CN111254719A - Fluorine-free water-drawing agent for polyurethane synthetic leather and preparation method thereof - Google Patents
Fluorine-free water-drawing agent for polyurethane synthetic leather and preparation method thereof Download PDFInfo
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- CN111254719A CN111254719A CN202010049489.7A CN202010049489A CN111254719A CN 111254719 A CN111254719 A CN 111254719A CN 202010049489 A CN202010049489 A CN 202010049489A CN 111254719 A CN111254719 A CN 111254719A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
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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
- C08G18/28—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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/28—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
- C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
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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
- C08G18/28—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
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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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
- C08G18/28—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
- C08G18/44—Polycarbonates
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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
- C08G18/28—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
- C08G18/61—Polysiloxanes
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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
- C08G18/28—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
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/128—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with silicon polymers
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1607—Degradability
- D06N2209/1621—Water-soluble, water-dispersible
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- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a fluorine-free water-drawing agent for polyurethane synthetic leather, which comprises the following components in parts by weight: 39.5 to 70 percent of effective solid component A, 29.5 to 60 percent of solvent B and 0.05 to 0.5 percent of auxiliary agent C; the effective solid component A is shown as the following formula 1, wherein PMS is a chain segment generated by reacting monohydroxy organosilicon with isocyanate group; PSI-PU is a polyurethane chain segment generated by the reaction of dihydroxy organic silicon, polyester polyol and diisocyanate, and contains 2-14 repeated units of carbamate; f is a chain segment generated by the reaction of polyol Y with 3-8 functionality and isocyanate group; m and n represent integers of 3-8, and the auxiliary agent C is modified organic silicon without a reactive group. The invention also discloses a preparation method of the composition. The water repellent prepared by the invention has excellent water repellent performance, and the hydrolysis resistance of the polyurethane synthetic leather can be obviously improved by adding a small amount of the water repellent into the polyurethane synthetic leather.
Description
Technical Field
The invention relates to a fluorine-free water-repellent agent and a preparation method thereof, in particular to a fluorine-free water-repellent agent for polyurethane synthetic leather and a preparation method thereof.
Background
The excellent characteristics of natural leather have been widely used in the fields of producing daily necessities and industrial products, and due to the increasing shortage of natural leather resources, the gradually strengthened environmental awareness of people and the continuous progress of industrial technology, the polyurethane synthetic leather with excellent performance becomes the best choice for replacing the natural leather. At present, the polyurethane synthetic leather is widely applied to clothing leather, luggage leather and shoe leather. However, since the common polyurethane resin contains a large amount of easily hydrolyzable groups (such as ester groups), the polyurethane resin is easily hydrolyzed under certain conditions, and thus the hydrolysis resistance is poor.
Generally, a certain amount of auxiliary agent is added into polyurethane resin to improve the hydrolysis resistance of polyurethane synthetic leather products. The auxiliary agent is generally an organic fluorine compound, and because the fluorine-containing compound has the characteristics of low free energy and difficult adhesion, the auxiliary agent can well block the attack of water molecules on easily hydrolyzed groups when being added into a polyurethane synthetic leather product, has the water-repellent effect and improves the hydrolysis resistance of the polyurethane synthetic leather product. However, PFOS (perfluorooctylsulfonyl compound) and PFOA (perfluorooctanoic acid) among organofluorine compounds have high persistence in the environment, accumulate in the environment and tissues of human and animals, and pose potential risks to human health and the environment.
Therefore, the auxiliary agent containing the harmful substances is forbidden in many countries all over the world, and the search for the replaceable fluorine-free surfactant becomes the first problem to be solved urgently by the industry.
