CN112300353B - Flexible sulfonic acid type hydrophilic chain extender and preparation method and application thereof - Google Patents
Flexible sulfonic acid type hydrophilic chain extender and preparation method and application thereof Download PDFInfo
- Publication number
- CN112300353B CN112300353B CN202011295246.8A CN202011295246A CN112300353B CN 112300353 B CN112300353 B CN 112300353B CN 202011295246 A CN202011295246 A CN 202011295246A CN 112300353 B CN112300353 B CN 112300353B
- Authority
- CN
- China
- Prior art keywords
- sulfonic acid
- chain extender
- flexible
- acid type
- hydrophilic chain
- 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.)
- Active
Links
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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- 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
-
- 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
-
- 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
- C08G18/4833—Polyethers containing oxyethylene units
-
- 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
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
-
- 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
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a flexible sulfonic acid type hydrophilic chain extender and a preparation method and application thereof. The molecular structure general formula of the flexible sulfonic acid type hydrophilic chain extender is shown as I:
wherein R is H or CH3(ii) a m is 1 or 2; n is any integer of 1-20; x is 1 or 2. The preparation method comprises the steps of reacting aldehyde containing sulfonic acid ion groups with ether diamine under the action of an acid catalyst to generate an aldimine intermediate product, and reducing the aldimine intermediate product by using a reducing agent to prepare the flexible sulfonic acid type hydrophilic chain extender. The invention also provides an application of the flexible sulfonic acid type hydrophilic chain extender or the flexible sulfonic acid type hydrophilic chain extender prepared by the preparation method in the synthesis of the aqueous polyurethane dispersoid. The chain extender further improves the toughness of the polyurethane on the basis of improving the emulsibility and the water resistance of the polyurethane.
Description
Technical Field
The invention relates to the field of polyurethane materials, in particular to a flexible sulfonic acid type hydrophilic chain extender and a preparation method and application thereof.
Background
With the increasingly strict global requirements on environmental protection, solvent-based materials with high Volatile Organic Compounds (VOCs) are gradually forbidden to be used, water-based materials with environmental protection, safety and low VOCs emission become competitive development alternative materials of various industries, and water-based materials become a mainstream direction of global industrial development.
The waterborne polyurethane takes polyurethane resin as a base material, water replaces an organic solvent to serve as a dispersion medium, and the dispersion liquid of the waterborne polyurethane does not contain or contains a little organic solvent, so that the waterborne polyurethane can be widely applied to the industries of textile printing and dyeing, leather processing, coating, adhesives, wood processing, biomedicine, electronic tags and the like due to the combination of the advantages of high performance of the solvent type polyurethane and low VOCs content of waterborne materials. Introducing hydrophilic groups into polyurethane molecular chains is a key for realizing polyurethane hydration, and among a plurality of synthetic means, introducing hydrophilic groups into a chain extender containing hydrophilic groups through a chain extender is the most common method at present, and reported chain extenders comprise: 2, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid, tartaric acid, ethylenediamine ethyl sodium sulfonate, 2, 4-diaminobenzene sodium sulfonate, 1, 2-dihydroxy-3-propane sodium sulfonate, 1, 4-butanediol-2-sodium sulfonate and the like. These hydrophilic chain extenders have the common feature that each chain extender contains only one ionic group. When the chain extenders are used for preparing the waterborne polyurethane, the content of hydrophilic groups on a polyurethane molecular chain is mainly determined by the using amount of the chain extenders. At a lower chain extender consumption, the obtained waterborne polyurethane is difficult to form a waterborne polyurethane dispersion with stable performance because of less hydrophilic groups introduced into the polyurethane molecular chain. However, the higher amount of the chain extender increases the proportion of hydrophilic chain segments in polyurethane molecular chains, greatly reduces the water resistance of the formed polyurethane film, and greatly hinders the industrial application of the waterborne polyurethane. In addition, because the chain extender is usually introduced into the polyurethane molecular chain in a hard segment manner, the proportion of the hard segment content in the polyurethane molecular chain is usually increased when the aqueous polyurethane is synthesized by the chain extender reported above, a polyurethane material with high toughness is difficult to obtain, and the practical application of the aqueous polyurethane in the fields of leather and high-toughness film products is greatly restricted.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: how to realize the improvement of the toughness of the polyurethane on the basis of improving the emulsibility and the water resistance of the polyurethane by the chain extender.
