CN113336913A - Polyurethane resin with explosion-proof needle function and preparation method thereof - Google Patents
Polyurethane resin with explosion-proof needle function and preparation method thereof Download PDFInfo
- Publication number
- CN113336913A CN113336913A CN202110834798.XA CN202110834798A CN113336913A CN 113336913 A CN113336913 A CN 113336913A CN 202110834798 A CN202110834798 A CN 202110834798A CN 113336913 A CN113336913 A CN 113336913A
- Authority
- CN
- China
- Prior art keywords
- explosion
- polyurethane resin
- function
- proof needle
- polyol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- 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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- 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
- C08G18/6666—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
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The application relates to the technical field of polyurethane resin, in particular to polyurethane resin with an anti-explosion needle function and a preparation method thereof. A polyurethane resin with an explosion-proof needle function is prepared from the following raw materials: aromatic isocyanate, modified hydroxyl siloxane, a chain extender, polyol, a catalyst and a cosolvent; the using amount of the chain extender accounts for 5-30% of the total weight of the polyol; the amount of the modified hydroxyl siloxane accounts for 5-30% of the total weight of the polyol; the catalyst accounts for 0.01 to 0.02 percent of the total weight of the ingredients; NCO in aromatic isocyanates: the molar ratio of the total amount of hydroxyl groups in the chain extender and the polyol is 1: 1. The automobile synthetic leather prepared by the method has a good anti-explosion needle effect, and has the advantages of good wear resistance, smoothness and scratch resistance.
Description
Technical Field
The application relates to the technical field of polyurethane resin, in particular to polyurethane resin with an explosion-proof needle function and a preparation method thereof.
Background
The polyurethane synthetic leather belongs to the class of polyurethane elastomers, has the advantages of soft gloss, soft hand feeling, excellent mechanical property, good cold resistance, convenient processing and the like, and is the most ideal substitute of natural leather. Polyurethane synthetic leather is widely applied to industries such as clothes, shoemaking, cases and the like.
At present, sewing can be involved in the polyurethane synthetic leather processing process, and a needle head and a thread can generate certain tension on the polyurethane synthetic leather, so that a needle hole is exploded, namely, the needle explosion phenomenon occurs, and the quality of a product made of the polyurethane synthetic leather is influenced. At present, the explosion-proof needle performance of polyurethane synthetic leather raw materials on the market is not ideal, and the application range of the polyurethane synthetic leather is limited. Accordingly, the inventors propose a polyurethane resin having a function of an explosion-proof needle.
Disclosure of Invention
In order to solve the problem that the anti-explosion needle performance of polyurethane synthetic leather raw materials on the market is not ideal, the application aims to provide polyurethane resin with an anti-explosion needle function and a preparation method thereof.
In a first aspect, the application provides a polyurethane resin with an explosion-proof needle function, which is realized by the following technical scheme:
the polyurethane resin with the function of an explosion-proof needle is prepared from the following raw materials: aromatic isocyanate, modified hydroxyl siloxane, a chain extender, polyol, a catalyst and a cosolvent; the using amount of the chain extender accounts for 5-30% of the total weight of the polyol; the amount of the modified hydroxyl siloxane accounts for 5-30% of the total weight of the polyol; the catalyst accounts for 0.01 to 0.02 percent of the total weight of the ingredients; aromatic heteroNCO in cyanate ester: the molar ratio of the total amount of hydroxyl groups in the chain extender and the polyol is 1: 1; the structural formula of the modified hydroxyl siloxane is as follows:
wherein n is more than or equal to 50 and less than or equal to 200.
Through adopting above-mentioned technical scheme, the car synthetic leather that adopts this application preparation has better explosion-proof needle effect, and has the advantage that the wearability is good, smooth, prevent the mar.
Preferably, the molecular weight of the modified hydroxy siloxane is 5000-.
By adopting the technical scheme, the polyol can be subjected to graft modification through the modified hydroxyl siloxane, so that the overall flexibility is improved, and a good explosion-proof needle effect is ensured.
Preferably, the modified hydroxy siloxane is FM-DA26 of Japanese JNC with a molecular weight of 15000.
By adopting the technical scheme, the main chain of the FM-DA26 modified hydroxyl siloxane is longer, and the main chain is grafted on the polyhydric alcohol and then serves as a branched chain, so that the overall flexibility is improved, and a better explosion-proof needle effect is ensured.
Preferably, the polyol is one or two of polycarbonate diol, polyester polyol and polytetramethylene ether glycol.
Through adopting above-mentioned technical scheme, guarantee that this application has better explosion-proof needle effect.
