CN110437416B - Preparation method of fluorosilicated polyurethane elastomer with comb-shaped structure - Google Patents
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Abstract
The invention belongs to the technical field of preparation of high polymer materials, and particularly relates to a preparation method of a fluorosilicated polyurethane elastomer with a comb-shaped structure. The micromolecule alcohol chain extender containing the siloxane side group and the polyether polyol or polyether amine containing the fluorine side group act together, so that both the soft section and the hard section of the polyurethane material have fluorine-containing and siloxane-containing chain segments capable of improving the surface performance of the material, are positioned in the side groups to form a comb-shaped structure, the modification effect of fluorine-containing and silicon-containing components on the surface of the material can be enhanced to a greater extent, and polyurethane elastomer materials with different hardness have excellent surface performance and can be used as antifouling materials to be applied to the intelligent wearing fields of watchbands, sheaths, bracelets and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of high polymer materials, and particularly relates to a preparation method of a fluorosilicated polyurethane elastomer with a comb-shaped structure.
Background
Fluoropolymers represented by polytetrafluoroethylene have a series of unique chemical and physical properties such as excellent thermal stability and chemical inertness, a low friction coefficient, a low adhesion property, hydrophobic and oleophobic properties, a low refractive index and the like, and thus, fluoropolymers have been widely used as a high value-added material in the fields of protective coatings, molded articles, electrical insulation. The fluorine-containing polyurethane is a novel functional material, and is prepared by modifying and modifying traditional polyurethane by using fluorine elements by various different means. The introduction of the fluorine-containing chain segment into the polyurethane can combine the respective advantages of the fluorine-containing material and the polyurethane material, and broaden the application prospect of the polyurethane material.
Several common methods for modifying and modifying polyurethane with fluorine mainly comprise: mechanical physical blending, which introduces fluorine by physically blending some fluoropolymers with polyurethanes using physically forced blending, generally suffers from compatibility issues; the principle of the polyurethane soft segment introduction method is that fluorine is introduced by taking a mixture of fluorine-containing polyol such as perfluoropolyether, semi-fluoropolyether, perfluoropolyester and the like and common polyol as a polyurethane soft segment, and the principle of the hard segment introduction method is that fluorinated polyisocyanate or fluorine-containing diol monomer is introduced as a chain extender, but fluorine is generally positioned in a polyurethane main chain by the soft segment and hard segment introduction method, the enrichment of fluorine on the surface of a material is low, and the used monomers such as perfluoropolyether, fluorinated isocyanate and the like have limited sources and high price, are greatly limited and only stay in the research level of a laboratory.
With the intensive research on fluorine-containing polyurethane materials, there are references in the literature to the preparation of fluorine-containing polyurethane materials using polyols containing fluorine in the pendant group, but the polyols containing fluorine in the pendant group are generally prepared by anion and cation initiated methods, and mainly include methods of preparing fluorinated polyether from fluorine-containing epoxide or reacting fluorine-containing small molecular alcohol monomer with isocyanate and then ethanolamine to obtain polyether containing fluorine in the pendant group, but the products synthesized by the two methods have low molecular weight and short pendant chain length, so that the problem of compatibility between the fluorine-containing polyether and other components is difficult to solve, the mechanical properties and the like are not good, the preparation method is complicated, and when the hardness of polyurethane materials is improved, the effect of fluorine modification is not good due to the reduction of the use amount of the fluorine-containing component in the soft segment.
Therefore, at present, a preparation method of a fluorine-containing component raw material and a fluorine-containing polyurethane elastomer is urgently needed, the synthesis difficulty and cost of the fluorine-containing polyurethane material are reduced, and the problems of compatibility of the fluorine-containing component in a polyurethane system, surface enrichment of fluorine and the like are solved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a fluorosilicated polyurethane elastomer with a comb-shaped structure.
