The molar ratio of the chlorine to the poly(propylene carbonate) is preferably (1-6):1; the temperature of the reaction is preferably 10 C.-100 C., more preferably 0 C.-80 C., and still more preferably 10 C.-60 C.; the time of the reaction is preferably 10-300 min, and more preferably 50-200 min.

(13) When the temperature of the reaction is lower than the glass transition temperature of the poly(propylene carbonate) (30 C.-40 C.), a first initiator is preferably added, and the first initiator is preferably one or more of a peroxide, an azo compound, tert-butyl perbenzoate, potassium persulfate, sodium sulfite, N,N-dimethylaniline, N,N-dimethyl-p-toluidine, and N,N-di(2-hydroxyethyl) p-toluidine, and more preferably a mixture of an oxidative initiator and a reductive initiator, wherein the molar ratio of the oxidative initiator to the reductive initiator is preferably greater than 1. The oxidative initiator is preferably a peroxide and/or tert-butyl perbenzoate, and more preferably one or more of dibenzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, tert-butyl hydroperoxide, and tert-butyl perbenzoate. The reductive initiator is preferably one or more of N,N-dimethylaniline, N,N-dimethyl-p-toluidine, and N,N-di(2-hydroxyethyl) p-toluidine. The mass of the first initiator is preferably 0.01%-5%, more preferably 0.1%-5% of the mass of the poly(propylene carbonate).

(14) When the temperature of the reaction is higher than the glass transition temperature of the poly(propylene carbonate), the first initiator may not be added, and the reaction may occur under the condition of heat initiation or ultraviolet initiation. The first initiator may also be added to accelerate the progress of the reaction, and at this point, the first initiator is preferably one or more of dibenzoyl peroxide, azobisisobutyronitrile, and potassium persulfate. The mass of the first initiator is preferably 0.01%-5%, more preferably 0.1%-3% of the mass of the poly(propylene carbonate).

(15) This invention further provides another method for preparing the chlorinated poly(propylene carbonate) represented by the above formula (I) through a solution method, comprising: mixing a poly(propylene carbonate) with an organic solvent, and introducing chlorine for performing reaction to obtain a chlorinated poly(propylene carbonate) represented by formula (I).

(16) wherein the organic solvent is not particularly limited, as long as it is one capable of dissolving poly(propylene carbonate)s that is well known by the person skilled in the art, and it is preferably carbon tetrachloride in the present invention; the ratio of the mass of the poly(propylene carbonate) to the volume of the organic solvent is preferably 1 g:(5-20) ml, more preferably 1 g:(8-15) ml.

(17) After the poly(propylene carbonate) is mixed with the organic solvent, chlorine is introduced for performing reaction, wherein the molar ratio of the chlorine to the poly(propylene carbonate) is preferably (1-6):1; the temperature of the reaction is preferably 10 C.-100 C., more preferably 0 C.-80 C., and still more preferably 10 C.-60 C.; the time of the reaction is preferably 10-300 min, and more preferably 50-200 min.

(18) When the temperature of the reaction is lower than the glass transition temperature of the poly(propylene carbonate) (30 C.-40 C.), a first initiator is preferably added, and the first initiator is preferably one or more of a peroxide, an azo compound, tert-butyl perbenzoate, potassium persulfate, sodium sulfite, N,N-dimethylaniline, N,N-dimethyl-p-toluidine, and N,N-di(2-hydroxyethyl) p-toluidine, and more preferably a mixture of an oxidative initiator and a reductive initiator, wherein the molar ratio of the oxidative initiator to the reductive initiator is preferably greater than 1. The oxidative initiator is preferably a peroxide and/or tert-butyl perbenzoate, and more preferably one or more of dibenzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, tert-butyl hydroperoxide, and tert-butyl perbenzoate. The reductive initiator is preferably one or more of N,N-dimethylaniline, N,N-dimethyl-p-toluidine, and N,N-di(2-hydroxyethyl) p-toluidine. The mass of the first initiator is preferably 0.01%-5%, more preferably 0.1%-5% of the mass of the poly(propylene carbonate).

