CN107936216B - Organic silicon modified isocyanate prepolymer for solvent-free synthetic leather and preparation method thereof - Google Patents
Organic silicon modified isocyanate prepolymer for solvent-free synthetic leather and preparation method thereof Download PDFInfo
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- CN107936216B CN107936216B CN201711323525.9A CN201711323525A CN107936216B CN 107936216 B CN107936216 B CN 107936216B CN 201711323525 A CN201711323525 A CN 201711323525A CN 107936216 B CN107936216 B CN 107936216B
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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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
- D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
- D06N3/0045—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers obtained by applying a ready-made foam layer; obtained by compressing, crinkling or crushing a foam layer, e.g. Kaschierverfahren für Schaumschicht
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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
- D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
- D06N3/0077—Embossing; Pressing of the surface; Tumbling and crumbling; Cracking; Cooling; Heating, e.g. mirror finish
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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
- D06N3/142—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 mixture of polyurethanes with other resins in the same layer
-
- 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
- D06N3/147—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 characterised by the isocyanates used
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses an organic silicon modified isocyanate prepolymer for solvent-free synthetic leather and a preparation method thereof, wherein the prepolymer contains the following structural compounds:
wherein R is aryl or aliphatic; a. b is a natural number. The preparation method comprises the following steps: (1) adding octamethylcyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane and an acidic catalyst into a reactor, then adding tetramethyldihydrodisiloxane, carrying out ring-opening polymerization reaction for 4-6 h at 60-80 ℃, cooling, neutralizing, washing with water, filtering, and removing small molecular by-products to obtain hydrogen-terminated methylphenyl polysiloxane; (2) reacting the hydrogeno-methyl phenyl polysiloxane obtained in the step (1) with allyl amine in H2PtCl6Reacting under a catalyst to prepare amino-terminated methylphenyl polysiloxane; (3) and (3) dehydrating the product in the step (2), and then reacting the product with an isocyanate monomer to generate a prepolymer with an NCO end group.
Description
Technical Field
The invention belongs to the field of solvent-free synthetic leather, and particularly relates to an organic silicon modified isocyanate prepolymer for preparing solvent-free synthetic leather and a preparation method thereof.
Background
Polyurethane (PU) synthetic leather is artificial leather produced by PU resin and base cloth. Traditional synthetic leather is mainly solvent type synthetic leather, and the solvent is mostly low boiling point volatile organic solvents such as dimethyl formamide, toluene, acetone, etc., and the proportion of the solvents reaches 70% -80%, and at present, the solvents can not be completely recycled, so that the environment is polluted, body damage is caused to staff, and the product quality is also influenced. With the increase of environmental protection pressure faced by solvent-based polyurethane synthetic leather, the development of more green polyurethane synthetic leather is urgent.
The solvent-free polyurethane synthetic leather is processed by adopting solvent-free polyurethane resin to replace solvent-based resin as a raw material, and preparing a finished leather product through a novel leather production line. The solvent-free polyurethane resin does not contain toxic organic chemical solvents, is harmless to the environment and meets the high requirements of ecological environmental protection. However, the solvent-free synthetic leather product has poor air permeability and moisture permeability, and the appearance and the handfeel flexibility of the solvent-free synthetic leather product are influenced, mainly because the foam pores in the foaming coating formed by the solvent-free synthetic leather are of a closed pore structure. Therefore, the improvement of the air permeability and the moisture permeability of the polyurethane synthetic leather has important significance.
Patent document CN106087451A discloses a preparation method of breathable synthetic leather, which is characterized in that polyether amino silicone oil modified polyurethane is prepared, then an auxiliary agent is added, and the breathable polyurethane synthetic leather is prepared by coating, solidifying, washing and drying, but the preparation process of the breathable polyurethane synthetic leather has the defects of large water consumption, 2-3 h for washing, drying and curing and long curing time, the method has the disadvantages of environmental pollution and low production efficiency, and the breathability of the prepared synthetic leather reaches 725ml/cm2H, moisture permeability 962g/m224 h. Patent document CN 104558494 a discloses a modified polyurethane with high moisture permeability and a preparation method thereof, wherein a synthetic leather surface layer resin is prepared, a prepolymerization treatment method is adopted to solve the problem of phase separation of dihydroxy alkyl polysiloxane and polyether polyol, but a large amount of organic solvent is still needed for preparing the organosilicon modified polyurethane, and the problem of solvent pollution cannot be solved.
Although the method can improve or change certain properties of the polyurethane through the organosilicon modified polyurethane, the method still has the defects of being not beneficial to environmental protection, having air permeability and moisture permeability which do not meet the requirements and the like.
Disclosure of Invention
The invention aims to solve the first technical problem of providing an organic silicon modified isocyanate prepolymer for solvent-free synthetic leather, wherein the structure of the prepolymer contains methyl phenyl polysiloxane, and the prepolymer is used as an isocyanate component and matched with a hydroxyl component, so that better hand feeling flexibility, air permeability and moisture permeability can be endowed to polyurethane synthetic leather.
The second technical problem to be solved by the invention is to provide a preparation method of an organic silicon modified isocyanate prepolymer for solvent-free synthetic leather, which is prepared by synthesizing double-end amino methyl phenyl polysiloxane from molecular structure modification and reacting the double-end amino methyl phenyl polysiloxane with isocyanate.
In order to solve the first technical problem, the invention provides an organic silicon modified isocyanate prepolymer for solvent-free synthetic leather, which comprises the following structural compounds:
wherein R is aryl or aliphatic group, and the carbon atom number is preferably 6-13; a. b is a natural number.
In order to solve the second technical problem, the technical scheme of the invention is as follows: a method for preparing an organic silicon modified isocyanate prepolymer for solvent-free synthetic leather comprises the following steps:
(1) adding octamethylcyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane and an acidic catalyst into a reactor, then adding tetramethyldihydrodisiloxane, carrying out ring-opening polymerization reaction for 4-6 h at 60-80 ℃, cooling after the reaction is finished, neutralizing a reaction product to be neutral by using alkali, washing with water, filtering, and removing small molecular byproducts to obtain hydrogen-terminated methylphenyl polysiloxane. The micromolecule by-products can be removed by adopting a rotary evaporator, and the rotary evaporation temperature is preferably 100-130 ℃.
(2) And (2) reacting the hydrogen-terminated methyl phenyl polysiloxane obtained in the step (1) with allyl amine under the catalyst of H2PtCl6 to obtain amino-terminated methyl phenyl polysiloxane. The reaction temperature is generally 50-60 ℃, and the reaction time is generally 3-5 h; the amount of the catalyst H2PtCl6 used is generally 10-30 ppm of the two reactants.
(3) And (3) dehydrating the product obtained in the step (2), and then reacting with an isocyanate monomer to generate a prepolymer with an NCO end group.
The acidic catalyst in the step (1) is preferably one or a combination of concentrated hydrochloric acid, concentrated sulfuric acid, trifluoromethanesulfonic acid, an acidic cation exchange resin, and the like, and is more preferably concentrated sulfuric acid.
The dosage of the acid catalyst used in the step (1) is generally 1 to 3 percent of the mass of the two cyclosiloxanes. After the acid catalyst is added into the system, the acid catalyst is preferably mixed and reacted for 30-40 min, and then tetramethyl dihydrodisiloxane is added for end capping reaction.
As a preferable scheme of the invention, the number average molecular weight of the hydrogen-terminated end-capped methyl phenyl polysiloxane designed in the step (1) is 500-4000, preferably 1000-3000, mainly based on the fact that the product viscosity is not too high in the prepolymer production process, and the flexibility is moderate.
In a preferred embodiment of the present invention, the isocyanate monomer in step (3) is at least one selected from isophorone diisocyanate (IPDI), Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), Hexamethylene Diisocyanate (HDI), Xylylene Diisocyanate (XDI), and methylcyclohexyl diisocyanate (HTDI), and is more preferably isophorone diisocyanate (IPDI) and diphenylmethane diisocyanate (MDI).
The invention provides an organic silicon modified isocyanate prepolymer for solvent-free synthetic leather and a preparation method thereof. The preparation method of the invention does not need solvent, is safe, environment-friendly and pollution-free, and has simple process.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
(1) 100g of octamethylcyclotetrasiloxane and 61g of tetramethyltetraphenylcyclotetrasiloxane were weighed into a three-necked flask equipped with a thermometer and a condensing reflux unit, and N2Protecting, heating to 60 deg.C, adding 4.83g concentrated sulfuric acid, stirring to react for 30min, adding 7.5g tetramethyl dihydro disiliconAnd (2) siloxane is stirred and reacts for 5 hours at the temperature of 60 ℃, after the reaction is finished, the temperature is reduced to room temperature, sodium bicarbonate is used for neutralizing the reaction liquid to be neutral, washing and filtering are carried out, a rotary evaporator is used for carrying out rotary evaporation at the temperature of 130 ℃ to remove micromolecule byproducts, rotary evaporation is carried out for 4 hours, and reduced pressure filtration is carried out to prepare hydrogen-terminated methylphenyl polysiloxane with the number average molecular weight of 3000.
(2) 100g of the hydrogen-terminated methylphenylpolysiloxane obtained in step (1) and 3.8g of allylamine were weighed out and charged into a reactor, the temperature was raised to 50 ℃ and 0.001g H was added2PtCl6And reacting for 4 hours by using a catalyst to prepare the amino-terminated methyl phenyl polysiloxane.
(3) Heating the amino-terminated methylphenyl polysiloxane obtained in the step (2) to 120 ℃, and performing dehydration treatment for 4 hours under reduced pressure for later use. Adding 100g of isophorone diisocyanate into a reactor, then dropwise adding 128g of amino-terminated methylphenyl polysiloxane into the reactor through a constant-pressure dropping funnel, controlling the reaction temperature at 70 ℃, reacting for 4 hours, and measuring the NCO content of a reaction product to be 14.6% to obtain the organosilicon modified isocyanate prepolymer.
Example 2
(1) Weighing 100g of octamethylcyclotetrasiloxane and 57.5g of tetramethyltetraphenylcyclotetrasiloxane, adding the octamethylcyclotetrasiloxane and 57.5g of tetramethyltetraphenylcyclotetrasiloxane into a reactor, heating to 80 ℃, adding 3.15g of concentrated sulfuric acid, stirring for 40min, adding 11.3g of tetramethyldihydrodisiloxane, stirring for 5h at 80 ℃, cooling to room temperature after the reaction is finished, neutralizing to be neutral by adopting sodium bicarbonate, washing with water, filtering, removing small molecular by-products by rotary evaporation at 130 ℃, rotary evaporation for 4h, and filtering under reduced pressure to prepare the hydrogen-terminated methylphenyl polysiloxane with the number average molecular weight of 2000.
(2) 100g of hydrogeno-terminated methylphenylpolysiloxane and 5.7g of allylamine were weighed into a reactor, the temperature was increased to 60 ℃ and 0.002g H was added2PtCl6And reacting for 4 hours by using a catalyst to prepare the amino-terminated methyl phenyl polysiloxane.
(3) Firstly, dehydrating the amino-terminated methylphenyl polysiloxane obtained in the step (2) at room temperature to 120 ℃ under reduced pressure for 4 hours for later use. Adding 100g of isophorone diisocyanate into a three-neck flask, controlling the reaction temperature at 70 ℃, then dropwise adding 118g of terminal aminomethyl phenyl polysiloxane into the flask through a constant-pressure dropping funnel, reacting for 4 hours, and determining the content of NCO in a reaction product to be 14.8% to obtain the organosilicon modified isocyanate prepolymer.
Example 3
(1) Weighing 100g of octamethylcyclotetrasiloxane and 46g of tetramethyltetraphenylcyclotetrasiloxane, adding the mixture into a reactor, heating to 75 ℃, adding 4.38g of concentrated sulfuric acid, stirring for reaction for 30min, adding 22.6g of tetramethyldihydrodisiloxane, stirring for reaction for 5h at 75 ℃, cooling to room temperature after the reaction is finished, neutralizing to be neutral by using sodium bicarbonate, washing with water, filtering, performing rotary evaporation at 130 ℃ by using a rotary evaporator to remove small molecular byproducts, performing rotary evaporation for 4h, and performing reduced pressure filtration to prepare the hydrogen-terminated methylphenyl polysiloxane with the number average molecular weight of 1000.
(2) 100g of hydrogen-terminated methylphenylpolysiloxane and 7.6g of allylamine were weighed into a reactor, the temperature was increased to 60 ℃ and 0.003g H was added2PtCl6And reacting for 4 hours by using a catalyst to prepare the amino-terminated methyl phenyl polysiloxane.
(3) And (3) heating the amino-terminated methylphenyl polysiloxane obtained in the step two to 120 ℃, and performing dehydration treatment for 4 hours under reduced pressure for later use. Adding 100g of isophorone diisocyanate into a three-neck flask, controlling the reaction temperature at 70 ℃, then dropwise adding 97.4g of amino-terminated methylphenyl polysiloxane into the flask through a constant-pressure dropping funnel, reacting for 4 hours, and determining that the content of NCO in a reaction product is 14.5 percent, thereby obtaining the organosilicon modified isocyanate prepolymer.
Example 4
(1) Weighing 100g of octamethylcyclotetrasiloxane and 61g of tetramethyltetraphenylcyclotetrasiloxane, adding the mixture into a reactor, heating to 60 ℃, adding 3.22g of concentrated sulfuric acid, stirring for reaction for 30min, adding 11.3g of tetramethyldihydrodisiloxane, stirring for reaction for 5h at 60 ℃, cooling to room temperature after the reaction is finished, neutralizing to be neutral by using sodium bicarbonate, washing with water, filtering, performing rotary evaporation at 130 ℃ by using a rotary evaporator to remove small molecular byproducts, performing rotary evaporation for 4h, and performing reduced pressure filtration to prepare hydrogen-terminated methylphenyl polysiloxane with the number-average molecular weight of 3000.
(2) 100g of hydrogen-terminated methylphenylpolysiloxane and 5.7g of allylamine were weighed into a reactor, the temperature was increased to 50 ℃ and 0.001g H was added2PtCl6And reacting for 4 hours by using a catalyst to prepare the amino-terminated methyl phenyl polysiloxane.
(3) And (3) heating the amino-terminated methyl phenyl polysiloxane obtained in the step two to 120 ℃, and performing dehydration treatment for 4 hours under reduced pressure for later use. 100g of toluene diisocyanate is added into a three-neck flask, the reaction temperature is controlled at 70 ℃, then 104g of amino-terminated methylphenyl polysiloxane is dropwise added into the flask through a constant-pressure dropping funnel for reaction for 4 hours, and the NCO content of a reaction product is measured to be 14.8 percent, so that the organosilicon modified isocyanate prepolymer is obtained.
Example 5
(1) 100g of octamethylcyclotetrasiloxane and 46g of tetramethyltetraphenylcyclotetrasiloxane were weighed into a three-necked flask with a thermometer and a condensation reflux unit, and placed in an oil bath, N2Protecting, heating to 80 ℃, adding 2.92g of concentrated sulfuric acid, stirring for reacting for 40min, adding 22.6g of tetramethyl dihydrodisiloxane, stirring for reacting for 5h at 80 ℃, cooling to room temperature after the reaction is finished, neutralizing to be neutral by using sodium bicarbonate, washing with water, filtering, removing small molecular byproducts by rotary evaporation at 130 ℃ by using a rotary evaporator, carrying out rotary evaporation for 5h, and carrying out reduced pressure filtration to prepare the hydrogen-terminated methylphenyl polysiloxane with the number average molecular weight of 1000.
(2) 100g of hydrogen-terminated methylphenylpolysiloxane and 5.7g of allylamine were weighed into a three-necked flask with a thermometer and a reflux condenser, the flask was placed in an oil bath, the temperature was raised to 70 ℃ and 0.002g H was added2PtCl6And reacting for 4 hours by using a catalyst to prepare the amino-terminated methyl phenyl polysiloxane.
(3) And (3) heating the amino-terminated methyl phenyl polysiloxane obtained in the step two to 120 ℃ in a three-neck flask, and performing dehydration treatment for 4 hours under reduced pressure for later use. 100g of toluene diisocyanate is added into a three-neck flask, the reaction temperature is controlled at 70 ℃, then 79.4g of amino-terminated methylphenyl polysiloxane is dropwise added into the flask through a constant-pressure dropping funnel for reaction for 4 hours, and the NCO content of the reaction product is measured to be 14.7 percent, so that the organosilicon modified isocyanate prepolymer is obtained.
The solvent-free polyurethane synthetic leather consists of a surface layer and a foaming layer, wherein the surface layer and the foaming layer are both made of double-component polyurethane resin, the double-component polyurethane resin consists of a component A and a component B, the component A for the surface layer is different from the component A for the foaming layer, and the component B for the surface layer is the same as the component B for the foaming layer. Wherein the component A is hydroxyl mixture resin, and the component B is isocyanate component. The component A for the surface layer is A without foaming agent1The component A for the foaming layer is A added with foaming agent2. A is to be1Instantly mixing the composition B by a casting machine, casting the mixture on release paper, and drying and curing the mixture at 110 ℃ for 3-5 min to obtain a surface layer; a is to be2And B, pouring the polyurethane resin coated on the surface layer by a pouring machine, uniformly scraping the polyurethane resin to the thickness of 1-2mm by using a scraper, conveying the polyurethane resin to a drying channel, heating for 1-2 min to semi-cure the resin, preparing a foaming layer, then adhering a non-woven fabric base fabric, and entering a subsequent drying box for curing for 3-5 min. And stripping release paper from the cured polyurethane synthetic leather, and rolling and storing.
And (3) performance testing: the moisture permeability test is carried out according to GB T12704-1991 'test method of textile fabric moisture permeability-moisture permeable cup method' at the ambient temperature of 20 +/-2 ℃ and the humidity of 65 +/-2%. Air permeability test the air permeability test was carried out according to GB 4689.2-1984 using a H.C Fisarov leather air permeability tester. The test data of air permeability and moisture permeability of the prepared solvent-free synthetic leather are shown in table 1.
TABLE 1 air and moisture permeability test data for solvent synthetic leather
As can be seen from the data in table 1, the prepolymer prepared by using the amino-terminated methylphenyl polysiloxane modified isocyanate is superior to the polyurethane synthetic leather prepared in patent document CN106087451A in air permeability and moisture permeability; because the organosilicon chain segment has excellent flexibility and air permeability, the air permeability and the moisture permeability of the prepared polyurethane synthetic leather are better along with the increase of the chain length of organosilicon molecules.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. An organic silicon modified isocyanate prepolymer for solvent-free synthetic leather is characterized by comprising the following structural compounds:
wherein R is aryl or aliphatic; a. b is a natural number; the carbon number of R is 6-13;
the content of isocyanate is 14.5 to 14.8 percent;
the preparation method of the organic silicon modified isocyanate prepolymer for the solvent-free synthetic leather comprises the following steps:
(1) adding octamethylcyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane and an acidic catalyst into a reactor, then adding tetramethyldihydrodisiloxane, carrying out ring-opening polymerization reaction for 4-6 h at 60-80 ℃, cooling after the reaction is finished, neutralizing a reaction product to be neutral by using alkali, washing with water, filtering, and removing small molecular byproducts to obtain hydrogen-terminated methylphenyl polysiloxane;
(2) reacting the hydrogeno-methyl phenyl polysiloxane obtained in the step (1) with allyl amine in H2PtCl6Reacting under a catalyst to prepare amino-terminated methylphenyl polysiloxane;
(3) and (3) dehydrating the product obtained in the step (2), and then reacting with an isocyanate monomer to generate a prepolymer with an NCO end group.
2. The solvent-free organic silicon modified isocyanate prepolymer for synthetic leather according to claim 1, wherein the small molecular by-product is removed in the step (1) by using a rotary evaporator, and the rotary evaporation temperature is 100-130 ℃.
3. The organic silicon modified isocyanate prepolymer for the solvent-free synthetic leather according to claim 1, wherein the reaction temperature in the step (2) is 50-60 ℃, and the reaction time is 3-5 hours; catalyst H used2PtCl6The dosage is 10-30 ppm of the mass of the two reactants.
4. The silicone modified isocyanate prepolymer for solvent-free synthetic leather according to claim 1, wherein the acidic catalyst in step (1) is one or a combination of concentrated hydrochloric acid, concentrated sulfuric acid, trifluoromethanesulfonic acid and acidic cation exchange resin; the dosage of the used acid catalyst is 1 to 3 percent of the sum of the weight of the octamethylcyclotetrasiloxane and the weight of the tetramethyltetraphenylcyclotetrasiloxane.
5. The solvent-free silicone modified isocyanate prepolymer for synthetic leather according to claim 1, wherein the acidic catalyst in step (1) is added into the system, then mixed and reacted for 30-40 min, and then tetramethyldihydrodisiloxane is added.
6. The organic silicon modified isocyanate prepolymer for the solvent-free synthetic leather according to claim 1, wherein the number average molecular weight of the hydrogen-terminated methyl phenyl polysiloxane designed in the step (1) is 500-4000.
7. The organic silicon modified isocyanate prepolymer for the solvent-free synthetic leather according to claim 6, wherein the number average molecular weight of the hydrogen-terminated methyl phenyl polysiloxane designed in the step (1) is 1000-3000.
8. The organic silicon modified isocyanate prepolymer for the solvent-free synthetic leather according to claim 1, wherein the isocyanate monomer is at least one of isophorone diisocyanate (IPDI), Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), Hexamethylene Diisocyanate (HDI), Xylylene Diisocyanate (XDI) or methylcyclohexyl diisocyanate (HTDI).
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| CN112961307B (en) * | 2021-02-09 | 2022-05-10 | 上海华峰新材料研发科技有限公司 | Solvent-free polyurethane resin, impregnation slurry, and preparation method and application thereof |
| CN118325096A (en) * | 2024-06-12 | 2024-07-12 | 杭州崇耀科技发展有限公司 | Isocyanate modified organosilicon polymer and preparation method thereof |
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| US9714363B2 (en) * | 2014-12-23 | 2017-07-25 | Super Skin Systems, Inc. | Silicone polyurea |
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