CN110407978A - One kind can the fluorine-based phenyl of cross-linking radiation N-() maleimide copolymer composition and its nylon 6 composite material preparation method - Google Patents
One kind can the fluorine-based phenyl of cross-linking radiation N-() maleimide copolymer composition and its nylon 6 composite material preparation method Download PDFInfo
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- CN110407978A CN110407978A CN201910819956.7A CN201910819956A CN110407978A CN 110407978 A CN110407978 A CN 110407978A CN 201910819956 A CN201910819956 A CN 201910819956A CN 110407978 A CN110407978 A CN 110407978A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
It can cross-linking radiation heat-proof modifier the invention discloses one kind, it is characterised in that: the modifying agent contains functional group N- (fluorine-based phenyl) maleimide.The present invention is prepared for the copolymer etc. of the binary of N- (fluorine-based phenyl) maleimide (FPMI) and FPMI containing particular functional group, ternary or more;The quasi polymer has good heat resistance, acts not only as the heat-proof modifier of the common plastics such as PVC, ABS, can also be used as the heat-proof modifier of the engineering plastics such as PA, PPO and work well.Although heat resisting temperature that such as N-phenylmaleimide/maleic anhydride of patent CN 104356297A, CN107474185B report and CPMI-KH550-St bipolymer can be improved PA, PPO etc., but when using equal quality number, heat resistance of the invention is improved more.
Description
Technical field
The present invention relates to one kind can cross-linking radiation N- (fluorine-based phenyl) maleimide copolymer composition, particularly belong to resin
Material synthesis field.
Background technique
Maleimide and its derivative are a kind of useful compounds as raw materials such as resin raw material, medical pesticides, special
Be not, in order to improve ABS resin, AS resin, AB resin, ACS resin, AES resin, AAS resin etc. phenylethylene resin series, with
And the heat resistance of Corvic, plexiglass, phenolic resin etc., mostly as one of copolymer composition and
It is used.Wherein, since N-phenylmaleimide is excellent in terms of reactivity and heat resistance, particularly made extensively
With.
Manufacturing method in relation to N-phenylmaleimide and its derivative, known from the prior art there are many methods.
Literature review and related patents have been reported that more: one-step method, acid anhydrides method, depickling method, esterification process and azeotropic method etc..
Copolymer in relation to N-phenylmaleimide and its derivative also has text as making and using for heat-resistant agent more
Offer report.But improve polymer heat-resistant temperature it is limited, the application especially in nylon 6, as patent CN104356297A,
The report of CN107474185B.
Summary of the invention
It can cross-linking radiation N- (fluorine-based phenyl) maleimide amine copolymer the technical problem to be solved by the present invention is providing one kind
Composition, it is limited to solve heat-resistant agent raising polymer heat-resistant temperature in the prior art, in the application especially in nylon 6
Limitation.
The technical scheme is that one kind can cross-linking radiation heat-proof modifier, the modifying agent contains functional group N-
(fluorine-based phenyl) maleimide.
The modifying agent is the copolymer of the binary containing N- (fluorine-based phenyl) maleimide, ternary or more.
It reacts as follows:
Wherein n=10-100.
It is described it is a kind of can cross-linking radiation heat-proof modifier preparation method, by FPMI, Triallyl isocyanurate, horse
Carry out anhydride copolymers, obtains ternary polymerization product, i.e. heat-proof modifier.
It is described it is a kind of can cross-linking radiation heat-proof modifier preparation method, the specific steps are as follows: heating oil bath pan to 76-
100 DEG C, reactor is added in FPMI, TAIC, MAH, catalyst and dimethylbenzene, and stir 40-60min at this temperature;Again plus
Enter dimethylbenzene, is passed through N2Gas, constant temperature 5-30min after stirring, being heated to 85-95 DEG C;It adds initiator DCP and is warming up to 100-
135 DEG C of reactions, react 2-4h, obtain head product, head product is dissolved in acetone while hot, and it is residual to make the removal of precipitating reagent reprecipitation with methanol
The monomer and small molecule stayed obtains powdery ter-polymer resin, i.e. heat-proof modifier by obtained product in vacuum drying.
The catalyst is benzoyl peroxide, azodiisobutyronitrile or the tertiary butyrite of peroxidating.
Beneficial effects of the present invention: the present invention is prepared for N- (fluorine-based phenyl) maleimide containing particular functional group
(FPMI) and the copolymer of the binary of FPMI, ternary or more etc.;The quasi polymer has good heat resistance, not only may be used
Using the heat-proof modifier as common plastics such as PVC, ABS, can also be used as the heat-proof modifier of the engineering plastics such as PA, PPO and
It works well.As patent CN 104356297A, CN107474185B report N-phenylmaleimide/maleic anhydride and
Although the bipolymers such as CPMI-KH550-St can be improved the heat resisting temperature of PA, PPO etc., but using equal quality part
When number, heat resistance of the invention is improved more.