The technical scheme for solving the technical problems is as follows: a preparation method of a fluorosilicated polyurethane elastomer with a comb-shaped structure comprises the following steps:
(1) preparation of polyether polyol or polyether amine containing fluorine side group: reacting polyether polyol or polyether amine with fluorine-containing acrylate resin under the action of a solid base catalyst at 60-110 ℃ for 4-10h until no fluorine-containing acrylate resin remains in the system; filtering to remove the solid base catalyst to obtain polyether polyol or polyether amine containing the fluorine side group;
(2) preparing a micromolecular diol chain extender containing silicon side groups: reacting pentamethyl disiloxane or heptamethyl trisiloxane with alkylene glycol under the catalysis of a noble metal catalyst at the temperature of 90-120 ℃ for 3-6h until no silicon-hydrogen residue exists in the system; carrying out vacuum low-boiling removal treatment for 2-4h to obtain the micromolecule diol chain extender containing the silicon side group;
(3) preparing a fluorosilicated polyurethane elastomer with a comb-shaped structure: taking 55-75 parts by weight of the polyether polyol or polyether amine containing the fluorine side group in the step (1), 10-25 parts by weight of the micromolecule diol chain extender containing the silicon side group in the step (2), 13-25 parts by weight of diisocyanate and 0-5 parts by weight of an auxiliary agent, granulating by a prepolymer method or a one-step reaction extrusion process, drying and curing to prepare the fluorine silicification polyurethane elastomer.
Further, the molecular weight of the polyether polyol or polyether amine in the step (1) is 6000g/mol and the functionality is 3-6.
Further, the structure of the fluorine-containing acrylate resin in the step (1) is CH2＝CR-COO(CH2)mCnF2n+1Wherein R is H or CH3，m≥1，n≥1。
Furthermore, the fluorine-containing acrylate resin is one or more of trifluoroethyl acrylate, trifluoroethyl methacrylate, hexafluorobutyl acrylate, dodecafluoroheptyl methacrylate or dodecafluorooctyl acrylate.
Further, the molecular weight of the polyether polyol or polyether amine containing the fluorine side group in the step (1) is 2500-7000g/mol, and the functionality is 2-2.5.
The polyether glycol or polyether amine side group containing the fluorine side group is in linkage with the fluorine-containing chain segment at the tail end of the long polyether chain segment, the problem of poor compatibility after fluorine modification can be solved due to the existence of the long polyether chain segment, and the long side chain segment is easier to move, so that the fluorine-containing unit at the tail end is more convenient to enrich on the surface of a product material, and the fluorine-containing unit has the functional effects of low fluorine content and high surface performance.
Further, in the step (2), the alkene diol is one or more than two of 2-butene-1, 4-diol, 2-pentene-1, 5-diol, 3-hexene-2, 5-diol or 6-heptene-2, 4-diol.
Further, the molecular weight of the silicon-containing side group-containing small-molecule glycol chain extender in the step (2) is 235-355 g/mol.
The chain extender has the beneficial effects that the chain extender molecule contains the silicon-containing side group, so that the hard segment of the polyurethane also has the siloxane chain segment which can be moved easily, and the siloxane chain segment can supplement with the fluorine-containing chain segment of the soft segment, so that fluorine and silicon are enriched on the surface of the material, the surface performance of the material is improved, and meanwhile, the excellent surface performance can be maintained even for a product with high hardness.
Further, the solid base catalyst in the step (1) is one or more than two of alkali metal compounds, alkaline earth metal compounds, hydrated talc solid bases or supported inorganic solid bases; the noble metal catalyst in the step (2) is one or more than two of platinum, rhodium, palladium, a platinum complex, a rhodium complex or a palladium complex.
Furthermore, the solid base catalyst in the step (1) is one or more than two of magnesium oxide, magnesium-aluminum hydrotalcite, potassium hydroxide loaded aluminum trioxide, potassium carbonate loaded aluminum trioxide, an alkali metal ion exchange molecular sieve or a metal active site solid base molecular sieve; the noble metal catalyst in the step (2) is one or more than two of rhodium chloride hydrate, rhodium acetate dimer, rhodium tetrafluoroborate, chloroplatinic acid and a complex of the chloroplatinic acid and isopropanol or platinum water.
Further, the diisocyanate in the step (3) is one or more of diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, dicyclohexylmethane diisocyanate, or xylylene diisocyanate;
the auxiliary agent is organic bismuth/organic tin catalyst, antioxidant and light stabilizer.
Further, the hardness of the obtained fluorosilicated polyurethane elastomer was 65 to 95A.
The invention has the characteristics and beneficial effects that:
(1) according to the invention, polyether polyol or polyether amine with high functionality is adopted to react with fluorine-containing acrylate, the hydroxyl of polyether or active hydrogen of polyether amine is subjected to addition reaction with double bonds of fluorine-containing acrylate monomers, and the double bonds of fluorine-containing acrylate and hydroxyl or amino are subjected to Michael addition reaction more easily due to the electron-withdrawing effect of fluorine-containing units, so that the tail end of a certain chain segment of the polyether polyol or polyether amine with high functionality is linked to form a fluorine-containing chain segment, and meanwhile, the functionality of the polyether polyol or polyether amine with high functionality is reduced, and the functionality of the product is adjusted to be 2-2.5 by adjusting the proportion of the polyether polyol or polyether amine with high functionality to form fluorine-containing polyether polyol or polyether amine with a long polyether chain segment modified by fluorine-containing units.
(2) The invention adopts the silicon-hydrogen bond in the molecule of pentamethyl disiloxane or heptamethyl trisiloxane and the double bond in the molecule of alkylene glycol to carry out the hydrosilylation reaction under the action of noble metal catalysts such as platinum and the like, so that the siloxane chain segment is grafted on the side group of the micromolecular alcohol.
(3) The preparation method of the polyether polyol or polyether amine containing the fluorine side group is simpler, the raw materials are easy to obtain, compared with materials such as perfluoropolyether and the like, the cost of the polyether polyol or polyether amine containing the fluorine side group is lower, the fluorine-containing units are located on the side groups, long polyether chain segments are in bonding connection with the fluorine-containing units, the compatibility is excellent, enrichment of surface fluorine elements is facilitated, and the surface performance of the material is more excellent.
(4) The micromolecule alcohol chain extender containing the siloxane side group and the polyether polyol or polyether amine containing the fluorine side group act together, so that both the soft section and the hard section of the polyurethane material have fluorine-containing and siloxane-containing chain segments capable of improving the surface performance of the material, are positioned in the side groups to form a comb-shaped structure, the modification effect of fluorine-containing and silicon-containing components on the surface of the material can be enhanced to a greater extent, and polyurethane elastomer materials with different hardness have excellent surface performance and can be used as antifouling materials to be applied to the intelligent wearing fields of watchbands, sheaths, bracelets and the like.
Detailed Description
The principles and features of this invention are described below in conjunction with examples, which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
A preparation method of a fluorosilicated polyurethane elastomer with a comb-shaped structure comprises the following steps:
(1) preparation of polyether amine containing fluorine side group: reacting 2000g of polyetheramine (functionality 3, molecular weight 4000g/mol) with 77.05g of trifluoroethyl acrylate monomer under the action of magnesium oxide at 85 ℃ for 5h until no trifluoroethyl acrylate monomer remains in the system; filtering to remove magnesium oxide to obtain polyether amine containing fluorine side groups, wherein the molecular weight is 4154 g/mol;
(2) preparing a micromolecular diol chain extender containing silicon side groups: reacting 500g of pentamethyl disiloxane with 299g of 2-butene-1, 4-diol under the catalysis of chloroplatinic acid at the temperature of 100 ℃ for 5 hours until no silicon hydrogen residue exists in the system; performing low-boiling removal treatment for 2h under vacuum of-0.1 MPa to obtain a micromolecular diol chain extender containing silicon side groups, wherein the molecular weight is 235.45 g/mol;
(3) preparing a fluorosilicated polyurethane elastomer with a comb-shaped structure: taking 700g of the polyether amine containing the fluorine side group in the step (1), 123.2g of the micromolecule diol chain extender containing the silicon side group in the step (2), 176.8g of diphenylmethane diisocyanate, 0.01g of organic tin catalyst, 10105g of antioxidant and 7883.5g of light stabilizer, granulating by a one-step reaction extrusion process, drying and curing for 16h, and obtaining the fluorosilicone polyurethane elastomer.
Example 2
A preparation method of a fluorosilicated polyurethane elastomer with a comb-shaped structure comprises the following steps:
(1) preparation of polyether polyol containing fluorine side group: reacting 2000g of polyether polyol (with the functionality of 3 and the molecular weight of 4000g/mol) with 77.05g of trifluoroethyl acrylate monomer under the action of a magnesium-aluminum hydrotalcite solid base catalyst at the temperature of 90 ℃ for 6 hours until no trifluoroethyl acrylate monomer remains in the system; filtering to remove the solid base catalyst to obtain polyether polyol containing fluorine side groups, wherein the molecular weight is 4154 g/mol;
(2) preparing a micromolecular diol chain extender containing silicon side groups: reacting 500g of pentamethyl disiloxane and 299g of 2-butylene-1, 4-diol for 5 hours at the temperature of 100 ℃ under the action of a platinum water catalyst until no silicon hydrogen residue exists in the system; performing low-boiling removal treatment for 2h under vacuum of-0.1 MPa to obtain a micromolecular diol chain extender containing silicon side groups, wherein the molecular weight is 235.45 g/mol;
(3) preparing a fluorosilicated polyurethane elastomer with a comb-shaped structure: and (2) taking 1220g of polyether polyol containing the fluorine side group in the step (1), 340.2g of micromolecular diol chain extender containing the silicon side group in the step (2), 353.6g of diphenylmethane diisocyanate, 0.04g of organic tin catalyst, 21510 g of antioxidant and 6227 g of light stabilizer, granulating by a one-step reaction extrusion process, drying and curing for 16h, and thus obtaining the fluorosilicone polyurethane elastomer.
Example 3
A preparation method of a fluorosilicated polyurethane elastomer with a comb-shaped structure comprises the following steps:
(1) preparation of polyether polyol containing fluorine side group: reacting 3000g of polyether polyol (with the functionality of 4.5 and the molecular weight of 6000g/mol) with 295.14g of hexafluorobutyl acrylate monomer under the action of magnesium oxide at 105 ℃ for 7h until no hexafluorobutyl acrylate monomer is left in the system; filtering to remove magnesium oxide to obtain polyether polyol containing fluorine side groups, wherein the molecular weight of the polyether polyol is 6590 g/mol;
(2) preparing a micromolecular diol chain extender containing silicon side groups: reacting 600g of heptamethyltrisiloxane with 275.4g of 2-butene-1, 4-diol under the catalysis of a rhodium acetate dimer at the temperature of 110 ℃ for 4 hours until no silicon hydrogen residue exists in the system; performing low-boiling removal treatment for 4h under vacuum of-0.1 MPa to obtain a micromolecular diol chain extender containing silicon side groups, wherein the molecular weight is 324.64 g/mol;
(3) preparing a fluorosilicated polyurethane elastomer with a comb-shaped structure: and (2) taking 975g of the polyether polyol containing the fluorine side group in the step (1), 272.55g of the micromolecule diol chain extender containing the silicon side group in the step (2), 252.45g of diphenylmethane diisocyanate, 0.045g of organic bismuth catalyst, 10107.5 g of antioxidant and 7885.25 g of light stabilizer, granulating by a one-step reaction extrusion process, drying and curing for 16h to obtain the fluorosilicone polyurethane elastomer.
Example 4
A preparation method of a fluorosilicated polyurethane elastomer with a comb-shaped structure comprises the following steps:
(1) preparation of polyether amine containing fluorine side group: reacting 3000g of polyetheramine (with the functionality of 3 and the molecular weight of 5000g/mol) with 100.8g of trifluoroethyl methacrylate monomer at 75 ℃ for 4h under the action of an alkali metal ion exchange molecular sieve until no fluorine-containing acrylate resin remains in the system; filtering to remove the solid base catalyst to obtain polyether amine containing the fluorine side group, wherein the molecular weight is 5168 g/mol;
(2) preparing a micromolecular diol chain extender containing silicon side groups: reacting 550g of pentamethyl disiloxane with 433.61g of 3-hexene-2, 5-diol under the action of a platinum water catalyst at the temperature of 110 ℃ for 4.5h until no silicon hydrogen residue exists in the system; performing low-boiling removal treatment for 3h under vacuum of-0.1 MPa to obtain a micromolecular diol chain extender containing a silicon side group, wherein the molecular weight is 263.5 g/mol;
(3) preparing a fluorosilicated polyurethane elastomer with a comb-shaped structure: and (2) taking 986g of polyether amine containing the fluorine side group in the step (1), 337.79g of micromolecule diol chain extender containing the silicon side group in the step (2), 376.21g of diphenylmethane diisocyanate, 0.085g of organic bismuth catalyst, 1685.95 g of antioxidant and 7707.65 g of light stabilizer, granulating by a one-step reaction extrusion process, drying and curing for 16 hours to obtain the fluorosilicone polyurethane elastomer.
The reaction principle of this example is as follows:
example 5
A preparation method of a fluorosilicated polyurethane elastomer with a comb-shaped structure comprises the following steps:
(1) preparation of polyether polyol containing fluorine side group: reacting 3000g of polyether polyol (with the functionality of 3.5 and the molecular weight of 2800g/mol) with 642.86g of dodecafluoroheptyl methacrylate monomer under the action of a metal active site solid base molecular sieve catalyst at the temperature of 95 ℃ for 5 hours until no dodecafluoroheptyl methacrylate monomer remains in the system; filtering to remove the solid base catalyst to obtain polyether polyol containing fluorine side groups, wherein the molecular weight is 3400 g/mol;
(2) preparing a micromolecular diol chain extender containing silicon side groups: reacting 400g of pentamethyl disiloxane with 352.93g of 6-heptylene-2, 4-diol under the catalysis of platinum water at the temperature of 110 ℃ for 5 hours until no silicon hydrogen residue exists in the system; performing low-boiling removal treatment for 2h under vacuum of-0.1 MPa to obtain a micromolecular diol chain extender containing silicon side groups, wherein the molecular weight of the micromolecular diol chain extender is 277.3 g/mol;
(3) preparing a fluorosilicated polyurethane elastomer with a comb-shaped structure: 1087.5g of polyether polyol containing the fluorine side group in the step (1), 172.05g of micromolecular diol chain extender containing the silicon side group in the step (2), 240.45g of diphenylmethane diisocyanate, 0.015g of organic tin catalyst, 10107.5 g of antioxidant and 7885.25 g of light stabilizer are taken, and the mixture is granulated through a one-step reaction extrusion process, dried and cured for 16 hours to prepare the fluorosilicone polyurethane elastomer.
The fluorosiliconized polyurethane elastomers obtained in examples 1 to 5 were subjected to the performance test, as shown in Table 1.
