CN116217871A - Preparation method of solvent-free polyurethane with self-repairing function and preparation method thereof - Google Patents
Preparation method of solvent-free polyurethane with self-repairing function and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of solvent-free self-repairing polyurethane, which comprises the following components in percentage by mass: (80-120), wherein the component A consists of polyalcohol, disulfide, 4' -dihydroxydiphenyl sulfone, catalyst, leveling agent and the like, and the component B consists of polyisocyanate and polyalcohol; A. the component B synthesizes polyurethane resin by a two-component pouring method. The polyurethane synthesized by the invention has the characteristics of environment friendliness and no solvent residue; the polyurethane synthesized by the invention has a rapid self-repairing function at 80 ℃, and can repair large-size damage; the polyurethane synthesized by the invention can be repeatedly used for many times; the solvent-free polyurethane resin prepared by the invention can be prepared into polyurethane synthetic leather, polyurethane elastomer, polyurethane adhesive and the like, and has wide application range.
Description
Technical Field
The invention relates to the field of high polymer material polyurethane, in particular to a preparation method of solvent-free polyurethane with a self-repairing function and a preparation method thereof.
Background
Polyurethane resin is a generic name of a class of high molecular compounds with carbamate group units on the main chain synthesized by taking isocyanate, polyol and small molecular chain extender as raw materials. The polyurethane resin can be made into polyurethane plastics, polyurethane fibers, polyurethane rubber, elastomers, polyurethane coatings, polyurethane adhesives, polyurethane synthetic leather and the like.
However, polyurethane resins often involve two common problems during use. Firstly, the product is easy to generate microscopic cracks due to scraping, collision and the like in use, the microscopic cracks develop into macroscopic cracks, and finally the material is permanently damaged, so that the appearance quality of the product is damaged, and the service life of the material is also influenced; secondly, the traditional solvent polyurethane is easy to release toxic and harmful gases in the preparation and use processes, so that the environment is polluted, and even the physical health of people is threatened.
In view of the above problem one, self-repairing polyurethane is a new direction capable of solving the above problem one well. At present, the research hot spot of polyurethane self-repairing function is intrinsic self-repairing, and the self-repairing of materials is realized by breaking and recombining chemical bonds. Common intrinsic self-repair mechanisms are S-S bonds, se-Se bonds, diels-Alder reactions, phenol-urethane bonds, hydrogen bonds, and the like. However, the conventional self-repairing polyurethane cannot repair large-scale damage, which limits the application range and application prospect of the material.
In view of the second problem, most of the existing synthetic schemes related to self-repairing polyurethane still need solvents to participate in the preparation process. However, some of the methods for synthesizing self-repairing polyurethane resins by solvent-free methods have disadvantages such as unsatisfactory mechanical properties.
The invention patent with publication number of CN108912371A discloses the preparation of self-repairing polyurethane resin by solvent-free method based on Diels-Alder bond, and the polyurethane resin with excellent repairing effect is prepared. However, the repairing effect can be achieved only at the high temperature of 120 ℃, the repairing temperature is too high, the repairing efficiency is low, large-scale damage cannot be repaired, and the application range is limited.
The invention patent with publication number of CN106750115A discloses a preparation method of self-repairing polyurethane hydrogel based on diselenide bond, wherein the hydrogel is prepared by performing polycondensation and crosslinking reaction on diisocyanate, polyethylene glycol, diselenide glycol and diethanolamine, and then soaking in deionized water. The polyurethane hydrogel can realize self-repairing under visible light, however, the polyurethane hydrogel is synthesized by using an organic solvent, is easy to cause environmental pollution, is only applied to the field of bioengineering, and cannot be applied to other polyurethane fields.
The invention patent with publication number of CN109762459A discloses a preparation method of self-repairing polyurethane based on diselenide bond. The solvent-free polyurethane resin with self-repairing function and hydrophobicity is prepared by adding small molecular diselendiol and hydroxyl-terminated fluorine-containing polysiloxane into raw materials. However, the polyurethane synthesized by the scheme has low mechanical property and low repair speed, and cannot directly realize large-scale damage repair.