Specific embodiment
The present invention is further illustrated below by specific example, but example is not intended to limit protection scope of the present invention.
Embodiment 1
The synthesis step of FPMI: (1) 1.078g MAH is dissolved in the DMF of 10mL;(2) by 1.51g to fluorine-based benzoic acid
It is dissolved in the DMF of 10mL, is then added drop-wise to solution in 15-30min in the DMF solution of MAH;(3) 6h is reacted under 40 degree;Instead
After answering, catalyst anhydrous sodium acetate, the 2mL dehydrating agent acetic anhydride, 0.2g hydroquinone of polymerization retarder of 0.2g is added, heats up,
By temperature control between 50-55 DEG C, 2h is reacted, solution becomes yellowish-brown transparence, after being cooled to room temperature, stands, by solution
It pours into precipitating in trash ice and a large amount of yellow needle-like crystals occurs, then filtered, washed, dried, it is brilliant to obtain pure yellowish-brown
Body-N- (the fluorine-based phenyl of 4-) maleimide (FPMI).
Resulting FPMI, Triallyl isocyanurate (TAIC) are copolymerized, binary copolymerization product is obtained.
Oil bath pan is heated to 76 DEG C, by the diformazan of 0.5gFPMI, 1.56gTAIC, azodiisobutyronitrile 0.035g and 25ml
Beaker is added in benzene, and stirs 40min at this temperature;Solution is transferred to, blender, condenser, thermometer, air guide are installed
In the 250ml four-necked bottle of pipe, 70ml dimethylbenzene is added, is passed through N2Gas, constant temperature 5min after stirring, being heated to 90 DEG C;It adds and draws
Hair agent DCP is simultaneously warming up to 125 DEG C of reactions, reacts 4h, obtains head product.Head product is dissolved in acetone while hot, is precipitated with methanol
Agent reprecipitation removes remaining monomer and small molecule, and obtained product and 60 DEG C are dried in vacuo for 24 hours, to remove small molecule, obtained
To powdery bipolymer resin sample.
Embodiment 2
By resulting FPMI, Triallyl isocyanurate (TAIC), maleic anhydride, ternary polymerization product is obtained.
Oil bath pan is heated to 80 DEG C, by 0.5gFPMI, 1.56gTAIC, 4.2g MAH, azodiisobutyronitrile 0.015-0.1g
Beaker is added with the dimethylbenzene of 25ml, and stirs 50min at this temperature;Solution is transferred to be equipped with blender, condenser,
Thermometer, gas-guide tube 250ml four-necked bottle in, be added 70ml dimethylbenzene, be passed through N2Gas, constant temperature after stirring, being heated to 86 DEG C
10min;It adds initiator DCP and is warming up to 135 DEG C of reactions, react 3h, obtain head product.Head product is dissolved in third while hot
Ketone makees precipitating reagent reprecipitation with methanol and removes remaining monomer and small molecule, and obtained product and 60 DEG C are dried in vacuo for 24 hours,
To remove small molecule, powdery ter-polymer resin sample is obtained.
Embodiment 3
The synthesis step of FPMI: (1) 10.78g MAH is dissolved in the DMF of 10mL;(2) by 15.1g to fluorine-based benzoic acid
It is dissolved in the DMF of 10mL, is then added drop-wise to solution in 15-30min in the DMF solution of MAH;(3) 6h is reacted under 40 degree;Instead
After answering, catalyst anhydrous sodium acetate, the 20mL dehydrating agent acetic anhydride, 2g hydroquinone of polymerization retarder of 2g is added, heats up, it will be warm
Degree control reacts 2h between 50-55 DEG C, and solution becomes yellowish-brown transparence, after being cooled to room temperature, stands, solution is poured into
There are a large amount of yellow needle-like crystals in precipitating in trash ice, then is filtered, washed, dried, and pure yellowish-brown crystal-N- is obtained
(the fluorine-based phenyl of 4-) maleimide (FPMI).
By resulting FPMI, Triallyl isocyanurate (TAIC), maleic anhydride, ternary polymerization product is obtained.
Heat oil bath pan to 90 DEG C, by 5gFPMI, 15.6gTAIC, 42g MAH, benzoyl peroxide 0.1-0.5g and
Beaker is added in the dimethylbenzene of 250ml, and stirs 40min at this temperature;Solution is transferred to be equipped with blender, condenser,
Thermometer, gas-guide tube 5000ml four-necked bottle in, be added 700ml dimethylbenzene, be passed through N2Gas, constant temperature after stirring, being heated to 95 DEG C
20min;It adds initiator DCP and is warming up to 100 DEG C of reactions, react 2h, obtain head product.Head product is dissolved in third while hot
Ketone makees precipitating reagent reprecipitation with methanol and removes remaining monomer and small molecule, and obtained product and 60 DEG C are dried in vacuo for 24 hours,
To remove small molecule, powdery ter-polymer resin sample is obtained.