(19) When the temperature of the reaction is higher than the glass transition temperature of the poly(propylene carbonate), the first initiator may not be added, and the reaction may occur under the condition of heat initiation or ultraviolet initiation. The first initiator may also be added to accelerate the progress of the reaction, and at this point, the first initiator is preferably one or more of dibenzoyl peroxide, azobisisobutyronitrile, and potassium persulfate. The mass of the first initiator is preferably 0.01%-5%, more preferably 0.1%-3% of the mass of the poly(propylene carbonate).

(20) After the reaction, the organic solvent is preferably removed, and upon drying, the chlorinated poly(propylene carbonate) represented by formula (I) is obtained. The process flow chart of this solution method is as shown in FIG. 2.

(21) This invention further provides a method for preparing the chlorinated poly(propylene carbonate) represented by the above formula (I) through a water phase suspension method, comprising: mixing a poly(propylene carbonate), an emulsion accelerator, a second dispersant with water, and introducing chlorine for performing reaction to obtain a chlorinated poly(propylene carbonate) represented by formula (I).

(22) Wherein the emulsion accelerator is not particularly limited, as long as it is one that is well known by the person skilled in the art, and it is preferably one or more of a polyoxyethylene fatty alcohol, a polyoxyethylene alkylphenol, and a polyoxyethylene fatty alcohol ether in the present invention; the second dispersant is not particularly limited, as long as it is one that is well known by the person skilled in the art, and it is preferably one or more of sodium polymethacrylate, polyvinyl pyrrolidone, and an ethylene oxide-propylene oxide copolymer in the present invention; the mass ratio between the poly(propylene carbonate), the emulsion accelerator, and the second dispersant is preferably 100:(0.1-10):(0.1-10); and the ratio of the mass of the poly(propylene carbonate) to the volume of water is preferably 1:(10-30), more preferably 1:(15-25).

(23) After the poly(propylene carbonate), the emulsion accelerator, the second dispersant, and the water are mixed, a second initiator is preferably further added. The second initiator is preferably one or more of a hydrogen peroxide-sodium nitrite system, a hydrogen peroxide-ferrous nitrate system, a hydrogen peroxide-silver nitrate system, a hydrogen peroxide-sodium bisulfate system, a hydrogen peroxide-ferrous ammonium sulfate system, a persulfate-sulfite system, a persulfate-mercaptan system, a dibenzoyl peroxide-ferrous sulfate system, a dibenzoyl peroxide-formic acid system, a dibenzoyl peroxide-mercaptan system, a dibenzoyl peroxide-thiophenol system, a lauroyl peroxide-ferrous sulfate system, a lauroyl peroxide-formic acid system, a lauroyl peroxide-mercaptan system, a lauroyl peroxide-thiophenol system, a cumene hydroperoxide-ferrous salt system, a cumene hydroperoxide-dihydroxyacetone system, a cumene hydroperoxide derivative-ferrous salt system, a cumene hydroperoxide derivative-dihydroxyacetone system, a furan hydroperoxide-ferrous salt system, a furan hydroperoxide-dihydroxyacetone system, a tert-butyl hydroperoxide-ferrous salt system, and a tert-butyl hydroperoxide-dihydroxyacetone system; and the mass ratio of the second initiator to the poly(propylene carbonate) is preferably (0.01-2):100, more preferably (0.1-2):100.

(24) When the second initiator is not added, the reaction can be performed under the condition of heat initiation or ultraviolet initiation.

(25) Chlorine is introduced for performing reaction, wherein the molar ratio of the chlorine to the poly(propylene carbonate) is preferably (1-6):1; the temperature of the reaction is preferably 4 C.-80 C., more preferably 10 C.-60 C., and still preferably 30 C.-60 C.; and the time of the reaction is preferably 10-300 min, and more preferably 50-200 min.

(26) After reaction, an alcohol is preferably added to precipitate a product, and after washing and drying, the chlorinated poly(propylene carbonate) represented by formula (I) is obtained. More preferably, methanol is added to precipitate a product. At this time, the process flow chart of this water phase suspension method is as shown in FIG. 3.

(27) In order to further illustrate this invention, the detailed description will be made in conjunction with the Examples below, with respect to a chlorinated poly(propylene carbonate) and the preparation method thereof.

(28) All reagents used in the Examples below are commercially available.

Example 1

(29) 100 g of 60-mesh poly(propylene carbonate) (PPC) powder, 0.5 g of a mixture of benzoyl peroxide and dimethylaniline (the molar ratio of benzoyl peroxide to dimethylaniline was 1.5:1), and 5 g of white carbon black were added to a reactor, stirred and gradually cooled under the condition of water bath. When the temperature was lower than 15 C., it began to introduce chlorine. Before the temperature reached 10 C., the introduction amount of the chlorine reached 60% of the total amount of the chlorine introduced. Then, cooling was continued to 10 C., and the introduction amount of the chlorine reached 95% of the total amount introduced. Finally, 5% of the chlorine was introduced when the temperature was decreased to 5 C. The total amount of the chlorine introduced was 240 g. The reaction was performed for 2 h, followed by driving off the residual chlorine using clean air, and a white powdery chlorinated poly(propylene carbonate) containing chlorine in an amount of 9% was obtained.

(30) The poly(propylene carbonate) used in Example 1 was coated on a silicon wafer and was analyzed using a scanning electron microscope to obtain a spectrogram of scanning electron microscope-energy dispersive spectrometry analysis, as shown in FIG. 4.

(31) The chlorinated poly(propylene carbonate) obtained in Example 1 was coated on a silicon wafer and was analyzed using a scanning electron microscope to obtain a spectrogram of scanning electron microscope-energy dispersive spectrometry analysis, as shown in FIG. 5.

(32) After the poly(propylene carbonate) used in Example 1 was coated on a silicon wafer, a water contact angle test was performed to obtain that the contact angle thereof was 90.

(33) After the chlorinated poly(propylene carbonate) obtained in Example 1 was coated on a silicon wafer, a water contact angle test was performed to obtain that the contact angle thereof was 65. The above tests illustrated that the polarity of the chlorinated poly(propylene carbonate) was larger than that of the poly(propylene carbonate).

Example 2

(34) 100 g of 60-mesh poly(propylene carbonate) (PPC) powder was added to a reactor and was gradually cooled under the condition of ice water bath, followed by adding 0.3 g of a mixture of benzoyl peroxide and dimethylaniline (the molar ratio of benzoyl peroxide to dimethylaniline was 1.5:1) and 5 g of white carbon black. Chlorine was introduced, and was gradually cooled to room temperature. The total amount of the chlorine introduced was 240 g. The reaction was performed for 2 h, followed by driving off the residual chlorine using clean air, and a white powdery chlorinated poly(propylene carbonate) containing chlorine in an amount of 12% was obtained.

Example 3

(35) 100 g of 60-mesh poly(propylene carbonate) (PPC) powder, 0.4 g of benzoyl peroxide, and 5 g of white carbon black were added to a reactor. Chlorine was introduced, and the temperature risen to 55 C. The total amount of the chlorine introduced was 240 g. The reaction was performed for 2 h, followed by driving off the residual chlorine using clean air, and a white powdery chlorinated poly(propylene carbonate) containing chlorine in an amount of 24% was obtained.

Example 4

(36) 100 g of 60-mesh poly(propylene carbonate) (PPC) powder and 5 g of white carbon black were added to a reactor. Chlorine was introduced under the irradiation of ultraviolet, and the temperature risen to 30 C. The total amount of the chlorine introduced was 240 g. The reaction was performed for 2 h, followed by driving off the residual chlorine using clean air, and a white powdery chlorinated poly(propylene carbonate) containing chlorine in an amount of 9% was obtained.

Example 5

(37) 15 g of 120-mesh poly(propylene carbonate) (PPC) powder, 170 g of a tap water and 0.75 g of white carbon black were added to a reactor. Chlorine was introduced at 60 C. The total amount of the chlorine introduced was 140 g. The reaction time of the chlorination reaction was about 5 h. Then, the product was subjected to washing by a tap water, neutralizing by an alkali solution and drying to obtain a white powdery chlorinated poly(propylene carbonate) CPPC containing chlorine in an amount of 30%.

(38) Those described above are merely the preferred embodiments of the invention, and it is to be indicated that, with respect to the person skilled in the art, various improvements and modifications can also be made without departing from the principle of this invention. These improvements and modifications should be considered as the scope to be protected by this invention.