CN109722899A - A kind of polyetherimide resin base carbon fibre suspension sizing agent and preparation method thereof - Google Patents
A kind of polyetherimide resin base carbon fibre suspension sizing agent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of polyetherimide resin base carbon fibre suspension sizing agents and preparation method thereof.Polyetherimide resin base carbon fibre suspension sizing agent is made of polyetherimide resin powder, Sodium Polyacrylate, alkyl phenol polyoxyethylene ether and deionized water；It is in terms of 100% by the gross mass of solid component, in which: polyetherimide resin 65~75wt% of powder, 12~17wt% of Sodium Polyacrylate, 13~18wt% of alkyl phenol polyoxyethylene ether.The starching carbon fiber that sizing agent prepared by the present invention is used to prepare is suitable for the intermediates such as polyetherimide resin based composites carbon fibre fabric, prepreg, and processing performance is good, and temperature tolerance and Interface adhesive strength are excellent.
Description
Technical field
The invention belongs to carbon fiber sizing agent technical field, in particular on a kind of polyetherimide resin base suspension-type
Starch agent and preparation method thereof.
Background technique
Polyetherimide resin is made of the alternately repeated ether of rule and imide ring, has excellent mechanical performance, resistance to
High temperature and dimensional stability are widely used in the high-end manufacturing fields such as the electric, industrial equipment of high temperature resistant.In polyetherimide
In resin, carbon fiber is added as reinforced phase, it is multiple that the fibre reinforced polyetherimide resin base haveing excellent performance can be prepared into
Condensation material.This kind of material combines carbon fiber and polyetherimide resin respectively characteristic, is with a wide range of applications.
The boundary layer of fibre reinforced polyetherimide resin based composites be influence multiple material properties of product it is important because
Element.Boundary layer is usually by carbon fiber-three phase composition of sizing agent-matrix resin, and wherein sizing agent plays crucial transition transmitting
Effect, should have that compatibility is high, high-temperature stability is good, process is without characteristics such as obvious chemical changes.Currently used carbon
Fiber sizing agent is epoxy resin-matrix emulsion pasting agent, is made of compoundings such as epoxy resin, surfactant, water, function additives.
The carbon fiber prepared using such sizing agent is had preferable compatibility and boundary strength with epoxy resin-base, but actually answered
With middle discovery, it is not suitable for the preparation that polyetherimide resin system answers material.It on the one hand is due to epoxy resin and polyethers acyl
The bond strength of imide resin is not high；On the other hand due in epoxy resin there are a large amount of high activity epoxy groups, in high temperature plus
It is easy open loop aging solidification in work treatment process, fiber is caused to reunite or be hardened, resin infiltration is deteriorated, product fault and defect
Increase.
Chinese patent 201410012914.X discloses a kind of polyetherimide aqueous emulsion type carbon fiber sizing agent, by 20%
~35% main slurry, 2%~7% emulsifier, 58%~78% deionized water composition, wherein main slurry is by polyetherimide resin
It is formed with dichloromethane solvent.This method can be improved interface bond strength between carbon fiber and polyetherimide, but wherein contain
A large amount of low boiling point volatile solvents, safety and the feature of environmental protection are bad, while product stability is easy to be affected.
Summary of the invention
In order to which solve that current epoxy resin sizing agent occurs in polyetherimide resin based composites various asks
Topic, the present invention propose a kind of stable suspension-type carbon fiber sizing agent and its system based on polyetherimide resin powder
Preparation Method.The polyetherimide resin powder process that the present invention uses is mature, can industrially scalable application.Using tradition side
Method prepares pure polyetherimide resin base carbon fibre sizing agent, it usually needs carries out grafting modification to polyetherimide resin
Processing is dissolved using a large amount of organic solvents, and preparation process is complicated, is related to the pollutants such as multi-solvents, dangerous waste, effect on environment
It is larger, it is less economical.It is only introduced in sizing agent component of the present invention and matrix resin polyetherimide with similar structure
For polyimide resin powder as host agent, compatibility and matching without epoxy resin or other resin Compositions and matrix resin are high,
Avoid the various application problems such as age hardening of epoxy group sizing agent.Sizing agent preparation method of the present invention avoids tradition
The problems such as grafting modification preparation is difficult, pollution is big, is not needed chemical synthesis modification, is processed by the way of physical mixed
Preparation, environmental-friendly, overall cost is lower.The carbon fiber sizing agent prepared using the method for the invention, can be coated uniformly on
Carbon fiber surface, prepared starching carbon fiber can be used for preparing polyetherimide resin based composites, and processing performance is good, heatproof
Property and Interface adhesive strength are excellent.