Product obtained in example 1 is added to PA6, and cross-linking radiation is carried out to composite material, improves the heat-resisting of nylon 6
Performance, as a result as shown in the table:
Note: No. 1 is to be not added with binary copolymerization in table, and No. 2 are added to 5 parts of binary copolymerizations, and No. 3 are added to 10 parts, No. 4 additions
15 parts.
Professional can be by N-phenylmaleimide the position of substitution that common sense is associated at ortho position, the chemical combination of meta position
Object is similarly subjected to protect;As long as the copolymer of binary, ternary containing FPMI or more is also within the scope of protection.
Claims (7)
1. one kind can cross-linking radiation heat-proof modifier, it is characterised in that: the modifying agent contains functional group N- (fluorine-based phenyl)
Maleimide.
2. one kind according to claim 1 can cross-linking radiation heat-proof modifier, it is characterised in that: the modifying agent be containing
There is the copolymer of binary, ternary of N- (fluorine-based phenyl) maleimide or more.
3. one kind as claimed in claim 1 or 2 can cross-linking radiation heat-proof modifier preparation method, it is characterised in that: reaction
It is as follows:
Wherein n=10-100.
4. one kind as claimed in claim 1 or 2 can cross-linking radiation heat-proof modifier preparation method, it is characterised in that: will
FPMI, Triallyl isocyanurate, maleic anhydride obtain ternary polymerization product, i.e. heat-proof modifier.
5. one kind according to claim 4 can cross-linking radiation heat-proof modifier preparation method, it is characterised in that: specific step
Rapid as follows: reactor is added to 76-100 DEG C, by FPMI, TAIC, MAH, catalyst and dimethylbenzene in heating oil bath pan, and warm herein
Degree is lower to stir 40-60min;Dimethylbenzene is added, N is passed through2Gas, constant temperature 5-30min after stirring, being heated to 85-95 DEG C;It adds
Initiator DCP is simultaneously warming up to 100-135 DEG C of reaction, reacts 2-4h, obtains head product, head product is dissolved in acetone while hot, use first
Alcohol reprecipitation obtains powdery ter-polymer resin, i.e. heat-proof modifier by obtained product in vacuum drying.
6. one kind according to claim 4 or 5 can cross-linking radiation heat-proof modifier preparation method, it is characterised in that: it is anti-
Answer the molar ratio of raw material are as follows:
FPMI:TAIC:MAH=1-2:3-4:19-20.
7. one kind according to claim 3 or 5 can cross-linking radiation heat-proof modifier preparation method, it is characterised in that: institute
The catalyst stated is benzoyl peroxide, azodiisobutyronitrile or the tertiary butyrite of peroxidating.
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CN201910819956.7A CN110407978B (en) | 2019-08-31 | 2019-08-31 | Irradiation crosslinking N- (fluorophenyl) maleimide copolymer composition and preparation method of nylon 6 composite material thereof |
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Citations (9)
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JPS5638310A (en) * | 1979-09-07 | 1981-04-13 | Hitachi Ltd | Bismaleimide-triallyl isocyanurate polymer and its preparation |
EP0035760A2 (en) * | 1980-03-11 | 1981-09-16 | Hitachi, Ltd. | Thermosetting resin composition, process for preparation thereof and cured product thereof |
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JPS5747335A (en) * | 1980-09-05 | 1982-03-18 | Hitachi Ltd | Resin composition for low-shrinking molding |
JPH08277265A (en) * | 1995-04-04 | 1996-10-22 | Maruzen Petrochem Co Ltd | New bisalkenyl-substituted nadiimide, its production, its curing method and thermosetting resin composition |
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CN109897136A (en) * | 2019-03-13 | 2019-06-18 | 贵州大学 | The method of N- (4-F- phenyl) maleimide-Styrene binary copolymer (PFS) and its Molecular weight regulation |
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Effective date of registration: 20220802 Address after: 561100 1, Longteng Road, Xia Yun Industrial Park, Pingba District, Anshun, Guizhou Patentee after: KANGMINGYUAN (GUIZHOU) TECHNOLOGY DEVELOPMENT Co.,Ltd. Address before: Science and Technology Department of Huaxi north campus, Guizhou University, Huaxi District, Guiyang City, Guizhou Province Patentee before: Guizhou University |