The main chain of the organic silicon compound is flexible, and the intermolecular action force of the organic silicon compound is much weaker than that of a hydrocarbon compound, so that the organic silicon compound has lower viscosity, weaker surface tension, smaller surface energy and stronger film forming capability than that of the hydrocarbon compound with the same molecular weight. This low surface tension and low surface energy make it versatile: excellent performances such as hydrophobicity, defoaming, stable foam, anti-sticking, lubrication and the like. Therefore, the organosilicon auxiliary agent can be used for replacing a fluorine auxiliary agent to achieve similar water repellent effect.
The fluorine-free water-drawing agent in the prior invention is only used for post-treatment of textiles, and the prior fluorine-free water-drawing agent used for polyurethane synthetic leather in the market has the defects of poor stability, unsatisfactory effect and the like.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a fluorine-free water-repellent agent for polyurethane synthetic leather. Is used for solving the defects of the existing water-drawing agent. The water-repellent agent can obviously improve the hydrolysis resistance of the polyurethane synthetic leather.
The invention also aims to provide a method for preparing the fluorine-free water repellent agent for synthetic leather.
In order to realize one of the purposes of the invention, the adopted technical scheme is as follows:
a fluorine-free water-repellent agent for polyurethane synthetic leather comprises the following components in parts by weight:
39.5% -70% of effective solid component A;
29.5% -60% of solvent B;
0.05-0.5% of auxiliary agent C;
wherein the content of the first and second substances,
the effective solid component A is shown as the following formula 1:
(PMS)m(PSI-PU)nF
formula 1
In the formula, PMS is a chain segment generated by the reaction of monohydroxy organosilicon and isocyanate group;
PSI-PU is a polyurethane chain segment generated by the reaction of dihydroxy organic silicon, polyester polyol and diisocyanate, and contains 2-14 repeated units of carbamate;
f is a segment formed by the reaction of a polyol Y with a functionality of 3-8 and an isocyanate group. m and n represent an integer of 3 to 8.
In a preferred embodiment of the present invention, m and n are equal integers.
In a preferred embodiment of the present invention, the solvent B is an organic solvent.
In a preferred embodiment of the invention, the auxiliary C is a modified silicone which is free of reactive groups. The assistant C is used for improving the compatibility of the polyurethane resin slurry and the water repellent agent and is beneficial to the uniform dispersion of the water repellent agent in the slurry.
In a preferred embodiment of the present invention, the monohydroxy silicone is a monohydroxy silicone represented by formula 2 having a number average molecular weight of 300-:
formula 2;
wherein R is1is-CH3or-CH2CH3。
In a preferred embodiment of the present invention, the dihydroxy silicone is any one or more of a single-ended dihydroxy silicone or a double-ended dihydroxy silicone.
In a preferred embodiment of the present invention, the single-ended dihydroxy organosilicon is a single-ended dihydroxy organosilicon with molecular weight of 300-4000g/mol as shown in formula 3:
formula 3;
wherein R is2is-CH3or-CH2CH3。
In a preferred embodiment of the present invention, the double-ended dihydroxy organosilicon is double-ended dihydroxy organosilicon with molecular weight of 1000-3000g/mol as shown in formula 4:
formula 4;
wherein R is3is-CH3or-CH2CH3。
In a preferred embodiment of the present invention, the polyester polyol is any one or a mixture of two or more of polycarbonate diol with molecular weight of 500-2000g/mol or polycaprolactone diol with molecular weight of 500-2000 g/mol.
In a preferred embodiment of the present invention, the diisocyanate is any one of aliphatic diisocyanate, aromatic diisocyanate, or a mixture of two or more of derivatives of aromatic diisocyanate.
In a preferred embodiment of the present invention, the aliphatic diisocyanate is any one or a mixture of two or more of 1, 6-Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (HMDI), or methylcyclohexyl diisocyanate (HTDI).
In a preferred embodiment of the present invention, the aromatic diisocyanate is any one or a mixture of two or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI) or Xylylene Diisocyanate (XDI), and Naphthalene Diisocyanate (NDI).
In a preferred embodiment of the present invention, the derivative of the aromatic diisocyanate is any one or a mixture of two or more of liquefied MDI or TDI dimer.