TABLE 1
The physical property data in table 1 show that the fluorosilicated polyurethane elastomer with a comb-shaped structure prepared by the method has normal mechanical properties, and the problem of remarkably poor performance after fluorine modification does not occur, which shows that the fluorine-containing and silicon-containing components in the method have good compatibility in a system, and the static water contact angle test shows that the contact angle is high, the surface is hydrophobic, no trace residue exists in the dirt resistance test, and the surface performance is excellent, so that the fluorosilicated polyurethane elastomer can be used as a dirt resistance material to be applied to the intelligent wearing fields of watchbands, sheaths, bracelets and the like.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. A preparation method of a fluorosilicated polyurethane elastomer with a comb-shaped structure is characterized by comprising the following steps:
(1) preparation of polyether polyol or polyether amine containing fluorine side group: reacting polyether polyol or polyether amine with a fluorine-containing acrylate monomer under the action of a solid base catalyst at 60-110 ℃ for 4-10h until no fluorine-containing acrylate monomer remains in the system; filtering to remove the solid base catalyst to obtain polyether polyol or polyether amine containing fluorine side groups, wherein the molecular weight of the polyether polyol or polyether amine is 2000-6000g/mol, the functionality of the polyether polyol or polyether amine is 3-6, and the structure of the fluorine-containing acrylate monomer is CH2=CR-COO(CH2)mCnF2n+1Wherein R is H or CH3，m≥1，n≥1；
(2) Preparing a micromolecular diol chain extender containing silicon side groups: reacting pentamethyl disiloxane or heptamethyl trisiloxane with alkylene glycol under the catalysis of a noble metal catalyst at the temperature of 90-120 ℃ for 3-6h until no silicon-hydrogen residue exists in the system; carrying out vacuum low-boiling removal treatment for 2-4h to obtain the micromolecule diol chain extender containing the silicon side group;
(3) preparing a fluorosilicated polyurethane elastomer with a comb-shaped structure: taking 55-75 parts by weight of the polyether polyol or polyether amine containing the fluorine side group in the step (1), 10-25 parts by weight of the micromolecule diol chain extender containing the silicon side group in the step (2), 13-25 parts by weight of diisocyanate and 0-5 parts by weight of an auxiliary agent, granulating by a prepolymer method or a one-step reaction extrusion process, drying and curing to prepare the fluorine silicification polyurethane elastomer.
2. The preparation method according to claim 1, wherein the fluorine-containing acrylate monomer is one or two of trifluoroethyl acrylate monomer and trifluoroethyl methacrylate monomer.
3. The process according to claim 1, wherein the polyether polyol or polyether amine having a pendant fluorine-containing group in step (1) has a molecular weight of 2500-7000g/mol and a functionality of 2-2.5.
4. The process according to claim 1, wherein the alkylene glycol in the step (2) is one or more selected from 2-butene-1, 4-diol, 2-pentene-1, 5-diol, 3-hexene-2, 5-diol and 6-heptene-2, 4-diol.
5. The method as claimed in claim 1, wherein the molecular weight of the silicon-containing pendant group-containing small molecule diol chain extender in step (2) is 235-355 g/mol.
6. The preparation method according to claim 1, wherein the solid base catalyst in step (1) is one or more of an alkali metal compound, an alkaline earth metal compound, a hydrotalcite-like solid base, or a supported inorganic solid base; the noble metal catalyst in the step (2) is one or more than two of platinum, rhodium, palladium, a platinum complex, a rhodium complex or a palladium complex.
7. The method according to claim 1, wherein the diisocyanate in step (3) is one or more of diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, dicyclohexylmethane diisocyanate, or xylylene diisocyanate;
the auxiliary agent is organic bismuth/organic tin catalyst, antioxidant and light stabilizer.
8. The process according to claim 1, wherein the hardness of the resulting fluorosilicated polyurethane elastomer is from 65 to 95A.
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| CN111154064B (en) * | 2020-01-03 | 2022-02-18 | 万华化学集团股份有限公司 | Fluorine-silicon type thermoplastic polyurethane elastomer and preparation method thereof |
| CN115521694A (en) * | 2022-11-01 | 2022-12-27 | 江南大学 | Method for preparing fluorine modified water-based UV cured polyurea-urethane coating |
| CN115677973A (en) * | 2022-11-11 | 2023-02-03 | 陕西立高涂料有限公司 | Fluorine-containing polyurethane emulsion and preparation method and application thereof |
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