Based on the above problems, on the one hand, the self-repairing problem of polyurethane needs to be solved, on the other hand, the pollution problem existing in the solvent preparation of polyurethane needs to be solved, and the existing technical scheme still needs to solve the new insufficient problems after solving the two problems, and a new technical scheme for preparing the self-repairing polyurethane by using a solvent-free method needs to be designed, by which the technical problems and the defects are solved.
Disclosure of Invention
The invention provides a preparation method of solvent-free polyurethane with a self-repairing function and a preparation method thereof.
According to the solvent-free polyurethane with the high-efficiency and large-damage self-repairing function and the preparation method thereof, the disulfide bond and the phenol-carbamate bond are used as self-repairing and breaking recombination chemical bonds, the disulfide bond and the phenol-carbamate bond can be triggered only at 80 ℃, and the scheme of combining the disulfide bond and the phenol-carbamate bond can realize excellent self-repairing effect under high temperature conditions, can repair large-scale damage, and has simple required repairing condition and wide application prospect. Meanwhile, the polyurethane synthesized by the invention does not need to use a solvent, and solves the problem of organic pollutant emission in the production and use processes of the solvent polyurethane.
Therefore, aiming at the problems, the invention adopts a solvent-free method to prepare the polyurethane resin with self-repairing function, which not only can improve the appearance quality and the service life, but also meets the environment-friendly requirement of green, and has wide application prospect.
The technical scheme adopted for solving the technical problems is as follows:
a solvent-free self-repairing polyurethane comprises a component A and a component B according to the following formula 1: the weight ratio of 0.8 to 1.2 is prepared by a pouring method, wherein:
the component A raw material composition comprises:
polyhydric alcohol
4,4' -dihydroxydiphenyl sulfone
Disulfide compounds
Catalyst
Leveling agent
The component B raw material composition comprises:
polyisocyanates
Polyhydric alcohol
Preferably, the mass percentage of hydroxyl groups in the component A is 8-12%, and the mass percentage of isocyanate groups in the component B is 15-25%.
Preferably, the molar ratio of isocyanate groups to hydroxyl groups in component B is from 1.0 to 1.2.
Preferably, the composition comprises, in parts by weight,
the component A raw material composition comprises: 60-90 parts of polyalcohol, 30-80 parts of 4,4' -dihydroxydiphenyl sulfone, 30-80 parts of disulfide, 0.1-1 part of catalyst and 0.1-1 part of flatting agent;
the component B raw material composition comprises: 100-250 parts of polyisocyanate and 30-100 parts of polyol.
Preferably, the disulfide molecule carries a dynamic disulfide bond in the chain.
Preferably, the disulfide is bis (4-hydroxyphenyl) disulfide or bis (2-hydroxyethyl) disulfide.
The bis (4-hydroxyphenyl) disulfide has the following structural formula:
the bis (2-hydroxyethyl) disulfide has the structural formula:
preferably, the structural formula of the 4,4' -dihydroxydiphenyl sulfone is as follows:
preferably, the polyisocyanate is one or more of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate and diphenylmethane diisocyanate;
the polyalcohol is one or more of polytetrahydrofuran ether glycol, polyethylene lactone glycol, polypropylene glycol, polycarbonate glycol and polyethylene glycol adipate glycol, and the relative molecular weight of the polyalcohol is 500-4000;
the catalyst is dibutyl tin dilaurate, stannous octoate or 1, 4-diazabicyclo [2.2.2] octane;
the leveling agent is BYK-UV3510.
The preparation method of the polyurethane comprises the following specific steps:
(1) Preparation of component A: according to the weight portions, 60 to 90 portions of polyalcohol, 30 to 80 portions of disulfide, 30 to 80 portions of 4,4' -dihydroxydiphenyl sulfone, 0.1 to 1 portion of catalyst and 0.1 to 1 portion of flatting agent are mixed and stirred for reaction to obtain a polymer containing hydroxyl end, namely a component A;
(2) Preparation of component B: according to parts by weight, 100-250 parts of polyisocyanate and 30-100 parts of polyol are mixed and stirred for reaction for 2-4 hours under the nitrogen atmosphere to obtain polyurethane prepolymer, namely component B;
(3) The prepared component A and component B are prepared according to a ratio of 1: adding the mixture into a reaction kettle in a weight ratio of 0.8-1.2 (further preferably 1:1-1.1), stirring and mixing at a high speed of 500-2000 r/min for 1-10 min, and curing at a temperature of 100-120 ℃ for 0.5-2 h to obtain the polyurethane with the solvent-free self-repairing function.