In a preferred embodiment of the present invention, the polyol with 3-8 functionalities is any one or a mixture of two or more of trimethylolpropane, glycerol, trimethylolethane, 1,2, 6-hexanetriol, pentaerythritol, xylitol, mannitol or sucrose.
In a preferred embodiment of the present invention, the solvent B is any one or a mixture of two or more of toluene, butanone, ethyl acetate, N-dimethylformamide, N-dimethylacetamide, or N-methylpyrrolidone.
In order to realize the second purpose of the invention, the adopted technical scheme is as follows:
a preparation method of a fluorine-free water-drawing agent for polyurethane synthetic leather comprises the following steps:
step 1:
mixing a mixture of N dihydroxy organic silicon and polyester polyol with (N +1) diisocyanate, putting the mixture into a partial solvent B for reaction until the hydroxyl in the system is completely reacted, and obtaining the prepolymer polyurethane chain segment PSI-PU after the weight percentage NCO% in the system reaches a theoretical value;
step 2: slowly adding the polyol Y into the system obtained in the step 1 in batches, and measuring the weight percentage NCO% of NCO in the system to reach a theoretical value after reacting for 1-2 hours;
then adding the monohydroxy organosilicon, and determining the reaction end point by testing the characteristic peak of the NCO-free group by an infrared spectrum tester;
and step 3:
and (3) adding the residual solvent B and the auxiliary agent C into the reaction product obtained in the step (2), and uniformly stirring to obtain the fluorine-free water-drawing agent for the polyurethane synthetic leather with the required concentration.
In a preferred embodiment of the present invention,
n in the step (1) is as follows: 1 to 7;
the number of the repeating units of the double-end-group organosilicon in the step (1) is as follows: 1 to 7;
the number of the repeating units of the polyester polyol in the step (1) is as follows: 0 to 3;
the isocyanate in the step (1) is added into the reaction system in batches;
the reaction temperature of the step (1) is controlled to be 50-80 ℃.
In a preferred embodiment of the present invention,
the proportion of the prepolymer PSI-PU and the polyol F in the step (2) is 3-8, and is determined according to the characteristic group number of the polyol Y;
the reaction temperature of the step (2) is controlled to be 40-60 ℃;
the addition amount of the auxiliary C in the step (3) is 0.05-0.5%, preferably 0.1-0.2%;
the required concentration of the step (3) is 40-70%, and preferably 50-70%.
The invention has the beneficial effects that:
(1) the water-repellent agent prepared by the invention has obvious water-repellent effect, and the hydrolysis resistance of synthetic leather can be obviously improved by adding a small amount of the water-repellent agent into the synthetic leather;
(2) the preparation process of the water-repellent agent is simple, the cost is low, the industrial production is easy, and the application prospect and the economic benefit are good;
(3) the water-repellent agent prepared by the invention is convenient to use, can be directly added into polyurethane resin slurry for preparing synthetic leather when in use, and can be stirred uniformly.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
(1) 400g of single-end dihydroxy organosilicon (1mol), 400g of polycarbonate diol (0.4mol), 500g N, N-dimethylformamide and 500g of toluene are put into a 5L four-mouth reaction bottle, stirred, 278.4g of Toluene Diisocyanate (TDI) (1.6mol) is added in batches at the temperature of 50-80 ℃ for reaction until the weight percentage of NCO reaches 0.81 percent, (2) 6.13g of glycerol is added in a dropwise manner, 1-2H is reacted at the temperature of 40-60 ℃, 100g of monohydroxy silicone oil (0.2mol) is added after the weight percentage of NCO reaches 0.40 percent, and the reaction end point is determined by detecting a characteristic peak without NCO groups by an infrared spectrometer. (3) 189.3g N, N-dimethylformamide and 4.75g of modified organic silicone oil are added and stirred uniformly to obtain the fluorine-free water repellent agent 1 for the polyurethane synthetic leather.