In the present invention, in order to make polyetherimide powder in an aqueous medium can fine dispersion, invention introduces poly-
Sodium acrylate is negatively charged after ionization as main dispersant, can be adsorbed on powder surface, make to generate electrostatic between powder particle
Repulsion forms electric double layer stability, reaches fine dispersion effect.Meanwhile introducing the alkyl phenol polyoxy second with aryl group
Alkene ether as stabilization aid, with the polyetherimide for containing a large amount of aromatic ring structures in molecular structure there is preferable absorption to be combined
Ability, at the same it is good amphipathic using its, promote in the micelle particle water of pps powder and Sodium Polyacrylate composition more
Add and is stabilized.
Technical solution of the present invention is specifically described as follows.
The present invention provides a kind of polyetherimide resin base carbon fibre suspension sizing agent, by polyetherimide resin powder
End, Sodium Polyacrylate, alkyl phenol polyoxyethylene ether and deionized water composition；By the gross mass of solid component be 100% in terms of,
In:
65~75wt% of polyetherimide resin powder
12~17wt% of Sodium Polyacrylate
13~18wt% of alkyl phenol polyoxyethylene ether.
In the present invention, shown in the structure of polyetherimide resin powder such as formula (1):
Wherein: n is the degree of polymerization of polyetherimide.
In the present invention, the number-average molecular weight of polyetherimide resin powder is between 2.5 ten thousand~3.5 ten thousand.
In the present invention, the number-average molecular weight of polyetherimide resin powder is preferably between 3.0 ten thousand~3.3 ten thousand.
In the present invention, the average diameter of the polyetherimide resin powder is between 10~60 microns.
In the present invention, the number-average molecular weight of the Sodium Polyacrylate is between 1000~5000.
In the present invention, the number-average molecular weight of the Sodium Polyacrylate is preferably between 2000~4000.
In the present invention, shown in the structure of the alkyl phenol polyoxyethylene ether such as formula (2):
Wherein: R is selected from C10~C25It is any in alkyl；Degree of polymerization m is the integer between 25~45.
In the present invention, mass content of the solid component in polyetherimide resin base carbon fibre suspension sizing agent exists
Between 5%~30%.
The present invention also provides a kind of preparation method of above-mentioned polyetherimide resin base carbon fibre suspension sizing agent, tools
Steps are as follows for body:
(1) polyetherimide resin powder and Sodium Polyacrylate are put in proportion into mixing vessel, deionized water are added,
When amount of water reaches polyetherimide resin powder and Sodium Polyacrylate 20~30wt% of total amount of feeding, mechanical stirring is opened,
And continuously add the water of surplus；100~200rpm of speed of agitator is controlled, 20~60min of stirring carries out homogenous disperse, obtains
Even white " milky " liquid；
(2) above-mentioned material is transferred in the silent device equipped with high speed emulsifier, quantitative alkyl phenol polyoxy second is added
Alkene ether makes mass percent 5%~30% of the above-mentioned all solids component in suspension sizing agent；
(3) high-speed emulsifying machine is opened, 10~30min of stirring is continued with 3000~8000rpm revolving speed, is obtained uniform and stable
Milk-white coloured suspension sizing agent.
Compared to the prior art, the beneficial effects of the present invention are:
(1) present invention is free of epoxy resin, is changed without other based on polyetherimide resin powder in constituent
Property agent component, be free of organic solvent, temperature tolerance is good, long term storage and application will not generate ageing hardening phenomenon.
(2) suspension carbon fiber sizing agent of the present invention introduces Sodium Polyacrylate as main dispersant, passes through double electricity
Layer effect makes toner generate fine dispersion；Introducing simultaneously, there is the alkyl phenol polyoxyethylene ether of aryl group to help as stabilization
Agent further increases the stability of polyetherimide resin powder particle in water, prepared polysulfones base suspension sizing agent
Excellent in stability is stored and applies, preparation is easy, environmentally friendly.
(3) carbon fiber of sizing agent of the present invention progress starching is used to can be used for preparing polyetherimide resin base compound
The intermediates such as material carbon fibre fabric, prepreg, processing performance is good, and temperature tolerance and Interface adhesive strength are excellent.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Comparative example 1
Test is starched on carbon fiber engineering line using modified epoxy resin emulsion type carbon fiber sizing agent on line.On
It starches agent model SP-2P (production of Chinese Academy of Sciences's Shanghai Institute of Organic Chemistry), principal component is that modified bisphenol F type epoxy resin and anionic surface are living
Property agent.Using impregnated starching, sizing agent concentration is 3.2%, dip time 40s, receives silk after dry and epoxy resin is prepared
Base starching carbon fiber.