Preferably, the polycarbonate diol has a molecular weight of 1000-3000; the molecular weight of the polyester polyol is 500-3000; the molecular weight of polytetramethylene ether glycol is 1000-3000.
Through adopting above-mentioned technical scheme, further guarantee that this application has better explosion-proof needle effect.
Preferably, the chain extender is one or more of ethylene glycol, 1, 4-butanediol and 1, 6-hexanediol.
Through adopting above-mentioned technical scheme, guarantee that this application has better explosion-proof needle effect.
Preferably, the cosolvent is one or more of DMF, ETAC and MEK; the catalyst is organic bismuth.
By adopting the technical scheme, the cosolvent is convenient for material dispersion, and the reaction can be smoothly carried out.
Preferably, the product formula also comprises dimethylglyoxime, and the dimethylglyoxime accounts for 1.0 to 5.0 percent of the total weight of the ingredients.
Through adopting above-mentioned technical scheme, contain the structure of oxime urethane in the car synthetic leather that polyurethane resin after the addition of dimethylglyoxime made, the molecular chain has certain mobility, can repair by oneself explosion needle department, further promotes the explosion-proof needle effect of this application.
In a second aspect, the application provides a preparation method of polyurethane resin with an explosion-proof needle function, which is realized by the following technical scheme:
a preparation method of polyurethane resin with an explosion-proof needle function comprises the following steps:
s1, uniformly mixing accurately measured modified hydroxyl siloxane, polyol, a chain extender, a catalyst and a cosolvent which accounts for 15-25% of the total weight of the cosolvent, and reacting at 50-60 ℃ for 20-40min to obtain a mixed solution;
s2, adding aromatic isocyanate into the mixed solution for multiple times at 70-80 ℃, adding the rest cosolvent into the mixed solution for multiple times, adding the aromatic isocyanate firstly, adding the cosolvent later, and controlling the reaction for 4-8 hours;
s3, viscosity increase to 6.0 x 104-1.6*105mPa · s, adding methanol to terminate the reaction.
By adopting the technical scheme, the preparation method is simple, and is convenient to popularize and apply and produce in batches.
In summary, the present application has the following advantages:
1. the automobile synthetic leather prepared by the method has a good anti-explosion needle effect, and has the advantages of good wear resistance, smoothness and scratch resistance.
2. The preparation method is simple, and is convenient to popularize and apply and produce in batches.
Drawings
FIG. 1 is a graph comparing the anti-pin-blast effects of synthetic leather prepared using the polyurethane resin of example 2 in the present application with synthetic leather prepared using the polyurethane resin of comparative example 1.
Detailed Description
The present application will be described in further detail with reference to examples.
Raw materials
Examples
Example 1
The application discloses a polyurethane resin with an explosion-proof needle function, which is prepared from the following raw materials: 68.88g of aromatic isocyanate (MDI), 7.5g of modified hydroxysiloxane (FM-DA26), 18g of 1, 4-butanediol, 150g of UH-200 polycarbonate diol of 2000 molecular weight, 0.1g of organobismuth, 470g of DMF and 118g of MEK.
A preparation method of polyurethane resin with an explosion-proof needle function comprises the following steps:
s1, putting accurately metered polycarbonate diol with the molecular weights of FM-DA26 and 2000, 1, 4-butanediol, organic bismuth and a mixed solution of DMF and MEK accounting for 20 percent of the total weight of the cosolvent into a reaction kettle, uniformly mixing, and reacting at 60 ℃ for 30min to obtain a mixed solution;
s2, adding aromatic isocyanate into the mixed solution in the S1 at 75 ℃ in five times, adding the rest cosolvent into the mixed solution in five times, adding the aromatic isocyanate firstly, adding the cosolvent later, and controlling the reaction for 6 hours;
s3, viscosity increase to 6.0 x 104-1.6*105Adding methanol between mPas to stop the reaction, and obtaining the finished resin.
Example 2
Example 2 differs from example 1 in that: the application discloses a polyurethane resin with an explosion-proof needle function, which is prepared from the following raw materials: 69g of aromatic isocyanate (MDI), 15g of modified hydroxysiloxane (FM-DA26), 18g of 1, 4-butanediol, 150g of UH-200 polycarbonate diol with a molecular weight of 2000, 0.1g of organobismuth, 470g of DMF and 118g of MEK.
Example 3
Example 3 differs from example 1 in that: the application discloses a polyurethane resin with an explosion-proof needle function, which is prepared from the following raw materials: 69.25g of aromatic isocyanate (MDI), 30g of modified hydroxysiloxane (FM-DA26), 18g of 1, 4-butanediol, 150g of UH-200 polycarbonate diol with a molecular weight of 2000, 0.1g of organobismuth, 470g of DMF and 118g of MEK.