Example 2
(1) Putting 800g of double-ended dihydroxy organic silicon (0.4mol), 200g of polycaprolactone diol (0.1mol), 500g of N, N-dimethylformamide and 500g of toluene into a 5L four-mouth reaction bottle, stirring, adding 104.4g of Toluene Diisocyanate (TDI) (0.6mol) in batches at the temperature of 50-80 ℃ for reaction until the weight percentage of NCO reaches 0.40 percent, (2) adding 3.07g of glycerol in a dropwise manner, reacting at 40-60 ℃ for 1-2H, measuring the weight percentage of NCO to reach 0.20 percent, then adding 50g of monohydroxy silicone oil (0.1mol), and detecting the characteristic peak of no NCO group by an infrared spectrometer to determine the reaction end point. (3) And then adding 162g N, N-dimethylformamide and 4.65g of modified organic silicone oil, and uniformly stirring to obtain the fluorine-free water repellent 2 for the polyurethane synthetic leather.
Example 3
(1) 400g of single-end dihydroxy organosilicon (1mol) and 800g N, N-dimethylformamide are put into a 5L four-mouth reaction bottle and stirred, 348g of Toluene Diisocyanate (TDI) (2mol) is added in batches at the temperature of 50-80 ℃ for reaction until the weight percentage of NCO reaches 5.43 percent, (2) 44.67g of trimethylolpropane is added in a dropwise manner for reaction at the temperature of 40-60 ℃ for 1-2H, 500g of monohydroxy silicone oil (1mol) is added after the weight percentage of NCO reaches 2.64 percent, and the reaction end point is determined by detecting the characteristic peak without NCO groups by an infrared spectrometer. (3) Then adding 63g N N-dimethylformamide and 2.16g of modified organic silicone oil, and uniformly stirring to obtain the fluorine-free water repellent agent 3 for the polyurethane synthetic leather.
Example 4
(1) 400g of single-end dihydroxy organosilicon (1mol) and 1000g N, N-dimethylformamide are put into a 5L four-mouth reaction bottle, stirred, 348g of Toluene Diisocyanate (TDI) (2mol) is added in batches at the temperature of 50-80 ℃ for reaction until the weight percentage of NCO reaches 4.81 percent, (2) 30.67g of glycerol is added in a dropwise manner, 1-2H is reacted at the temperature of 40-60 ℃, 500g of monohydroxy silicone oil (1mol) is added after the weight percentage of NCO reaches 2.36 percent, and the reaction end point is determined by detecting a characteristic peak without NCO groups by an infrared spectrometer. (3) And adding 283.5g N, N-dimethylformamide and 5.14g of modified organic silicone oil, and uniformly stirring to obtain the fluorine-free water repellent 4 for the polyurethane synthetic leather.
Example 5
(1) 600g of single-ended dihydroxy organosilicon (1.5mol) and 800g N, N-dimethylformamide are put into a 5L four-mouth reaction bottle, stirred, 522g of Toluene Diisocyanate (TDI) (3mol) is added in batches at the temperature of 50-80 ℃ for reaction until the weight percentage of NCO reaches 6.56 percent, (2) 46g of glycerol is added in a dropwise manner, 1-2H is reacted at the temperature of 40-60 ℃, 750g of monohydroxy silicone oil (1.5mol) is added after the weight percentage of NCO reaches 3.20 percent, and the reaction end point is determined by detecting the characteristic peak without NCO groups by an infrared spectrometer. (3) And adding 24g N, N-dimethylformamide and 5.49g of modified organic silicone oil, and uniformly stirring to obtain the fluorine-free water repellent agent 5 for the polyurethane synthetic leather.
