CN117700759A - Polyaryletherketone emulsifier and preparation method and application thereof - Google Patents
Polyaryletherketone emulsifier and preparation method and application thereof Download PDFInfo
- Publication number
- CN117700759A CN117700759A CN202311724057.1A CN202311724057A CN117700759A CN 117700759 A CN117700759 A CN 117700759A CN 202311724057 A CN202311724057 A CN 202311724057A CN 117700759 A CN117700759 A CN 117700759A
- Authority
- CN
- China
- Prior art keywords
- polyaryletherketone
- emulsifier
- amorphous
- resin
- nonionic surfactant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920006260 polyaryletherketone Polymers 0.000 title claims abstract description 76
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 32
- 229920005989 resin Polymers 0.000 claims abstract description 32
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 15
- 239000004593 Epoxy Substances 0.000 claims abstract description 11
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- 239000003999 initiator Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 8
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 7
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- -1 fatty acid ester Chemical class 0.000 claims description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 3
- 229920000053 polysorbate 80 Polymers 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 5
- 239000000839 emulsion Substances 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000004945 emulsification Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 238000002329 infrared spectrum Methods 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 125000004185 ester group Chemical group 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229940057838 polyethylene glycol 4000 Drugs 0.000 description 1
- 229940057847 polyethylene glycol 600 Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention discloses a polyaryletherketone emulsifier, a preparation method and application thereof, and belongs to the technical field of materials. The polyaryletherketone emulsifier is prepared by reacting the amorphous polyaryletherketone resin containing the epoxy end group with the nonionic surfactant containing the alcoholic hydroxyl group, and has the advantages of high temperature resistance, high emulsification efficiency, low raw material cost, industrialized mass production and the like. The polyaryletherketone emulsifier can be applied to water emulsion taking semi-crystalline or amorphous polyaryletherketone resin and the like as main bodies, the compatibility of the emulsifier and the main body resin is good, the prepared emulsion has small particle size, the emulsifier cannot be decomposed to generate defects in high-temperature treatment, the coating performance is good, and the polyaryletherketone emulsifier can be applied to the high-tech fields of aerospace, medical treatment and the like.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a polyaryletherketone emulsifier, a preparation method and application thereof.
Background
The polyaryletherketone resin belongs to the top end of a special engineering plastic pyramid, has excellent high temperature resistance, high strength, impact resistance, corrosion resistance and other outstanding characteristics, and is widely applied to the fields of aerospace, rail transit, medical treatment, ships and the like.
With the increasing demand of the market for high-performance materials, the application of polyaryletherketone resin as a coating is increased. Among them, semi-crystalline polyether-ether-ketone and other resins have outstanding comprehensive properties, but are insoluble in conventional organic solvents, so that stable suspension is difficult to form in aqueous phase systems, and the binding force between the resin and the substrate is poor due to the fact that the resin has fewer polar functional groups. The polyaryletherketone resin with an amorphous structure is soluble in organic solvents, but does not meet the environmental protection requirement. Most of commercial aqueous polyaryletherketone emulsion is added with surfactant to improve the stability of the emulsion, but the heat treatment temperature of the polyaryletherketone is generally 350-400 ℃, excessive use of the surfactant with low temperature resistance can cause the surfactant to be decomposed and carbonized at high temperature to cause local defects of the product, and the service life of the product can be influenced.
CN 110157016A discloses a preparation method of polyether-ether-ketone aqueous dispersion, which adopts iodine-containing surface modifier which is not resistant to high temperature and polyethylene glycol 600 as surfactant. CN 107385918A discloses a thermoplastic sizing agent for carbon fibers and a preparation method thereof, wherein xanthan gum with lower decomposition temperature is adopted as an emulsifier.
The surface active agent used by the dispersion liquid or sizing agent is not high-temperature resistant, and the performance and the service life of the material are affected.
Disclosure of Invention
Aiming at the defects, the invention provides a polyaryletherketone emulsifier, a preparation method and application thereof, and the polyaryletherketone emulsifier has good high temperature resistance effect and long service life.
The first aspect of the invention provides a polyaryletherketone emulsifier, the structure of which is shown in formula I:
in the formula I, m is more than or equal to 0, n is more than 0, and Ar is selected from the following groups:
one or two or more of them.
Further, the polyaryletherketone emulsifier is prepared by reacting amorphous polyaryletherketone resin with nonionic surfactant under the condition of having an initiator.