The invention takes polyisocyanate, polyalcohol, disulfide, 4' -dihydroxydiphenyl sulfone and the like as raw materials, and firstly synthesizes the material A and the material B by a two-component method to prepare the solvent-free polyurethane resin capable of realizing self-repairing at 80 ℃ and realizing large-scale damage repairing. In addition, the synthetic method of the invention does not need to use solvent, and polyurethane resin with excellent performance and self-repairing performance can be prepared by directly reacting raw materials.
The disulfide is small molecular dihydric alcohol with disulfide bond in one molecular chain, and can trigger reversible reaction under high temperature condition to realize excellent self-repairing effect.
The phenol-carbamate bond synthesized by the 4,4' -dihydroxydiphenyl sulfone and the isocyanate can be dissociated under the high-temperature condition, so that dynamic recombination is realized, and an excellent self-repairing effect is realized.
The polyurethane synthesized by the invention has high repair efficiency, can realize large-scale damage repair, has simple repair conditions, and can still keep excellent mechanical properties after repair. Repairing for 10min at 80 ℃, wherein the repairing effect of tensile stress and elongation at break can reach 90%; and the defects with the diameter of 1mm and the depth of 1mm can be repaired, and large-scale damage repair is realized.
The beneficial effects of the invention are as follows:
the polyurethane synthesized by disulfide and 4,4' -dihydroxydiphenyl sulfone can realize rapid damage repair at a high temperature of 80 ℃, and the product can be repeatedly used.
The invention can repair large-scale damage by the synergistic contact of the dynamic disulfide bond and the dynamic phenol-carbamate bond at 80 ℃ and realize the effect of prolonging the service time of the product.
The self-repairing polyurethane is synthesized by a solvent-free two-component method, does not release toxic and harmful gases, is healthy and environment-friendly, has excellent mechanical properties and high production efficiency, and solves the problems of environmental pollution and resource waste of solvent polyurethane.
Drawings
FIG. 1 is a photomicrograph of a fracture repair wound;
FIG. 2 is a graph of stress strain before and after sample repair.
Detailed Description
Representative embodiments based on the drawings will now be further refined. It should be understood that the following description is not intended to limit the embodiments to one preferred embodiment. On the contrary, it is intended to cover alternatives, modifications, and equivalents as may be included within the spirit and scope of the embodiments as defined by the appended claims.
The invention provides solvent-free self-repairing polyurethane, which comprises a component A and a component B according to the following weight ratio of 100: (80-120), namely, the weight ratio of 1:0.8-1.2 is prepared by a pouring method.
Wherein, according to the weight portions,
the component A raw material composition comprises: 60-90 parts of polyalcohol, 30-80 parts of disulfide, 30-80 parts of 4,4' -dihydroxydiphenyl sulfone, 0.1-1 part of catalyst and 0.1-1 part of flatting agent;
the component B raw material composition comprises: 100-250 parts of polyisocyanate and 30-100 parts of polyol.
The mass percentage of the hydroxyl in the component A is 8-12%, the mass percentage of the isocyanate group in the component B is 15-25%, and the mol ratio of the isocyanate group to the hydroxyl is 1.0-1.2.
With respect to the components used for component A and component B, wherein:
the polyisocyanate is one or more of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate and diphenylmethane diisocyanate;
the polyalcohol is one or more of polytetrahydrofuran ether glycol, polyethylene lactone glycol, polypropylene glycol, polycarbonate glycol and polyethylene glycol adipate glycol, and the relative molecular weight of the polyalcohol is 500-4000; the catalyst is dibutyl tin dilaurate, stannous octoate or 1, 4-diazabicyclo [2.2.2] octane; the leveling agent is BYK-UV3510.
The disulfide is a bis (4-hydroxyphenyl) disulfide or a bis (2-hydroxyethyl) disulfide, and carries a dynamic disulfide bond in the molecular chain.