In order to solve the technical problems, the invention provides a flexible sulfonic acid type hydrophilic chain extender and a preparation method and application thereof.
A flexible sulfonic acid type hydrophilic chain extender is disclosed, wherein the molecular structure general formula of the flexible sulfonic acid type hydrophilic chain extender is shown as I:
wherein R is H or CH3(ii) a m is 1 or 2; n is any integer of 1-20; x is 1 or 2.
Further, the flexible sulfonic acid type hydrophilic chain extender is prepared by reacting aldehyde containing sulfonic acid ion groups with ether diamine under an acid catalyst to generate an aldimine intermediate product, and then reducing the aldimine intermediate product by using a reducing agent.
The invention also provides a preparation method of the flexible sulfonic acid type hydrophilic chain extender, which comprises the following steps of reacting aldehyde containing sulfonic acid ion groups with ether diamine under the action of an acid catalyst to generate an aldimine intermediate product, and reducing the aldimine intermediate product by using a reducing agent to prepare the flexible sulfonic acid type hydrophilic chain extender, wherein the reaction formula is as follows:
wherein R is H or CH3(ii) a m is 1 or 2; n is any integer of 1-20; x is 1 or 2.
Further, the molar ratio of the aldehyde containing a sulfonic acid ionic group to the ether diamine is 2-2.2: 1.
Further, the adding mass of the acidic catalyst is 1-2 wt% of the using amount of the ether diamine.
Further, the addition amount of the reducing agent is 3-3.2 times of the molar amount of the ether diamine.
Further, the acid catalyst is one or two of p-toluenesulfonic acid and sulfuric acid; and/or the reducing agent is one or more of sodium borohydride, sodium cyanoborohydride, sodium triacetoxyborohydride and lithium aluminum hydride.
In addition, the invention also provides an application of the flexible sulfonic acid type hydrophilic chain extender or the flexible sulfonic acid type hydrophilic chain extender prepared by the preparation method in the synthesis of the aqueous polyurethane dispersion.
Further, the above applications include:
mixing polymer polyol with isocyanate, and reacting at 50-80 ℃ to obtain a polyurethane prepolymer;
and mixing the polyurethane prepolymer with the flexible sulfonic acid type hydrophilic chain extender, reacting at 50-80 ℃, and dispersing in water to obtain the aqueous polyurethane dispersion.
Further, mixing the polyurethane prepolymer and the flexible sulfonic acid type hydrophilic chain extender according to the mass usage of the flexible sulfonic acid type hydrophilic chain extender being 3-15 wt% of the polyurethane prepolymer.
Compared with the prior art, the invention has the advantages that: the flexible sulfonic acid type hydrophilic chain extender provided by the invention takes a flexible ether chain as a skeleton, contains a plurality of sulfonic acid ion groups and has secondary amino groups which can participate in polyurethane chain extension reaction, and in the later-stage volatilization film-forming process of the aqueous polyurethane dispersion prepared by the chain extender, the skeleton structure of the flexible ether chain can weaken the risk of reducing the flexibility of a polyurethane molecular chain caused by the formation of urea bonds on the one hand, and can effectively avoid the problem that the toughness of a polyurethane material is reduced because the proportion of hard segments in the polyurethane molecular chain is increased by adopting a chain extension means in the prior art; on the other hand, the micro-phase separation degree of the soft and hard sections of the waterborne polyurethane in the film volatilization process can be reduced, and a waterborne polyurethane material with high toughness can be obtained. In addition, 2 or 4 sulfonic acid ion hydrophilic groups can endow more hydrophilic groups on a polyurethane molecular chain under the condition of lower chain extender consumption, so that the emulsifying property and the long-term stability of polyurethane are ensured, the water resistance of a polyurethane film formed by the aqueous polyurethane dispersion is improved, and the industrial application of the aqueous polyurethane in the fields of leather and high-toughness film products is facilitated.