The amorphous polyaryletherketone resin is an epoxy end group-containing amorphous polyaryletherketone resin with the number average molecular weight of 1000-5000, and the structure of the epoxy end group-containing amorphous polyaryletherketone resin is shown as a formula II:
in the formula II, m is more than or equal to 0, n is more than 0, and Ar is selected from the following groups:
one or two or more of them;
the nonionic surfactant is nonionic surfactant containing alcoholic hydroxyl groups.
Further, the nonionic surfactant containing the alcoholic hydroxyl group is one of polyethylene glycol, tween 80, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether or polyol polyoxyethylene ether fatty acid ester.
Further, the initiator is potassium persulfate.
Further, the number average molecular weight of the polyaryletherketone emulsifier is 2000-13000.
The preparation method of the polyaryletherketone emulsifier for protecting the second aspect of the invention comprises the following steps:
s1, dissolving amorphous polyaryletherketone resin in an organic solvent, and adding a nonionic surfactant to obtain a mixed solution.
S2, adding an initiator into the mixed solution under a certain temperature condition, and stirring and reacting to obtain the polyaryletherketone emulsifier.
Further, the mass ratio of the amorphous polyaryletherketone resin to the nonionic surfactant to the organic solvent is 8-12: 5-30: 20 to 100.
Further, the mass of the initiator accounts for 1-3% of the total mass of the amorphous polyaryletherketone resin and the nonionic surfactant.
Further, the organic solvent is one of methyl ethyl ketone, dichloroethane, anisole, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone.
Further, the certain temperature is 70-100 ℃; after the initiator is added, stirring and reacting for 2-8 h.
The third aspect of the invention protects the application of the polyaryletherketone emulsifier in the high-temperature-resistant emulsifier.
The polyaryletherketone emulsifier provided by the invention can be dissolved in an environment-friendly low-boiling-point organic solvent to replace the emulsifier in the aqueous emulsion taking the original semi-crystalline or amorphous polyaryletherketone resin and the like as a main body, the dosage of the emulsifier accounts for 4-10wt% of the main body resin, and the low-boiling-point solvent is removed by decompressing or heating at room temperature.
The invention has the beneficial effects that: the invention provides a polyaryletherketone emulsifier, a preparation method and application thereof. The polyaryletherketone emulsifier disclosed by the invention is high-temperature resistant, the 5% thermal weight loss temperature is more than 3800 ℃, and the mechanical property and long-term service life of a product are not affected. The cost of raw materials is low, the industrialized mass production can be realized, the compatibility of the emulsifier and the polyaryletherketone resin is good, the emulsifying efficiency is high, and the particle size of the prepared aqueous emulsion is small.
Drawings
FIG. 1 is an infrared spectrum of the polyaryletherketone emulsifier of example 1;
FIG. 2 is an infrared spectrum of the polyaryletherketone emulsifier of example 2;
FIG. 3 is an infrared spectrum of the polyaryletherketone emulsifier of example 3;
FIG. 4 is a graph showing the thermal weight loss of the ethereal aryl ketone emulsifiers of examples 1-3.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way.
Example 1
10g of amorphous polyaryletherketone resin containing epoxy end groups is dissolved in 50g of dichloroethane, 8g of polyethylene glycol 4000 is added, the temperature is raised to 80 ℃ and the mixture is uniformly mixed, 0.2g of potassium persulfate is added, the mixture is stirred and reacted for 6 hours under the nitrogen atmosphere, and the obtained solution is subjected to centrifugal removal of inorganic salt at 10000rpm and then is subjected to rotary evaporation to remove the dichloroethane, so that the polyaryletherketone emulsifier is obtained.
The amorphous polyaryletherketone resin containing the epoxy end group has the following structure:
the number average molecular weight was 5000.
The structural formula of the polyaryletherketone emulsifier obtained in the embodiment is as follows:
the number average molecular weight of the polyaryletherketone emulsifier is 13000.
The infrared spectrum of the polyaryletherketone emulsifier obtained in the embodiment is shown in figure 1. 3400cm -1 Is a-OH stretching vibration peak of 2230cm -1 Is a characteristic peak of nitrile group, 1115cm -1 Is an-O-C-O-stretching vibration peak, 1773cm -1 Is 1630cm as an ester group stretching vibration peak -1 Is the stretching vibration peak of the fluoroketone carbonyl.
Example 2
2g of amorphous polyaryletherketone resin containing epoxy end groups is dissolved in 10g of N, N-dimethylacetamide, 1.2g of Tween 80 is added, the temperature is raised to 90 ℃ and the mixture is uniformly mixed, 0.05g of potassium persulfate is added for reaction under the nitrogen atmosphere, stirring is carried out for 4 hours, the obtained solution is filtered by an ultrafiltration membrane to remove inorganic salt, the inorganic salt is poured into absolute ethanol solution for repeated washing, and the polyaryletherketone emulsifier is obtained after drying.
The amorphous polyaryletherketone resin containing the epoxy end group has the following structure:
the number average molecular weight was 2000.
The structural formula of the polyaryletherketone emulsifier obtained in the embodiment is as follows:
the number average molecular weight of the polyaryletherketone emulsifier is 3000.
The infrared spectrum of the polyaryletherketone emulsifier obtained in the embodiment is shown in figure 2. 3400cm -1 is-OH stretching vibration peak, 1115cm -1 Is an-O-C-O-stretching vibration peak, 1773cm -1 Is 1630cm as an ester group stretching vibration peak -1 Is the stretching vibration peak of fluoroketone carbonyl, 1465cm -1 Is the C-H bending vibration peak.
Example 3
10g of amorphous polyaryletherketone resin containing epoxy end groups is dissolved in 40g of anisole, 4g of OP-10 (octylphenol polyoxyethylene ether) is added, the temperature is raised to 70 ℃ and the mixture is uniformly mixed, 0.4g of potassium persulfate is added for reaction, stirring is carried out for reaction for 8h under the nitrogen atmosphere, the obtained solution is filtered by an ultrafiltration membrane to remove inorganic salt, and then anisole is removed by rotary evaporation to obtain the polyaryletherketone emulsifier.
The amorphous polyaryletherketone resin containing the epoxy end group has the following structure:
the number average molecular weight was 1500.
The structural formula of the polyaryletherketone emulsifier obtained in the embodiment is as follows:
the number average molecular weight of the polyaryletherketone emulsifier is 2300.
The infrared spectrum of the polyaryletherketone emulsifier obtained in the embodiment is shown in figure 3. 3400cm -1 is-OH stretching vibration peak, 1115cm -1 Is an-O-C-O-stretching vibration peak, 1773cm -1 Is 1630cm as an ester group stretching vibration peak -1 Is the stretching vibration peak of fluoroketone carbonyl and is 860-800 cm -1 Is a characteristic peak of benzene ring.
The thermal weight loss curves of the polyaryletherketone emulsifiers prepared in examples 1-3 are shown in fig. 4, and it can be seen from the graph that the 5% thermal weight loss temperature of the emulsifiers in examples 1-3 is higher than 400 ℃, and the thermal weight loss curves better meet the technological requirements of high-temperature processing of the polyaryletherketone.
The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, and yet fall within the scope of the invention.
Claims (10)
1. The polyaryletherketone emulsifier is characterized by having a structure shown in a formula I:
in the formula I, m is more than or equal to 0, n is more than 0, and Ar is selected from the following groups:
one or two or more of them.
2. The polyaryletherketone emulsifier of claim 1, wherein the polyaryletherketone emulsifier is prepared by reacting an amorphous polyaryletherketone resin with a nonionic surfactant in the presence of an initiator;
the amorphous polyaryletherketone resin is an epoxy end group-containing amorphous polyaryletherketone resin with the number average molecular weight of 1000-5000, and the structure of the epoxy end group-containing amorphous polyaryletherketone resin is shown as a formula II:
in the formula II, m is more than or equal to 0, n is more than 0, and Ar is selected from the following groups:
one or two or more of them;
the nonionic surfactant is nonionic surfactant containing alcoholic hydroxyl groups.
3. The polyaryletherketone emulsifier of claim 2, wherein the non-ionic surfactant containing alcoholic hydroxyl groups is one of polyethylene glycol, tween 80, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether or polyol polyoxyethylene ether fatty acid ester.
4. The polyaryletherketone emulsifier of claim 2, wherein the initiator is potassium persulfate.
5. A method for preparing the polyaryletherketone emulsifier according to any one of claims 1 to 4, comprising the steps of:
s1, dissolving the amorphous polyaryletherketone resin in an organic solvent, and adding the nonionic surfactant to obtain a mixed solution;
s2, adding the initiator into the mixed solution at a certain temperature, and stirring for reaction to obtain the polyaryletherketone emulsifier.
6. The method for preparing the polyaryletherketone emulsifier according to claim 5, wherein the mass ratio of the amorphous polyaryletherketone resin, the nonionic surfactant and the organic solvent is 8-12: 5-30: 20 to 100.
7. The method for preparing the polyaryletherketone emulsifier according to claim 5, wherein the mass of the initiator is 1-3% of the total mass of the amorphous polyaryletherketone resin and the nonionic surfactant.
8. The method for preparing polyaryletherketone emulsifier according to claim 5, wherein the organic solvent is one of methyl ethyl ketone, dichloroethane, anisole, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide or N-methylpyrrolidone.
9. The method for preparing polyaryletherketone emulsifier according to claim 5, wherein in the step S2, the certain temperature is 70-100 ℃; after the initiator is added, stirring and reacting for 2-8 h.
10. Use of the polyaryletherketone emulsifier according to any one of claims 1 to 4 or prepared by the preparation method according to any one of claims 5 to 9 in a high temperature emulsifier resistant to 300 to 400 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311724057.1A CN117700759A (en) | 2023-12-14 | 2023-12-14 | Polyaryletherketone emulsifier and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311724057.1A CN117700759A (en) | 2023-12-14 | 2023-12-14 | Polyaryletherketone emulsifier and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117700759A true CN117700759A (en) | 2024-03-15 |
Family
ID=90158404
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311724057.1A Pending CN117700759A (en) | 2023-12-14 | 2023-12-14 | Polyaryletherketone emulsifier and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117700759A (en) |
-
2023
- 2023-12-14 CN CN202311724057.1A patent/CN117700759A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107459816B (en) | High-temperature-resistant enhanced thermoplastic composite material and preparation method thereof | |
| CN101003664B (en) | Latex of epoxy resin of aqueous phenolic aldehyde, and preparation method | |
| WO2012088759A1 (en) | Meltable polyimide moulding plastic and preparation method therefor | |
| CN114395216A (en) | Bio-based hyperbranched polymer epoxy resin and preparation method thereof | |
| JP4785732B2 (en) | Conductive polyaniline composition, method for producing the same, and polyaniline dopant | |
| EP2832768A1 (en) | Preparation method of polyimide | |
| CN111423584B (en) | Preparation method of bismaleimide containing adamantane structure | |
| CN114561010B (en) | Self-emulsifying nonionic aqueous polyamide imide and preparation method thereof, carbon fiber sizing agent and preparation method and application thereof | |
| CN112661920A (en) | Preparation method and application of phenolated lignin-phenolic resin nanospheres | |
| CN117700759A (en) | Polyaryletherketone emulsifier and preparation method and application thereof | |
| CN111690083B (en) | Preparation method of polyvinyl butyral resin | |
| CN111704719B (en) | Thermosetting polyimide resin, prepolymer, preparation method and application | |
| CN112574411A (en) | Polyimide precursor, polyimide film, preparation method of polyimide film and display device | |
| CN114149586B (en) | Chain-extended polysulfate and preparation method thereof | |
| CN112110839B (en) | High-fluorine-containing interface compatibilizer and preparation method and application thereof | |
| CN106633104B (en) | Preparation method of water-based polyether sulfone dispersion liquid | |
| CN112063116A (en) | Modified epoxy resin composition and preparation method thereof | |
| CN111944083B (en) | Preparation method of modified macroporous acidic cation exchange resin | |
| CN114960206B (en) | High-temperature-resistant water-soluble thermoplastic sizing agent for carbon fibers and preparation method and application thereof | |
| CN114479062A (en) | Polyaryletherketone containing naphthalene structure and preparation method thereof | |
| CN113637128B (en) | Phenolic resin microsphere prepared by two-step forward suspension polymerization method and preparation method thereof | |
| CN111154099A (en) | Polyimide mutually soluble with bisphenol epoxy resin and having biphenyl structure and preparation method thereof | |
| CN113774665B (en) | Polyether-polylactic acid-acrylic ester sizing agent and preparation method and application thereof | |
| CN110256670B (en) | Thermoplastic polyimide containing fluorene group and preparation method and application thereof | |
| CN1107688C (en) | Process for preparing solution of polyimid-base resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |