CN120965969A - A modified polyurethane resin and its preparation method - Google Patents
A modified polyurethane resin and its preparation methodInfo
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- CN120965969A CN120965969A CN202511065386.9A CN202511065386A CN120965969A CN 120965969 A CN120965969 A CN 120965969A CN 202511065386 A CN202511065386 A CN 202511065386A CN 120965969 A CN120965969 A CN 120965969A
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- polyurethane resin
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- modified polyurethane
- chitosan
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- 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
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/757—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the cycloaliphatic ring by means of an aliphatic group
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- 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
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- C08G18/40—High-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- 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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- 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
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7685—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing two or more non-condensed aromatic rings directly linked to each other
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
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Abstract
The invention relates to the field of polyurethane resin, in particular to modified polyurethane resin and a preparation method thereof. The modified polyurethane resin comprises, by mass, 60-70 parts of diisocyanate, 5-10 parts of tetraisocyanate, 30-35 parts of polyether polyol, 6-12 parts of polydimethylsiloxane, 3-5 parts of dihydric alcohol, 3-5 parts of tetraol, 3-5 parts of polyamine, 0.8-1 part of N-ethylmorpholine, 2-5 parts of modified chitosan, 0-2 parts of an auxiliary agent and 0-150 parts of a solvent. The preparation method comprises the following steps of S1, S2, chain extension reaction and secondary chain extension reaction, and S3, wherein the modified polyurethane resin is prepared. The modified polyurethane resin prepared by the invention has good air permeability, antibacterial property and wide application scene, and can be applied to industries such as artificial leather and the like.
Description
Technical Field
The invention relates to the field of polyurethane resin, in particular to modified polyurethane resin and a preparation method thereof.
Background
Polyurethane resins are a highly diverse polymeric material formed by the reaction of diisocyanates and polyols, and sometimes contain chain extenders and other additives. It can exhibit a wide range of applications, from flexible foams to rigid plastics, and a variety of elastomers in between, depending on the chemical structure and preparation conditions.
Polyurethane resins are widely used based on their excellent properties, among which the applications in leather are mainly:
1. the polyurethane resin is used as leather finishing agent, and can provide excellent surface protection and beautiful effect. It is classified into a plurality of categories of a healing agent, a primer coating agent, a middle layer coating agent, a top layer coating agent, etc., each having its specific functions such as increasing gloss, improving abrasion resistance, water resistance, etc. Waterborne polyurethane finishes are particularly popular for environmental protection and low VOC.
2. Retanning agent polyurethane retanning agent is used for improving the physical properties of leather, such as softness, fullness and flexing resistance, and improving the touch feeling and color uniformity of leather in the leather tanning process.
3. The filling resin is used for filling treatment of leather, can fill micropores on the surface of the leather, increases the compactness and smoothness of the leather, and improves the subsequent processing performance, such as the uniformity of finishing and the physical and mechanical properties of the leather.
4. The polyurethane resin is an important adhesive material in the shoe industry, is used for bonding the vamp and the sole and fixing other parts, and ensures the durability of the shoes.
5. The synthetic polyurethane leather is made of polyurethane resin as main material and through different processing steps, and has similar appearance and hand feeling to natural leather, and may be used widely in clothing, luggage, furniture, etc. The application of polyurethane resin in artificial leather is not limited to coating, but also includes the synthesis of base material, thereby creating leather substitute which is environment-friendly and has excellent performance.
CN115894851B provides a preparation method of organosilicon modified waterborne polyurethane for leather finishing, which relates to the field of organic chemistry. The preparation method comprises the steps of mixing 5-10 parts by mass of dihydroxyl polyether modified siloxane and 20-30 parts by mass of polyester dihydric alcohol, dehydrating, cooling, adding isophorone diisocyanate, dropwise adding stannous octoate, reacting for 1.5-2.5 hours at 65-75 ℃, then adding 2-4 parts by mass of dimethylolpropionic acid, continuously reacting for 1-3 hours at 65-75 ℃ to obtain a prepolymer, cooling to 40-50 ℃, adding 2-4 parts by mass of triethylamine, adding 35-45 parts by mass of water and 1-3 parts by mass of ethylenediamine under stirring, and reacting for 1-2 hours to obtain the organosilicon modified aqueous polyurethane emulsion. The prepared organosilicon modified aqueous polyurethane emulsion is stable by introducing the dihydroxyl polyether modified siloxane structure into polyurethane, and the prepared film has the characteristics of low water absorption and excellent mechanical property. But its air permeability is poor.
Disclosure of Invention
The invention aims to provide a modified polyurethane resin and a preparation method thereof, wherein the prepared polyurethane resin has good air permeability, and the preparation method is simple and easy for industrial application, and is particularly suitable for application in leather.
The invention provides modified polyurethane resin which comprises the following components in parts by weight:
60-70 parts of diisocyanate
5-10 Parts of tetraisocyanate
30-35 Parts of polyether polyol
6-12 Parts of polydimethylsiloxane
3-5 Parts of dihydric alcohol
3-5 Parts of tetrahydric alcohol
3-5 Parts of polyamine
0.8-1 Part of N-ethylmorpholine
2-5 Parts of modified chitosan
0-2 Parts of auxiliary agent
0-150 Parts of a solvent.
The tetraisocyanate and the tetraol are introduced into the formula, so that a chain structure can be formed in the longitudinal direction and the transverse direction, a ring structure can be formed, and a ring middle gap and crisscross gaps of the ring structure can be used as ventilation holes to increase ventilation property.
Further, the diisocyanate is dimer acid diisocyanate (DDI) or dicyclohexylmethane diisocyanate (HMDI), the tetraisocyanate is 2,2' -dimethyl-3, 3', 5' -triphenylmethane tetraisocyanate, the tetraisocyanate has more functional groups, the proportion of hard segments is higher, and the air permeability of the prepared product is increased.
Further, the polyether polyol is a mixture of polyether 220 and polyether 330, and the mass ratio of polyether 220 to polyether 330 is 1:1.
Further, the dihydric alcohol is a mixture of 3-fluoro-1, 2-propanediol and 1, 4-butanediol, the mass ratio of 3-fluoro-1, 2-propanediol to 1, 4-butanediol is (0-1) to 1, the product performance can be improved by adding fluorine atoms, the tetraol is pentaerythritol, and the tetraol contains more hydroxyl groups, so that hydrophilic components are added, and the air permeability can be improved.
Further, the polyamine is 1, 4-butanediamine or 1, 5-pentanediamine.
Further, the auxiliary agent is modified ammonium nitrate or ammonium bicarbonate, the modified ammonium nitrate is modified ammonium nitrate for an automobile safety airbag, the auxiliary agent can be decomposed in the heating process, micropores are formed in the material, the air permeability of the product is improved, and when the modified ammonium nitrate for the automobile safety airbag is adopted, the effect is better than that of the common ammonium nitrate, because the common ammonium nitrate is easy to absorb water, the performance is poor, and the use is influenced.
Further, the solvent is ethyl acetate.
The invention also provides a preparation method of the modified polyurethane resin, which comprises the following steps:
s1, adding a solvent into a reaction kettle, adding diisocyanate, tetraisocyanate, polyether polyol, polydimethylsiloxane and N-ethylmorpholine, mixing, and reacting at the temperature of 80-120 ℃ for 2-4 hours to obtain a prepolymer;
S2, crushing and mixing an auxiliary agent and modified chitosan uniformly, adding the crushed and mixed auxiliary agent and modified chitosan into the prepolymer obtained in the S1, adding dihydric alcohol and tetrahydric alcohol, performing chain extension reaction, adding polyamine, performing secondary chain extension reaction, and obtaining a mixture, wherein the chain extension reaction temperature is 90-140 ℃, the reaction time is 1-2 hours, the secondary chain extension reaction temperature is 100-150 ℃, the reaction time is 1-2 hours, the crushed and mixed auxiliary agent and modified chitosan are added after being uniformly crushed and mixed, so that the inside of the prepolymer is uniformly dispersed, and if the crushed and mixed auxiliary agent and modified chitosan are added after chain extension, macropores appear in the product, the performance is reduced, and the hollow holes are not uniformly formed;
And S3, uniformly scraping the mixture obtained in the step S2 on the velvet-feel release paper, keeping the temperature at 120-150 ℃, drying for 2-3 hours, then attaching to the non-woven fabric base fabric, continuously drying for 1 hour, slowly cooling to room temperature, and stripping to obtain the modified polyurethane resin, wherein the cooling speed in the slow cooling process is 0.1-0.2 ℃ per minute.
Further, the modified polyurethane resin needs further treatment, the treatment process is that the prepared modified polyurethane resin is heated to 150 ℃ and then rapidly cooled to 10 ℃, then the cooled modified polyurethane resin is heated to 150 ℃ and then rapidly cooled to 10 ℃ again, the treated modified polyurethane resin is obtained, the cooling speed is 10-15 ℃ per minute, the internal pores of the prepared product can be increased after the temperature is raised, and the product is continuously cooled and then contracted, because the temperature is rapidly lowered, the increased pores can not be recovered to the original size, the ventilation holes in the product are further increased, and the ventilation performance is further enhanced.
Further, the preparation of the modified chitosan comprises the following steps:
s21, soaking chitosan in 3wt% hydrogen peroxide solution for 30min, filtering and drying;
s22, soaking the chitosan dried in the step S21 in 0.2wt% sodium hydroxide solution for 30min, filtering and drying;
s23, performing ultrasonic action on the chitosan dried in the step S22 for 1h to obtain modified chitosan, wherein the ultrasonic frequency is 25kHz, active groups of the modified chitosan are increased, the antibacterial performance of the product is enhanced, and the modified chitosan can be used as a nucleating agent and the air permeability of the product is improved.
The modified polyurethane resin prepared by the invention has good air permeability, antibacterial property and wide application scene, and can be applied to industries such as artificial leather and the like.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The modified polyurethane resin comprises the following components in parts by mass:
dimer acid diisocyanate 60kg
5Kg of 2,2' -dimethyl-3, 3', 5' -triphenylmethane tetraisocyanate
15Kg of polyether 220 and 15kg of polyether 330
Polydimethylsiloxane 6kg
1.5Kg of 3-fluoro-1, 2-propanediol and 1.5kg of 1, 4-butanediol
Pentaerythritol 3kg
1, 4-Butanediamine 3kg
N-ethylmorpholine 0.8kg
Modified chitosan 3kg
Ammonium bicarbonate 1kg
Ethyl acetate 80kg.
The preparation of the modified chitosan comprises the following steps:
s21, soaking chitosan in 3wt% hydrogen peroxide solution for 30min, filtering, and drying, wherein the mass of the 3wt% hydrogen peroxide solution is five times that of the chitosan;
s22, soaking the chitosan dried in the step S21 in 0.2wt% sodium hydroxide solution for 30min, filtering, and drying, wherein the mass of the 0.2wt% sodium hydroxide solution is 4 times that of the dried chitosan;
S23, performing ultrasonic action on the chitosan dried in the step S22 for 1h to obtain modified chitosan, wherein the ultrasonic frequency is 25kHz.
The preparation method of the modified polyurethane resin comprises the following steps:
S1, adding ethyl acetate into a reaction kettle, and then adding dimer acid diisocyanate, 2' -dimethyl-3, 3', 5' -triphenylmethane, polyether 220, polyether 330, polydimethylsiloxane and N-ethylmorpholine, mixing and then reacting at the reaction temperature of 80-100 ℃ for 3 hours to obtain a prepolymer;
S2, crushing and uniformly mixing ammonium bicarbonate and modified chitosan, adding the crushed and uniformly mixed ammonium bicarbonate and modified chitosan into the prepolymer obtained in the S1, adding 3-fluoro-1, 2-propanediol, 1, 4-butanediol and pentaerythritol for chain extension reaction, and then adding 1, 4-butanediamine for secondary chain extension reaction, so as to obtain a mixture, wherein the chain extension reaction temperature is 100-120 ℃, the reaction time is 2 hours, the secondary chain extension reaction temperature is 120-140 ℃, and the reaction time is 2 hours;
and S3, uniformly scraping the mixture obtained in the step S2 on the velvet-feel release paper, keeping the temperature at 120-130 ℃, drying for 2 hours, then attaching to the non-woven fabric base fabric, continuously drying for 1 hour, slowly cooling to room temperature, and stripping to obtain the modified polyurethane resin, wherein the cooling speed in the slow cooling process is 0.1 ℃ per minute.
The modified polyurethane resin needs further treatment, the treatment process is that the prepared modified polyurethane resin is heated to 150 ℃ and then rapidly cooled to 10 ℃, then the cooled modified polyurethane resin is heated to 150 ℃ and then rapidly cooled to 10 ℃ again, and the treated modified polyurethane resin is obtained, wherein the cooling speed is 12 ℃ per minute.
Example 2
The modified polyurethane resin comprises the following components in parts by mass:
dicyclohexylmethane diisocyanate 70kg
8Kg of 2,2' -dimethyl-3, 3', 5' -triphenylmethane tetraisocyanate
15Kg of polyether 220 and 15kg of polyether 330
Polydimethylsiloxane 10kg
2Kg of 3-fluoro-1, 2-propanediol and 2kg of 1, 4-butanediol
Pentaerythritol 3kg
4Kg of 1, 5-pentanediamine
N-ethylmorpholine 0.8kg
Modified chitosan 3kg
Modified ammonium nitrate 1kg for automobile safety airbag
100Kg of ethyl acetate.
The preparation of the modified chitosan comprises the following steps:
s21, soaking chitosan in 3wt% hydrogen peroxide solution for 30min, filtering, and drying, wherein the mass of the 3wt% hydrogen peroxide solution is five times that of the chitosan;
s22, soaking the chitosan dried in the step S21 in 0.2wt% sodium hydroxide solution for 30min, filtering, and drying, wherein the mass of the 0.2wt% sodium hydroxide solution is 4 times that of the dried chitosan;
S23, performing ultrasonic action on the chitosan dried in the step S22 for 1h to obtain modified chitosan, wherein the ultrasonic frequency is 25kHz.
The preparation method of the modified polyurethane resin comprises the following steps:
S1, adding ethyl acetate into a reaction kettle, adding dicyclohexylmethane diisocyanate, 2' -dimethyl-3, 3', 5' -triphenylmethane, polyether 220, polyether 330, polydimethylsiloxane and N-ethylmorpholine, mixing, and reacting at a reaction temperature of 100-120 ℃ for 3 hours to obtain a prepolymer;
S2, crushing and uniformly mixing modified ammonium nitrate and modified chitosan for an automobile safety airbag, adding the crushed and uniformly mixed modified ammonium nitrate and the modified chitosan into the prepolymer obtained in the S1, adding 3-fluoro-1, 2-propanediol, 1, 4-butanediol and pentaerythritol for chain extension reaction, and then adding 1, 5-pentanediamine for secondary chain extension reaction to obtain a mixture, wherein the chain extension reaction temperature is 130-150 ℃, the reaction time is 2 hours, the secondary chain extension reaction temperature is 120-140 ℃, and the reaction time is 2 hours;
And S3, uniformly scraping the mixture obtained in the step S2 on the velvet-feel release paper, keeping the temperature at 130-150 ℃, drying for 2 hours, then attaching to the non-woven fabric base fabric, continuously drying for 1 hour, slowly cooling to room temperature, and stripping to obtain the modified polyurethane resin, wherein the cooling speed in the slow cooling process is 0.1 ℃ per minute.
The modified polyurethane resin needs further treatment, the treatment process is that the prepared modified polyurethane resin is heated to 150 ℃ and then rapidly cooled to 10 ℃, then the cooled modified polyurethane resin is heated to 150 ℃ and then rapidly cooled to 10 ℃ again, and the treated modified polyurethane resin is obtained, wherein the cooling speed is 12 ℃ per minute.
Example 3
The modified polyurethane resin comprises the following components in parts by mass:
Dicyclohexylmethane diisocyanate 60kg
5Kg of 2,2' -dimethyl-3, 3', 5' -triphenylmethane tetraisocyanate
15Kg of polyether 220 and 15kg of polyether 330
Polydimethylsiloxane 8kg
1.5Kg of 3-fluoro-1, 2-propanediol and 1.5kg of 1, 4-butanediol
Pentaerythritol 3kg
1, 4-Butanediamine 3kg
N-ethylmorpholine 0.8kg
Modified chitosan 3kg
Ammonium bicarbonate 1kg
100Kg of ethyl acetate.
The preparation of the modified chitosan comprises the following steps:
s21, soaking chitosan in 3wt% hydrogen peroxide solution for 30min, filtering, and drying, wherein the mass of the 3wt% hydrogen peroxide solution is five times that of the chitosan;
s22, soaking the chitosan dried in the step S21 in 0.2wt% sodium hydroxide solution for 30min, filtering, and drying, wherein the mass of the 0.2wt% sodium hydroxide solution is 4 times that of the dried chitosan;
S23, performing ultrasonic action on the chitosan dried in the step S22 for 1h to obtain modified chitosan, wherein the ultrasonic frequency is 25kHz.
The preparation method of the modified polyurethane resin comprises the following steps:
s1, adding ethyl acetate into a reaction kettle, adding dicyclohexylmethane diisocyanate, 2' -dimethyl-3, 3', 5' -triphenylmethane, polyether 220, polyether 330, polydimethylsiloxane and N-ethylmorpholine, mixing, and reacting at the reaction temperature of 80-100 ℃ for 3 hours to obtain a prepolymer;
S2, crushing and uniformly mixing ammonium bicarbonate and modified chitosan, adding the crushed and uniformly mixed ammonium bicarbonate and modified chitosan into the prepolymer obtained in the S1, adding 3-fluoro-1, 2-propanediol, 1, 4-butanediol and pentaerythritol for chain extension reaction, and then adding 1, 4-butanediamine for secondary chain extension reaction, so as to obtain a mixture, wherein the chain extension reaction temperature is 100-120 ℃, the reaction time is 2 hours, the secondary chain extension reaction temperature is 120-140 ℃, and the reaction time is 2 hours;
and S3, uniformly scraping the mixture obtained in the step S2 on the velvet-feel release paper, keeping the temperature at 120-130 ℃, drying for 2 hours, then attaching to the non-woven fabric base fabric, continuously drying for 1 hour, slowly cooling to room temperature, and stripping to obtain the modified polyurethane resin, wherein the cooling speed in the slow cooling process is 0.1 ℃ per minute.
The modified polyurethane resin needs further treatment, the treatment process is that the prepared modified polyurethane resin is heated to 150 ℃ and then rapidly cooled to 10 ℃, then the cooled modified polyurethane resin is heated to 150 ℃ and then rapidly cooled to 10 ℃ again, and the treated modified polyurethane resin is obtained, wherein the cooling speed is 12 ℃ per minute.
Example 4
The modified polyurethane resin comprises the following components in parts by mass:
dimer acid diisocyanate 60kg
5Kg of 2,2' -dimethyl-3, 3', 5' -triphenylmethane tetraisocyanate
15Kg of polyether 220 and 15kg of polyether 330
Polydimethylsiloxane 6kg
1, 4-Butanediol 3kg
Pentaerythritol 3kg
1, 4-Butanediamine 3kg
N-ethylmorpholine 0.8kg
Modified chitosan 3kg
Ethyl acetate 80kg.
The preparation of the modified chitosan comprises the following steps:
s21, soaking chitosan in 3wt% hydrogen peroxide solution for 30min, filtering, and drying, wherein the mass of the 3wt% hydrogen peroxide solution is five times that of the chitosan;
s22, soaking the chitosan dried in the step S21 in 0.2wt% sodium hydroxide solution for 30min, filtering, and drying, wherein the mass of the 0.2wt% sodium hydroxide solution is 4 times that of the dried chitosan;
S23, performing ultrasonic action on the chitosan dried in the step S22 for 1h to obtain modified chitosan, wherein the ultrasonic frequency is 25kHz.
The preparation method of the modified polyurethane resin comprises the following steps:
S1, adding ethyl acetate into a reaction kettle, and then adding dimer acid diisocyanate, 2' -dimethyl-3, 3', 5' -triphenylmethane, polyether 220, polyether 330, polydimethylsiloxane and N-ethylmorpholine, mixing and then reacting at the reaction temperature of 80-100 ℃ for 3 hours to obtain a prepolymer;
S2, crushing and uniformly mixing modified chitosan, adding the crushed and uniformly mixed chitosan into the prepolymer obtained in the S1, adding 3-fluoro-1, 2-propanediol, 1, 4-butanediol and pentaerythritol for chain extension reaction, and then adding 1, 4-butanediamine for secondary chain extension reaction, thereby obtaining a mixture, wherein the chain extension reaction temperature is 100-120 ℃, the reaction time is 2 hours, the secondary chain extension reaction temperature is 120-140 ℃, and the reaction time is 2 hours;
and S3, uniformly scraping the mixture obtained in the step S2 on the velvet-feel release paper, keeping the temperature at 120-130 ℃, drying for 2 hours, then attaching to the non-woven fabric base fabric, continuously drying for 1 hour, slowly cooling to room temperature, and stripping to obtain the modified polyurethane resin, wherein the cooling speed in the slow cooling process is 0.1 ℃ per minute.
The modified polyurethane resin needs further treatment, the treatment process is that the prepared modified polyurethane resin is heated to 150 ℃ and then rapidly cooled to 10 ℃, then the cooled modified polyurethane resin is heated to 150 ℃ and then rapidly cooled to 10 ℃ again, and the treated modified polyurethane resin is obtained, wherein the cooling speed is 12 ℃ per minute.
Example 5
The modified polyurethane resin comprises the following components in parts by mass:
dimer acid diisocyanate 60kg
5Kg of 2,2' -dimethyl-3, 3', 5' -triphenylmethane tetraisocyanate
15Kg of polyether 220 and 15kg of polyether 330
Polydimethylsiloxane 6kg
1.5Kg of 3-fluoro-1, 2-propanediol and 1.5kg of 1, 4-butanediol
Pentaerythritol 3kg
1, 4-Butanediamine 3kg
N-ethylmorpholine 0.8kg
Modified chitosan 3kg
Ammonium bicarbonate 1kg.
The preparation of the modified chitosan comprises the following steps:
s21, soaking chitosan in 3wt% hydrogen peroxide solution for 30min, filtering, and drying, wherein the mass of the 3wt% hydrogen peroxide solution is five times that of the chitosan;
s22, soaking the chitosan dried in the step S21 in 0.2wt% sodium hydroxide solution for 30min, filtering, and drying, wherein the mass of the 0.2wt% sodium hydroxide solution is 4 times that of the dried chitosan;
S23, performing ultrasonic action on the chitosan dried in the step S22 for 1h to obtain modified chitosan, wherein the ultrasonic frequency is 25kHz.
The preparation method of the modified polyurethane resin comprises the following steps:
S1, adding dimer acid diisocyanate, 2' -dimethyl-3, 3', 5' -triphenylmethane, polyether 220, polyether 330, polydimethylsiloxane and N-ethylmorpholine into a reaction kettle, mixing and then reacting at the reaction temperature of 80-100 ℃ for 3 hours to obtain a prepolymer;
S2, crushing and uniformly mixing ammonium bicarbonate and modified chitosan, adding the crushed and uniformly mixed ammonium bicarbonate and modified chitosan into the prepolymer obtained in the S1, adding 3-fluoro-1, 2-propanediol, 1, 4-butanediol and pentaerythritol for chain extension reaction, and then adding 1, 4-butanediamine for secondary chain extension reaction, so as to obtain a mixture, wherein the chain extension reaction temperature is 100-120 ℃, the reaction time is 2 hours, the secondary chain extension reaction temperature is 120-140 ℃, and the reaction time is 2 hours;
and S3, uniformly scraping the mixture obtained in the step S2 on the velvet-feel release paper, keeping the temperature at 120-130 ℃, drying for 2 hours, then attaching to the non-woven fabric base fabric, continuously drying for 1 hour, slowly cooling to room temperature, and stripping to obtain the modified polyurethane resin, wherein the cooling speed in the slow cooling process is 0.1 ℃ per minute.
The heating method in the steps S1, S2, S3 is microwave heating.
The modified polyurethane resin needs further treatment, the treatment process is that the prepared modified polyurethane resin is heated to 150 ℃ and then rapidly cooled to 10 ℃, then the cooled modified polyurethane resin is heated to 150 ℃ and then rapidly cooled to 10 ℃ again, and the treated modified polyurethane resin is obtained, wherein the cooling speed is 12 ℃ per minute.
Comparative example 1
The modified chitosan component in example 1 was removed, and the details thereof are not repeated in the same manner as in example 1.
Comparative example 2
The modified polyurethane resin in example 1 was further processed to remove the modified polyurethane resin, and the modified polyurethane resin in example 1 is not repeated.
Comparative example 3
The addition of the auxiliary agent and the modified chitosan in the step S2 of the embodiment 1 before the chain extension reaction is changed into the addition after the direct chain extension, the pre-crushing and the mixing are omitted, and the other steps are the same as the embodiment 1 and are not repeated.
The modified polyurethane resins prepared in the above examples and comparative examples were subjected to performance test, and the test results are shown in table 1.
TABLE 1 Performance test results
From the data in Table 1, it can be seen that the modified polyurethanes prepared in examples 1 to 5 are good in air permeability, water vapor permeability, elongation at break and antibacterial rate, the auxiliary agent is reduced in example 4, the air permeability and water vapor permeability are reduced, the product can be still obtained in example 5 under the conditions of no solvent and microwave heating, and the performance is slightly reduced. The data of comparative example 1 shows that the antibacterial performance of the modified chitosan powder is good, the data of comparative example 2 shows that the polyurethane resin can improve the air permeability of the product in the further treatment process, and the data of comparative example 3 shows that the addition mode of the auxiliary agent and the modified chitosan can obviously influence the performance of the product.
Claims (10)
1. The modified polyurethane resin is characterized by comprising 60-70 parts by weight of diisocyanate
5-10 Parts of tetraisocyanate
30-35 Parts of polyether polyol
6-12 Parts of polydimethylsiloxane
3-5 Parts of dihydric alcohol
3-5 Parts of tetrahydric alcohol
3-5 Parts of polyamine
0.8-1 Part of N-ethylmorpholine
2-5 Parts of modified chitosan
0-2 Parts of auxiliary agent
0-150 Parts of a solvent.
2. The modified polyurethane resin of claim 1, wherein the diisocyanate is a dimer acid diisocyanate or a dicyclohexylmethane diisocyanate and the tetraisocyanate is 2,2' -dimethyl-3, 3', 5' -triphenylmethane tetraisocyanate.
3. The modified polyurethane resin of claim 1, wherein the polyether polyol is a mixture of polyether 220 and polyether 330, and the mass ratio of polyether 220 to polyether 330 is 1:1.
4. The modified polyurethane resin according to claim 1, wherein the dihydric alcohol is a mixture of 3-fluoro-1, 2-propanediol and 1, 4-butanediol, the mass ratio of 3-fluoro-1, 2-propanediol to 1, 4-butanediol is (0 to 1) to 1, and the tetrahydric alcohol is pentaerythritol.
5. The modified polyurethane resin of claim 1, wherein the polyamine is 1, 4-butanediamine or 1, 5-pentanediamine.
6. The modified polyurethane resin according to claim 1, wherein the auxiliary agent is modified ammonium nitrate or ammonium bicarbonate, and the modified ammonium nitrate is modified ammonium nitrate for an automobile airbag.
7. The modified polyurethane resin of claim 1, wherein the solvent is ethyl acetate.
8. The modified polyurethane resin of claim 1, wherein the preparation of the modified chitosan comprises the steps of:
s21, soaking chitosan in 3wt% hydrogen peroxide solution for 30min, filtering and drying;
s22, soaking the chitosan dried in the step S21 in 0.2wt% sodium hydroxide solution for 30min, filtering and drying;
S23, performing ultrasonic action on the chitosan dried in the step S22 for 1h to obtain modified chitosan, wherein the ultrasonic frequency is 25kHz.
9. A method for producing the modified polyurethane resin according to any one of claims 1 to 8, comprising the steps of:
s1, adding a solvent into a reaction kettle, adding diisocyanate, tetraisocyanate, polyether polyol, polydimethylsiloxane and N-ethylmorpholine, mixing, and reacting at the temperature of 80-120 ℃ for 2-4 hours to obtain a prepolymer;
s2, crushing and uniformly mixing an auxiliary agent and modified chitosan, adding the crushed and uniformly mixed auxiliary agent and modified chitosan into the prepolymer obtained in the S1, adding dihydric alcohol and tetrahydric alcohol, performing chain extension reaction, adding polyamine, performing secondary chain extension reaction, and obtaining a mixture, wherein the chain extension reaction temperature is 90-140 ℃, the reaction time is 1-2 hours, the secondary chain extension reaction temperature is 100-150 ℃, and the reaction time is 1-2 hours;
And S3, uniformly scraping the mixture obtained in the step S2 on the velvet-feel release paper, keeping the temperature at 120-150 ℃, drying for 2-3 hours, then attaching to the non-woven fabric base fabric, continuously drying for 1 hour, slowly cooling to room temperature, and stripping to obtain the modified polyurethane resin, wherein the cooling speed in the slow cooling process is 0.1-0.2 ℃ per minute.
10. The method for preparing modified polyurethane resin according to claim 9, wherein the modified polyurethane resin is further processed, the processing process is that the prepared modified polyurethane resin is heated to 150 ℃ and then rapidly cooled to 10 ℃, and then the cooled modified polyurethane resin is heated to 150 ℃ and then rapidly cooled to 10 ℃ again, so as to obtain the processed modified polyurethane resin, and the cooling speed is 10-15 ℃ per min.
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