Comparative example 2
Test is starched on carbon fiber engineering line using conventional epoxies emulsion type carbon fiber sizing agent on line.On
Starch agent model SP-4A (productions of Chinese Academy of Sciences's Shanghai Institute of Organic Chemistry), principal component be bisphenol A-type/bisphenol-f type composite epoxy resin and it is negative from
Sub- surfactant.Using impregnated starching, sizing agent concentration is 5.1%, dip time 45s, receives silk after dry and is prepared
Epoxy resin-matrix starching carbon fiber.
Examples 1 to 8
Quantitative polyetherimide resin powder and Sodium Polyacrylate are successively put into stirred tank A, are gradually added dropwise quantitative
Deionized water is opened mechanical stirring, is continuously stirred with certain revolving speed, and continue when amount of water reaches total amount of feeding 25wt%
The water of surplus is added, stirring obtains flat-white emulsion after a certain period of time, discharges and be transferred to equipped with high speed emulsifier
In stirred tank B, quantitative alkyl phenol polyoxyethylene ether is added, opens high-speed emulsifying machine, continues to stir with fixed rotating speed, discharging system
Obtain milk-white coloured suspension sizing agent.
The polyetherimide powder comes from General Electric Company, the Sodium Polyacrylate, alkylphenol-polyethenoxy
Ether comes from BASF AG.Suspension sizing agent solid component prepared by Examples 1 to 8 is shown in Table 1, sizing agent group
2 are shown in Table at dosage, sizing agent preparation technology parameter is shown in Table 3.
It is enterprising in carbon fiber engineering line using polyetherimide resin base suspension sizing agent prepared by above-described embodiment
Row impregnated starching, dip time 50s, drying obtain starching carbon fiber after receiving silk.
1 sizing agent solid component of table
2 sizing agent of table forms dosage
3 sizing agent preparation technology parameter of table
Test analysis
The present invention tests sizing agent pH value using plum Teller pH meter；Using BROOKFIELD company DV
ProVISCOMETER viscosity apparatus tests the rotary viscosity of institute's sizing agent；Using the prepared sizing agent of ocular estimate observation
Whether obvious layering is had；Tested using concentration of the weighting method after dried to prepared suspension, and with lower layer's concentration relative to
The change rate of upper layer concentration characterizes the stability of prepared sizing agent, is calculated according to the following equation:
Lower layer's change rate of concentration (%)=(lower layer's concentration-upper layer concentration)/upper layer concentration * 100%
Gained suspension sizing agent Evaluation results are shown in Table 4.The prepared suspension starching it can be seen from result in table
Agent pH is totally in neutrality, reliable and stable.Viscosity is low, good fluidity, easy to clean, not roll banding.Sizing agent has no layering, lower layer's concentration
Opposite upper layer change rate of concentration is less than 4% and emulsion-type sizing agent lower layer change rate of concentration is in same level, shows polyetherimide
Amine powder reunion situation is lighter, good dispersion between powder, and stability is high, and online storage and production more manageability, product is more evenly
Stablize.
4 suspension sizing agent Evaluation results of table
| pH | Viscosity (mPas) | Whether it is layered | Lower layer's concentration changes (%) | |
| Comparative example 1 | 7.5 | 76.8 | It is not layered | 3.0 |
| Comparative example 2 | 6.4 | 69.9 | It is not layered | 2.8 |
| Embodiment 1 | 7.9 | 41.8 | It is not layered | 1.1 |
| Embodiment 2 | 7.3 | 55.0 | It is not layered | 2.4 |
| Embodiment 3 | 6.8 | 46.0 | It is not layered | 1.7 |
| Embodiment 4 | 7.2 | 43.0 | It is not layered | 1.3 |
| Embodiment 5 | 7.7 | 50.5 | It is not layered | 2.3 |
| Embodiment 6 | 7.2 | 48.1 | It is not layered | 2.0 |
| Embodiment 7 | 6.4 | 40.0 | It is not layered | 0.9 |
| Embodiment 8 | 7.8 | 52.0 | It is not layered | 2.5 |
It tests to obtain the contact angle of polyetherimide resin Yu starching carbon fiber using OCA20 contact angle measurement；Using
Japanese Dong Rong industry companies MODEL HM410 interface performance evaluating apparatus is tested to obtain polyetherimide resin and starching carbon fiber
Interface shear strength, using the U.S. TA company Q500 test starching carbon fiber thermal decomposition temperature.
