CN107700213A - A kind of carbon fiber sizing agent and preparation method thereof and a kind of fibre reinforced PP composite material and preparation method thereof - Google Patents
A kind of carbon fiber sizing agent and preparation method thereof and a kind of fibre reinforced PP composite material and preparation method thereof Download PDFInfo
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- 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
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- C08F222/06—Maleic anhydride
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
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Abstract
The invention provides a kind of carbon fiber sizing agent, is maleic anhydride and long-chain olefin and/or the copolymer emulsion of long alkine.It has good adhesion property, and dip time is greatly shortened, and good bridge joint effect is played between carbon fiber and polypropylene matrix, so as to further improve the mechanical property of composite.Carbon fiber is pre-processed using above-mentioned carbon fiber sizing agent, the fibre reinforced PP composite material of preparation has excellent mechanical property.
Description
Technical field
The present invention relates to carbon fibre composite technical field, more particularly to a kind of carbon fiber sizing agent and preparation method thereof
A kind of and fibre reinforced PP composite material and preparation method thereof.
Background technology
Polypropylene (PP) is a kind of low density, abundant raw material, cheap, widely used high polymer material, belongs to heat
Plastic resin.But polyacrylic notch impact toughness is relatively low, shrinkage factor is big, causes polypropylene in use by external force
Influence and there is stress whitening, limit its widespread popularity to a certain extent.Carbon fiber is a kind of high ratio modulus, height
The elite clone that specific strength, density are low, high temperature resistant, thermal coefficient of expansion are small, is widely used in the high-end neck such as space flight and aviation, automobile
Domain.
The advantages of by combining polypropylene and carbon fiber, high intensity, light-weighted composite can be prepared.However, carbon
Surface chemistry inertia is presented in fiber, and surface energy is low and almost without chemical group.In addition, polypropylene belongs to non-polar polymer, this
Cause when prepared by carbon fiber/polypropylene composite material that interface binding intensity is poor between the two, have a strong impact on the enhancing of carbon fiber
Effect.Carbon fiber, which carries out starching processing and addition compatilizer, can improve its interface performance, such as Chinese patent very well
CN201310698084.6, CN201510439653.4, CN201610253742.4 are specifically mentioned to using silane coupler
The aqueous solution carries out long-time immersion treatment to carbon fiber, and a certain amount of compatilizer is added in recombination process, by increasing capacitance it is possible to increase carbon
The mechanical property of fiber/polypropylene composite material.But the adhesion property of the small molecule silane coupler in the above method difference and
Raising to interface performance is extremely limited.
More than being based on, develop a kind of high-adhesiveness energy macromolecule carbon fiber sizing agent and processing raising carbon fibre is carried out to carbon fiber
Dimension and polypropylene compatible, reduce the usage amount of compatilizer while meet that material mechanical performance has turned into the important directions of development.
The content of the invention
In view of this, the technical problem to be solved in the present invention be to provide a kind of carbon fiber sizing agent and preparation method thereof with
And a kind of fibre reinforced PP composite material and preparation method thereof, the carbon fiber sizing agent has good adhesiveness
Can, dip time is greatly shortened.
The invention provides a kind of carbon fiber sizing agent, for the copolymerization of maleic anhydride and long-chain olefin and/or long alkine
Thing emulsion.
The long-chain olefin is the one or more in 1- laurylenes, 1- hexadecylenes, 1- octadecylenes and 1- icosa alkenes.
The long alkine is the one or more in 1- n-heptylacetylenes, 1- decine, 1- dodecynes and 1- hexadecines.
The mol ratio of the maleic anhydride and long-chain olefin and the total amount of long alkine is preferably 1：(0.05~3).
The invention provides the preparation method of above-mentioned carbon fiber sizing agent, comprise the following steps：
A) under conditions of nitrogen protection, 30~70 DEG C, long-chain olefin and/or long alkine are dissolved in maleic anhydride to be had
Solvent；
B initiator) is added, controls 80~130 DEG C, 200~1000rpm of mixing speed of temperature, is reacted 0.5~6 hour；
C high speed shear dispersion emulsifying machine agitating solution) is used, mixing speed is 500~30000rpm, and stirring is added dropwise and gone simultaneously
Ionized water, after continuing stirring 0.5~3 hour, solution is rotated and removes organic solvent, obtain polymer emulsion sizing agent.