Detailed Description
The specific embodiment provides a flexible sulfonic acid type hydrophilic chain extender, wherein the molecular structure general formula of the flexible sulfonic acid type hydrophilic chain extender is shown as I:
wherein R is H or CH3(ii) a m is 1 or 2; n is any integer of 1-20; x is 1 or 2.
Further, the flexible sulfonic acid type hydrophilic chain extender is prepared by reacting aldehyde containing sulfonic acid ion groups with ether diamine under an acid catalyst to generate an aldimine intermediate product, and then reducing the aldimine intermediate product by using a reducing agent.
The specific embodiment also provides a preparation method of the flexible sulfonic acid type hydrophilic chain extender, which comprises the steps of reacting aldehyde containing sulfonic acid ion groups with ether diamine under the action of an acid catalyst for 5-6 hours to generate an aldimine intermediate product, and reducing the aldimine intermediate product by a reducing agent for 5-6 hours to obtain the flexible sulfonic acid type hydrophilic chain extender, wherein the molar ratio of the aldehyde containing sulfonic acid ion groups to the ether diamine is 2-2.2: 1; the adding mass of the acidic catalyst is 1-2 wt% of the using amount of the ether diamine; the addition amount of the reducing agent is 3-3.2 times of the molar amount of the ether diamine; the reaction formula is as follows:
wherein R is H or CH3(ii) a m is 1 or 2; n is any integer of 1-20; x is 1 or 2.
Further, the acid catalyst is one or two of p-toluenesulfonic acid and sulfuric acid; and/or the reducing agent is one or more of sodium borohydride, sodium cyanoborohydride, sodium triacetoxyborohydride and lithium aluminum hydride.
In addition, the specific embodiment also provides an application of the flexible sulfonic acid type hydrophilic chain extender or the flexible sulfonic acid type hydrophilic chain extender prepared by the preparation method in the synthesis of the aqueous polyurethane dispersion.
Further, the application includes:
mixing the dehydrated polymer polyol with the molecular weight of 200-10000 and isocyanate in a reactor, and then reacting for 4-10 hours at 50-80 ℃ to obtain a polyurethane prepolymer;
according to the mass usage of the flexible sulfonic acid type hydrophilic chain extender being 3-15 wt% of the polyurethane prepolymer, the polyurethane prepolymer is cooled, then the flexible sulfonic acid type hydrophilic chain extender is added, then the reaction is carried out for 4-6 hours at 50-80 ℃, and then the reaction is carried out for 4-6 hours at room temperature under high-speed shearing and then the aqueous polyurethane dispersion is obtained after the reaction is dispersed in water.
Further, the polymer polyol is polyether polyol and/or polyester polyol; the polyether polyol is one or more of polyethylene glycol, polypropylene glycol and polytetrahydrofuran glycol, and the polyester polyol is one or more of polyhexamethylene adipate glycol, polybutylene adipate glycol, polyethylene adipate glycol, polycaprolactone glycol or polycarbonate glycol; the isocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, naphthalene diisocyanate, xylylene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.
Further, in the above application, the molar ratio of the sum of hydroxyl groups and secondary amino groups to isocyanate groups is 1: 1.
The following detailed description of the preferred embodiments of the invention, which is to be taken in an illustrative rather than a limiting sense, illustrates the principles of the invention.
Example 1
Adding 18.1 g of ether diamine a, 22.9g of sodium benzaldehyde-2-sulfonate, 0.1g of p-toluenesulfonic acid and 50mL of dimethyl sulfoxide into a reaction bottle, and reacting at room temperature for 5 hours under stirring; adding 6.1g of sodium borohydride, and reacting at room temperature for 5 hours; and precipitating the reaction mixed system in acetone for 2 times, washing the obtained solid with a large amount of acetone, and drying in vacuum to obtain the chain extender I-126.5 g.
The reaction formula is as follows:
example 2
Adding ether diamine a-211.1 g, benzaldehyde-4-sodium sulfonate 21.8g, p-toluenesulfonic acid 0.11g and dimethyl sulfoxide 50mL into a reaction bottle, and reacting at room temperature for 5h under stirring; adding 5.9g of sodium borohydride, and reacting at room temperature for 5 hours; and precipitating the reaction mixed system in acetone for 2 times, washing the obtained solid with a large amount of acetone, and drying in vacuum to obtain chain extender I-229.2 g.
