CN102040737A - Polyetheretherketone-modified phenol formaldehyde resin and preparation method thereof - Google Patents
Polyetheretherketone-modified phenol formaldehyde resin and preparation method thereof Download PDFInfo
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- CN102040737A CN102040737A CN 201010545186 CN201010545186A CN102040737A CN 102040737 A CN102040737 A CN 102040737A CN 201010545186 CN201010545186 CN 201010545186 CN 201010545186 A CN201010545186 A CN 201010545186A CN 102040737 A CN102040737 A CN 102040737A
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Abstract
The invention relates to a polyetheretherketone-modified phenol formaldehyde resin and a preparation method thereof. The polyetheretherketone-modified phenol formaldehyde resin is technically characterized by comprising the following components: 100 parts of phenol, 40 to 50 parts of solid formaldehyde, 1 to 10 parts of polyetheretherketone, a catalyst, a sulfonating agent and a chloromethylating agent. Through reaction, an active group is introduced into the molecular structure of the polyetheretherketone, and the polyetheretherketone having the active group undergoes copolymerization with phenol formaldehyde resin to form the polyetheretherketone-modified phenolic resin. The invention has the advantages that: without sewage discharge, a synthesis process is safe and environmentally-friendly; and the obtained polyetheretherketone-modified phenol formaldehyde resin has higher heat resistance than unmodified phenolic resin, the ductility of the product of periodic heating solidification is improved by about 30 percent, and the polyetheretherketone-modified phenol formaldehyde resin demonstrates typical ductile rupture.
Description
Technical field
The present invention relates to a kind of polyether-ether-ketone resin modified phenol resin and preparation method thereof of utilizing, mainly adopting phenol, formaldehyde, polyether-ether-ketone, catalyzer, sulphonating agent, chloromethylation reagent etc. is raw material, prepares by copolycondensation.
Background technology
Resol (Phenol formaldehyde resin is called for short PF) is to realize industrialized synthetic resins the earliest, and is cheap owing to its raw material is easy to get, production technique and equipment maturation, and over-all properties is better, so purposes is comparatively extensive.Shortcoming such as but resol also exists, and fragility is big, shrinking percentage is high, not alkaline-resisting, the easy moisture absorption and electrical property are relatively poor.Oxidation can if surpass 200 ℃, just take place stable use the below 200 ℃ in unmodified resol significantly; Enter the thermolysis stage from 340～360 ℃; Degrade fully during to 600～900 ℃, discharge CO, CO
2, H
2Material such as O, phenol.Usually the method that improves the resistance toheat of resol mainly contains: (1) is introduced aromatic ring or is contained fragrant heterocyclic polymkeric substance at the resol molecular structure; (2) close with the phenolic hydroxyl group etherificate of resol, esterification or with the heavy metal huge legendary turtle; (3) strict after fixing condition, increasing hardener dose etc.Purpose is that the molecular chain rigidity is increased, thereby improves resol resistance toheat and toughness.
Polyether-ether-ketone (Polyetheretherketone, be called for short polyether-ether-ketone) is a kind of semi-crystalline state aromatic thermoplastic polymkeric substance, is that the repeating unit by polyaryletherketone constitutes, and its molecular structural formula is as follows:
Owing to contain the inflexible phenyl ring on its macromolecular chain
Flexible ehter bond (O-) and the stronger ketone group of polarity
And compound with regular structure, thereby have excellent thermotolerance, second-order transition temperature (T
g) be 143 ℃ and fusing point (T
m) be 340 ℃, the load heat-drawn wire is (30% glass fibre or carbon fiber strengthen the trade mark) up to 316 ℃, can be at 250 ℃ of following life-time service; Chemical proofing can only be dissolved in the vitriol oil; Rub resistance descends higher wear resistance of maintenance and low frictional coefficient at 250 ℃; Flame retardant properties reaches 145mm (0.057in) ULV-0 level; At high temperature still have higher mechanical strength, polyether-ether-ketone also has advantages such as fracture toughness property height, coefficient of linear expansion are little, antifatigue, hydrolysis, insulation in addition.Therefore polyether-ether-ketone is widely used in fields such as aerospace, automobile making, electronic apparatus, machinery instrument, medical treatment and food-processing.
If the advantages such as heat-resisting, good toughness of polyether-ether-ketone can be incorporated in the resol, improve the thermotolerance and the toughness of resol, will help enlarging the use range of resol.The problem that exists is at present: the polyether-ether-ketone solvent resistance is good, be difficult to react,, on molecule, introduce active function groups if can carry out modification from polyether-ether-ketone molecular structure aspect with other reagent, improve the reactive behavior of polyether-ether-ketone, it is connected in the resol.
Summary of the invention
The technical problem that solves
For fear of the deficiencies in the prior art part, the present invention proposes a kind of polyether-ether-ketone resin modified phenol resin and preparation method thereof of utilizing, overcome the defective of polyether-ether-ketone indissoluble, make the polyether-ether-ketone can be in building-up process and the resol polymerization reaction take place, the molecule of polyether-ether-ketone is introduced in the resol, improved the thermotolerance and the fracture toughness property of resol.
Technical scheme
A kind of polyether-ether-ketone resin modified phenol resin of utilizing is characterized in that component is 100 parts of phenol, 2～6 parts of metal oxide barium oxide, 40～50 parts of solid formaldehydes, 1～10 part of sulfonation chloromethylation polyether-ether-ketone; Described sulfonation chloromethylation polyether-ether-ketone is to adopt sulphonating agent and polyether-ether-ketone is carried out sulfonation to chloromethyl agent and the chloromethylation modification makes; Described umber is a mass parts.
Described sulphonating agent is the methylsulphonic acid and the vitriol oil mixed solution of the vitriol oil, chlorsulfonic acid or 3: 2.
Described chloromethylation reagent is the formaldehyde and the hydrochloric acid mixed solution of chloromethyl ether, chloromethyl alkyl oxide or 2: 1.
A kind of method for preparing the polyether-ether-ketone resin modified phenol resin is characterized in that step is as follows:
Step 1: the polyether-ether-ketone that drying is crossed adds in the sulphonating agent, at N
2Protection is stirred normal-temperature reaction 24h, standing sedimentation down;
Step 2: the sediment of vacuum filtration step 1 is neutral with distilled water wash sulfonated polyether-ether-ketone to filtrate, vacuum-drying;
Step 3: the sulfonated polyether-ether-ketone that drying is good adds in the chloromethylation reagent, stirring reaction 6h, standing sedimentation;
Step 4: the sediment of vacuum filtration step 3, be neutral with distilled water wash sulfonation chloromethylation polyether-ether-ketone to filtrate, vacuum-drying is standby;
Step 5: in having the reactor of reflux condensate device, under the agitation condition 100 parts of phenol are heated 50～60 ℃ to fusion, add 2～6 parts of catalyzer, add 40～50 parts of solid formaldehydes reaction 3-5h again, obtain the transparent glue of light brown;
Step 6: add the sulfonation chloromethylation polyether-ether-ketone that 1～10 part of step 4 obtains, reaction 2-3h when recording reactant gel time reaction terminating when being 55～110s on the set plate at 50 ± 1 ℃, obtains the polyether-ether-ketone resin modified phenol resin.
Beneficial effect
The present invention proposes utilizes polyether-ether-ketone resin modified phenol resin and preparation method thereof, by in the building-up process of resol, adding polyether-ether-ketone through oversulfonate and chloromethylation, overcome the defective of polyether-ether-ketone indissoluble, make the polyether-ether-ketone can be in building-up process and the resol polymerization reaction take place, the molecule of polyether-ether-ketone is introduced in the resol, improved the thermotolerance and the fracture toughness property of resol.Simultaneously because polyether-ether-ketone and resol generation copolyreaction utilize phenyl ring density higher in the polyether-ether-ketone molecular chain to improve the thermotolerance of resin; Utilize flexible ehter bond to improve the toughness of resol; Utilize the bigger ketone group of polarity can improve the adhesiveproperties of resol.
The polyether-ether-ketone modified phenolic resins of the present invention development and the Fourier infrared spectrum (FT-IR) of unmodified resol figure, thermal weight loss (TG) curve and impact fracture scanning electron microscope (SEM) microscopic appearance figure respectively as 1, Fig. 2 and shown in Figure 3.
Description of drawings
Fig. 1: polyether-ether-ketone modified phenolic resins and unmodified resol FT-IR curve
Fig. 2: polyether-ether-ketone modified phenolic resins and unmodified resol TG curve
Fig. 3: polyether-ether-ketone modified phenolic resins and unmodified resol impact fracture SEM photo
A. unmodified resol; B. polyether-ether-ketone modified phenolic resins;
Embodiment
Now in conjunction with the embodiments, accompanying drawing is further described the present invention:
Embodiment 1:
Step 1: the polyether-ether-ketone that drying is crossed joins in the flask that fills sulphonating agent, at N
2Protection is stirred normal-temperature reaction 24h, standing sedimentation down fast;
Step 2: the vacuum filtration sediment spends dried up repetitive scrubbing sulfonated polyether-ether-ketone to filtrate and is neutral, vacuum-drying; Described sulphonating agent is the vitriol oil;
Step 3: the sulfonated polyether-ether-ketone that drying is good joins in the flask that fills chloromethylation reagent, stirs fast to be warming up to 60 ℃ of reaction 6h, standing sedimentation; Described chloromethylation reagent is chloromethyl ether;
Step 4: the vacuum filtration sediment is neutral with deionized water repetitive scrubbing sulfonation chloromethylation polyether-ether-ketone to filtrate, vacuum-drying;
Step 5: have in the reactor of reflux exchanger at device, agitation condition adds 100 parts of phenol down at 50～60 ℃ of heating and meltings, adds 2 parts of catalyzer;
Step 6: under agitation condition, add 40 parts of solid formaldehydes, at 80～90 ℃ down behind the reaction 2-3h, arrive the transparent glue of light brown;
Step 7: add 3 parts of sulfonation chloromethylations of people polyether-ether-ketone, reaction 2-3h;
Step 8: reaction terminating is with the control of the gelation time of reactant, when recording reactant gel time reaction terminating when being 55～110s on the set plate at 50 ± 1 ℃, obtains utilizing the polyether-ether-ketone resin modified phenol resin.
Embodiment 2:
Step 1: the polyether-ether-ketone that drying is crossed joins in the flask that fills sulphonating agent, at N
2Protection is stirred normal-temperature reaction 24h, standing sedimentation down fast; Described sulphonating agent is a chlorsulfonic acid;
Step 2: the vacuum filtration sediment spends dried up repetitive scrubbing sulfonated polyether-ether-ketone to filtrate and is neutral, vacuum-drying;
Step 3: the sulfonated polyether-ether-ketone that drying is good joins in the flask that fills chloromethylation reagent, stirs fast to be warming up to 60 ℃ of reaction 6h, standing sedimentation; Described chloromethylation reagent is the chloromethyl alkyl oxide;
Step 4: the vacuum filtration sediment is neutral with deionized water repetitive scrubbing sulfonation chloromethylation polyether-ether-ketone to filtrate, vacuum-drying;
Step 5: have in the reactor of reflux exchanger at device, agitation condition adds 100 parts of phenol down at 50～60 ℃ of heating and meltings, adds 4 parts of catalyzer;
Step 6: under agitation condition, add, add 45 parts of solid formaldehydes, at 80～90 ℃ down behind the reaction 2-3h, arrive the transparent glue of light brown
Step 7: add 5 parts of sulfonation chloromethylations of people polyether-ether-ketone, reaction 2-3h;
Step 8: reaction terminating is with the control of the gelation time of reactant, when recording reactant gel time reaction terminating when being 55～110s on the set plate at 50 ± 1 ℃, obtains utilizing the polyether-ether-ketone resin modified phenol resin.