The organic solvent is preferably dimethylbenzene, N, N-dimethylformamide and N, one kind or more in N dimethyl acetamide
The mixture of kind.
The initiator is preferably azodiisobutyronitrile, ABVN, benzoyl peroxide and diacetyl peroxide
In one or more.
The carbon fiber sizing agent molecular weight being prepared is 5000~100000Kg/mol.
The invention provides a kind of preparation method of fibre reinforced PP composite material, comprise the following steps：
A impregnated carbon fiber) is subjected to 1~3min of dipping in carbon fiber sizing agent under normal temperature；
B) polypropylene, carbon fiber, antioxidant, lubricant are added in banbury, 170~200 DEG C, after 3~5min of kneading
Discharging, obtains elastomeric compound；
C) by above-mentioned elastomeric compound successively it is hot-forming, cold pressing it is qualitative, obtain fibre reinforced PP composite material.
The carbon fiber is preferably 7 μm of diameter, and length is 2~10mm chopped carbon fiber.
The step A) dipping after, it is preferred that to carbon fiber at 20~80 DEG C, carry out 0.5~1h drying and processings.
The polypropylene, carbon fiber, antioxidant, the mass ratio of lubricant and carbon fiber sizing agent are preferably 100：(3~
50)：(0.1~3)：(1~3)：(0.1~2).
The antioxidant be preferably four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, 2,2 '-
Di-2-ethylhexylphosphine oxide (4- methyl-6-tert-butylphenols), 4,4'- thiobis (the 6- tert-butyl group -3- methylphenols) and the three [uncles of 2,4- bis-
Butyl phenyl] one or more in phosphite ester.
The lubricant is preferably the one or more in haloflex, paraffin oil, odium stearate and silicone powder.
It is described it is hot-forming preferably be specially：
Obtained elastomeric compound is laid in flat plate mold, is placed in compression molding instrument, controls 160~190 DEG C of temperature,
0.5 ton of 10~50min of preheating of pressure.Further press on 10~25 tons and carry out 5~20min of hot pressing.
The cold pressing is qualitative to be preferably specially：
Compression molding instrument temperature is down to normal temperature and keeps 5~20 tons of pressure, 10~30min.
Present invention also offers fibre reinforced PP composite material prepared by above-mentioned preparation method.
The invention provides a kind of carbon fiber sizing agent, for the copolymerization of maleic anhydride and long-chain olefin and/or long alkine
Thing emulsion.It has good adhesion property, and dip time is greatly shortened, and plays between carbon fiber and polypropylene matrix good
Good bridge joint effect, so as to further improve the mechanical property of composite.Carbon fiber is entered using above-mentioned carbon fiber sizing agent
Row pretreatment, the fibre reinforced PP composite material of preparation have excellent mechanical property.
Brief description of the drawings
Fig. 1 is the impact fracture surface scanning electron microscope (SEM) photograph of fibre reinforced PP composite material made from embodiment 2；
Fig. 2 is the impact fracture surface scanning electron microscope (SEM) photograph of fibre reinforced PP composite material made from embodiment 3.
Embodiment
In order to further illustrate the present invention, with reference to embodiment to carbon fiber sizing agent provided by the invention and its preparation
Method and a kind of fibre reinforced PP composite material are described in detail.
Embodiment 1
The preparation of sizing agent
(1) under conditions of nitrogen protection, 30 DEG C, by benzene and maleic anhydride according to 1.0:The amount of 1.0 materials it
Than being dissolved in dimethylbenzene；
(2) azo-bis-isobutyl cyanide is added, controls 80 DEG C, mixing speed 200rpm of temperature, is reacted 0.5 hour；
(3) high speed shear dispersion emulsifying machine agitating solution, mixing speed 500rpm are used, deionization is added dropwise simultaneously in stirring
Water, after continuing stirring 0.5 hour, solution is rotated and removes acetone, obtain polymer emulsion sizing agent.
