CN114560994A - Fluorine-containing polyester polyurethane, preparation method and application thereof - Google Patents

Fluorine-containing polyester polyurethane, preparation method and application thereof Download PDF

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CN114560994A
CN114560994A CN202210187182.2A CN202210187182A CN114560994A CN 114560994 A CN114560994 A CN 114560994A CN 202210187182 A CN202210187182 A CN 202210187182A CN 114560994 A CN114560994 A CN 114560994A
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fluorine
containing polyester
prepolymer
diisocyanate
perfluoropolyether
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CN114560994B (en
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代功强
霍永峰
谭鑫
熊邦虎
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Chengdu Hengkun Guangxian Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/2885—Compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
    • C08G18/3865—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms
    • C08G18/3868—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms the sulfur atom belonging to a sulfide group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42

Abstract

The invention discloses fluorine-containing polyester polyurethane, a preparation method and application thereof, wherein the fluorine-containing polyester polyurethane is prepared by pre-polymerizing polyester dihydric alcohol and modified diisocyanate, and then sealing two ends of a prepolymer by a perfluoropolyether monohydroxy compound; the modified diisocyanate is obtained by performing addition reaction of an isocyanate group and a hydroxyl group on 2, 5-diphenyl (phenol thioether) -1, 4-diphenol and 4,4' -dicyclohexylmethane diisocyanate. The invention modifies the diisocyanate curing agent, adopts the modified diisocyanate and the polyester diol to carry out prepolymerization, and then adopts the perfluoropolyether monohydroxy compound to carry out end capping on both ends of the prepolymer, thereby promoting the polymer to form different crystallization areas, and the difference of the crystallization areas can obtain the refractive index characteristic required by optical display, thereby being applicable to optical display film materials.