Embodiment 3:
Step 1: the polyether-ether-ketone that drying is crossed joins in the flask that fills sulphonating agent, at N
2Protection is stirred normal-temperature reaction 24h, standing sedimentation down fast; Described sulphonating agent is 3: 2 methylsulphonic acid and a vitriol oil mixed solution;
Step 2: the vacuum filtration sediment spends dried up repetitive scrubbing sulfonated polyether-ether-ketone to filtrate neutrality, vacuum-drying;
Step 3: the sulfonated polyether-ether-ketone that drying is good joins in the flask that fills chloromethylation reagent, stirs fast to be warming up to 60 ℃ of reaction 6h, standing sedimentation; Described chloromethylation reagent is 2: 1 formaldehyde and hydrochloric acid mixed solution;
Step 4: the vacuum filtration sediment is neutral with deionized water repetitive scrubbing sulfonation chloromethylation polyether-ether-ketone to filtrate, vacuum-drying;
Step 5: have in the reactor of reflux exchanger at device, agitation condition adds 100 parts of phenol down at 50～60 ℃ of heating and meltings, adds 6 parts of catalyzer;
Step 6: under agitation condition, add, add 50 parts of solid formaldehydes, at 80～90 ℃ down behind the reaction 2-3h, arrive the transparent glue of light brown
Step 7: add 10 parts of sulfonation chloromethylations of people polyether-ether-ketone, reaction 2-3h;
Step 8: reaction terminating is with the control of the gelation time of reactant, when recording reactant gel time reaction terminating when being 55～110s on the set plate at 50 ± 1 ℃, obtains utilizing the polyether-ether-ketone resin modified phenol resin.
Polyether-ether-ketone modified phenolic resins and unmodified resol Fourier infrared spectrum (FT-IR) figure by analysis and research Fig. 1, comparative study is found, modified phenolic resins and unmodified resol infrared spectra curve basically identical illustrate that the agent structure of resol does not change.At 3440～3245cm
-1There is phenolic hydroxyl group Ar-OH stretching vibration peak in the place; At 1450cm
-1, 1500cm
-1, 1585cm
-1And 1600cm
-1There is phenyl ring skeleton stretching vibration peak in the place, and at 750cm
-1And 690cm
-1Stronger ortho position substituted benzene and para-orientation benzene vibration absorption peak appear in the place; At 2930cm
-1, 2860cm
-1And 990cm
-1CH appears respectively in the place
2Flexible peak of the flexible peak of unsymmetrically, symmetry and twisting vibration peak, illustrate that the primary structure of resol does not change.And the polyether-ether-ketone modified phenolic resins is at 1010cm
-1(with CH
2The flexible peak of unsymmetrically overlap, the peak type broadens) and 1235cm
-1Aromatic oxide C-O-C stretching vibration peak appears in the place, at 1690cm
-1Aromatic ketone C=O stretching vibration peak appears in the place, and the result shows that polyether-ether-ketone is introduced in the resol structure.
By analysis and research Fig. 2 polyether-ether-ketone modified phenolic resins and unmodified resol thermal weight loss (TG) curve, as seen from Figure 2, in the initial temperature rise period, weight resin begins to descend, a less equilibrium stage appears then, this stage is unreacted small molecules volatilization and the further crosslinking curing of resin in the resin, and along with small-molecule substance volatilization curing complete and resin is perfect, the mass loss of resin reduces gradually; When the further rising of temperature, reach 300 ℃ of later resol mass loss rates and begin to accelerate, this stage is the degraded of resin, and degraded product is along with shielding gas is discharged, and along with the quickening of degradation rate, the mass loss of resin is also accelerated; When temperature reaches after 700 ℃, the mass loss of resin begins to reduce, this be because, the residue in the resin begins carbonization, mass loss reduces gradually.Unmodified phenolic aldehyde is a bit larger tham in mass loss at initial room-temperature to 300 ℃ stage polyether-ether-ketone modified phenolic, and the mass loss of polyether-ether-ketone modified phenolic is much smaller than unmodified phenolic aldehyde in the time of still between 300～930 ℃.The temperature of unmodified resol weightlessness 1%, 5%, 10% and 50% o'clock is respectively 63.40 ℃, 149.35 ℃, 333.99 ℃, 725.32 ℃; And the temperature of polyether-ether-ketone modified phenolic resins weightlessness 1%, 5%, 10% and 50% o'clock is respectively 66.59 ℃, 141.62 ℃, 355.26 ℃ and 844.79 ℃.The more unmodified resol of presentation of results polyether-ether-ketone modified phenolic resins resistance toheat when high temperature improves a lot.