Fibre reinforced PP composite material is prepared in accordance with the following methods：
(4) pre-treatment of carbon fiber：Impregnated carbon fiber is subjected to rapid impregnation 1min in sizing agent under normal temperature, at 20 DEG C,
0.5 hour drying and processing.
(5) it is kneaded：By 100 parts of polypropylene, 3 parts of carbon fiber, antioxidant 1010：0.1 part, 1 part of addition of haloflex it is close
In mill, it is 170 DEG C to control temperature, is discharged after kneading 3min, obtains elastomeric compound.
(6) it is hot-forming：Above-mentioned elastomeric compound is laid in flat plate mold, is placed in compression molding instrument, control temperature
160 DEG C of degree, 0.5 ton of preheating 10min of pressure.Further press on 10 tons and carry out hot pressing 5min.
(7) cold pressing sizing：Compression molding instrument temperature is down to normal temperature and keeps 5 tons, 10min of pressure, obtains carbon fiber increasing
Strong PP composite material.
Embodiment 2
The preparation of sizing agent
(1) under conditions of nitrogen protection, 30~70 DEG C, by dodecyne and maleic anhydride according to 1.0:The amount of 2.0 materials
The ratio between be dissolved in DMF；
(2) benzoyl peroxide is added, controls 90 DEG C, mixing speed 500rpm of temperature, is reacted 3 hours；
(3) high speed shear dispersion emulsifying machine agitating solution, mixing speed 10000rpm are used, deionization is added dropwise simultaneously in stirring
Water, after continuing stirring 1.5 hours, solution is rotated and removes organic solvent, obtain polymer emulsion sizing agent.
Fibre reinforced PP composite material is prepared in accordance with the following methods：
(4) pre-treatment of carbon fiber：Impregnated carbon fiber is subjected to rapid impregnation 2min in sizing agent under normal temperature, at 60 DEG C,
40min drying and processings.
(5) it is kneaded：By 100 parts of polypropylene, 11 parts of carbon fiber, antioxidant 300：0.1 part, 5 parts of additions of haloflex it is close
In mill, it is 190 DEG C to control temperature, is discharged after kneading 5min, obtains elastomeric compound.
(6) it is hot-forming：Above-mentioned elastomeric compound is laid in flat plate mold, is placed in compression molding instrument, control temperature
185 DEG C of degree, 1 ton of preheating 30min of pressure.Further press on 20 tons and carry out hot pressing 10min.
(7) cold pressing sizing：Compression molding instrument temperature is down to normal temperature and keeps 15 tons, 15min of pressure, obtains carbon fiber increasing
Strong PP composite material.
Mechanics Performance Testing is carried out to the composite of preparation, it is that carbon fiber prepared by the application increases as a result to see Fig. 1, Fig. 1
The impact fracture surface scanning electron microscope (SEM) photograph of strong PP composite material, carbon fiber extraction section surface can be observed by Fig. 1 and be stained with necessarily
Measure matrix resin, then prove during being hit between carbon fiber and matrix interface have good adhesive attraction so as to improve increase
Potent fruit.
Embodiment 3
The preparation of sizing agent
(1) under conditions of nitrogen protection, 50 DEG C, by octadecylene and maleic anhydride according to 1.0:The ratio between amount of 0.8 material
It is dissolved in dimethylbenzene；
(2) benzoyl peroxide is added, controls 90 DEG C, mixing speed 600rpm of temperature, is reacted 4 hours；
(3) high speed shear dispersion emulsifying machine agitating solution, mixing speed 3000rpm are used, deionization is added dropwise simultaneously in stirring
Water, after continuing stirring 2 hours, solution is rotated and removes organic solvent, obtain polymer emulsion sizing agent.
Fibre reinforced PP composite material is prepared in accordance with the following methods：
(4) pre-treatment of carbon fiber：Impregnated carbon fiber is subjected to rapid impregnation 3min in sizing agent under normal temperature, at 80 DEG C,
1h drying and processings.