The bis (4-hydroxyphenyl) disulfide has the following structural formula:
the bis (2-hydroxyethyl) disulfide has the structural formula:
the structural formula of the 4,4' -dihydroxydiphenyl sulfone is as follows:
the concrete steps of the pouring method adopted are as follows:
(1) Preparation of component A: according to the weight portions, 60 to 90 portions of polyalcohol, 30 to 80 portions of disulfide, 30 to 80 portions of 4,4' -dihydroxydiphenyl sulfone, 0.1 to 1 portion of catalyst and 0.1 to 1 portion of flatting agent are mixed and stirred for reaction to obtain a polymer containing terminal hydroxyl groups, namely a component A;
(2) Preparation of component B: according to parts by weight, 100-250 parts of polyisocyanate and 30-100 parts of polyol are mixed and stirred for reaction for 2-4 hours under the nitrogen atmosphere to obtain polyurethane prepolymer, namely component B;
(3) The prepared component A and component B are prepared according to a ratio of 1: adding the mixture into a reaction kettle in a weight ratio of 0.8-1.2, stirring and mixing, and curing at 105-125 ℃ to obtain the polyurethane with the solvent-free self-repairing function.
Example 1:
the preparation method of the solvent-free polyurethane with the self-repairing function comprises the following steps:
the raw materials are prepared according to the following proportion,
the raw materials of the component A: 85 parts of polypropylene glycol (molecular weight 1500, zhang Jia Kong, fei-Chen technology Co., ltd., FH-3170), 30 parts of bis (2-hydroxyethyl) disulfide, 40 parts of 4,4' -dihydroxydiphenyl sulfone, 1 part of dibutyltin dilaurate and 35101 parts of a flatting agent BYK-UV; the mass percentage of hydroxyl in the component A is 11%.
The raw materials of the component B: 100 parts of isophorone diisocyanate and 75 parts of polypropylene glycol (molecular weight 1500, zhangjiu harbor, flying technology Co., ltd., FH-3170). The mass percentage of isocyanate groups in the component B is 18 percent. The molar ratio of isocyanate groups to hydroxyl groups in component B was 1.0.
Then, 100 parts of isophorone diisocyanate and 75 parts of polypropylene glycol were mixed by the above method, and stirred at a high speed of 1500 rpm for 10 minutes to prepare a material B. To 85 parts of polypropylene glycol, 30 parts of bis (2-hydroxyethyl) disulfide, 40 parts of 4,4' -dihydroxydiphenyl sulfone, 1 part of dibutyltin dilaurate and 1 part of a leveling agent BYK-UV3510 were gradually added to prepare a component A.
Then, adding the material B into the material A, reacting for 10 minutes under high-speed 1500 r/min stirring, putting into a mould, scraping and coating to form a film, putting into a 100 ℃ oven for 1h, and curing to form a film, thus obtaining the solvent-free self-repairing polyurethane.
Example 2:
the preparation method of the solvent-free polyurethane with the self-repairing function comprises the following steps:
the raw materials are prepared according to the following proportion,
the raw materials of the component A: 45 parts of polytetrahydrofuran ether glycol (molecular weight 2000, zhang Jiang, feisha technology Co., ltd., FH-6330), 40 parts of polyethylene lactone glycol, 40 parts of bis (4-hydroxyphenyl) disulfide, 30 parts of 4,4' -dihydroxydiphenyl sulfone, 1 part of dibutyltin dilaurate and 35100.1 parts of a leveling agent BYK-UV; the mass percentage of hydroxyl in the component A is 12 percent.
The raw materials of the component B: 78 parts of toluene diisocyanate, 40 parts of polytetrahydrofuran ether glycol, 35 parts of polyethylene lactone glycol (molecular weight 2000, zhejiang Hexin technology Co., ltd., FH-2130); the mass percentage of isocyanate groups in the component B is 20 percent. The molar ratio of isocyanate groups to hydroxyl groups in component B was 1.1.
