CN114014985B - Alpha-methylstyrene copolymer and preparation method and application thereof - Google Patents
Alpha-methylstyrene copolymer and preparation method and application thereof Download PDFInfo
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- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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Abstract
The invention discloses an alpha-methylstyrene copolymer, a preparation method and application thereof, wherein the copolymer has a branched chain structure of functionalized polyacrylonitrile and a main chain structure of the copolymer containing alpha-methylstyrene-styrene-cycloolefin ester derivatives. According to the invention, cycloolefin ester derivatives are introduced into the main chain structure of the copolymer, so that the main chain has a conformational fixed cyclic group, the bond energy is enhanced to improve the heat stability of the main chain and the glass transition temperature of the polymer; meanwhile, the flexible ester side chain effectively inhibits cyclization of the polyacrylonitrile cyano through molecular chain vibration, and improves the color change in the polymer processing process. Compared with linear molecules with the same molecular weight, the polymer with the branched structure has lower melt viscosity and solution viscosity, better fluidity, and Tg is not influenced by the molecular structure, thus being capable of reducing the devolatilization and processing temperature of the polymer.
Description
Technical Field
The invention relates to a copolymer, in particular to an alpha-methylstyrene copolymer, a preparation method and application thereof.
Background
Poly (alpha-methylstyrene-styrene-acrylonitrile) (AMSAN) is a linear terpolymer and is commonly used as a heat-resistant modifier for PVC and ABS.
The AMSAN can be polymerized by emulsion to obtain a polymer with high molecular weight and wide distribution, but small molecular assistants such as an emulsifier in the polymer are difficult to remove, and the product is easy to yellow in the post-processing process. The bulk polymerization can avoid introducing a large amount of small molecule auxiliary agents, is a good way for solving the problems, but the method needs to raise the temperature to remove unpolymerized monomers after the polymerization is completed, and the AMSAN copolymer has poor thermal stability and is easy to degrade at high temperature, and meanwhile, the system has higher viscosity and poor fluidity in the later stage of polymerization, and the devolatilization and post-processing temperature of the polymer are also influenced. In addition, the higher the α -methylstyrene content, the greater the linear molecular chain rigidity, the higher the melt viscosity, and the higher the processing temperatures required for devolatilization and post-processing of the polymer, the higher the temperature is, which is susceptible to thermal degradation of the polymer and cyanocyclization of the polyacrylonitrile, which results in yellowing of the article.
Therefore, it is highly desirable to develop an α -methylstyrene copolymer that is stable in heat resistance, good in fluidity, and less prone to yellowing.
Disclosure of Invention
In order to solve the technical problems, the invention provides an alpha-methylstyrene copolymer with high fluidity and thermal stability, and a preparation method and application thereof. According to the invention, cycloolefin ester derivatives are introduced into the main chain structure of the copolymer, so that the main chain has a conformational fixed cyclic group, the bond energy is enhanced to improve the heat stability of the main chain and the glass transition temperature of the polymer; meanwhile, the flexible ester side chain effectively inhibits cyclization of the polyacrylonitrile cyano through molecular chain vibration, and improves the color change in the polymer processing process. In addition, compared with linear molecules with the same molecular weight, the polymer with the branched structure has lower melt viscosity and solution viscosity, better fluidity, and Tg is not influenced by the molecular structure, thus being capable of reducing the devolatilization and processing temperature of the polymer.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
an α -methylstyrene copolymer having a branched structure of a functionalized polyacrylonitrile and a main chain structure comprising an α -methylstyrene-styrene-cycloolefin ester derivative copolymer; the alpha-methylstyrene copolymer has the following molecular structural expression:
in the formula I, R is optionally substituted or unsubstituted C 2 -C 6 Unsaturated alkyl, preferably vinyl orn, x, y, z, k are respectively different polymerization degrees, wherein n=70 to 120, x=300 to 600, y=70 to 200, z=1 to 10, k=1 to 25; and co represents only the connection mode of random copolymerization of each chain segment, and no specific definition exists.
In some preferred examples, the alpha-methylstyrene copolymer has a weight average molecular weight of 8X 10 4 ～10×10 4 g/mol, and the molecular weight distribution is 1.8-2.5.
A process for the preparation of an α -methylstyrene copolymer as described hereinbefore, comprising the steps of:
adding a mixture of an organic solvent, a comonomer, a cycloolefin ester derivative and a peroxidation initiator into a reactor, heating to 110-120 ℃, and carrying out bulk polymerization reaction for 3-4 hours; the comonomer comprises alpha-methyl styrene, functionalized polyacrylonitrile of terminal styryl;
after the reaction is finished, continuously heating to 180-200 ℃, gradually vacuumizing to the vacuum degree of-0.08 MPa to-0.1 MPa, maintaining for 30-40 min, and removing unpolymerized monomers to obtain the alpha-methylstyrene copolymer.