The reaction formula is as follows:
example 3
Adding ether diamine a-328.0 g, benzaldehyde-4-sodium sulfonate 2.08g, p-toluenesulfonic acid 0.56g and dimethyl sulfoxide 80mL into a reaction bottle, and reacting at room temperature for 5h under stirring; adding 1.0g of sodium cyanoborohydride, and reacting at room temperature for 5 h; and precipitating the reaction mixed system in acetone for 2 times, washing the obtained solid with a large amount of acetone, and drying in vacuum to obtain the chain extender I-327.2 g.
The reaction formula is as follows:
example 4
Adding ether diamine a-410.2 g, benzaldehyde-2-sodium sulfonate 20.8g, p-toluenesulfonic acid 0.1g and dimethyl sulfoxide 70mL into a reaction bottle, and reacting at room temperature for 5h under stirring; adding 5.7g of sodium borohydride, and reacting at room temperature for 5 hours; and precipitating the reaction mixed system in acetone for 2 times, washing the obtained solid with a large amount of acetone, and drying in vacuum to obtain chain extender I-428.5 g.
The reaction formula is as follows:
example 5
Adding ether diamine a-513.1 g, benzaldehyde-4-disulfonic acid sodium 4.2g, p-toluenesulfonic acid 0.15g and dimethyl sulfoxide 40mL into a reaction bottle, and reacting at room temperature for 5h under stirring; adding 1.2g of sodium borohydride, and reacting at room temperature for 5 hours; and precipitating the reaction mixed system in acetone for 2 times, washing the obtained solid with a large amount of acetone, and drying in vacuum to obtain chain extender I-515.6 g.
The reaction formula is as follows:
example 6
Adding ether diamine a-211.1 g, benzaldehyde-2, 4-disulfonic acid sodium 30.9g, p-toluenesulfonic acid 0.11g and dimethyl sulfoxide 80mL into a reaction bottle, and reacting at room temperature for 5h under stirring; adding 5.7g of sodium borohydride, and reacting at room temperature for 5 hours; and precipitating the reaction mixed system in acetone for 2 times, washing the obtained solid with a large amount of acetone, and drying in vacuum to obtain chain extender I-638.4 g.
The reaction formula is as follows:
example 7
Adding ether diamine a-328.0 g, benzaldehyde-3, 5-disulfonic acid sodium 31.0g, p-toluenesulfonic acid 0.30g and dimethyl sulfoxide 80mL into a reaction bottle, and reacting at room temperature for 5h under stirring; adding 0.6g of sodium borohydride, and reacting for 5 hours at room temperature; and precipitating the reaction mixed system in acetone for 2 times, washing the obtained solid with a large amount of acetone, and drying in vacuum to obtain chain extender I-753.1 g.
The reaction formula is as follows:
example 8
Adding ether diamine a-624.7 g, benzaldehyde-2, 4-disulfonic acid sodium 30.9g, p-toluenesulfonic acid 0.25g and dimethyl sulfoxide 80mL into a reaction bottle, and reacting at room temperature for 5h under stirring; adding 5.7g of sodium borohydride, and reacting for 5 hours at room temperature; and precipitating the reaction mixed system in acetone for 2 times, washing the obtained solid with a large amount of acetone, and drying in vacuum to obtain chain extender I-850.8 g.
The reaction formula is as follows:
application example 1
10g of polyethylene glycol (molecular weight is 1000) is added into a reaction kettle, 1.85g of toluene diisocyanate is added after dehydration, and the reaction is carried out for 4 hours at 50 ℃. And (2) cooling to 40 ℃, adding 0.36g of chain extender of the I-1 polysulfonic acid ionic group, reacting for 6 hours at 50 ℃, cooling to room temperature, and dispersing in water under high-speed shearing to obtain the aqueous polyurethane dispersion, wherein the aqueous polyurethane dispersion is emulsion-shaped, and the solid content can reach 61%.
Application example 2
10g of polypropylene glycol (molecular weight is 200) is added into a reaction kettle, 11.50g of isophorone diisocyanate is added after dehydration, and the reaction lasts for 6h at 60 ℃. And (3) cooling to 40 ℃, adding 3.25g of chain extender of I-5 polysulfonic acid ionic group, reacting for 4h at 80 ℃, cooling to room temperature, and dispersing in water under high-speed shearing to obtain the aqueous polyurethane dispersion, wherein the aqueous polyurethane dispersion is emulsion and has a solid content of 62%.
Application example 3
10g of polypropylene glycol (molecular weight is 10000) is added into a reaction kettle, 0.40g of toluene diisocyanate is added after dehydration, and the reaction lasts 10 hours at 80 ℃. Cooling to 40 ℃, adding 1.0g of chain extender of I-6 polysulfonic acid ionic group, reacting for 5h at 60 ℃, cooling to room temperature, and dispersing in water under high-speed shearing to obtain the aqueous polyurethane dispersion, wherein the aqueous polyurethane dispersion is emulsion-shaped, and the solid content can reach 58%.
Application example 4
10g of polycaprolactone diol (with the molecular weight of 1000) is added into a reaction kettle, 2.43g of isophorone diisocyanate is added after dehydration, and the reaction lasts for 8h at the temperature of 80 ℃. Cooling to 40 ℃, adding 1.0g of chain extender of I-8 polysulfonic acid ionic group, reacting for 6h at 60 ℃, cooling to room temperature, and dispersing in water under high-speed shearing to obtain the aqueous polyurethane dispersion, wherein the aqueous polyurethane dispersion is emulsion-shaped, and the solid content can reach 67%.
Comparative example 1
The difference from application example 2 is that the polysulfonic acid chain extender adopted in the comparative example is a control sample III
The addition amount of the contrast chain extender sample, the types and the use amounts of other raw materials and the synthesis method are the same as those in application example 2, and the synthesized waterborne polyurethane is dispersed in water under high-speed shearing to obtain a waterborne polyurethane dispersion which is emulsion-shaped and has the solid content of 60%.
Comparative example 2
The difference from application example 4 is that the polysulfonic acid chain extender adopted in the comparative example is used as a control sample IV
The addition amount of the control chain extender sample, the kinds and the amounts of other raw materials, and the synthesis method were the same as in application example 4. The synthesized waterborne polyurethane is dispersed in water under high-speed shearing to obtain a waterborne polyurethane dispersion which is emulsion-shaped and has a solid content of 65 percent.
After the prepared polyurethane emulsion is volatilized to form a film, the mechanical properties of the obtained film product are shown in the following table 1.
Table 1 mechanical properties of film products obtained in application examples 1-4, comparative example 1 and comparative example 2
| Sample (I) | Tensile strength/MPa | Elongation at break/% |
| Application example 1 | 11.3 | 975 |
| Application example 2 | 10.1 | 1530 |
| Application example 3 | 9.8 | 1059 |
| Application example 4 | 11.2 | 1650 |
| Comparative example 1 | 12.5 | 482 |
| Comparative example 2 | 10.3 | 491 |
The mechanical property test of the film product shows that the tensile strength of the waterborne polyurethane material prepared by the chain extender taking the flexible ether chain as the skeleton can be equal to that of a reference sample, the elongation at break is far better than that of the waterborne polyurethane material prepared by the reference sample, and the flexible chain extender can effectively improve the toughness of the waterborne polyurethane material.
Other beneficial effects are as follows:
1) the invention is based on secondary amine sulfonate anion chain extender, and increases the ionic strength of hydrophilic ionic group, regulates the aggregation state of ionic charge on the polyurethane molecular chain and reduces the proportion of hydrophilic chain segment in the polyurethane molecular chain by increasing the number of bonding ionic groups on the chain extender and utilizing the increase of charge density caused by the combined action of multiple sulfonate ionic groups. Meanwhile, the flexible ether chain structure of the chain extender is also beneficial to the compatibility among polyurethane molecular chains and the space mobility of hydrophilic groups. The chain extenders have the essential characteristics that more hydrophilic groups can be endowed on a polyurethane molecular chain under the condition of lower chain extender consumption when the waterborne polyurethane is synthesized, the dispersibility and long-term stability of the polyurethane in water are ensured, the water resistance of a polyurethane film formed by the waterborne polyurethane dispersion is improved, and the industrial application of the waterborne polyurethane is facilitated; in addition, the number of sulfonic acid ion groups on the chain extender is increased, so that the surface charge of micelles in the aqueous polyurethane emulsion can be increased to a certain extent, and the solid content of the emulsion can be improved.
2) The chain extender synthesized by the invention takes the flexible ether chain as the skeleton, and when the water-based polyurethane is prepared by using the chain extender, on one hand, the skeleton structure of the flexible ether chain can weaken the risk of reducing the flexibility of a polyurethane molecular chain caused by the formation of a urea bond, and the problem of reducing the toughness of a polyurethane material caused by increasing the proportion of hard segments in the polyurethane molecular chain by adopting a chain extension means in the prior art can be effectively solved; on the other hand, the micro-phase separation degree of the soft and hard sections of the waterborne polyurethane in the volatilization film forming process can be reduced, so that a waterborne polyurethane material with high toughness can be obtained, and the industrial application of the waterborne polyurethane in the fields of leather and high-toughness film products is facilitated.
3) The invention adopts the conventional organic synthesis means to synthesize the chain extender for the waterborne polyurethane with two or four sulfonic acid ion groups; the synthesis method is simple and efficient, and the raw materials and reagents used in the reaction process are cheap and easy to obtain, so that the amplification of the operation process is easy, and the industrial production is realized.
4) The invention takes the number of ionic groups contained in the hydrophilic chain extender for the waterborne polyurethane as a breakthrough, is expected to break through the technical bottleneck that the excellent dispersibility and good water resistance of the current waterborne polyurethane are difficult to balance and unify, and simultaneously provides a new way for synthesizing the waterborne polyurethane material based on the hydrophilic chain extender.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (9)
1. The flexible sulfonic acid type hydrophilic chain extender is characterized in that the molecular structure general formula of the flexible sulfonic acid type hydrophilic chain extender is shown as I:
wherein R is H or CH3(ii) a m is 1 or 2; n is any integer of 1-20; x is 1 or 2;
the flexible sulfonic acid type hydrophilic chain extender is prepared by reacting aldehyde containing sulfonic acid ion groups with ether diamine under an acid catalyst to generate an aldimine intermediate product, and then reducing the aldimine intermediate product by using a reducing agent.
2. A preparation method of the flexible sulfonic acid type hydrophilic chain extender of claim 1, which is characterized in that aldehyde containing sulfonic acid ion groups reacts with ether diamine under the action of an acid catalyst to generate an aldimine intermediate product, and then the aldimine intermediate product is reduced by a reducing agent to prepare the flexible sulfonic acid type hydrophilic chain extender, wherein the reaction formula is as follows:
wherein R is H or CH3(ii) a m is 1 or 2; n is any integer of 1-20; x is 1 or 2.
3. The method according to claim 2, wherein the molar ratio of the aldehyde having a sulfonic acid ion group to the ether diamine is 2 to 2.2: 1.
4. The method according to claim 2, wherein the acidic catalyst is added in an amount of 1 to 2 wt% based on the amount of the etherdiamine.
5. The method according to claim 2, wherein the reducing agent is added in an amount of 3 to 3.2 times the molar amount of the ether diamine.
6. The production method according to claim 2, wherein the acidic catalyst is one or both of p-toluenesulfonic acid and sulfuric acid; and/or the reducing agent is one or more of sodium borohydride, sodium cyanoborohydride, sodium triacetoxyborohydride and lithium aluminum hydride.
7. Use of the flexible sulfonic acid type hydrophilic chain extender of claim 1 or the flexible sulfonic acid type hydrophilic chain extender prepared by the preparation method of any one of claims 2 to 6 in synthetic aqueous polyurethane dispersions.
8. The use according to claim 7, comprising:
mixing polymer polyol with isocyanate, and reacting at 50-80 ℃ to obtain a polyurethane prepolymer;
and mixing the polyurethane prepolymer with the flexible sulfonic acid type hydrophilic chain extender, reacting at 50-80 ℃, and dispersing in water to obtain the aqueous polyurethane dispersion.