78 parts of toluene diisocyanate, 40 parts of polytetrahydrofuran ether glycol and 35 parts of polyethylene lactone glycol are mixed and stirred at a high speed of 1500 rpm for 10 minutes to prepare a material B. A material A was prepared by gradually adding 40 parts of bis (4-hydroxyphenyl) disulfide, 30 parts of 4,4' -dihydroxydiphenyl sulfone, 1 part of dibutyltin dilaurate and 0.1 part of a leveling agent to 45 parts of polytetrahydrofuran ether glycol and 40 parts of polyethylene lactone glycol.
And (3) adding the material B into the material A, reacting for 8 minutes under stirring at a high speed of 1500 revolutions per minute, putting into a die, scraping, coating to form a film, putting into a 100 ℃ oven for 2 hours, and curing to form a film to obtain the solvent-free self-repairing polyurethane.
Example 3:
the preparation method of the solvent-free polyurethane with the self-repairing function comprises the following steps:
the raw materials are prepared according to the following proportion,
the raw materials of the component A: 45 parts of polytetrahydrofuran ether glycol (molecular weight 2000, zhang Jiang, feisha technology Co., ltd., FH-6330), 40 parts of polypropylene glycol, 45 parts of bis (4-hydroxyphenyl) disulfide, 65 parts of 4,4' -dihydroxydiphenyl sulfone, 0.1 part of dibutyltin dilaurate and 35100.1 parts of a leveling agent BYK-UV; the mass percentage of hydroxyl in the component A is 12 percent.
The raw materials of the component B: 100 parts of isophorone diisocyanate, 40 parts of polytetrahydrofuran ether glycol, 35 parts of polypropylene glycol (molecular weight 1500, FH-3170, division of flying technology in Zhangjiu harbor, inc.); the mass percentage of isocyanate groups in the component B is 20 percent. The molar ratio of isocyanate groups to hydroxyl groups in component B was 1.1.
Then, 100 parts of isophorone diisocyanate and 40 parts of polytetrahydrofuran ether glycol and 35 parts of polypropylene glycol were mixed, and the mixture was stirred at a high speed of 1500 rpm for 10 minutes to prepare a material B. 45 parts of bis (4-hydroxyphenyl) disulfide, 65 parts of 4,4' -dihydroxydiphenyl sulfone, 0.1 part of dibutyltin dilaurate and 0.1 part of a leveling agent BYK-UV3510 were gradually added to 45 parts of polytetrahydrofuran ether glycol and 40 parts of polypropylene glycol to prepare a material A.
And (3) adding the material B into the material A, reacting for 5 minutes under high-speed stirring at 1500 rpm, putting into a die, scraping, coating to form a film, putting into a 100 ℃ oven for 1h, and curing to form a film to obtain the solvent-free self-repairing polyurethane.
Example 4:
the preparation method of the solvent-free polyurethane with the self-repairing function comprises the following steps:
the raw materials are prepared according to the following proportion,
the raw materials of the component A: 85 parts of polypropylene glycol (molecular weight 1500, zhang Jia Kong, fei-Chen technology Co., ltd., FH-3170), 45 parts of bis (2-hydroxyethyl) disulfide, 65 parts of 4,4' -dihydroxydiphenyl sulfone, 0.1 part of dibutyltin dilaurate and 35100.1 parts of a leveling agent BYK-UV; the mass percentage of hydroxyl in the component A is 12 percent.
The raw materials of the component B: toluene diisocyanate 78 parts, polypropylene glycol (molecular weight 1500, zhangjiu harbor, flying technology Co., ltd., FH-3170) 75 parts; the mass percentage of isocyanate groups in the component B is 18 percent. The molar ratio of isocyanate groups to hydroxyl groups in component B was 1.1.
78 parts of toluene diisocyanate and 75 parts of polypropylene glycol were mixed and stirred at a high speed of 1500 rpm for 8 minutes to prepare a material B. 45 parts of bis (2-hydroxyethyl) disulfide, 65 parts of 4,4' -dihydroxydiphenyl sulfone, 0.1 part of dibutyltin dilaurate and 0.1 part of a leveling agent are gradually added into 85 parts of polypropylene glycol to prepare a material A.
And (3) adding the material B into the material A, reacting for 4 minutes under high-speed stirring at 1500 rpm, putting into a die, scraping, coating to form a film, putting into a 100 ℃ oven for 1.5 hours, and curing to form a film to obtain the solvent-free self-repairing polyurethane.
Example 5:
the preparation method of the solvent-free polyurethane with the self-repairing function comprises the following steps:
the raw materials are prepared according to the following proportion,
the raw materials of the component A: 85 parts of polytetrahydrofuran ether glycol (molecular weight 1000, zhejiang Hexin technology Co., ltd., FH-4210), 50 parts of bis (2-hydroxyethyl) disulfide, 60 parts of 4,4' -dihydroxydiphenyl sulfone, 0.1 part of dibutyltin dilaurate and 35100.1 parts of a leveling agent BYK-UV; the mass percentage of hydroxyl in the component A is 10 percent.
The raw materials of the component B: 100 parts of isophorone diisocyanate and 75 parts of polytetrahydrofuran ether glycol (molecular weight 2000, zhejiang euphoria technology Co., ltd., FH-8450); the mass percentage of isocyanate groups in the component B is 23 percent. The molar ratio of isocyanate groups to hydroxyl groups in component B was 1.05.
100 parts of isophorone diisocyanate and 75 parts of polytetrahydrofuran ether glycol are mixed and stirred at a high speed of 1500 rpm for 10 minutes to prepare material B. To 85 parts of polytetrahydrofuran ether glycol, 50 parts of bis (2-hydroxyethyl) disulfide, 60 parts of 4,4' -dihydroxydiphenyl sulfone, 0.1 part of dibutyltin dilaurate and 0.1 part of a leveling agent BYK-UV3510 were gradually added to prepare a material A.
And (3) adding the material B into the material A, reacting for 5 minutes under high-speed stirring at 1500 rpm, putting into a die, scraping, coating to form a film, putting into a 100 ℃ oven for 1h, and curing to form a film to obtain the solvent-free self-repairing polyurethane.
According to test standard ISO 3376:2011, performance tests are performed on the self-repairing polyurethane materials prepared in the above examples, and the results are shown in table 1.
Table 1:
from table 1, various performance data according to national standard tests can be obtained.
There are a number of self-healing polyurethanes available in the current market for test properties as shown in Table 2 (data).
Table 2: test Performance of self-healing polyurethane
| Principle of application | Diels-Alder bond [1] | Disulfide bond [2] | Hydrogen bonding [3] | Diselenide bond [4] |
| Preparation conditions | Solvent-borne polyurethanes | Solvent-borne polyurethanes | Solvent-free polyurethanes | Water-based polyurethane |
| Tensile Strength | 1.62MPa | 0.85MPa | 10kPa | 16.31MPa |
| Young's modulus | —— | —— | 1.31MPa | —— |
| Repair conditions | 110℃、10h | Ultraviolet ray for 24 hours | Room temperature for 6h | Illumination for 2h |
| Repair efficiency | 88.15％ | 97％ | 87％ | 80.5％ |
[1]Li M,Ding H,Yang X,et al.Preparation and properties of self-healing polyurethane elastomer derived from tung-oil-based polyphenol[J].ACS omega,2019,5(1):529-536.
[2]Rekondo A,Martin R,de Luzuriaga A R,et al.Catalyst-free room-temperature self-healing elastomers based on aromatic disulfide metathesis[J].Materials Horizons,2014,1(2):237-240.
[3]Yao Y,Xu Z,Liu B,et al.Multiple H-Bonding Chain Extender-Based Ultrastiff Thermoplastic Polyurethanes with Autonomous Self-Healability,Solvent-Free Adhesiveness,and AIE Fluorescence[J].Advanced Functional Materials,2021,31(4):2006944.
[4]Fan W,Jin Y,Shi L.Mechanically robust and tough waterborne polyurethane films based on diselenide bonds and dual H-bonding interactions with fast visible-light-triggered room-temperature self-healability[J].Polymer Chemistry,2020,11(34):5463-5474.
The performance comparison of the self-repairing polyurethane prepared by the invention and the self-repairing polyurethane prepared by the principles of Diels-Alder bond, disulfide bond, hydrogen bond and the like at present can be known: the polyurethane synthesized by the invention has high repair efficiency and simple repair condition, and the repaired material can still maintain excellent mechanical properties. The repairing effect of the tensile stress and the elongation at break can reach 90 percent after the repairing for 30 minutes at 80 ℃.
As shown in FIG. 1, for a micrograph of a broken repair wound, the two broken samples healed together on a scale of 10 μm with the wound completely connected.
As shown in FIG. 2, the tensile strength of the original sample is 16.59MPa, the tensile strength of the fracture repaired sample is 15.05MPa, and the performance after repair is excellent.
From comprehensive evaluation, the self-repairing polyurethane obtained by the technical scheme provided by the invention has more excellent performance.
The above-described embodiments are intended to illustrate the present invention, not to limit the present invention, and any modifications and variations of the present invention fall within the spirit of the present invention and the scope of the appended claims.
Claims (10)
1. A solvent-free polyurethane with self-repairing function is characterized in that: the mass ratio of the composition A to the composition B is 1:0.8 to 1.2, wherein: composition a comprises a polyol, a disulfide, 4' -dihydroxydiphenyl sulfone, a catalyst and a leveling agent; composition B includes a polyisocyanate and a polyol.
2. The solvent-free self-healing polyurethane of claim 1, wherein: the mass ratio of hydroxyl groups in the composition A is 8-12%, and the mass ratio of isocyanate groups in the composition B is 15-25%.
3. The solvent-free self-healing functional polyurethane of claim 1, wherein: the molar ratio of isocyanate groups to hydroxyl groups in the composition B is 1.0-1.2.
4. The solvent-free self-healing functional polyurethane of claim 1, wherein: the composition A comprises the following components in parts by weight:
60-90 parts of polyol;
30-80 parts of disulfide;
30-80 parts of 4,4' -dihydroxydiphenyl sulfone;
0.1-1 part of catalyst;
0.1 to 1 part of leveling agent.
5. The solvent-free self-healing functional polyurethane of claim 1, wherein: the composition B comprises the following components in parts by weight:
100-250 parts of isocyanate;
30-100 parts of polyol.
6. The solvent-free self-healing functional polyurethane according to claim 1 or 4, wherein: the disulfide is one or two of bis (4-hydroxyphenyl) disulfide and bis (2-hydroxyethyl) disulfide.
7. The solvent-free self-healing functional polyurethane of claim 6, wherein: the bis (4-hydroxyphenyl) disulfide and the bis (2-hydroxyethyl) disulfide have the following structures:
bis (4-hydroxyphenyl) disulfide;
bis (2-hydroxyethyl) disulfide.
8. The solvent-free self-healing functional polyurethane according to claim 1 or 4, wherein: the 4,4' -dihydroxydiphenyl sulfone has the following structure:
9. the solvent-free self-healing functional polyurethane of claim 1, wherein:
the polyisocyanate is one or more of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate and diphenylmethane diisocyanate;
the polyalcohol is one or more of polytetrahydrofuran ether glycol, polyethylene lactone glycol, polypropylene glycol, polycarbonate glycol and polyethylene adipate glycol, and the relative molecular weight is 1000-2000;
the catalyst is dibutyl tin dilaurate, stannous octoate or 1, 4-diazabicyclo [2.2.2] octane;
the leveling agent is BYK-UV3510.
10. The method for producing a solvent-free self-repairing polyurethane according to any one of claims 1 to 9, comprising the steps of:
(1) Preparation of composition A: according to the weight portions, mixing and stirring polyol, disulfide, 4' -dihydroxydiphenyl sulfone, a catalyst and a leveling agent for reaction to obtain a hydroxyl-terminated polymer, namely a composition A;
(2) Preparation of composition B: according to the parts by weight, mixing and stirring polyisocyanate and polyol under the nitrogen atmosphere for 2-4 hours to obtain polyurethane prepolymer, namely the composition B;
(3) Adding the prepared component A and component B into a reaction kettle, stirring and mixing at a high speed of 500-2000 r/min for 1-10 min, and curing at 100-120 ℃ for 0.5-2 h to obtain the solvent-free self-repairing polyurethane.
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| CN117247728A (en) * | 2023-11-01 | 2023-12-19 | 广东百川化工有限公司 | Water-based two-component high-permeability scratch-resistant paint and preparation method thereof |
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