In some preferred examples, the comonomer comprises 50 to 70wt%, 10 to 20wt% and 20 to 30wt% of alpha-methylstyrene, styrene and terminal styryl functionalized polyacrylonitrile;
preferably, the dosage of the cycloolefin ester derivative is 1-5 wt% of the total mass of the comonomer; more preferably, the cyclic olefin ester derivative is dicyclopentadienyloxyethyl acrylate or dicyclopentadienyloxyethyl methacrylate.
In some preferred examples, the peroxidation initiator is one or more of 1, 1-bis (t-butylperoxy) -3, 5-trimethylcyclohexane, 1-bis (t-butylperoxy) -2-methylcyclohexane, t-butyl peroxy-3, 5-trimethylhexanoate, preferably a mixture of 1, 1-bis (t-butylperoxy) -3, 5-Trimethylcyclohexane (TMCH) and t-butyl peroxy-3, 5-Trimethylhexanoate (TBPIN), more preferably a mixture of TMCH in an amount of 80 to 85wt% and TBPIN in an amount of 15 to 50 wt%.
Preferably, the peroxide initiator is used in an amount of 0.15 to 0.2wt% based on the total mass of the comonomer.
In some preferred examples, the method of preparing the functionalized polyacrylonitrile of terminal styryl group comprises the following steps:
an anion polymerization method is adopted, an organic solvent, acrylonitrile and a molecular weight regulator are sequentially added into a reactor, the temperature is kept at 40-50 ℃ for 10-20 min, an initiator is added for polymerization for 1-2 hours, the temperature of the reaction solution is reduced to minus 10 ℃ to 0 ℃, p-chloromethyl styrene is added for end-capping reaction for 0.5-1 hour, and finally ethanol sedimentation, filtration and drying are carried out to obtain the functionalized polyacrylonitrile with the end styryl.
In some preferred examples, the initiator is one or more of n-butyllithium, sec-butyllithium, tert-butyllithium;
preferably, the initiator is used in an amount of 0.9 to 1.3% by mole based on the molar amount of the acrylonitrile monomer.
In some preferred examples, the molecular weight regulator is one or more of tetrahydrofuran, tetramethyl vinyl diamine, triethylamine;
preferably, the molecular weight regulator is used in an amount of 5 to 20 times the molar amount of the initiator.
In some preferred examples, the addition amount of the p-chloromethyl styrene is 1.1 to 1.2 times of the molar amount of the initiator;
preferably, the organic solvent is one or more of cyclohexane, toluene, xylene and ethylbenzene. Further, in the preparation process of the functionalized polyacrylonitrile with the end styryl, the addition amount of the organic solvent is 4-8 times of that of the acrylonitrile monomer; in the bulk polymerization process of the alpha-methylstyrene copolymer, the addition amount of the organic solvent is 5 to 10 weight percent of the total mass of the comonomer.
In some preferred examples, the number average molecular weight of the terminal styryl-functionalized polyacrylonitrile is 4×10 3 ～6×10 3 g/mol, and the molecular weight distribution is 1.0-1.2.
Use of an alpha-methylstyrene copolymer as described hereinbefore as a heat-resistant modifier for PVC or ABS.
Without being specifically stated, "wt%" in the present invention refers to mass percent.
The invention designs and synthesizes the branched copolymer with the main chain of poly (alpha-methylstyrene-co-styrene-co-cycloolefin esters) and the branched chain of polyacrylonitrile, and the copolymer has the advantages of definite branched chain structure, high heat resistance and melt flow rate, good heat stability and the like.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
The copolymer related structure and performance test method is as follows:
glass transition temperature (Tg): testing with a Switzerland METLER instrument, in units of deg.C;
relative molecular mass (Mw) and molecular weight distribution (PDI): the test is carried out by adopting a Japanese island jin 20AD instrument, and the relative molecular mass unit g/mol is adopted;
monomer residue (GC): testing by an Agilent 7890B instrument, wherein the unit ppm is;
color (b value): the yellowness index of the samples was measured using a Hunter Lab colorimeter;
melt index (MVR): test is carried out by using CEAST MF30 melt finger instrument with unit cm 3 /10min；
Thermal decomposition loss Temperature (TGA) the thermal decomposition temperature in degrees Celsius at which the weight of the material lost 1% by weight was measured using METLER, switzerland.