Description

Fluorine-containing polyester polyurethane, preparation method and application thereof
Technical Field
The invention belongs to the field of optical special functional polymer materials, and particularly relates to fluorine-containing polyester polyurethane, and a preparation method and application thereof.
Background
In order to improve the refraction state of light in a polymer medium and obtain better display effect, a small amount of functional filler with different refractive indexes is usually added into the medium. Common refractive index functional fillers are polymethyl methacrylate, polystyrene, polydimethylsiloxane, and the like. The dispersion state of the functional filler in the medium has a direct influence on the display effect of the final image. When the functional filler is added into the medium, the accumulation, agglomeration, flocculation and the like of the filler are difficult to avoid, so that local filler concentration difference is generated, which has inevitable influence on the refraction uniformity of light and finally causes the deviation of the display effect. How to directly obtain the refractive index characteristics required by optical display in a single medium becomes an important technical difficulty in the field of optical display.
The invention aims to develop a new fluorine-containing polyester type polyurethane material by uniquely designing an optical display material, and ensure good uniformity by designing a unique crystallization region in a polymer chain segment to ensure that a single-phase polymer substance realizes the refractive index characteristic required by optical display.
In chinese patent publication No. CN 102643406 a entitled "polyester side chain fluorinated polyurethane material and method for making same", a polyester side chain fluorinated polyurethane material is disclosed, which is formed by alternately copolymerizing a flexible chain segment composed of polyester diol with a rigid chain segment composed of diisocyanate and a chain extender, wherein the chain extender is selected from diol having perfluoroalkyl group on the side chain or a mixture thereof with other low molecular weight diols or amines. The novel fluorine-containing polyester polyurethane material disclosed by the invention has fluorine-containing functional groups distributed on side chains, and aims to improve the chemical stability, wear resistance, heat resistance and mechanical properties of polyester polyurethane.
Disclosure of Invention
The invention aims to provide fluorine-containing polyester polyurethane for an optical display film material, and a preparation method and application thereof.
The technical scheme of the invention is as follows:
a fluorine-containing polyester type polyurethane is prepared by pre-polymerizing polyester dihydric alcohol and modified diisocyanate, and then sealing the two ends of the prepolymer by perfluoropolyether monohydroxy compound; the modified diisocyanate is obtained by performing addition reaction of an isocyanate group and a hydroxyl group on 2, 5-diphenyl (phenol thioether) -1, 4-diphenol and 4,4' -dicyclohexylmethane diisocyanate.
In some embodiments, the modified diisocyanate has a molar ratio of 5-bis-phenyl (phenolthioether) -1, 4-diol to 4,4' -dicyclohexylmethane diisocyanate of (2-2.05): 1.
in some embodiments, the polyester diol is poly neopentyl glycol adipate diol.
In some embodiments, the perfluoropolyether monohydroxy compound is perfluoroalkyl alcohol polyoxyethylene ether.
In some embodiments, the prepolymer has a mass content of isocyanate groups of 2% to 3%.
In some embodiments, the amount of the perfluoropolyether monohydroxy compound added is 17% to 28% of the total mass of the reaction raw materials, which refers to the total mass of the perfluoropolyether monohydroxy compound and the prepolymer.
The preparation method of the fluorine-containing polyester polyurethane comprises the following steps:
(1)2, 5-diphenyl (phenol thioether) -1, 4-diphenol and 4,4' -dicyclohexylmethane diisocyanate are subjected to addition reaction at the temperature of 40-70 ℃, and a modified diisocyanate compound solution is obtained after 2-6 h reaction;
(2) mixing the modified diisocyanate compound solution with polyester dihydric alcohol, carrying out prepolymerization reaction at the temperature of 60-70 ℃, and reacting for 2-3 h to obtain a prepolymer containing isocyanate groups;
(3) mixing the perfluoropolyether monohydroxy compound with the prepolymer, and reacting for 4 to 6 hours at the temperature of between 70 and 80 ℃ to obtain the fluorine-containing polyester type polyurethane.
In step (1) of some embodiments, butyl acetate is used as the reaction solvent.
In step (1) of some embodiments, dibutyltin dilaurate and triethylamine are used as catalysts.
The fluorine-containing polyester polyurethane has excellent refractive index characteristics and can be used as an optical display film material.
Compared with the prior art, the invention has the following characteristics:
(1) the diisocyanate curing agent is modified, modified diisocyanate and polyester diol are subjected to prepolymerization, and then a perfluoropolyether monohydroxy compound is adopted to carry out end capping on two ends of a prepolymer, so that the polymer is promoted to form different crystallization areas, and the refractive index characteristics required by optical display can be obtained through the difference of the crystallization areas, so that the modified diisocyanate and polyester diol can be applied to optical display film materials.
(2) The fluorine-containing polyester type polyurethane has excellent refractive index characteristic without adding a refractive index functional filler, so that the non-uniformity caused by adding the refractive index functional filler can be avoided
Detailed Description
The following will describe the detailed embodiments and technical effects of the present invention in detail with reference to the examples.
In order to obtain a suitable refractive index of a urethane segment crystalline region of a diisocyanate and polyester diol cured product, the curing agent diisocyanate is mainly modified, namely: 4,4' -dicyclohexylmethane diisocyanate (CAS: 5124-30-1) was modified with 2, 5-bis-phenyl (phenol thioether) -1, 4-diol (CAS: 80632-58-2). The structure of 4,4' -dicyclohexylmethane diisocyanate is shown in the following formula (I), and the structural formula of 2, 5-diphenyl (phenol thioether) -1, 4-diphenol is shown in the following formula (II). In this example, 2, 5-bis-phenyl (phenol thioether) -1, 4-diol and 4,4' -dicyclohexylmethane diisocyanate were commercially available.
Figure BDA0003523193240000031
Figure BDA0003523193240000032
The following will provide a specific process for preparing the fluorine-containing polyester urethane in this embodiment, including:
(1) a modified diisocyanate compound is prepared.
Taking butyl acetate subjected to redistillation and zeolite dehydration as a solvent, taking 100 g of butyl acetate, adding into a closed container with a condensing device, adding 16.32 g (0.05 mol) of 2, 5-diphenyl (phenol thioether) -1, 4-diphenol, and stirring until the butyl acetate is dissolved. Then, 1 g of dibutyltin dilaurate and 0.5 g of triethylamine were added and stirred until dissolved, with dibutyltin dilaurate and triethylamine as catalysts. Finally, under stirring, 55.02 to 56.41 g (i.e., 0.10 mol to 0.1075 mol) of a butyl acetate solution of 4,4 '-dicyclohexylmethane diisocyanate and a butyl acetate solution of 4,4' -dicyclohexylmethane diisocyanate were added dropwise so that the mass concentration of 4,4 '-dicyclohexylmethane diisocyanate in the butyl acetate solution of 4,4' -dicyclohexylmethane diisocyanate was 50%. 4,4' -dicyclohexylmethane diisocyanate and 2, 5-diphenyl (phenol thioether) -1, 4-diphenol are subjected to addition reaction of isocyanate groups and hydroxyl groups, the reaction temperature is 40-70 ℃, and the reaction time is 2-6 h, so that a modified diisocyanate compound solution is obtained.
The reaction of 4,4' -dicyclohexylmethane diisocyanate with 2, 5-bis-phenyl (phenolthioether) -1, 4-diol is shown below
Formula (III):
Figure BDA0003523193240000041
the structural formula of the obtained modified diisocyanate compound is shown as the formula (IV).
Figure BDA0003523193240000042
(2) Preparation of a prepolymer
In order to further improve the coating effect on the substrate, a weather-resistant polyester polyol with strong affinity to the substrate is introduced, in this example, a poly neopentyl glycol adipate diol with a molecular weight of 2000 and a chemical structural formula shown in the following formula (v) is adopted. The neopentyl glycol adipate diol and the modified diisocyanate compound are subjected to prepolymerization reaction to obtain a prepolymer with the molecular weight of 1000-2000, wherein the molecular weight of the prepolymer is preferably 1000, and the higher the n value is, the lower the activity is.
Figure BDA0003523193240000051
The specific process for preparing the prepolymer in this example is as follows:
86.42 g of the modified isocyanate compound solution obtained in the step (1) is taken and slowly added dropwise into 80-100 g of neopentyl glycol adipate diol. After the dropwise addition is finished, the temperature is raised to 60-70 ℃, and the reaction lasts for 2-3 h. A small amount of sample is taken and dissolved by toluene di-n-butylamine, bromocresol blue is used as an indicator, hydrochloric acid is used for titration, and when the-NCO% value is basically unchanged, the reaction reaches the end point, so that a prepolymer containing 2% -5% of NCO (isocyanate group) is obtained, wherein 2% -5% refers to the mass content.
(3) End capping of prepolymers
In order to meet the requirement of optical display refractive index of the polymer, perfluoroalkyl alcohol polyoxyethylene ether (FEO-500) is introduced to be terminated on the basis of a prepolymer, so that the polymer can be better promoted to form different crystal regions, and the chemical structural formula of the perfluoroalkyl alcohol polyoxyethylene ether is shown in the following formula (VI), wherein a is 3-6, and b is 10-12.
Figure BDA0003523193240000052
And (3) adding 20-50 g of perfluoroalkyl alcohol polyoxyethylene ether (FEO-500) into 93.21 g of the prepolymer obtained in the step (2), heating to 70-80 ℃, and carrying out heat preservation reaction for 4-6 h to obtain the fluorine-terminated modified polyester type polyurethane. Because of the refractive index difference of the crystallization area formed by the carbamate and the perfluoroalkyl alcohol polyoxyethylene ether in the fluorine-terminated modified polyester type polyurethane structure, the required optical display refraction characteristic is realized, and the image contrast definition of the optical display can be improved.
The invention realizes the refractive index characteristic required by optical display through the unique crystalline region design in the polymer chain segment, thereby meeting the requirement on ideal medium materials. 2, 5-diphenyl (phenol thioether) -1, 4-diphenol is adopted to modify 4,4' -dicyclohexyl methane diisocyanate. Then introducing weather-resistant polyester polyol (poly neopentyl glycol adipate diol is adopted in the embodiment) with strong affinity to the base material, and further carrying out prepolymerization reaction with modified diisocyanate to obtain a prepolymer with enough molecular weight. The perfluoropolyether monohydroxy compound (perfluoroalkyl alcohol polyoxyethylene ether (FEO-500) is adopted for end capping in the embodiment) is introduced into the prepolymer, so that the polymer can be better promoted to form different crystal regions.
The invention provides 2 groups of examples and 2 groups of comparative proportions, and the corresponding preparation process and performance parameters are shown in table 1.
TABLE 1 preparation Process and Performance parameters of the examples
Figure BDA0003523193240000061
As can be seen from Table 1, examples 1-2 have excellent refractive index properties, and when used as optical display films, significantly better display effects can be obtained; the comparative examples 1 and 2 have slightly poor refractive index performance and obviously reduced light transmittance, and are difficult to meet the use requirements of optical display film materials.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
It will be understood that the invention is not limited to what has been described above and that various modifications and changes can be made without departing from the scope thereof. The scope of the invention is limited only by the appended claims.