The water-repellent agent of the present invention was used in comparison with an imported water-repellent agent A-750 (Korea NURI Co.):
the performance of the water repellent agent is tested by adopting the following two methods:
(1) taking two parts of the same polyurethane resin slurry to prepare synthetic leather, adding the water-repellent agent and A-750 of the invention according to the weight ratio of the water-repellent agent/polyurethane slurry to be 0.5/100 respectively, taking part of the prepared synthetic leather product and completely immersing the part into 10% sodium hydroxide solution, keeping the temperature at 25 ℃ for 24 hours, taking out, cleaning, drying, comparing the peel strength of the synthetic leather product before and after immersion, and testing the loss rate X:
x ═ 1-peel strength after immersion/peel strength before immersion X100%
The average of 3 data was taken for the experiment. The large value of X indicates that the resin is seriously hydrolyzed and has poor water-repellent effect.
(2) Taking two parts of the same polyurethane resin slurry to prepare the synthetic leather, adding the water-repellent agent and A-750 of the invention into the synthetic leather according to the weight ratio of the water-repellent agent/the polyurethane resin slurry of 0.5/100, cutting the prepared synthetic leather into a sample strip of 10cm x 2cm, vertically placing the sample strip, immersing the lower part of the sample strip in water, wetting the sample strip upwards by water along the sample strip, recording the wetting time required by a waterline exceeding the water surface by 5cm, and using t to represent the wetting time. The longer the infiltration time, the better the effect of the water-repellent agent. The test results are shown in table 1 below:
TABLE 1
| Name (R) | Loss rate X (%) | Soaking time t (min) |
| Water-repellent agent 1 | 4.1 | 40 |
| Water-repellent agent 2 | 4.0 | 41 |
| Water-repellent agent 3 | 3.0 | 50 |
| Water-repellent agent 4 | 3.4 | 45 |
| Water-repellent agent 5 | 2.7 | 55 |
| A-750 | 5.0 | 30 |
As can be seen from Table 1, the water-repelling effect of the water-repelling agents obtained in examples 1 to 5 was better than that of imported A-750 (about 70% of the effective solid content).
Therefore, the water-repellent agent prepared by the invention has excellent water-repellent performance, and the polyurethane synthetic leather product has good hydrolysis resistance by adding the water-repellent agent.
The above description is only a part of the preferred embodiments of the present invention, and it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the technical principles of the present invention, and these modifications and variations should also be considered as the scope of the present invention.
Claims (16)
1. The fluorine-free water-repellent agent for polyurethane synthetic leather is characterized by comprising the following components in parts by weight:
39.5% -70% of effective solid component A;
29.5% -60% of solvent B;
0.05-0.5% of auxiliary agent C;
wherein the content of the first and second substances,
the effective solid component A is shown as the following formula 1:
(PMS)m(PSI-PU)nF
formula 1
In the formula, PMS is a chain segment generated by the reaction of monohydroxy organosilicon and isocyanate group;
PSI-PU is a polyurethane chain segment generated by the reaction of dihydroxy organic silicon, polyester polyol and diisocyanate, and contains 2-14 repeated units of carbamate;
f is a segment formed by the reaction of a polyol Y with a functionality of 3-8 and an isocyanate group. m and n represent an integer of 3 to 8.
2. The fluorine-free water repellent agent for polyurethane synthetic leather according to claim 1, wherein m and n are equal integers.
3. The fluorine-free water repellent agent for polyurethane synthetic leather according to claim 1, wherein the solvent B is an organic solvent.
4. The fluorine-free water repellent agent for polyurethane synthetic leather according to claim 1, wherein the auxiliary agent C is a modified silicone containing no reactive group.
5. The fluorine-free water repellent agent for polyurethane synthetic leather according to claim 1, wherein the monohydroxy silicone is monohydroxy silicone having a number average molecular weight of 300-1000g/mol and a functionality of 1 and represented by formula 2:
wherein R is1is-CH3or-CH2CH3。
6. The fluorine-free water repellent agent for polyurethane synthetic leather according to claim 1, wherein the dihydroxy organosilicon is one or more of single-end dihydroxy organosilicon or double-end dihydroxy organosilicon.