Example 4
Example 4 differs from example 1 in that: the application discloses a polyurethane resin with an explosion-proof needle function, which is prepared from the following raw materials: 69.5g of aromatic isocyanate (MDI), 45g of modified hydroxysiloxane (FM-DA26), 18g of 1, 4-butanediol, 150g of UH-200 polycarbonate diol with a molecular weight of 2000, 0.1g of organobismuth, 470g of DMF and 118g of MEK.
Example 5
Example 5 differs from example 1 in that: the application discloses a polyurethane resin with an explosion-proof needle function, which is prepared from the following raw materials: 69.5g of aromatic isocyanate (MDI), 15g of modified hydroxysiloxane (FM-DA21), 18g of 1, 4-butanediol, 150g of UH-200 polycarbonate diol with a molecular weight of 2000, 0.1g of organobismuth, 470g of DMF and 118g of MEK.
Example 6
Example 6 differs from example 1 in that: the application discloses a polyurethane resin with an explosion-proof needle function, which is prepared from the following raw materials: 69g of aromatic isocyanate (MDI), 45g of modified hydroxysiloxane (FM-DA26), 18g of 1, 4-butanediol, 150g of 2000 molecular weight polybutylene hexanediol, 0.1g of organobismuth, 470g of DMF and 118g of MEK.
Example 7
Example 7 differs from example 1 in that: the application discloses a polyurethane resin with an explosion-proof needle function, which is prepared from the following raw materials: 69g of aromatic isocyanate (MDI), 45g of modified hydroxysiloxane (FM-DA26), 18g of 1, 4-butanediol, 150g of 2000 molecular weight polytetramethylene ether glycol, 0.1g of organobismuth, 470g of DMF and 118g of MEK.
Example 8
Example 8 differs from example 1 in that: the application discloses a polyurethane resin with an explosion-proof needle function, which is prepared from the following raw materials: 69g of aromatic isocyanate (MDI), 45g of modified hydroxysiloxane (FM-DA26), 18g of 1, 4-butanediol, 75g of 2000 molecular weight UH-200 polycarbonate diol, 75g of 2000 molecular weight polyhexamethylene glycol butanediol adipate, 0.1g of organobismuth, 470g of DMF and 118g of MEK.
Example 9
Example 9 differs from example 1 in that: the application discloses a polyurethane resin with an explosion-proof needle function, which is prepared from the following raw materials: 69.5g of aromatic isocyanate (MDI), 45g of modified hydroxysiloxane (FM-DA26), 18g of 1, 4-butanediol, 75g of 2000 molecular weight polytetramethylene ether glycol, 75g of 2000 molecular weight polyhexamethylene glycol butanediol adipate, 0.1g of organobismuth, 470g of DMF and 118g of MEK.
Example 10
Example 10 differs from example 1 in that: the application discloses a polyurethane resin with an explosion-proof needle function, which is prepared from the following raw materials: 69g of aromatic isocyanate (MDI), 45g of modified hydroxysiloxane (FM-DA26), 18g of 1, 4-butanediol, 75g of 2000 molecular weight polytetramethylene ether glycol, 75g of 2000 molecular weight UH-200 polycarbonate diol, 0.1g of organobismuth, 470g of DMF and 118g of MEK.
Example 11
Example 11 differs from example 1 in that: the application discloses a polyurethane resin with an explosion-proof needle function, which is prepared from the following raw materials: 56.5g of aromatic isocyanate (MDI), 15g of modified hydroxysiloxane (FM-DA26), 6.2g of ethylene glycol, 150g of UH-200 polycarbonate diol with a molecular weight of 2000, 0.1g of organobismuth, 470g of DMF and 118g of MEK.
Example 12
Example 12 differs from example 1 in that: the application discloses a polyurethane resin with an explosion-proof needle function, which is prepared from the following raw materials: 56.5g of aromatic isocyanate (MDI), 15g of modified hydroxysiloxane (FM-DA26), 17.7g of 1, 6-hexanediol, 150g of UH-200 polycarbonate diol with a molecular weight of 2000, 0.1g of organobismuth, 470g of DMF and 118g of MEK.
Example 13
Example 13 differs from example 1 in that: the application discloses a polyurethane resin with an explosion-proof needle function, which is prepared from the following raw materials: 63.75g of aromatic isocyanate (MDI), 15g of modified hydroxysiloxane (FM-DA26), 1.86g of ethylene glycol, 9g of 1, 4-butanediol, 150g of UH-200 polycarbonate diol with a molecular weight of 2000, 0.1g of organobismuth, 470g of DMF and 118g of MEK.