(5) it is kneaded：By 100 parts of polypropylene, 20 parts of carbon fiber, antioxidant 1010：2 parts of 0.5 part, paraffin oil addition banburies
In, it is 187 DEG C to control temperature, is discharged after kneading 3.5min, obtains elastomeric compound.
(6) it is hot-forming：Above-mentioned elastomeric compound is laid in flat plate mold, is placed in compression molding instrument, control temperature
190 DEG C of degree, 0.5 ton of preheating 25min of pressure.Further press on 25 tons and carry out hot pressing 10min.
(7) it is cold-pressed qualitative：Compression molding instrument temperature is down to normal temperature and keeps 20 tons, 20min of pressure, obtains carbon fiber increasing
Strong PP composite material.
Mechanics Performance Testing is carried out to the composite of preparation, it is that carbon fiber prepared by the application increases as a result to see Fig. 2, Fig. 2
The impact fracture surface scanning electron microscope (SEM) photograph of strong PP composite material, as shown in Figure 2 as fiber starching agent content improves, fiber and base
Interface interaction between body becomes stronger.
Embodiment 4
The preparation of sizing agent
(1) under conditions of nitrogen protection, 60 DEG C, by decene and maleic anhydride according to 1.0:The ratio between the amount of 0.5 material is molten
In N, N dimethyl acetamide；
(2) benzoyl peroxide is added, controls 100 DEG C, mixing speed 700rpm of temperature, is reacted 6 hours；
(3) high speed shear dispersion emulsifying machine agitating solution, mixing speed 1000rpm are used, deionization is added dropwise simultaneously in stirring
Water, after continuing stirring 3 hours, solution is rotated and removes organic solvent, obtain polymer emulsion sizing agent.
Fibre reinforced PP composite material is prepared in accordance with the following methods：
(4) pre-treatment of carbon fiber：Impregnated carbon fiber is subjected to rapid impregnation 1min in sizing agent under normal temperature, at 30 DEG C,
0.5h drying and processings.
(5) it is kneaded：By 100 parts of polypropylene, 5 parts of carbon fiber, antioxidant 300：1.9 parts of 0.1 part, silicone powder addition banburyings
In machine, it is 177 DEG C to control temperature, is discharged after kneading 5min, obtains elastomeric compound.
(6) it is hot-forming：Above-mentioned elastomeric compound is laid in flat plate mold, is placed in compression molding instrument, control temperature
185 DEG C of degree, 0.5 ton of preheating 16min of pressure.Further press on 13 tons and carry out hot pressing 15min.
(7) it is cold-pressed qualitative：Compression molding instrument temperature is down to normal temperature and keeps 15 tons, 30min of pressure, obtains carbon fiber increasing
Strong PP composite material.
Embodiment 5
The preparation of sizing agent
(1) under conditions of nitrogen protection, 30 DEG C, by tetradecene and maleic anhydride according to 1.0:The ratio between amount of 1.0 materials
It is dissolved in dimethylbenzene；
(2) azo-bis-isobutyl cyanide is added, controls 80 DEG C, mixing speed 800rpm of temperature, is reacted 4.5 hours；
(3) high speed shear dispersion emulsifying machine agitating solution, mixing speed 7000rpm are used, deionization is added dropwise simultaneously in stirring
Water, after continuing stirring 2 hours, solution is rotated and removes organic solvent, obtain polymer emulsion sizing agent.
Fibre reinforced PP composite material is prepared in accordance with the following methods：
(4) pre-treatment of carbon fiber：Impregnated carbon fiber is subjected to rapid impregnation 2min in sizing agent under normal temperature, at 50 DEG C,
0.5h drying and processings.
(5) it is kneaded：By 100 parts of polypropylene, 27 parts of carbon fiber, antioxidant 2246：1.8 parts of 0.2 part, haloflex additions
In banbury, it is 190 DEG C to control temperature, is discharged after kneading 5min, obtains elastomeric compound.