9. The application of the polyurethane prepolymer as claimed in claim 8, wherein the polyurethane prepolymer and the flexible sulfonic acid type hydrophilic chain extender are mixed according to the mass usage of the flexible sulfonic acid type hydrophilic chain extender being 3-15 wt% of the polyurethane prepolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011295246.8A CN112300353B (en) | 2020-11-18 | 2020-11-18 | Flexible sulfonic acid type hydrophilic chain extender and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011295246.8A CN112300353B (en) | 2020-11-18 | 2020-11-18 | Flexible sulfonic acid type hydrophilic chain extender and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112300353A CN112300353A (en) | 2021-02-02 |
| CN112300353B true CN112300353B (en) | 2022-06-07 |
Family
ID=74336177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011295246.8A Active CN112300353B (en) | 2020-11-18 | 2020-11-18 | Flexible sulfonic acid type hydrophilic chain extender and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112300353B (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015166442A (en) * | 2013-12-26 | 2015-09-24 | 三洋化成工業株式会社 | Active hydrogen compound having sulfonic acid (salt) group and polyurethane resin using the same |
| CN109896982A (en) * | 2017-12-08 | 2019-06-18 | 中国科学院青岛生物能源与过程研究所 | The preparation method of aqueous polyurethane chain extender containing more azochlorosulfonate acid ion groups |
| CN110938186A (en) * | 2019-10-24 | 2020-03-31 | 江汉大学 | High-solid-content polyurethane emulsion and preparation method thereof |
-
2020
- 2020-11-18 CN CN202011295246.8A patent/CN112300353B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112300353A (en) | 2021-02-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106800632B (en) | Preparation method of high-solid-content aqueous polyurethane emulsion | |
| CN104628982B (en) | A kind of preparation method of alkali lignin base water polyurethane | |
| US5496908A (en) | Water-soluble polyurethane and use thereof to thicken water-based systems such as water-based paints | |
| WO2021077793A1 (en) | High-solid-content polyurethane emulsion and preparation method therefor | |
| CN108330712B (en) | Poly (carbonate-ether) type polyurethane emulsion for printing adhesive cement and preparation method thereof | |
| CN108003313B (en) | Block type polycarbodiimide water-based cross-linking agent and preparation method thereof | |
| CN112409564A (en) | Non-desolventizing water-based nonionic polyurethane and preparation method thereof | |
| CN112300353B (en) | Flexible sulfonic acid type hydrophilic chain extender and preparation method and application thereof | |
| CN111019078A (en) | Waterborne polyurethane curing agent and preparation method and application thereof | |
| JP4421490B2 (en) | Aqueous polyurethane resin composition and method for producing the same | |
| CN104745009A (en) | Pigment dispersant composition containing lignin structure and preparation method thereof | |
| DE3713858A1 (en) | AROMATIC POLYAMINE, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR THE PRODUCTION OF POLYURETHANE PLASTICS | |
| CN112708102B (en) | Synthesis of waterborne polyurethane dispersion containing quadruple hydrogen bonds based on ureido triazine structure and preparation method thereof | |
| CN113956418A (en) | Anionic solvent-free aqueous polyurethane resin and preparation method and application thereof | |
| CN114945615A (en) | Polyaziridine compounds | |
| CN104592469A (en) | Anionic polyurethane aqueous dispersion, prepolymer monomer and preparation process thereof | |
| CN109651582B (en) | Waterborne polyurethane ink binder and preparation method thereof | |
| WO2020073155A1 (en) | Aqueous polyurethane dispersions for artificial leather applications | |
| CN113549187B (en) | Aqueous polyurethane for microfiber leather and preparation method thereof | |
| CN104211898A (en) | Amino-terminated aqueous polyurethane dispersion and preparation method thereof | |
| CN112500548A (en) | Waterborne polyurethane-polyurea and preparation method thereof | |
| CN114671996A (en) | Polyurethane epoxy toughening agent and epoxy resin composition composed of same | |
| CN112321798A (en) | Hydrophilic chain extender containing polysulfonic acid ion groups and preparation method and application thereof | |
| CN107266641A (en) | A kind of environment-friendly water-based polyurethane resin based on degradable biological base class and preparation method thereof | |
| CN112409557A (en) | Vegetable oil-based polyurethane film and preparation 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 |