The main raw material information is shown in table 1:
TABLE 1 Main raw Material information
| Raw materials | CAS | Purity of | Manufacturer(s) |
| Alpha-methylstyrene (AMS) | 98-83-9 | 99.0％ | Aladdin |
| Styrene (SM) | 100-42-5 | 99.9％ | Sigma-Aldrich |
| Acrylonitrile (AN) | 107-13-1 | 99.9％ | Sigma-Aldrich |
| Dicyclopentadienyloxyethyl acrylate (DPOM) | 65983-31-5 | 99.5％ | Sigma-Aldrich |
| Dicyclopentadienyloxyethyl methacrylate (DPOMA) | 68586-19-6 | 99.5％ | Beijing Rabo dragon |
| N-butyllithium | 203-698-7 | 1.6mol/L | Aladdin |
| Para chloromethyl styrene | 1592-20-7 | 99.9％ | Aladdin |
| 1, 1-bis (t-butylperoxy) -3, 5-Trimethylcyclohexane (TMCH) | 6731-36-8 | 75.0％ | Aladdin |
| Tert-butyl peroxy-3, 5-Trimethylhexanoate (TBPIN) | 13122-18-4 | 99.9％ | Sigma-Aldrich |
Preparation of functionalized Polyacrylonitrile with terminal styryl groups PAN-1, PAN-2, PAN-3, respectively
Sequentially adding metered toluene and acrylonitrile into a reactor with the capacity of 1L by adopting an anion polymerization method, preserving heat for 20min at 45 ℃, adding an n-butyllithium initiator with the concentration of 1.6mol/L, reacting for 1 h, cooling the reaction solution to 0 ℃, adding metered p-chloromethylstyrene VBC (with the molar ratio of 1.2:1) and carrying out end capping reaction for 40min, and finally settling the reaction solution with 2L ethanol, filtering and drying to obtain the functionalized polyacrylonitrile with the end styryl of the target molecular weight, wherein the reaction is carried out under the protection of argon. The number average molecular weight and molecular weight distribution of the product are shown in Table 2.
TABLE 2 raw material amounts and corresponding product analysis results in preparation examples
| Sequence number | Toluene/g | Acrylonitrile/g | THF/ml | N-butyllithium/ml | VBC/g | Mn(g/mol) | PDI |
| PAN-1 | 500 | 100 | 13.5 | 10.4 | 3.06 | 6000 | 1.12 |
| PAN-2 | 500 | 100 | 14.4 | 12.5 | 3.67 | 5000 | 1.15 |
| PAN-3 | 500 | 100 | 18.0 | 15.6 | 4.59 | 4000 | 1.09 |
[ example 1 ]
The alpha-methylstyrene copolymer is prepared as follows:
10g of toluene, 70g of alpha-methylstyrene, 10g of styrene, 20g of PAN-1,1g of cyclopentadienyl ethyl caproate, 0.144g of TMCH and 0.036g of TBPIN are mixed in a reactor by adopting a free radical bulk polymerization method, and the reactor is heated to 110 ℃ for reaction for 4 hours; the reactor is continuously heated to 200 ℃, and is gradually vacuumized until the vacuum degree is minus 0.1MPa, and is kept for 30min, and the alpha-methylstyrene copolymer is obtained after the unpolymerized monomer is removed. The results of the product analysis and the copolymer property test are shown in Table 3.
Examples 2 to 10
The α -methylstyrene copolymers were prepared with reference to the corresponding reaction conditions in Table 2, respectively. The results of the product analysis and the copolymer property test are shown in Table 3, respectively.
Comparative example 1
Copolymers were prepared by substantially the same procedure as in example 1 except that cycloolefin ester derivative monomers were not added, and the results of product analysis and copolymer property test are shown in Table 3, respectively.
Comparative example 2
Copolymers were prepared in substantially the same manner as in example 1, except that the functionalized polyacrylonitrile was replaced with acrylonitrile of the same quality, and the results of product analysis and copolymer property test are shown in Table 3, respectively.
[ comparative example 3 ]
A copolymer was prepared by substantially the same procedure as in example 1 except that the cycloolefin ester derivative monomer was not added, and the functionalized polyacrylonitrile was replaced with acrylonitrile of the same quality, and the results of the product analysis and the copolymer property test are shown in Table 3, respectively.
According to the test results in Table 3, the alpha-methylstyrene copolymer prepared by the present invention has higher fluidity, thermal stability and heat resistance, and the resin has a low monomer residue and a whiter color.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.
Table 3, reaction conditions and product test results for examples 1 to 10 and comparative examples 1 to 3
Claims (19)
1. An α -methylstyrene copolymer, wherein the α -methylstyrene copolymer has a branched structure of a functionalized polyacrylonitrile and a backbone structure comprising an α -methylstyrene-styrene-cycloolefin ester derivative copolymer; the alpha-methylstyrene copolymer has the following molecular structural expression:
in the formula I, R is optionally substituted or unsubstituted C 2 -C 6 Unsaturated alkyl; n, x, y, z, k are respectively different polymerization degrees, wherein n=70 to 120, x=300 to 600, y=70 to 200, z=1 to 10, k=1 to 25; and co represents the connection mode of random copolymerization of each chain segment.
2. The alpha-methylstyrene copolymer as recited in claim 1 wherein R is vinyl or
3. The alpha-methylstyrene copolymer according to claim 1, wherein the alpha-methylstyrene copolymer has a weight average molecular weight of 8X 10 4 ～10×10 4 g/mol, and the molecular weight distribution is 1.8-2.5.
4. A process for the preparation of an α -methylstyrene copolymer according to any one of claims 1 to 3, comprising the steps of:
adding a mixture of an organic solvent, a comonomer, a cycloolefin ester derivative and a peroxidation initiator into a reactor, heating to 110-120 ℃, and carrying out bulk polymerization reaction for 3-4 hours; the comonomer comprises alpha-methyl styrene, functionalized polyacrylonitrile of terminal styryl;
after the reaction is finished, continuously heating to 180-200 ℃, gradually vacuumizing to the vacuum degree of-0.08 MPa to-0.1 MPa, maintaining for 30-40 min, and removing unpolymerized monomers to obtain the alpha-methylstyrene copolymer.
5. The method for producing an alpha-methylstyrene copolymer according to claim 4, wherein the comonomer comprises 50 to 70wt%, 10 to 20wt% and 20 to 30wt% of the functionalized polyacrylonitrile of alpha-methylstyrene, styrene and terminal styrene groups, respectively.
6. The method for producing an alpha-methylstyrene copolymer according to claim 5, wherein the cycloolefin derivative is used in an amount of 1 to 5% by weight based on the total mass of the comonomer.
7. The method for producing an α -methylstyrene copolymer according to claim 6, wherein the cycloolefin derivative is dicyclopentadienyloxyethyl acrylate or dicyclopentadienyloxyethyl methacrylate.
8. The method for producing an α -methylstyrene copolymer according to claim 5, wherein the peroxidation initiator is one or more of 1, 1-bis (t-butylperoxy) -3, 5-trimethylcyclohexane, 1-bis (t-butylperoxy) cyclohexane, 1-bis (t-butylperoxy) -2-methylcyclohexane, t-butyl peroxy-3, 5-trimethylhexanoate.
9. The method for producing an α -methylstyrene copolymer according to claim 8, wherein the peroxidation initiator is a mixture of 1, 1-bis (t-butylperoxy) -3, 5-trimethylcyclohexane and t-butyl peroxy-3, 5-trimethylhexanoate.
10. The method for preparing an alpha-methylstyrene copolymer according to claim 8, wherein the peroxide initiator is used in an amount of 0.15 to 0.2% by weight based on the total mass of the comonomer.
11. The method for producing an α -methylstyrene copolymer according to any one of claims 4 to 10, wherein the method for producing a functionalized polyacrylonitrile of terminal styryl group comprises the steps of:
an anion polymerization method is adopted, an organic solvent, acrylonitrile and a molecular weight regulator are sequentially added into a reactor, the temperature is kept at 40-50 ℃ for 10-20 min, an initiator is added for polymerization for 1-2 hours, the temperature of the reaction solution is reduced to minus 10 ℃ to 0 ℃, p-chloromethyl styrene is added for end-capping reaction for 0.5-1 hour, and finally ethanol sedimentation, filtration and drying are carried out to obtain the functionalized polyacrylonitrile with the end styryl.
12. The method for producing an α -methylstyrene copolymer according to claim 11, wherein the initiator is one or more of n-butyllithium, sec-butyllithium and tert-butyllithium.
13. The method for producing an α -methylstyrene copolymer according to claim 12, wherein the initiator is used in an amount of 0.9 to 1.3% by mole based on the amount of acrylonitrile monomer.
14. The method for producing an α -methylstyrene copolymer according to claim 12, wherein the molecular weight modifier is one or more of tetrahydrofuran, tetramethylethylenediamine and triethylamine.
15. The method for producing an alpha-methylstyrene copolymer according to claim 14, wherein the molecular weight modifier is used in an amount of 5 to 20 times the molar amount of the initiator.
16. The method for producing an α -methylstyrene copolymer according to claim 12, wherein the amount of p-chloromethylstyrene added is 1.1 to 1.2 times the molar amount of the initiator.
17. The method for producing an α -methylstyrene copolymer according to claim 16, wherein the organic solvent is one or more of cyclohexane, toluene, xylene, and ethylbenzene.
18. The method for producing an α -methylstyrene copolymer according to claim 11, wherein the number average molecular weight of the styrene-terminated functionalized polyacrylonitrile is 4×10 3 ～6×10 3 g/mol, and the molecular weight distribution is 1.0-1.2.
19. Use of an alpha-methylstyrene copolymer according to any one of claims 1 to 3 and an alpha-methylstyrene copolymer prepared by the process according to any one of claims 4 to 18, characterized in that the alpha-methylstyrene copolymer is used as a heat-resistant modifier for PVC or ABS.
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