(6) it is hot-forming：Above-mentioned elastomeric compound is laid in flat plate mold, is placed in compression molding instrument, control temperature
190 DEG C of degree, 0.5 ton of preheating 20min of pressure.Further press on 25 tons and carry out hot pressing 15min.
(7) it is cold-pressed qualitative：Compression molding instrument temperature is down to normal temperature and keeps 20 tons, 25min of pressure, obtains carbon fiber increasing
Strong PP composite material.
Embodiment 6
The preparation of sizing agent
(1) under conditions of nitrogen protection, 70 DEG C, by 14 alkynes and maleic anhydride according to 1.0:The ratio between amount of 1.2 materials
It is dissolved in dimethylbenzene；
(2) benzoyl peroxide is added, controls 110 DEG C, mixing speed 1000rpm of temperature, is reacted 4 hours；
(3) high speed shear dispersion emulsifying machine agitating solution, mixing speed 1000rpm are used, deionization is added dropwise simultaneously in stirring
Water, after continuing stirring 2 hours, solution is rotated and removes organic solvent, obtain polymer emulsion sizing agent.
Fibre reinforced PP composite material is prepared in accordance with the following methods：
(4) pre-treatment of carbon fiber：Impregnated carbon fiber is subjected to rapid impregnation 1min in sizing agent under normal temperature, at 30 DEG C,
0.5h drying and processings.
(5) it is kneaded：By 100 parts of polypropylene, 30 parts of carbon fiber, antioxidant 1010：0.1 part, 1.9 parts of additions of odium stearate it is close
In mill, it is 200 DEG C to control temperature, is discharged after kneading 4min, obtains elastomeric compound.
(6) it is hot-forming：Above-mentioned elastomeric compound is laid in flat plate mold, is placed in compression molding instrument, control temperature
190 DEG C of degree, 0.5 ton of preheating 16min of pressure.Further press on 25 tons and carry out hot pressing 15min.
(7) it is cold-pressed qualitative：Compression molding instrument temperature is down to normal temperature and keeps 25 tons, 30min of pressure, obtains carbon fiber increasing
Strong PP composite material.
Embodiment 7
The preparation of sizing agent
(1) under conditions of nitrogen protection, 70 DEG C, by laurylene and maleic anhydride according to 1.0:The ratio between amount of 1.0 materials
It is dissolved in dimethylbenzene；
(2) benzoyl peroxide is added, controls 130 DEG C, mixing speed 1000rpm of temperature, is reacted 6 hours；
(3) high speed shear dispersion emulsifying machine agitating solution, mixing speed 30000rpm are used, deionization is added dropwise simultaneously in stirring
Water, after continuing stirring 3 hours, solution is rotated and removes organic solvent, obtain polymer emulsion sizing agent.
Fibre reinforced PP composite material is prepared in accordance with the following methods：
(4) pre-treatment of carbon fiber：Impregnated carbon fiber is subjected to rapid impregnation 1min in sizing agent under normal temperature, at 80 DEG C,
1h drying and processings.
(5) it is kneaded：By 100 parts of polypropylene, 50 parts of carbon fiber, antioxidant 1010：3 parts of 3 parts, haloflex addition banburyings
In machine, it is 200 DEG C to control temperature, is discharged after kneading 5min, obtains elastomeric compound.
(6) it is hot-forming：Above-mentioned elastomeric compound is laid in flat plate mold, is placed in compression molding instrument, control temperature
190 DEG C of degree, 0.5 ton of preheating 50min of pressure.Further press on 25 tons and carry out hot pressing 20min.
(7) it is cold-pressed qualitative：Compression molding instrument temperature is down to normal temperature and keeps 20 tons, 30min of pressure, obtains carbon fiber increasing
Strong PP composite material.
Comparative example 1
(1) pre-treatment of carbon fiber：Impregnated carbon fiber is subjected to rapid impregnation 3min in deionized water under normal temperature, 80
DEG C, 1h drying and processings.
Fibre reinforced polypropylene composite materials material is prepared with step (5)~(7) in embodiment 3 in step (2)~(4)
Material.
The composite prepared to above-described embodiment 1~7 and comparative example 1 carries out mechanical test, the results are shown in Table shown in 1.
Compound Material Engineering test result prepared by the embodiment 1~7 of table 1 and comparative example 1
From above-described embodiment and comparative example, the present invention uses the sizing agent of specific components, carbon fiber is located in advance
Reason, shortens dip time, the composite of preparation has excellent mechanical property.
The explanation of above example is only intended to help the method and its core concept for understanding the present invention.It should be pointed out that pair
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (9)
1. a kind of carbon fiber sizing agent, it is characterised in that for maleic anhydride and the copolymer of long-chain olefin and/or long alkine breast
Liquid；
The long-chain olefin be 1- laurylenes, 1- hexadecylenes, 1- octadecylenes and 1- icosa alkenes in one or more, the long-chain
Alkynes is the one or more in 1- n-heptylacetylenes, 1- decine, 1- dodecynes and 1- hexadecines.
2. carbon fiber sizing agent according to claim 1, it is characterised in that the maleic anhydride and long-chain olefin and long-chain
The mol ratio of the total amount of alkynes is 1：(0.05~3).
3. the preparation method of the carbon fiber sizing agent described in any one of claim 1~2, it is characterised in that comprise the following steps：
A) in nitrogen protection, under conditions of 30~70 DEG C, long-chain olefin and/or long alkine are dissolved in maleic anhydride organic molten
Agent；
B initiator) is added, controls 80~130 DEG C, 200~1000rpm of mixing speed of temperature, is reacted 0.5~6 hour；
C high speed shear dispersion emulsifying machine agitating solution) is used, mixing speed is 500~30000rpm, and deionization is added dropwise simultaneously in stirring
Water, after continuing stirring 0.5~3 hour, solution is rotated and removes organic solvent, obtain polymer emulsion sizing agent.
4. preparation method according to claim 3, it is characterised in that the organic solvent is dimethylbenzene, N, N dimethyl first
Acid amides and N, one or more mixtures in N dimethyl acetamide.
5. a kind of preparation method of fibre reinforced PP composite material, it is characterised in that comprise the following steps：
A impregnated carbon fiber) is subjected to 1~3min of dipping in carbon fiber sizing agent under normal temperature；
B) polypropylene, carbon fiber, antioxidant, lubricant are added in banbury, 170~200 DEG C, discharged after 3~5min of kneading,
Obtain elastomeric compound；
C) by above-mentioned elastomeric compound successively it is hot-forming, cold pressing it is qualitative, obtain fibre reinforced PP composite material.
6. preparation method according to claim 5, it is characterised in that the polypropylene, carbon fiber, antioxidant, lubricant
Mass ratio with carbon fiber sizing agent is 100：(3~50)：(0.1~3)：(1~3)：(0.1~2).
7. preparation method according to claim 5, it is characterised in that the antioxidant be four [β-(3,5- di-t-butyls-
4- hydroxy phenyls) propionic acid] pentaerythritol ester, 2,2 '-di-2-ethylhexylphosphine oxide (4- methyl-6-tert-butylphenols), 4,4'- thiobis (6-
The tert-butyl group -3- methylphenols) and three [2,4- di-tert-butyl-phenyls] phosphite esters in one or more.
8. preparation method according to claim 5, it is characterised in that the lubricant is haloflex, paraffin oil, hard
One or more in resin acid sodium and silicone powder.
9. fibre reinforced PP composite material prepared by the preparation method described in any one of claim 5~8.
Priority Applications (1)
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| CN113445323A (en) * | 2021-07-07 | 2021-09-28 | 长春工业大学 | Preparation method of lignin-based sizing agent for composite carbon nano tube and application of lignin-based sizing agent in polyolefin |
| CN113717389A (en) * | 2021-07-07 | 2021-11-30 | 东北师范大学 | Preparation method of lignin-based hydrophilic sizing agent and application of lignin-based hydrophilic sizing agent in polyolefin composite material |
| CN114213751A (en) * | 2021-12-09 | 2022-03-22 | 福建师范大学泉港石化研究院 | Carbon fiber reinforced polypropylene composite material and preparation method thereof |
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