7. The fluorine-free water repellent agent for polyurethane synthetic leather according to claim 6, wherein the single-ended dihydroxy organosilicon is a single-ended dihydroxy organosilicon with molecular weight of 300-4000g/mol as shown in formula 3:
wherein R is2is-CH3or-CH2CH3。
8. The fluorine-free water repellent agent for polyurethane synthetic leather according to claim 6, wherein the double-end dihydroxy organosilicon is double-end dihydroxy organosilicon with molecular weight of 1000-3000g/mol as shown in formula 4:
wherein R is3is-CH3or-CH2CH3。
9. The fluorine-free water repellent agent for polyurethane synthetic leather as claimed in claim 1, wherein the polyester polyol is one or a mixture of more than two of polycarbonate diol with molecular weight of 500-2000g/mol or polycaprolactone diol with molecular weight of 500-2000 g/mol.
10. The fluorine-free water repellent agent for polyurethane synthetic leather according to claim 1, wherein the diisocyanate is one or a mixture of two or more of aliphatic diisocyanate, aromatic diisocyanate or a derivative of aromatic diisocyanate.
11. The fluorine-free water repellent agent for polyurethane synthetic leather according to claim 1,
the aliphatic diisocyanate is any one or a mixture of more than two of 1, 6-Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (HMDI) or methylcyclohexyl diisocyanate (HTDI);
the aromatic diisocyanate is any one or mixture of more than two of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI) or Xylylene Diisocyanate (XDI) and Naphthalene Diisocyanate (NDI);
the derivative of the aromatic diisocyanate is any one or a mixture of more than two of liquefied MDI or TDI dimer.
12. The fluorine-free water repellent agent for polyurethane synthetic leather according to claim 1, wherein the polyhydric alcohol with 3-8 functionalities is any one or a mixture of more than two of trimethylolpropane, glycerol, trimethylolethane, 1,2, 6-hexanetriol, pentaerythritol, xylitol, mannitol or sucrose.
13. The fluorine-free water repellent agent for polyurethane synthetic leather according to claim 1, wherein the solvent B is one or a mixture of two or more of toluene, butanone, ethyl acetate, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
14. The method for preparing the fluorine-free water repellent agent for polyurethane synthetic leather according to any one of claims 1 to 13, which comprises the following steps:
step 1:
mixing a mixture of N dihydroxy organic silicon and polyester polyol with (N +1) diisocyanate, putting the mixture into a partial solvent B for reaction until the hydroxyl in the system is completely reacted, and obtaining the prepolymer polyurethane chain segment PSI-PU after the weight percentage NCO% in the system reaches a theoretical value;
step 2:
slowly adding the polyol Y into the system obtained in the step 1 in batches, and measuring the weight percentage NCO% of NCO in the system to reach a theoretical value after reacting for 1-2 hours;
then adding the monohydroxy organosilicon, and determining the reaction end point by testing the characteristic peak of the NCO-free group by an infrared spectrum tester;
and step 3:
and (3) adding the residual solvent B and the auxiliary agent C into the reaction product obtained in the step (2), and uniformly stirring to obtain the fluorine-free water-drawing agent for the polyurethane synthetic leather with the required concentration.
15. The method for preparing the fluorine-free water repellent agent for polyurethane synthetic leather according to claim 14, wherein N in the step (1) is: 1 to 7;
the number of the repeating units of the double-end-group organosilicon in the step (1) is as follows: 1 to 7;
the number of the repeating units of the polyester polyol in the step (1) is as follows: 0 to 3;
the isocyanate in the step (1) is added into the reaction system in batches;
the reaction temperature of the step (1) is controlled to be 50-80 ℃.