Example 14
Example 14 differs from example 1 in that: the application discloses a polyurethane resin with an explosion-proof needle function, which is prepared from the following raw materials: 64g of aromatic isocyanate (MDI), 15g of modified hydroxysiloxane (FM-DA26), 1.86g of ethylene glycol, 9g of 1, 4-butanediol, 5.9g of 1, 6-hexanediol, 150g of UH-200 polycarbonate diol with a molecular weight of 2000, 0.1g of organobismuth, 470g of DMF and 118g of MEK.
Example 15
Example 15 differs from example 1 in that: the application discloses a polyurethane resin with an explosion-proof needle function, which is prepared from the following raw materials: 87.75g of aromatic isocyanate (MDI), 15g of modified hydroxysiloxane (FM-DA26), 18g of 1, 4-butanediol, 150g of UH-100 polycarbonate diol with a molecular weight of 1000, 0.1g of organobismuth, 470g of DMF and 118g of MEK.
Example 16
Example 17 differs from example 1 in that: the application discloses a polyurethane resin with an explosion-proof needle function, which is prepared from the following raw materials: 62.75g of aromatic isocyanate (MDI), 15g of modified hydroxysiloxane (FM-DA26), 18g of 1, 4-butanediol, 150g of UH-300 polycarbonate diol with a molecular weight of 3000, 0.1g of organobismuth, 470g of DMF and 118g of MEK.
Example 17
The polyurethane resin with the function of the explosion-proof needle is prepared from a component A and a component B. Wherein the component A is a prepolymer and is prepared from the following raw materials: MDI, 1, 6-hexanediol, polytetrahydrofuran diol (Aladdin China) with molecular weight of 3000, organic bismuth, dimethylglyoxime (98%, national drug group) and butanone. The component B is prepared from the following raw materials: MDI, 1, 6-hexanediol, polytetramethylene ether glycol with the molecular weight of 3000, FM-DA26 modified hydroxyl siloxane and methyl ethyl ketone MEK.
A preparation method of polyurethane resin with an explosion-proof needle function comprises the following steps:
s1: preparing a prepolymer A component;
s11: 115.11g of MDI, 300g of polytetrahydrofuran diol with the molecular weight of 3000, 32.5g of dimethylglyoxime, 4.73g of 1, 6-hexanediol, 500ml of butanone and 0.05g of organic bismuth are weighed, after the 1, 6-hexanediol and the butanone are uniformly mixed, the dimethylglyoxime is dissolved in the butanone/1, 6-hexanediol mixed solution to form colorless transparent liquid;
s12: adding MDI and organic bismuth with accurate measurement, mixing for 3min at 60rpm, and reacting for 4h at 45 ℃ to obtain a prepolymer A component for later use;
s2: uniformly mixing accurately measured modified hydroxyl siloxane, polyol, a chain extender, a catalyst and a cosolvent which accounts for 20 percent of the total weight of the cosolvent, and reacting at 50 ℃ for 30min to obtain a mixed solution;
s22: and (2) adding MDI into the mixed solution for multiple times at 70-80 ℃, adding the rest DMF into the mixed solution for multiple times, adding MDI first and DMF later, adding the prepolymer A component into the mixed solution when the addition of the MDI reaches more than 60%, mixing at 120rpm for 5min, adding the rest MDI into the mixed solution for four times, and controlling the reaction to be 8 hours to obtain the polyurethane resin.
Comparative example
Comparative example 1
The application discloses a polyurethane resin with an explosion-proof needle function, which is prepared from the following raw materials: 68.75g of aromatic isocyanate (MDI), 18g of 1, 4-butanediol, 150g of a 2000 molecular weight polycarbonate diol, 0.1g of organobismuth, 470g of DMF and 118g of MEK.
A preparation method of polyurethane resin with an explosion-proof needle function comprises the following steps:
s1, putting the polycarbonate diol with the accurate measurement of 2000 molecular weight, 1, 4-butanediol, organic bismuth and the mixed solution of DMF and MEK which accounts for 20 percent of the total weight of the cosolvent into a reaction kettle, uniformly mixing, and reacting at 60 ℃ for 30min to obtain mixed solution;
s2, adding aromatic isocyanate into the mixed solution in the S1 at 75 ℃ in five times, adding the rest cosolvent into the mixed solution in five times, adding the aromatic isocyanate firstly, adding the cosolvent later, and controlling the reaction for 6 hours;
s3, viscosity increase to 6.0 x 104-1.6*105Adding methanol between mPas to stop the reaction, and obtaining the finished resin.