Claims (10)

1. A fluorine-containing polyester type polyurethane is characterized in that:
the prepolymer is prepared by pre-polymerizing polyester diol and modified diisocyanate and then sealing two ends of the prepolymer by perfluoropolyether monohydroxy compound; the modified diisocyanate is obtained by performing addition reaction of an isocyanate group and a hydroxyl group on 2, 5-diphenyl (phenol thioether) -1, 4-diphenol and 4,4' -dicyclohexylmethane diisocyanate.
2. The fluorine-containing polyester urethane according to claim 1, wherein:
in the modified diisocyanate, the molar ratio of 5-diphenyl (phenol thioether) -1, 4-diphenol to 4,4' -dicyclohexylmethane diisocyanate is (2-2.05): 1.
3. the fluorine-containing polyester urethane according to claim 1, wherein:
the polyester dihydric alcohol is poly neopentyl glycol adipate dihydric alcohol.
4. The fluorine-containing polyester urethane according to claim 1, wherein:
the perfluoropolyether monohydroxy compound is perfluoroalkyl alcohol polyoxyethylene ether.
5. The fluorine-containing polyester urethane according to claim 1, wherein:
the mass content of the isocyanate group in the prepolymer is 2-3%.
6. The fluorine-containing polyester urethane according to claim 1, wherein:
the addition amount of the perfluoropolyether monohydroxy compound is 17-28% of the total mass of the reaction raw materials, and the total mass of the reaction raw materials refers to the total mass of the perfluoropolyether monohydroxy compound and the prepolymer.
7. The process for producing a fluorine-containing polyester urethane according to claim 1, which comprises:
(1)2, 5-diphenyl (phenol thioether) -1, 4-diphenol and 4,4' -dicyclohexylmethane diisocyanate are subjected to addition reaction at the temperature of 40-70 ℃, and a modified diisocyanate compound solution is obtained after 2-6 h reaction;
(2) mixing the modified diisocyanate compound solution with polyester dihydric alcohol, carrying out prepolymerization reaction at the temperature of 60-70 ℃, and reacting for 2-3 h to obtain a prepolymer containing isocyanate groups;
(3) mixing the perfluoropolyether monohydroxy compound with the prepolymer, and reacting for 4 to 6 hours at the temperature of between 70 and 80 ℃ to obtain the fluorine-containing polyester type polyurethane.
8. The method of claim 7, wherein:
in the step (1), butyl acetate is used as a reaction solvent.
9. The method of claim 7, wherein:
in the step (1), dibutyltin dilaurate and triethylamine are used as catalysts.
10. Use of the fluorine-containing polyester urethane according to any one of claims 1 to 6 as an optical display film material.
CN202210187182.2A 2022-02-28 2022-02-28 Fluorine-containing polyester polyurethane, and preparation method and application thereof Active CN114560994B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111057462A (en) * 2019-12-16 2020-04-24 中昊北方涂料工业研究设计院有限公司 Ultra-low refractive index high fluorine content UV curing polyurethane acrylate coating
CN112574384A (en) * 2019-09-27 2021-03-30 万华化学集团股份有限公司 Thermoplastic polyurethane elastomer material and preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
CN112574384A (en) * 2019-09-27 2021-03-30 万华化学集团股份有限公司 Thermoplastic polyurethane elastomer material and preparation method and application thereof
CN111057462A (en) * 2019-12-16 2020-04-24 中昊北方涂料工业研究设计院有限公司 Ultra-low refractive index high fluorine content UV curing polyurethane acrylate coating

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Title
卢少忠编著: "《建筑涂料工程-性能•生产•施工》", vol. 1, 中国建材工业出版社, pages: 40 *

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