16. The method for preparing the fluorine-free water repellent agent for polyurethane synthetic leather according to claim 14, wherein the ratio of prepolymer PSI-PU to polyol F in the step (2) is 3-8;
the reaction temperature of the step (2) is controlled to be 40-60 ℃;
the addition amount of the auxiliary C in the step (3) is 0.05-0.5%;
the required concentration of the step (3) is 40-70%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116143994A (en) * | 2022-12-29 | 2023-05-23 | 广州海豚新材料有限公司 | Aqueous organosilicon modified polyurethane dispersoid, preparation method thereof, synthetic leather surface layer containing aqueous organosilicon modified polyurethane dispersoid and luggage leather |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101979756A (en) * | 2010-09-20 | 2011-02-23 | 上海汇得化工有限公司 | Drying agent for polyurethane synthetic leather and preparation method thereof |
| CN102174167A (en) * | 2011-02-17 | 2011-09-07 | 陈华 | Organic silicon modified polyurethane resin for synthetic leather and preparation method thereof |
| CN102604026A (en) * | 2011-02-17 | 2012-07-25 | 浙江深蓝轻纺科技有限公司 | Organic silicon-modified polyurethane resin for synthetic leather and preparation method thereof |
| CN103205894A (en) * | 2013-04-02 | 2013-07-17 | 嘉兴禾大科技化学有限公司 | Finished and brightened polyurethane leather surface treatment agent with real-feather feel and preparation method thereof |
| US20150086713A1 (en) * | 2013-09-23 | 2015-03-26 | Tamkang University | Non-fluoro hydrophobic aqueous-based polyurethane resin dispersion, and production method and use thereof |
| CN110194830A (en) * | 2019-06-14 | 2019-09-03 | 合肥安利聚氨酯新材料有限公司 | A kind of no-solvent polyurethane shoes leather Isocyanate prepolymers body mixture and preparation method thereof, purposes |
-
2020
- 2020-01-16 CN CN202010049489.7A patent/CN111254719B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101979756A (en) * | 2010-09-20 | 2011-02-23 | 上海汇得化工有限公司 | Drying agent for polyurethane synthetic leather and preparation method thereof |
| CN102174167A (en) * | 2011-02-17 | 2011-09-07 | 陈华 | Organic silicon modified polyurethane resin for synthetic leather and preparation method thereof |
| CN102604026A (en) * | 2011-02-17 | 2012-07-25 | 浙江深蓝轻纺科技有限公司 | Organic silicon-modified polyurethane resin for synthetic leather and preparation method thereof |
| CN103205894A (en) * | 2013-04-02 | 2013-07-17 | 嘉兴禾大科技化学有限公司 | Finished and brightened polyurethane leather surface treatment agent with real-feather feel and preparation method thereof |
| US20150086713A1 (en) * | 2013-09-23 | 2015-03-26 | Tamkang University | Non-fluoro hydrophobic aqueous-based polyurethane resin dispersion, and production method and use thereof |
| CN110194830A (en) * | 2019-06-14 | 2019-09-03 | 合肥安利聚氨酯新材料有限公司 | A kind of no-solvent polyurethane shoes leather Isocyanate prepolymers body mixture and preparation method thereof, purposes |
Non-Patent Citations (2)
| Title |
|---|
| 童身毅: "封闭型异氰酸酯树脂化学", 《现代涂料与涂装》 * |
| 韦军: "《高分子合成工艺学》", 28 February 2011, 华东理工大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116143994A (en) * | 2022-12-29 | 2023-05-23 | 广州海豚新材料有限公司 | Aqueous organosilicon modified polyurethane dispersoid, preparation method thereof, synthetic leather surface layer containing aqueous organosilicon modified polyurethane dispersoid and luggage leather |
| CN116143994B (en) * | 2022-12-29 | 2023-09-15 | 广州海豚新材料有限公司 | Aqueous organosilicon modified polyurethane dispersoid, preparation method thereof, synthetic leather surface layer containing aqueous organosilicon modified polyurethane dispersoid and luggage leather |
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