By analysis and research Fig. 3 polyether-ether-ketone modified phenolic resins and unmodified resol impact fracture scanning electron microscope (SEM) microscopic appearance figure.Resol is poured in the mould that was coated with releasing agent, in interim 120 ℃ * 2h → 150 ℃ of heating up of normal pressure * 2h → 170 ℃ * 2h solidifies and obtains the Impact Test batten.Obtain the resol impact property by GB/T 1013.1-2008 test, the result shows that the shock strength of unmodified resol is 4.32kJ/m
2, the shock strength of polyether-ether-ketone modified phenolic resins reaches 5.60kJ/m
2, increase rate reaches 29.6%.As seen from Figure 3, unmodified resol impact fracture demonstrates the smooth smooth flat of brittle rupture, and polyether-ether-ketone modified phenolic resins impact fracture surface is comparatively coarse, the section and the fracture dimple of different levels occurred, shows as typical ductile rupture feature.
Claims (4)
1. one kind is utilized the polyether-ether-ketone resin modified phenol resin, it is characterized in that component is 100 parts of phenol, 2～6 parts of metal oxide barium oxide, 40～50 parts of solid formaldehydes, 1～10 part of sulfonation chloromethylation polyether-ether-ketone; Described sulfonation chloromethylation polyether-ether-ketone is to adopt sulphonating agent and polyether-ether-ketone is carried out sulfonation to chloromethyl agent and the chloromethylation modification makes; Described umber is a mass parts.
2. the polyether-ether-ketone resin modified phenol resin of utilizing according to claim 1 is characterized in that: described sulphonating agent is the methylsulphonic acid and the vitriol oil mixed solution of the vitriol oil, chlorsulfonic acid or 3: 2.
3. the polyether-ether-ketone resin modified phenol resin of utilizing according to claim 1 is characterized in that: described chloromethylation reagent is the formaldehyde and the hydrochloric acid mixed solution of chloromethyl ether, chloromethyl alkyl oxide or 2: 1.
4. method for preparing any polyether-ether-ketone resin modified phenol resin of claim 1～3 is characterized in that step is as follows:
Step 1: the polyether-ether-ketone that drying is crossed adds in the sulphonating agent, stirs normal-temperature reaction 24h, standing sedimentation under the N2 protection;
Step 2: the sediment of vacuum filtration step 1 is neutral with distilled water wash sulfonated polyether-ether-ketone to filtrate, vacuum-drying;
Step 3: the sulfonated polyether-ether-ketone that drying is good adds in the chloromethylation reagent, stirring reaction 6h, standing sedimentation;
Step 4: the sediment of vacuum filtration step 3, be neutral with distilled water wash sulfonation chloromethylation polyether-ether-ketone to filtrate, vacuum-drying is standby;
Step 5: in having the reactor of reflux condensate device, under the agitation condition 100 parts of phenol are heated 50～60 ℃ to fusion, add 2～6 parts of catalyzer, add 40～50 parts of solid formaldehydes reaction 3-5h again, obtain the transparent glue of light brown;
Step 6: add the sulfonation chloromethylation polyether-ether-ketone that 1～10 part of step 4 obtains, reaction 2-3h when recording reactant gel time reaction terminating when being 55～110s on the set plate at 50 ± 1 ℃, obtains the polyether-ether-ketone resin modified phenol resin.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102504155A (en) * | 2011-09-29 | 2012-06-20 | 山东圣泉化工股份有限公司 | Modified thermoplastic phenolic resin and preparation method for same |
| CN103012073A (en) * | 2012-12-27 | 2013-04-03 | 山东圣泉化工股份有限公司 | Preparation method of chloromethylated cardanol |
| CN108373560A (en) * | 2018-02-05 | 2018-08-07 | 高源� | A kind of degradable polymeric packaging material of the transparency and preparation method thereof |
| CN109097014A (en) * | 2018-07-19 | 2018-12-28 | 中国石油天然气股份有限公司 | It is a kind of to use the underground crosslinked type resin plugging agent and its application that seawater is prepared |
| CN109233529A (en) * | 2018-09-28 | 2019-01-18 | 韶关市合众化工有限公司 | A kind of Soluble PEEK modified acroleic acid aqueous industrial baking vanish and preparation method thereof |
| CN109370394A (en) * | 2018-09-27 | 2019-02-22 | 合众（佛山）化工有限公司 | A kind of polyether-ether-ketone modified waterborne alkyd antirusting paint |
| CN109486380A (en) * | 2018-09-27 | 2019-03-19 | 合众（佛山）化工有限公司 | A kind of PEEK acid modified alcoholic full-shield infrared ray and ultraviolet light water transparent heat insulation paint |
| CN109486385A (en) * | 2018-09-27 | 2019-03-19 | 合众（佛山）化工有限公司 | A kind of PEEK modified polyurethane full-shield infrared ray and ultraviolet light water transparent heat insulation paint |
| CN114243205A (en) * | 2021-11-19 | 2022-03-25 | 惠州锂威新能源科技有限公司 | Diaphragm, preparation method thereof and electrochemical device |
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| CN101845198A (en) * | 2010-04-15 | 2010-09-29 | 西北工业大学 | Method for preparing thermosetting phenolic resin film |
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| CN101845198A (en) * | 2010-04-15 | 2010-09-29 | 西北工业大学 | Method for preparing thermosetting phenolic resin film |
Non-Patent Citations (1)
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| CN102504155A (en) * | 2011-09-29 | 2012-06-20 | 山东圣泉化工股份有限公司 | Modified thermoplastic phenolic resin and preparation method for same |
| CN102504155B (en) * | 2011-09-29 | 2013-08-21 | 山东圣泉化工股份有限公司 | Modified thermoplastic phenolic resin and preparation method for same |
| CN103012073A (en) * | 2012-12-27 | 2013-04-03 | 山东圣泉化工股份有限公司 | Preparation method of chloromethylated cardanol |
| CN103012073B (en) * | 2012-12-27 | 2015-04-22 | 山东圣泉新材料股份有限公司 | Preparation method of chloromethylated cardanol |
| CN108373560A (en) * | 2018-02-05 | 2018-08-07 | 高源� | A kind of degradable polymeric packaging material of the transparency and preparation method thereof |
| CN109097014A (en) * | 2018-07-19 | 2018-12-28 | 中国石油天然气股份有限公司 | It is a kind of to use the underground crosslinked type resin plugging agent and its application that seawater is prepared |
| CN109370394A (en) * | 2018-09-27 | 2019-02-22 | 合众（佛山）化工有限公司 | A kind of polyether-ether-ketone modified waterborne alkyd antirusting paint |
| CN109486380A (en) * | 2018-09-27 | 2019-03-19 | 合众（佛山）化工有限公司 | A kind of PEEK acid modified alcoholic full-shield infrared ray and ultraviolet light water transparent heat insulation paint |
| CN109486385A (en) * | 2018-09-27 | 2019-03-19 | 合众（佛山）化工有限公司 | A kind of PEEK modified polyurethane full-shield infrared ray and ultraviolet light water transparent heat insulation paint |
| CN109486385B (en) * | 2018-09-27 | 2021-01-08 | 合众（佛山）化工有限公司 | PEEK modified polyurethane water-based transparent heat-insulating coating capable of fully shielding infrared rays and ultraviolet rays |
| CN109233529A (en) * | 2018-09-28 | 2019-01-18 | 韶关市合众化工有限公司 | A kind of Soluble PEEK modified acroleic acid aqueous industrial baking vanish and preparation method thereof |
| CN114243205A (en) * | 2021-11-19 | 2022-03-25 | 惠州锂威新能源科技有限公司 | Diaphragm, preparation method thereof and electrochemical device |
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