Comparative example 2
Comparative example 2 differs from comparative example 1 in that: the application discloses a polyurethane resin with an explosion-proof needle function, which is prepared from the following raw materials: 62.8g of aromatic isocyanate (MDI), 10g of 1, 4-butanediol, 180g of 2000 molecular weight polycarbonate diol, 0.1g of organobismuth, 472g of DMF and 118g of MEK.
Detection method
Preparation of polyurethane synthetic leather
The polyurethane synthetic leather prepared by the preparation method of the anti-siphon hydrolysis-resistant polyurethane synthetic leather disclosed by the publication number CN105113267A is taken as a reference. The preparation method of the anti-siphon hydrolysis-resistant polyurethane synthetic leather comprises the following steps: a white woven single-sided napped cloth having a weight of 155g/m2, a width of 1.55m and a thickness of 0.55mm was used as the base cloth of the wet base cloth. The smooth surface of the base cloth is selected as a coating surface, the base cloth is placed on a cloth placing frame and sent to a wet-method Bass production line, and the base cloth is processed by a pre-coagulation tank, an ironing roller, a coating machine, a main coagulation tank, a rinsing tank, a printing roller, an oven and a cooling roller in sequence to form wet-method Bass which is rolled for standby. Wherein, the formulation compositions and the proportions of coating slurry of the wet bass are shown in examples 1-17 and comparative example 1 (slurry viscosity VIS:5000 +/-1000 cps/35 +/-4 ℃), and the process parameters of each part of the production line of the wet bass are set as follows: the mass percentage of DMF in the pre-coagulation tank is 21Percent, the production speed is 13m/min, the tension of a production line is 1.2MPa, the gap between tool bits is 1.55mm, the mass percent of DMF in a main coagulation tank is 21 percent, the temperature is 33 ℃, the Bess width of a coagulation outlet tank is 1.41m, the thickness is 0.92mm, the water temperature of a washing tank is 40 ℃, a 160-mesh roller is selected at a printing roller, 17 parts of HY-803 water-based water-sprinkling agent (the viscosity VIS of slurry is 15 +/-5 cps/25 +/-5 ℃) are fully coated, the width of a Bess entering oven is 1.40m, and the temperature of the main oven is: the front section is 155 ℃, the middle section is 155 ℃ and the rear section is 140 ℃. And (3) Beth width of a finished product in a wet method: 1.40 m; thickness: 0.85 mm; gram weight: 385g/m2. And the obtained wet-process bass is subjected to a dry-process surface-making transfer release paper pattern technology to obtain the polyurethane synthetic leather.
Firstly, testing an explosion-proof needle: the synthetic leather prepared in examples 1-17 and comparative examples 1-2 was woven with 20cm gauge needles with 60-75 needle holes at a speed of 1.3m/min, and the needle explosion rate of the synthetic leather was calculated. Needle explosion rate [% of needle explosion holes/total needle turning holes ] } 100
Secondly, testing the elongation and breaking rate of the resin film: the resins prepared in examples 1 to 17 and comparative example 1 were cured at 130 ℃ to give a film to be tested, and the elongation at break of the film to be tested was measured by the following method. Testing of elongation at break:
1. the range is as follows: the present standard specifies a test method for determining elongation at break by applying a static tensile load to a test specimen. The standard is suitable for testing the elongation at break of the mastic produced in a viscose workshop.
2. Normative citation document: the provisions in the documents refer to the test methods for the properties of resin castings in GB/T2567-1997 and GB/T2567-2008.
3. The test principle is as follows: and applying a static tensile load at a constant speed along the axial direction of the sample until the sample breaks, measuring the elongation length of the sample at the moment, and dividing the elongation length by the gauge length of the sample to obtain the breaking elongation.
4. And (3) testing conditions are as follows: the laboratory standard test conditions were: temperature (23+2) ° c, relative humidity (50+ 5)%.
