CN104211848B - A kind of preparation method of the heat-proof modifier of N phenyl maleimides class - Google Patents
A kind of preparation method of the heat-proof modifier of N phenyl maleimides class Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of the heat-proof modifier of N phenyl maleimides class, comprise the following steps：Styrene, maleic anhydride, azodiisobutyronitrile, trithiocarbonic acid dimethyl ester and the Thiobenzimidazole benzyl ester of 2 methyl two composition polymerization system are added in solvent cyclohexanone; polymerisation 2~6 hours between 60~120 DEG C under nitrogen protection; then 60 DEG C are cooled to; add aniline, acetic anhydride and sodium acetate; reacted 2~6 hours between being warming up to 100~150 DEG C; then room temperature is cooled to, reactant is poured into polymer is settled out in ethanol, then through filtering, being dried to obtain finished product.Through the above way, the present invention can easily control molecular weight and its distribution of polymeric reaction product, and the polymer molecular weight of preparation is distributed in less than 1.3, and comparatively speaking, molecular weight distribution is narrower, and technique is relatively easy, with higher economic worth.
Description
Technical field
The present invention relates to a kind of preparation method of the good heat-proof modifier of heat resistance, being used more particularly, to one kind can
Inverse addition-fracture chain transfer polymerization prepares the preparation of the narrower N-phenyl maleimide heatproof modifying agent of molecular weight distribution
Method.
Background technology
(Acrylonitrile butadiene Styrene copolymers, acrylonitrile-butadiene-styrene (ABS) is common for ABS
Polymers) resin is one of five big synthetic resin, with impact resistance, low temperature resistant, chemicals-resistant, easy processing shaping and lustrous surface are good
Etc. excellent combination property.Therefore, have in fields such as auto industry, electronics, electrical equipment, weaving, utensil and building materials and widely should
With.But the heat distortion temperature highest of ABS resin can not be more than 100 DEG C, and this is restricted the application of ABS resin.
N-phenyl maleimide heatproof modifying agent is the improvement ABS resin heat resistance grown up in decades recently
The multiple copolymer of the monomers such as one important channel of energy, N-phenylmaleimide and styrene and maleic anhydride formation, both
The glass transition temperature and heat decomposition temperature of polymer can be improved, compatibility can be increased again, improves the processability of material
Energy.ABS resin can improve its heat distortion temperature, highest can after N-phenyl maleimide heatproof modifying agent is added
Up to 150 DEG C, this has widened the application field of ABS resin significantly.
At present, the preparation method report for preparing N-phenyl maleimide heatproof modifying agent is more.Such as Patent No.
The Chinese invention patent of ZL200710069041.6 is disclosed using suspension method one-step synthesis styrene/acrylonitrile/N- phenyl horses
Carry out the method for imide terpolymer；Du Miao et al. is in article《N-phenylmaleimide/styrene emulsion copolymerization
Research》Elaborate to synthesize binary with emulsion polymerisation process in (" Hebei University of Technology's journal ", the 2nd phase, volume 26 in 1997)
Copolymer.It is how many with few in copolymer because suspension polymerisation and emulsion polymerisation process have used dispersant and emulsifying agent respectively
Amount dispersant or emulsifying agent residue, it is difficult to eliminate completely, this will influence the quality of copolymer.Meanwhile, these methods are all used
N-phenylmaleimide carries out copolymerization as raw material, and the preparation of the N-phenylmaleimide of high-purity is more complicated, and
The features such as with corrosivity, made troubles to production.
Japan Patent JP57100104,1982, disclose and use solution reaction system, prepared according to radical polymerization mechanism
The copolymer of styrene and maleic anhydride, then carries out imidization reaction, finally with the maleic anhydride in aniline and copolymer
Obtain the copolymer containing N-phenylmaleimide.The method does not use N-phenylmaleimide as raw material, but adopts
Prepared with common radical polymerization mechanism, it is impossible to efficiently control the molecular weight and molecualr weight distribution of polymer, what is obtained is poly-
The distribution of adduct molecule amount is general all more than 1.5.
The content of the invention
For above-mentioned prior art exist shortcoming and defect, it is an object of the invention to provide one kind using reversible addition-
Fracture chain transfer polymerization prepares the preparation method of the narrower N-phenyl maleimide heatproof modifying agent of molecular weight distribution.
To realize the object of the invention, inventor provides following technical scheme：
A kind of preparation method of the heat-proof modifier of N-phenylmaleimide class, comprises the following steps：
Styrene, maleic anhydride, azodiisobutyronitrile, trithiocarbonic acid dimethyl ester and 2- first are added in solvent cyclohexanone
The Thiobenzimidazole of base-two benzyl ester constitutes polymerization system, under nitrogen protection polymerisation 2~6 hours between 60~120 DEG C,
Then 60 DEG C are cooled to, aniline, acetic anhydride and sodium acetate is added, reaction 2~6 hours between being warming up to 100~150 DEG C, then
Room temperature is cooled to, reactant is poured into polymer is settled out in ethanol, then through filtering, being dried to obtain finished product.
In above-mentioned technical proposal, azodiisobutyronitrile is used as initiator, and trithiocarbonic acid dimethyl ester and 2- methyl-two are thio
Benzimidazole benzyl ester as chain-transferring agent, also known as RAFT (reversible addition-fragmentation chain
Transfer, reversible addion-fragmentation chain transfer) reagent, acetic anhydride and sodium acetate as imidization reaction dehydration catalyst,
Wherein, concentration of the initiator in polymerization system is 10-3~10-2mol·L-1, concentration of the RAFT reagents in polymerization system is
10-2~10-1mol·L-1, the weight ratio of trithiocarbonic acid dimethyl ester and the Thiobenzimidazole benzyl ester of 2- methyl-two is 1: 1, horse
Carry out concentration of the acid anhydrides in polymerization system for 0.5~0.7molL-1；Concentration of the styrene in polymerization system be 1.1~
1.3mol·L-1, the weight ratio of aniline and maleic anhydride is 0.9: 1, and concentration of the dehydration catalyst in polymerization system is 10-2~
10-1mol·L-1, the weight ratio of acetic anhydride and sodium acetate is 9: 1.
The method of the present invention is by changing initiator, the proportioning of RAFT reagents can effectively control the molecular weight of polymerizate
And distribution, so as to get polymerizate number-average molecular weight 1 × 104~30 × 104Between, molecular weight distribution is below 1.3.
Preferably, according to a kind of preparation side of the heat-proof modifier of N-phenylmaleimide class of the present invention
Method, wherein, described initiator is azodiisobutyronitrile.
Preferably, according to a kind of preparation side of the heat-proof modifier of N-phenylmaleimide class of the present invention
Method, wherein, described chain-transferring agent is trithiocarbonic acid dimethyl ester and the Thiobenzimidazole benzyl ester of 2- methyl-two.
Preferably, according to a kind of preparation side of the heat-proof modifier of N-phenylmaleimide class of the present invention
Method, wherein, described dehydration catalyst is acetic anhydride and sodium acetate.
Preferably, according to a kind of preparation side of the heat-proof modifier of N-phenylmaleimide class of the present invention
Method, wherein, described solvent is cyclohexanone.
Preferably, according to a kind of preparation side of the heat-proof modifier of N-phenylmaleimide class of the present invention
Method, wherein, described polymerization system needs nitrogen to protect.
Because above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：
1st, present invention process is relatively easy, and without using N-phenylmaleimide for raw material, course of reaction is gently easy
Control, economic worth is had more compared to N-phenylmaleimide is used for the method for raw material.
2nd, the present invention can easily control molecular weight and its distribution of polymeric reaction product, the polymer molecular weight of preparation
Less than 1.3 are distributed in, comparatively speaking, molecular weight distribution is narrower.
Embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1
In the polymerization bottle with backflow and agitating device, add 1.1mol styrene, 0.5mol maleic anhydrides,
0.001mol azodiisobutyronitriles, 0.001mol trithiocarbonic acids dimethyl ester, the Thiobenzimidazole benzyl of 0.001mol2- methyl-two
Ester and 1L cyclohexanone, react 5 hours under nitrogen protection at 70 DEG C, are cooled to 60 DEG C, add 0.45mol aniline, 0.009mol
Acetic anhydride and 0.001mol sodium acetates, are warming up to 130 DEG C and react 5 hours, be cooled to room temperature, reactant is poured into ethanol and precipitated
Go out polymer, then through filtering, being dried to obtain finished product.
Polymer number-average molecular weight obtained by the present embodiment is 25 × 104, molecular weight distribution is 1.23.
Embodiment 2
In the polymerization bottle with backflow and agitating device, add 1.1mol styrene, 0.6mol maleic anhydrides,
0.001mol azodiisobutyronitriles, 0.003mol trithiocarbonic acids dimethyl ester, the Thiobenzimidazole benzyl of 0.003mol2- methyl-two
Ester and 1L cyclohexanone, react 3 hours at 75 DEG C under nitrogen protection, are cooled to 60 DEG C, add 0.54mol aniline, 0.018mol
Acetic anhydride and 0.002mol sodium acetates, are warming up to 140 DEG C and react 4 hours, be cooled to room temperature, reactant is poured into ethanol and precipitated
Go out polymer, then through filtering, being dried to obtain finished product.
Polymer number-average molecular weight obtained by the present embodiment is 21 × 104, molecular weight distribution is 1.18.
Embodiment 3
In the polymerization bottle with backflow and agitating device, add 1.2mol styrene, 0.6mol maleic anhydrides,
0.005mol azodiisobutyronitriles, 0.003mol trithiocarbonic acids dimethyl ester, the Thiobenzimidazole benzyl of 0.003mol2- methyl-two
Ester and 1L cyclohexanone, react 3 hours under nitrogen protection at 80 DEG C, are cooled to 60 DEG C, add 0.54mol aniline, 0.027mol
Acetic anhydride and 0.003mol sodium acetates, are warming up to 140 DEG C and react 4 hours, are cooled to room temperature, reactant is poured into ethanol and is precipitated
Go out polymer, then through filtering, being dried to obtain finished product.
Polymer number-average molecular weight obtained by the present embodiment is 18 × 104, molecular weight distribution is 1.15.
Embodiment 4
In the polymerization bottle with backflow and agitating device, add 1.3mol styrene, 0.7mol maleic anhydrides,
0.007mol azodiisobutyronitriles, 0.004mol trithiocarbonic acids dimethyl ester, the Thiobenzimidazole benzyl of 0.004mol2- methyl-two
Ester and 1L cyclohexanone, react 3 hours at 80 DEG C under nitrogen protection, are cooled to 60 DEG C, add 0.63mol aniline, 0.036mol
Acetic anhydride and 0.004mol sodium acetates, are warming up to 150 DEG C and react 2 hours, are cooled to room temperature, reactant is poured into ethanol and is precipitated
Go out polymer, then through filtering, being dried to obtain finished product.
Polymer number-average molecular weight obtained by the present embodiment is 15 × 104, molecular weight distribution is 1.12.
Embodiment 5
In the polymerization bottle with backflow and agitating device, add 1.2mol styrene, 0.7mol maleic anhydrides,
0.008mol azodiisobutyronitriles, 0.004mol trithiocarbonic acids dimethyl ester, the Thiobenzimidazole benzyl of 0.004mol2- methyl-two
Ester and 1L cyclohexanone, react 3 hours under nitrogen protection at 85 DEG C, are cooled to 60 DEG C, add 0.63mol aniline, 0.036mol
Acetic anhydride and 0.004mol sodium acetates, are warming up to 100 DEG C and react 6 hours, be cooled to room temperature, reactant is poured into ethanol and precipitated
Go out polymer, then through filtering, being dried to obtain finished product.
Polymer number-average molecular weight obtained by the present embodiment is 12 × 104, molecular weight distribution is 1.1.
Embodiment 6
In the polymerization bottle with backflow and agitating device, add 1.3mol styrene, 0.6mol maleic anhydrides,
0.009mol azodiisobutyronitriles, 0.005mol trithiocarbonic acids dimethyl ester, the Thiobenzimidazole benzyl of 0.005mol2- methyl-two
Ester and 1L cyclohexanone, react 2 hours at 100 DEG C under nitrogen protection, are cooled to 60 DEG C, add 0.54mol aniline, 0.063mol
Acetic anhydride and 0.007mol sodium acetates, are warming up to 150 DEG C and react 4 hours, are cooled to room temperature, reactant is poured into ethanol and is precipitated
Go out polymer, then through filtering, being dried to obtain finished product.
Polymer number-average molecular weight obtained by the present embodiment is 7 × 104, molecular weight distribution is 1.1.
Performance test
Polymer prepared by embodiment 1,2,3,4,5,6 is carried out into performance test, indices and result are as shown in table 1.
Finished product index prepared by each embodiment of table 1
| Embodiment | Glass transition temperature/DEG C | Vicat softening point/DEG C | Melt index (MI)/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 it can be seen from table 1 the glass transition temperature and Vicat softening point of copolymer are with the increase of molecular weight of copolymer
Raise, illustrate the heat resistance of copolymer increases with the increase of molecular weight, meanwhile, melt index (MI) is with the increase of molecular weight
And reduce, therefore suitable copolymer can be prepared according to the need for the modification demand and processing method of different resins.
The heat-proof modifier of embodiment 2 is added in ABS resin in 50% ratio, modified ABS resin is determined
Indices, compared with the ABS resin that is not added with heat-proof modifier, as a result such as table 2.
Table 2 adds copolymer and the ABS resin indices for being not added with copolymer
Note：1,2 be to add copolymer ratio to be 50% and be not added with the ABS resin of copolymer respectively in table 2.
From table 2 it can be seen that the addition of the heat-proof modifier of N-phenylmaleimide class can improve the resistance to of ABS resin
Hot property and mechanical property.
Claims (1)
1. a kind of preparation method of the heat-proof modifier of N-phenylmaleimide class, it is characterised in that described method includes
Following steps：
Added in solvent cyclohexanone styrene, maleic anhydride, azodiisobutyronitrile, trithiocarbonic acid dimethyl ester and 2- methyl-
Two Thiobenzimidazole benzyl esters constitute polymerization system, and nitrogen protects lower 70~120 DEG C of polymerisations 2~6 hours, is then cooled to
60 DEG C, aniline, acetic anhydride and sodium acetate are added, 100~150 DEG C is warming up to and reacts 2~6 hours, be then cooled to room temperature, will be anti-
Answer thing to pour into and polymer be settled out in ethanol, then through filtering, being dried to obtain finished product, wherein, azodiisobutyronitrile as initiator,
, used as chain-transferring agent, acetic anhydride and sodium acetate are used as acyl for trithiocarbonic acid dimethyl ester and the Thiobenzimidazole benzyl ester of 2- methyl-two
The dehydration catalyst of imidization, concentration of the initiator in polymerization system is 10-3~10-2mol·L-1, RAFT reagents exist
Concentration in polymerization system is 10-2~10-1mol·L-1, trithiocarbonic acid dimethyl ester and the Thiobenzimidazole benzyl of 2- methyl-two
The weight ratio of ester is 1: 1, and concentration of the maleic anhydride in polymerization system is 0.5~0.7molL-1；Styrene is in polymerization system
In concentration be 1.1~1.3molL-1, aniline is 0.9: 1 with the weight ratio of maleic anhydride, and dehydration catalyst is in polymerization system
In concentration be 10-2~10-1mol·L-1, the weight ratio of acetic anhydride and sodium acetate is 9: 1.
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| 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 |
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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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- 2014-09-02 CN CN201410442429.6A patent/CN104211848B/en active Active
Patent Citations (3)
| 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 |
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| Direct Polymer Reaction of Poly(styrene-co-maleic anhydride): Polymeric Imidization;SANG-SOO LEE等;《Journal of Applied Polymer Science》;19990108;第71卷;第1187-1196页 * |
| 马来酸酐和苯乙烯的可逆加成-断链链转移聚合及新型嵌段共聚物的合成;朱明强等;《高分子学报》;20010630(第3期);第415-417页 * |
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