Starching carbon fiber and polyetherimide resin are carried out according to the mass ratio of 4:6 after mixing, using twin-screw
Extruder carries out extruding pelletization, and is prepared into fibre reinforced polyetherimide composite material standard sample according to associated test standards
Item.Sample preparation test is carried out to batten tensile strength and elongation at break referring to national standard GB/T1040-2006, referring to national standard GB/
T9341-2008 tests batten bending strength.
The performance test results of starching carbon fiber and prepared composite material are shown in Table 5.By data in table 5 it is found that with comparison
Example 1-2 is compared, and the contact angle of starching carbon fiber and polyetherimide resin prepared by embodiment is smaller, and temperature tolerance is stronger, is gathered
Infiltration sprawls etc. that processing performances are more excellent, and product uniformity and stability are good, and interface is cut between etherimide matrix resin and fiber
Shearing stress, tensile strength, elongation at break and bending strength etc. are obviously improved.
5 starching carbon fiber of table and fibre reinforced polyetherimide composite material Evaluation results
Although the present invention discloses preferred embodiment as above, the content that however, it is not to limit the invention is any ripe
Know this those skilled in the art, do not departing from main spirits and context of the invention, when can make it is various change and retouch, because of the invention
Protection scope should be subject to the actual claim range applied for a patent.
Claims (10)
1. a kind of polyetherimide resin base carbon fibre suspension sizing agent, which is characterized in that it is by polyetherimide resin powder
End, Sodium Polyacrylate, alkyl phenol polyoxyethylene ether and deionized water composition；By the gross mass of solid component be 100% in terms of,
In:
65~75wt% of polyetherimide resin powder
12~17wt% of Sodium Polyacrylate
13~18wt% of alkyl phenol polyoxyethylene ether.
2. polyetherimide resin base carbon fibre suspension sizing agent according to claim 1, which is characterized in that polyethers acyl
Shown in the structure of imide resin powder such as formula (1):
Wherein: n is the degree of polymerization of polyetherimide.
3. polyetherimide resin base carbon fibre suspension sizing agent according to claim 1, which is characterized in that polyethers acyl
The number-average molecular weight of imide resin powder is between 2.5 ten thousand~3.5 ten thousand.
4. polyetherimide resin base carbon fibre suspension sizing agent according to claim 1 or 3, which is characterized in that poly-
The number-average molecular weight of etherimide toner is between 3.0 ten thousand~3.3 ten thousand.
5. polyetherimide resin base carbon fibre suspension sizing agent according to claim 1, it is characterised in that: described
The average diameter of polyetherimide resin powder is between 10~60 microns.
6. polyetherimide resin base carbon fibre suspension sizing agent according to claim 1, which is characterized in that described
The number-average molecular weight of Sodium Polyacrylate is between 1000~5000.
7. polyetherimide resin base carbon fibre suspension sizing agent according to claim 1 or 6, which is characterized in that institute
The number-average molecular weight for the Sodium Polyacrylate stated is between 2000~4000.
8. polyetherimide resin base carbon fibre suspension sizing agent according to claim 1, which is characterized in that described
Shown in the structure of alkyl phenol polyoxyethylene ether such as formula (2):
Wherein: R is selected from C10~C25It is any in alkyl；Degree of polymerization m is the integer between 25~45.
9. polyetherimide resin base carbon fibre suspension sizing agent according to claim 1, which is characterized in that solid group
Divide the mass content in polyetherimide resin base carbon fibre suspension sizing agent between 5%~30%.
10. a kind of preparation of polyetherimide resin base carbon fibre suspension sizing agent described in one of -9 according to claim 1
Method, which is characterized in that specific step is as follows:
(1) polyetherimide resin powder and Sodium Polyacrylate are put in proportion into mixing vessel, deionized water is added, it is to be added
When water reaches polyetherimide resin powder and Sodium Polyacrylate 20~30wt% of total amount of feeding, unlatching mechanical stirring, and after
The continuous water that surplus is added；100~200rpm of speed of agitator is controlled, 20~60min of stirring carries out homogenous disperse, obtains uniformly white
Color emulsion；
(2) above-mentioned material is transferred in the silent device equipped with high speed emulsifier, quantitative alkyl phenol polyoxyethylene ether is added,
Make mass percent 5%~30% of the above-mentioned all solids component in suspension sizing agent；
(3) high-speed emulsifying machine is opened, 10~30min of stirring is continued with 3000~8000rpm revolving speed, is obtained uniform and stable milky white
Color suspension sizing agent.
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