5. Testing equipment: 1. universal testing machine: shimadzu universal tester AGS-X type; 2. measuring tool: the digital display vernier caliper has the precision of 0.01 mm. The testing steps are as follows: 1. sample preparation: the shape of the sample. Using wine for standard sample preparation moldAfter fine scrubbing, coating a release agent, standing and airing for thousands of hours. And filling the female die cavity with mastic, and scraping off the redundant part. And (3) placing the die frame in an oven at 30 ℃ for 7 days continuously until the die frame is completely dried, and then demolding. The number of the effective patterns in each group is not less than 5, and the effective patterns are placed for at least 24 hours under standard environmental conditions before the experiment. 2. And starting the universal testing machine, and preheating for at least 15 min. Fixing an upper limit bolt and a lower limit bolt, installing a test elongation clamping device, opening a test method for testing the elongation at break, resetting a software load, resetting a stroke and correcting the load; 3. clamping the sample, enabling the sample to be located on a vertical plane of the upper clamp and the lower clamp, and finely adjusting the position of the upper clamp to enable the sample to be completely straightened but not stressed; 4. measuring the distance between the upper clamp and the lower clamp by using a vernier caliper, and recording the distance as a gauge length Lo; 5. resetting the stroke, starting the test by pressing a start button, stopping the test when the sample is damaged, and reading the stroke at the moment; 6. and (3) calculating: elongation at break εl＝(△Lb/Lo) 100%; wherein epsilonl-elongation at break of the test specimen; delta Lb-the elongation in the gauge length at break of the sample, i.e. the stroke mm read at break; lo measures the gauge length mm.
And thirdly, testing the wear resistance according to a GMW 3208 and 2012 rotating wear test.
And fourthly, testing the peel strength: the polyurethane resins in examples 1-17 and comparative examples 1-2 were respectively blade-coated with 1.0mm of polyurethane resin on a microfiber substrate (model BGI-W-X, Hexin Colorado), and reacted with 110 ℃ for 8min to cure and crosslink the resin for molding, and the release paper was peeled off after curing and molding, and the peel strength measured after standing for 24 hours was the final peel strength. Peel Strength testing reference is made to GB/T2791-.
Fifthly, jungle testing: according to the requirement of QB/T4671-2014 'determination of hydrolysis resistance of artificial leather test method', a constant temperature and humidity hydrolysis resistance method is adopted for jungle test, the products prepared in the example 1-and the comparative example 1-are coated on sample leather with the size of (220 +/-2) mmX (150 +/-2) mm and according with the specification of QB/T2706 + 2005, the sample leather is placed in a constant temperature and humidity tester for 3 weeks, wherein the temperature of the constant temperature and humidity tester is 70 ℃ and the relative humidity is not 95%, and the phenomena of obvious lubricating color change, cracking, delamination and the like on the surface of the test sample are observed.
Sixthly, comparing the effects of the explosion-proof needle: the polyurethane resin in example 2 is used as a raw material, and the test synthetic leather is prepared according to a preparation method of the anti-siphon hydrolysis-resistant polyurethane synthetic leather; the polyurethane resin in comparative example 1 was used as a raw material, and a comparative synthetic leather was prepared according to a preparation method of the anti-siphon hydrolysis-resistant polyurethane synthetic leather. The test synthetic leather and the comparative synthetic leather showed the anti-knocking effect as shown in fig. 1.
Data analysis
Table 1 shows the test parameters of examples 1 to 17 and comparative examples 1 to 2
By combining examples 1-17 and comparative examples 1-2 and table 1, it can be seen that the explosion-proof needle rate of the automobile leather prepared by using the polyurethane resin in examples 1-17 is more than 95%, which is obviously superior to the explosion-proof needle rate of the automobile leather prepared by using the polyurethane resin in comparative example 1, and therefore, the automobile synthetic leather prepared by using the method has a better explosion-proof needle effect.
As can be seen by combining examples 1-17 and comparative examples 1-2 with Table 1, the automobile leather CS-101 KG prepared by using the polyurethane resin in examples 1-17 has no damage for 500 times, so the automobile synthetic leather prepared by using the method has the advantages of good wear resistance, smoothness and scratch resistance.
As can be seen by combining examples 1-17 and comparative examples 1-2 with Table 1, the automobile leather prepared by using the polyurethane resin in examples 1-17 has no obvious change after 3 weeks of jungle test, so that the automobile synthetic leather prepared by using the method has better anti-aging performance.
By combining examples 1 to 17 and comparative examples 1 to 2 and table 1, it can be seen that the automobile leather prepared by using the polyurethane resin in example 17 has a self-healing function, can achieve a better anti-explosion needle effect, and is suitable for the high-end automobile leather market.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (9)
1. A polyurethane resin with an explosion-proof needle function is characterized in that: the product is prepared from the following raw materials: aromatic isocyanate, modified hydroxyl siloxane, a chain extender, polyol, a catalyst and a cosolvent; the using amount of the chain extender accounts for 5-30% of the total weight of the polyol; the dosage of the modified hydroxyl siloxane accounts for 5-30% of the total weight of the polyalcohol; the catalyst accounts for 0.01 to 0.02 percent of the total weight of the ingredients; NCO in the aromatic isocyanate: the molar ratio of the total amount of hydroxyl groups in the chain extender and the polyol is 1: 1; the structural formula of the modified hydroxyl siloxane is as follows:
wherein n is more than or equal to 50 and less than or equal to 200.
