CN104211848A - Preparation method of N-phenyl maleimide heat-resistant modifier - Google Patents
Preparation method of N-phenyl maleimide heat-resistant modifier Download PDFInfo
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- CN104211848A CN104211848A CN201410442429.6A CN201410442429A CN104211848A CN 104211848 A CN104211848 A CN 104211848A CN 201410442429 A CN201410442429 A CN 201410442429A CN 104211848 A CN104211848 A CN 104211848A
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Abstract
The invention discloses a preparation method of an N-phenyl maleimide heat-resistant modifier. The preparation method comprises the following steps: adding styrene, maleic anhydride, azodiisobutyronitrile, trithio dimethyl carbonate and 2-methyl-dithiobenzimidazole benzyl ester to form a polymerization system; carrying out a polymerization reaction for 2-6 hours at 60-120 DEG C under nitrogen protection; then, cooling to 60 DEG C, adding aniline, acetic anhydride and sodium acetate, and raising the temperature to 100-150 DEG C to react for 2-6 hours; and finally, cooling to room temperature, pouring the reactants into ethanol to settle a polymer, and filtering and drying to obtain a finished product. Through the above manner, the molecular weight and distribution of the product of the polymerization reaction can be conveniently controlled. The molecular weight of the prepared polymer is distributed below 1.3. Comparatively speaking, the molecular weight distribution is relatively narrow, the process is relatively simple, and the N-phenyl maleimide heat-resistant modifier has a relatively high economic value.
Description
Technical field
The present invention relates to the good heat-proof modifier of a kind of thermotolerance preparation method, especially relate to a kind of adopt reversible addition-fracture chain transfer polymerization prepare the narrower N-phenylmaleimide class heat-proof modifier of molecular weight distribution preparation method.
Background technology
ABS (Acrylonitrile butadiene Styrene copolymers, acrylonitrile-butadiene-styrene copolymer) resin is one of five large synthetic resins, there is the over-all properties of the excellences such as shock-resistant, low temperature resistant, chemicals-resistant, easily machine-shaping and surface luster are good.Therefore, have a wide range of applications in fields such as automotive industry, electronics, electrical equipment, weaving, utensil and building materials.Can not exceed 100 DEG C but the heat-drawn wire of ABS resin is the highest, this is restricted the range of application of ABS resin.
N-phenylmaleimide class heat-proof modifier is the important channel of improving ABS resin resistance toheat growing up in decades recently, the multiple copolymer that the monomers such as N-phenylmaleimide and vinylbenzene and maleic anhydride form, both second-order transition temperature and the heat decomposition temperature of polymkeric substance can have been improved, can increase again consistency, improve Drawing abillity.ABS resin, adding after N-phenylmaleimide class heat-proof modifier, can improve its heat-drawn wire, reaches as high as 150 DEG C, and this has widened the Application Areas of ABS resin greatly.
At present, prepare N-phenylmaleimide class heat-proof modifier preparation method report more.The Chinese invention patent that is ZL200710069041.6 as the patent No. discloses the method for employing suspension method one-step synthesis styrene/acrylonitrile/N-phenylmaleimide terpolymer; The people such as Du Miao have set forth with the synthetic copolymer of emulsion polymerisation process in article " research of N-phenylmaleimide/styrene emulsion copolymerization " (" Hebei University of Technology's journal ",, the 2nd phase, the 26th volume in 1997).Because suspension polymerization and emulsion polymerisation process have used respectively dispersion agent and emulsifying agent, how much in multipolymer to be difficult to eliminate completely with a small amount of dispersion agent or emulsifying agent residue, this will affect the quality of multipolymer.Meanwhile, these methods all adopt N-phenylmaleimide to carry out copolymerization as starting material, and the preparation of highly purified N-phenylmaleimide is more complicated, and have the features such as corrodibility, make troubles to production.
Japanese Patent JP57100104,1982, employing solution reaction system is disclosed, prepare the multipolymer of vinylbenzene and maleic anhydride according to radical polymerization mechanism, then carry out imidization reaction with the maleic anhydride in aniline and multipolymer, finally obtain the multipolymer containing N-phenylmaleimide.This method does not adopt N-phenylmaleimide as raw material, but adopts common radical polymerization mechanism preparation, can not effectively control the molecular weight and molecualr weight distribution of polymkeric substance, and the molecular weight distribution obtaining is generally all more than 1.5.
Summary of the invention
The shortcoming and defect existing for above-mentioned prior art, the object of this invention is to provide a kind of adopt reversible addition-fracture chain transfer polymerization prepare the narrower N-phenylmaleimide class of molecular weight distribution heat-proof modifier preparation method.
For realizing the object of the invention, contriver provides following technical scheme:
A preparation method for the heat-proof modifier of N-phenylmaleimide class, comprises the steps:
In solvent pimelinketone, add vinylbenzene, maleic anhydride, Diisopropyl azodicarboxylate, trithiocarbonic acid dimethyl ester and 2-methyl-dithio benzoglyoxaline benzyl ester composition polymerization system; polyreaction 2～6 hours between 60～120 DEG C under nitrogen protection; then be cooled to 60 DEG C; add aniline, acetic anhydride and sodium-acetate; be warming up between 100～150 DEG C and react 2～6 hours; then be cooled to room temperature, reactant poured into and in ethanol, is settled out polymkeric substance, more after filtration, the dry finished product that obtains.
In technique scheme, Diisopropyl azodicarboxylate is as initiator, trithiocarbonic acid dimethyl ester and 2-methyl-dithio benzoglyoxaline benzyl ester are as chain-transfer agent, claim again RAFT (reversible addition-fragmentation chain transfer, reversible addition-fracture chain shifts) reagent, acetic anhydride and sodium-acetate are as the dehydration catalyst of imidization reaction, and wherein, the concentration of initiator in polymerization system is 10
-3～10
-2molL
-1, the concentration of RAFT reagent in polymerization system is 10
-2～10
-1molL
-1, the weight ratio of trithiocarbonic acid dimethyl ester and 2-methyl-dithio benzoglyoxaline benzyl ester is 1: 1, the concentration of maleic anhydride in polymerization system is 0.5～0.7molL
-1; The concentration of vinylbenzene in polymerization system is 1.1～1.3molL
-1, the weight ratio of aniline and maleic anhydride is 0.9: 1, the concentration of dehydration catalyst in polymerization system is 10
-2～10
-1molL
-1, the weight ratio of acetic anhydride and sodium-acetate is 9: 1.
Method of the present invention can effectively be controlled molecular weight and the distribution of polymerisate by the proportioning that changes initiator, RAFT reagent, makes the polymerisate number-average molecular weight obtaining 1 × 10
4～30 × 10
4between, molecular weight distribution is below 1.3.
As preferably, according to the preparation method of the heat-proof modifier of a kind of N-phenylmaleimide class of the present invention, wherein, described initiator is Diisopropyl azodicarboxylate.
As preferably, according to the preparation method of the heat-proof modifier of a kind of N-phenylmaleimide class of the present invention, wherein, described chain-transfer agent is trithiocarbonic acid dimethyl ester and 2-methyl-dithio benzoglyoxaline benzyl ester.
As preferably, according to the preparation method of the heat-proof modifier of a kind of N-phenylmaleimide class of the present invention, wherein, described dehydration catalyst is acetic anhydride and sodium-acetate.
As preferably, according to the preparation method of the heat-proof modifier of a kind of N-phenylmaleimide class of the present invention, wherein, described solvent is pimelinketone.
As preferably, according to the preparation method of the heat-proof modifier of a kind of N-phenylmaleimide class of the present invention, wherein, described polymerization system needs nitrogen protection.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1, technique of the present invention is relatively simple, is raw material without adopting N-phenylmaleimide, and reaction process is gentle easily to be controlled, and compares and adopts the method that N-phenylmaleimide is raw material to have more economic worth.
2, the present invention can control molecular weight and the distribution thereof of polymeric reaction product easily, and the molecular weight distribution of preparation is below 1.3, and comparatively speaking, molecular weight distribution is narrower.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
In the polymerization bottle with backflow and whipping appts; add 1.1mol vinylbenzene, 0.5mol maleic anhydride, 0.001mol Diisopropyl azodicarboxylate; 0.001mol trithiocarbonic acid dimethyl ester, 0.001mol2-methyl-dithio benzoglyoxaline benzyl ester and 1L pimelinketone; under nitrogen protection, at 70 DEG C, react 5 hours; be cooled to 60 DEG C; add 0.45mol aniline, 0.009mol acetic anhydride and 0.001mol sodium-acetate; be warming up to 130 DEG C of reactions 5 hours; be cooled to room temperature; reactant is poured into and in ethanol, is settled out polymkeric substance, more after filtration, the dry finished product that obtains.
The polymkeric substance number-average molecular weight of the present embodiment gained is 25 × 10
4, molecular weight distribution is 1.23.
Embodiment 2
In the polymerization bottle with backflow and whipping appts; add 1.1mol vinylbenzene, 0.6mol maleic anhydride, 0.001mol Diisopropyl azodicarboxylate; 0.003mol trithiocarbonic acid dimethyl ester, 0.003mol2-methyl-dithio benzoglyoxaline benzyl ester and 1L pimelinketone; under nitrogen protection, at 75 DEG C, react 3 hours; be cooled to 60 DEG C; add 0.54mol aniline, 0.018mol acetic anhydride and 0.002mol sodium-acetate; be warming up to 140 DEG C of reactions 4 hours; be cooled to room temperature; reactant is poured into and in ethanol, is settled out polymkeric substance, more after filtration, the dry finished product that obtains.
The polymkeric substance number-average molecular weight of the present embodiment gained is 21 × 10
4, molecular weight distribution is 1.18.
Embodiment 3
In the polymerization bottle with backflow and whipping appts; add 1.2mol vinylbenzene, 0.6mol maleic anhydride, 0.005mol Diisopropyl azodicarboxylate; 0.003mol trithiocarbonic acid dimethyl ester, 0.003mol2-methyl-dithio benzoglyoxaline benzyl ester and 1L pimelinketone; under nitrogen protection, at 80 DEG C, react 3 hours; be cooled to 60 DEG C; add 0.54mol aniline, 0.027mol acetic anhydride and 0.003mol sodium-acetate; be warming up to 140 DEG C of reactions 4 hours; be cooled to room temperature; reactant is poured into and in ethanol, is settled out polymkeric substance, more after filtration, the dry finished product that obtains.
The polymkeric substance number-average molecular weight of the present embodiment gained is 18 × 10
4, molecular weight distribution is 1.15.
Embodiment 4
In the polymerization bottle with backflow and whipping appts; add 1.3mol vinylbenzene, 0.7mol maleic anhydride, 0.007mol Diisopropyl azodicarboxylate; 0.004mol trithiocarbonic acid dimethyl ester, 0.004mol2-methyl-dithio benzoglyoxaline benzyl ester and 1L pimelinketone; under nitrogen protection, at 80 DEG C, react 3 hours; be cooled to 60 DEG C; add 0.63mol aniline, 0.036mol acetic anhydride and 0.004mol sodium-acetate; be warming up to 150 DEG C of reactions 2 hours; be cooled to room temperature; reactant is poured into and in ethanol, is settled out polymkeric substance, more after filtration, the dry finished product that obtains.
The polymkeric substance number-average molecular weight of the present embodiment gained is 15 × 10
4, molecular weight distribution is 1.12.
Embodiment 5
In the polymerization bottle with backflow and whipping appts; add 1.2mol vinylbenzene, 0.7mol maleic anhydride, 0.008mol Diisopropyl azodicarboxylate; 0.004mol trithiocarbonic acid dimethyl ester, 0.004mol2-methyl-dithio benzoglyoxaline benzyl ester and 1L pimelinketone; under nitrogen protection, at 85 DEG C, react 3 hours; be cooled to 60 DEG C; add 0.63mol aniline, 0.036mol acetic anhydride and 0.004mol sodium-acetate; be warming up to 100 DEG C of reactions 6 hours; be cooled to room temperature; reactant is poured into and in ethanol, is settled out polymkeric substance, more after filtration, the dry finished product that obtains.
The polymkeric substance number-average molecular weight of the present embodiment gained is 12 × 10
4, molecular weight distribution is 1.1.
Embodiment 6
In the polymerization bottle with backflow and whipping appts; add 1.3mol vinylbenzene, 0.6mol maleic anhydride, 0.009mol Diisopropyl azodicarboxylate; 0.005mol trithiocarbonic acid dimethyl ester, 0.005mol2-methyl-dithio benzoglyoxaline benzyl ester and 1L pimelinketone; under nitrogen protection, at 100 DEG C, react 2 hours; be cooled to 60 DEG C; add 0.54mol aniline, 0.063mol acetic anhydride and 0.007mol sodium-acetate; be warming up to 150 DEG C of reactions 4 hours; be cooled to room temperature; reactant is poured into and in ethanol, is settled out polymkeric substance, more after filtration, the dry finished product that obtains.
The polymkeric substance number-average molecular weight of the present embodiment gained is 7 × 10
4, molecular weight distribution is 1.1.
Performance test
The polymkeric substance of embodiment 1,2,3,4,5,6 preparations is carried out to performance test, and indices and result are as shown in table 1.
Finished product index prepared by the each embodiment of table 1
| Embodiment | Second-order transition temperature/DEG C | Vicat softening point/DEG C | Melt index/g/10min |
| 1 | 213.2～217.1 | 225.8～231.3 | 1.9～2.5 |
| 2 | 202.5～206.9 | 215.1～219.5 | 3.5～4.1 |
| 3 | 191.3～196.8 | 203.3～208.5 | 4.8～5.2 |
| 4 | 180.6～184.1 | 196.2～199.7 | 5.7～6.1 |
| 5 | 173.3～178.5 | 188.4～193.1 | 6.3～6.7 |
| 6 | 164.3～169.9 | 174.8～179.1 | 7.1～7.3 |
As can be seen from Table 1, second-order transition temperature and the Vicat softening point of multipolymer raise along with the increase of molecular weight of copolymer, the resistance toheat that multipolymer is described increases along with the increase of molecular weight, simultaneously, melt index reduces along with the increase of molecular weight, therefore can prepare suitable multipolymer according to the needs of the modification demand of different resins and working method.
The heat-proof modifier of embodiment 2 is added in ABS resin in 50% ratio, measure the indices of the ABS resin after modification, compare with the ABS resin of not adding heat-proof modifier, result is as table 2.
Table 2 adds multipolymer and the ABS resin indices that does not add multipolymer
Note: in table 21,2 be respectively add multipolymer ratio be 50% with the ABS resin of not adding multipolymer.
As can be seen from Table 2, the interpolation of the heat-proof modifier of N-phenylmaleimide class can improve resistance toheat and the mechanical property of ABS resin.
Claims (6)
1. a preparation method for the heat-proof modifier of N-phenylmaleimide class, is characterized in that, described method comprises the steps:
In solvent pimelinketone, add vinylbenzene, maleic anhydride, Diisopropyl azodicarboxylate, trithiocarbonic acid dimethyl ester and 2-methyl-dithio benzoglyoxaline benzyl ester composition polymerization system, polyreaction 2～6 hours between 60～120 DEG C under nitrogen protection, then be cooled to 60 DEG C, add aniline, acetic anhydride and sodium-acetate, be warming up between 100～150 DEG C and react 2～6 hours, then be cooled to room temperature, reactant is poured into and in ethanol, is settled out polymkeric substance, again after filtration, the dry finished product that obtains, wherein, Diisopropyl azodicarboxylate is as initiator, trithiocarbonic acid dimethyl ester and 2-methyl-dithio benzoglyoxaline benzyl ester are as chain-transfer agent, acetic anhydride and sodium-acetate are as the dehydration catalyst of imidization reaction, the concentration of initiator in polymerization system is 10
-3～10
- 2molL
-1, the concentration of RAFT reagent in polymerization system is 10
-2～10
-1molL
-1, the weight ratio of trithiocarbonic acid dimethyl ester and 2-methyl-dithio benzoglyoxaline benzyl ester is 1: 1, the concentration of maleic anhydride in polymerization system is 0.5～0.7molL
-1, the concentration of vinylbenzene in polymerization system is 1.1～1.3molL
- 1, the weight ratio of aniline and maleic anhydride is 0.9: 1, the concentration of dehydration catalyst in polymerization system is 10
- 2～10
-1molL
-1, the weight ratio of acetic anhydride and sodium-acetate is 9: 1.
2. the preparation method of the heat-proof modifier of a kind of N-phenylmaleimide class as claimed in claim 1, is characterized in that, described initiator is Diisopropyl azodicarboxylate.
3. the preparation method of the heat-proof modifier of a kind of N-phenylmaleimide class as claimed in claim 1, is characterized in that, described chain-transfer agent is trithiocarbonic acid dimethyl ester and 2-methyl-dithio benzoglyoxaline benzyl ester.
4. the preparation method of the heat-proof modifier of a kind of N-phenylmaleimide class as claimed in claim 1, is characterized in that, described dehydration catalyst is acetic anhydride and sodium-acetate.
5. the preparation method of the heat-proof modifier of a kind of N-phenylmaleimide class as claimed in claim 1, is characterized in that, described solvent is pimelinketone.
6. the preparation method of the heat-proof modifier of a kind of N-phenylmaleimide class as claimed in claim 1, is characterized in that, described polymerization system needs nitrogen protection.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104961861A (en) * | 2015-06-01 | 2015-10-07 | 上海化学试剂研究所有限公司 | Preparation method of ABS plastic heatproof assistant |
| CN112063155A (en) * | 2020-09-07 | 2020-12-11 | 裕克施乐塑料制品（太仓）有限公司 | Special functional TPU powder for SLS forming impact-resistant and insolation-proof automobile instrument panel and preparation method thereof |
| CN112157909A (en) * | 2020-09-07 | 2021-01-01 | 裕克施乐塑料制品（太仓）有限公司 | Manufacturing process of TPU (thermoplastic polyurethane) -based high-performance automobile instrument panel |
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| US6407197B1 (en) * | 1998-03-04 | 2002-06-18 | Dsm N.V. | Aqueous dispersion of a polymer |
| CN103059187A (en) * | 2011-10-18 | 2013-04-24 | 日农科技股份有限公司 | Preparation method of styrene-N-phenylmaleimide copolymer |
| CN103193909A (en) * | 2013-04-01 | 2013-07-10 | 北京化工大学 | Preparation method of large-size polystyrene latex microspheres |
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2014
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6407197B1 (en) * | 1998-03-04 | 2002-06-18 | Dsm N.V. | Aqueous dispersion of a polymer |
| CN103059187A (en) * | 2011-10-18 | 2013-04-24 | 日农科技股份有限公司 | Preparation method of styrene-N-phenylmaleimide copolymer |
| CN103193909A (en) * | 2013-04-01 | 2013-07-10 | 北京化工大学 | Preparation method of large-size polystyrene latex microspheres |
Non-Patent Citations (2)
| Title |
|---|
| SANG-SOO LEE等: "Direct Polymer Reaction of Poly(styrene-co-maleic anhydride): Polymeric Imidization", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104961861A (en) * | 2015-06-01 | 2015-10-07 | 上海化学试剂研究所有限公司 | Preparation method of ABS plastic heatproof assistant |
| CN112063155A (en) * | 2020-09-07 | 2020-12-11 | 裕克施乐塑料制品（太仓）有限公司 | Special functional TPU powder for SLS forming impact-resistant and insolation-proof automobile instrument panel and preparation method thereof |
| CN112157909A (en) * | 2020-09-07 | 2021-01-01 | 裕克施乐塑料制品（太仓）有限公司 | Manufacturing process of TPU (thermoplastic polyurethane) -based high-performance automobile instrument panel |
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