2. The polyurethane resin with the function of the explosion-proof needle as claimed in claim 1, wherein: the molecular weight of the modified hydroxyl siloxane is 5000-15000.
3. The polyurethane resin with the function of the explosion-proof needle as claimed in claim 2, wherein: the modified hydroxyl siloxane is FM-DA26 of Japanese JNC, and has a molecular weight of 15000.
4. The polyurethane resin with the function of the explosion-proof needle as claimed in claim 1, wherein: the polyol is one or the combination of two of polycarbonate diol, polyester polyol and polytetramethylene ether glycol.
5. The polyurethane resin with the function of the explosion-proof needle as claimed in claim 4, wherein: the molecular weight of the polycarbonate diol is 1000-3000; the molecular weight of the polyester polyol is 500-3000; the molecular weight of polytetramethylene ether glycol is 1000-3000.
6. The polyurethane resin with the function of the explosion-proof needle as claimed in claim 1, wherein: the chain extender is one or a combination of more of ethylene glycol, 1, 4-butanediol and 1, 6-hexanediol.
7. The polyurethane resin with the function of the explosion-proof needle as claimed in claim 1, wherein: the cosolvent is one or more of DMF, ETAC and MEK; the catalyst is organic bismuth.
8. The polyurethane resin with the function of the explosion-proof needle as claimed in claim 1, wherein: the product formula also comprises dimethylglyoxime, and the dimethylglyoxime accounts for 1.0 to 5.0 percent of the total weight of the ingredients.
9. The method for preparing a polyurethane resin having an explosion-proof needle function according to any one of claims 1 to 8, wherein: the method comprises the following steps:
s1, uniformly mixing accurately measured modified hydroxyl siloxane, polyol, a chain extender, a catalyst and a cosolvent which accounts for 15-25% of the total weight of the cosolvent, and reacting at 50-60 ℃ for 20-40min to obtain a mixed solution;
s2, adding aromatic isocyanate into the mixed solution for multiple times at 70-80 ℃, adding the rest cosolvent into the mixed solution for multiple times, adding the aromatic isocyanate firstly, adding the cosolvent later, and controlling the reaction for 4-8 hours;
s3, viscosity increase to 6.0 x 104-1.6*105mPa · s, adding methanol to terminate the reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110834798.XA CN113336913B (en) | 2021-07-23 | 2021-07-23 | Polyurethane resin with explosion-proof needle function and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110834798.XA CN113336913B (en) | 2021-07-23 | 2021-07-23 | Polyurethane resin with explosion-proof needle function and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113336913A true CN113336913A (en) | 2021-09-03 |
| CN113336913B CN113336913B (en) | 2022-05-13 |
Family
ID=77480270
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110834798.XA Active CN113336913B (en) | 2021-07-23 | 2021-07-23 | Polyurethane resin with explosion-proof needle function and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113336913B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114133527A (en) * | 2021-12-30 | 2022-03-04 | 浙江禾欣科技有限公司 | Polyurethane for solvent-free foot pad leather and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007119749A (en) * | 2005-09-27 | 2007-05-17 | Dai Ichi Kogyo Seiyaku Co Ltd | Aqueous polyurethane resin dispersion composition for surface skin layer of fibrous laminate material, method for producing fibrous laminate material and synthetic leather |
| CN107531861A (en) * | 2016-04-14 | 2018-01-02 | Dic株式会社 | Aqueous urethane resin composition and synthetic leather |
| CN108314763A (en) * | 2017-01-17 | 2018-07-24 | 中国科学院化学研究所 | A kind of dynamic based on oxime can repair polyurethane and preparation method thereof |
| CN109705300A (en) * | 2018-12-24 | 2019-05-03 | 东华大学 | A kind of selfreparing polyurethane and preparation method thereof |
| CN111108244A (en) * | 2017-09-19 | 2020-05-05 | Dic株式会社 | Synthetic leather |
| CN111201347A (en) * | 2017-09-19 | 2020-05-26 | Dic株式会社 | Synthetic leather |
| CN111269390A (en) * | 2020-03-19 | 2020-06-12 | 浙江华峰合成树脂有限公司 | Polyurethane resin for synthetic leather surface layer and preparation method thereof |
-
2021
- 2021-07-23 CN CN202110834798.XA patent/CN113336913B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007119749A (en) * | 2005-09-27 | 2007-05-17 | Dai Ichi Kogyo Seiyaku Co Ltd | Aqueous polyurethane resin dispersion composition for surface skin layer of fibrous laminate material, method for producing fibrous laminate material and synthetic leather |
| CN107531861A (en) * | 2016-04-14 | 2018-01-02 | Dic株式会社 | Aqueous urethane resin composition and synthetic leather |
| CN108314763A (en) * | 2017-01-17 | 2018-07-24 | 中国科学院化学研究所 | A kind of dynamic based on oxime can repair polyurethane and preparation method thereof |
| CN111108244A (en) * | 2017-09-19 | 2020-05-05 | Dic株式会社 | Synthetic leather |
| CN111201347A (en) * | 2017-09-19 | 2020-05-26 | Dic株式会社 | Synthetic leather |
| CN109705300A (en) * | 2018-12-24 | 2019-05-03 | 东华大学 | A kind of selfreparing polyurethane and preparation method thereof |
| CN111269390A (en) * | 2020-03-19 | 2020-06-12 | 浙江华峰合成树脂有限公司 | Polyurethane resin for synthetic leather surface layer and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 橡胶工业原材料与装备简明手册编审委员会编著: "《橡胶工业原材料与装备简明手册 原材料与工艺耗材分册》", 31 January 2019, 北京理工大学出版社 * |
| 马兴元 等编著: "《合成革化学与工艺学》", 30 November 2015, 中国轻工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114133527A (en) * | 2021-12-30 | 2022-03-04 | 浙江禾欣科技有限公司 | Polyurethane for solvent-free foot pad leather and preparation method thereof |
| CN114133527B (en) * | 2021-12-30 | 2023-06-13 | 浙江禾欣科技有限公司 | Polyurethane for solvent-free foot pad leather and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113336913B (en) | 2022-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105237725B (en) | A kind of middle hard height resists cold heat resistanceheat resistant adhesion agreeable type minute surface face layer polyurethane resin and preparation method thereof | |
| CN101591420B (en) | Spraying plastic polyurethane composition as well as preparation method and application thereof | |
| CN105153399B (en) | A kind of wet wax sense dry method surface layer resin of hydrolysis ultra-soft matter and preparation method thereof | |
| KR20070067151A (en) | Polyurethane resin and process for producing polyurethane resin solution | |
| JP2009538938A (en) | Method for producing flexible composite elastomeric polyurethane skin | |
| CN107501514B (en) | Casting type polyurethane elastomer semi-prepolymer for producing screen printing rubber scraper | |
| CN113336913B (en) | Polyurethane resin with explosion-proof needle function and preparation method thereof | |
| KR101398113B1 (en) | Scratch self-healing polyol composition and polyurethane mouldings produced therefrom | |
| CN108546323A (en) | Cation is from matting resin and its preparation method and application | |
| CN113583213B (en) | Solvent-free polyurethane capable of absorbing lines and preparation method thereof | |
| KR101790514B1 (en) | Method of manufacturing artificial leather using two-component type non-solvent polyurethane adhesive | |
| CN104163909A (en) | Polyurethane resin for hydrolysis-resistant sofa leather and preparation method thereof | |
| CN111704709B (en) | Low-modulus solvent-free polyurethane resin for synthetic leather and preparation method thereof | |
| CN111645393A (en) | Automobile interior decoration plate with self-repairing function and preparation method thereof | |
| CN109232856A (en) | The preparation method of high highly-elastic urethane elastomer thoroughly | |
| CN110591533A (en) | Environment-friendly laminating coating composition and preparation method thereof | |
| JPS642711B2 (en) | ||
| CN112280283B (en) | Double-component polyurethane resin for automobile leather and preparation method thereof | |
| CN108252115B (en) | Solvent-free high-transparency and high-flexibility-resistant polyurethane resin for leather, and preparation method and application thereof | |
| KR100263375B1 (en) | Manufacturing method of synthetic leather using waterborne polyurethane resin | |
| WO2003078534A1 (en) | Polyol mixture for the production of polyurethane gelcoats | |
| CN107227139A (en) | A kind of leather and sole polyurethane binder and preparation method thereof | |
| CN109337035B (en) | Polyurethane resin for high-toluene-resistance superfine fiber synthetic leather and preparation method thereof | |
| CN103665314B (en) | A kind of casting type polyurethane elastomer and preparation method thereof | |
| CN105801795A (en) | 6-functionality-degree polycaprolactone urethane acrylate and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |