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CN114806489B - Water-based polyurethane binder and preparation method and application thereof - Google Patents

Water-based polyurethane binder and preparation method and application thereof Download PDF

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CN114806489B
CN114806489B CN202210551451.9A CN202210551451A CN114806489B CN 114806489 B CN114806489 B CN 114806489B CN 202210551451 A CN202210551451 A CN 202210551451A CN 114806489 B CN114806489 B CN 114806489B
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aqueous polyurethane
polyurethane binder
diisocyanate
sulfonate
preparation
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CN114806489A (en
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欧华新
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Guangdong Xinhui Chemical Co ltd
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Guangdong Xinhui Chemical Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—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
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    • C08G18/30—Low-molecular-weight compounds
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    • C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • 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
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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    • C08G2170/00—Compositions for adhesives
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a waterborne polyurethane binder, and a preparation method and application thereof. The invention provides a waterborne polyurethane binder, which is prepared from the following raw materials in parts by weight: 100 parts of aromatic diisocyanate; 70-80 parts of aliphatic diisocyanate; 150-200 parts of sulfonate dihydric alcohol; 4-20 parts of polyol; 1-5 parts of fluorine-containing monomer; 15-25 parts of chain extender; 0.1-3 parts of molecular weight regulator; the chain extender comprises at least one of acrylic acid monoglyceride and sodium bis (hydroxymethyl) propionate; the sulfonate glycol has a number average molecular weight of 300 to 2000. The waterborne polyurethane binder provided by the invention optimizes the curing speed and yellowing resistance. The invention also provides a preparation method and application of the aqueous polyurethane binder.

Description

Water-based polyurethane binder and preparation method and application thereof
Technical Field
The invention belongs to the technical field of aqueous polyurethane binders, and particularly relates to an aqueous polyurethane binder, a preparation method and application thereof.
Background
The polyurethane can be obtained by the reaction of isocyanate and polyol, and the polyurethane binder is polyurethane with binding property, and the polyurethane binder contains carbamate groups (-NHCOO-) or isocyanate groups (-NCO) on the molecular chain, shows high activity and polarity, and has excellent chemical binding force with porous materials such as foam, plastic, wood, leather, fabric, paper, ceramic and the like, and materials with smooth surfaces such as metal, glass, rubber, plastic and the like. The method is widely applied to the preparation process of shoe bags, plastic tracks and the like.
Polyurethane binders can be classified into aqueous polyurethane binders and solvent polyurethane binders according to the dispersion system. The content of volatile organic compounds in the aqueous polyurethane binder is low, the pollution to the environment is less, and the harm to manufacturers and users is very low, so that the aqueous polyurethane binder is a current research and application trend.
However, the aqueous polyurethane binder has the performance problems of low curing speed, poor water resistance, poor mechanical property, poor high temperature resistance and the like. The range of use is thus greatly limited.
Since aromatic diisocyanates are significantly more reactive than aliphatic diisocyanates, there have been attempts to prepare aqueous isocyanate adhesives using aromatic diisocyanates (e.g., TDI) in order to increase the curing rate of aqueous polyurethane adhesives. Thus, the three problems are faced, the reactivity of the aromatic diisocyanate and water is high, side reactions are easy to occur in the preparation and use processes of the adhesive, and carbon dioxide gas generated at the same time affects the use of the aqueous polyurethane adhesive after curing. Secondly, the reaction speed of the aromatic diisocyanate is high, the molecular weight uniformity of the obtained polyurethane is poor, and most importantly, the yellowing resistance of the aqueous polyurethane adhesive prepared from the aromatic diisocyanate is poor.
In summary, it is difficult to balance the curing speed and yellowing resistance of the existing aqueous polyurethane adhesive.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides the waterborne polyurethane adhesive, which optimizes the curing speed without losing the yellowing resistance.
The invention also provides a preparation method of the aqueous polyurethane binder.
The invention also provides application of the aqueous polyurethane binder.
According to one aspect of the invention, an aqueous polyurethane binder is provided, and the aqueous polyurethane binder is prepared from the following raw materials in parts by weight:
Figure BDA0003655131960000021
the chain extender comprises at least one of monoglyceride acrylate (CAS: 5919-74-4) and sodium bis (hydroxymethyl) propionate;
the sulfonate glycol has a number average molecular weight of 300 to 2000.
According to the invention, the preferable aqueous polyurethane binder has at least the following beneficial effects:
(1) The preparation raw materials adopted by the invention comprise fluorine-containing monomers with certain hydrophobic performance, so that after the aqueous polyurethane binder is solidified, the water resistance of the adhesive film is improved;
as is clear from the raw materials for preparation, the aqueous polyurethane adhesive contains at least an acrylic acid chain segment (provided by acrylic acid monoglyceride and sodium bis-methylol propionate) and a fluorine-containing chain segment (provided by a fluorine-containing monomer). Because of the polarity difference between the two chain segments and other chain segments, the acrylic acid chain segments and the fluorine-containing chain segments tend to migrate to the surface in the curing process of the aqueous polyurethane adhesive, and the film formed by the acrylic acid chain segments is more compact, which is equivalent to the compact protective film formed on the surface of the cured adhesive film, so that the entry of water vapor is prevented, and the water resistance of the aqueous polyurethane adhesive is improved.
That is, a synergistic effect occurs between the fluorine-containing monomer and the special chain extender, and the water resistance of the obtained aqueous polyurethane binder is improved.
In addition, the acrylic chain segment and the fluorocarbon chain segment brought by the fluorine-containing monomer have stronger yellowing resistance. After the chain segments migrate to the surface, the chain segments play a role in protecting aromatic urethane generated by aromatic diisocyanate, and the yellowing resistance is improved.
(2) Through the coordination effect between the molecular weight regulator and other preparation raw materials, the molecular weight distribution of the obtained aqueous polyurethane binder is narrower, and the dispersibility is better. Meanwhile, due to the fact that aromatic diisocyanate is introduced, the curing speed of the obtained aqueous polyurethane adhesive is higher.
(3) The preparation raw material provided by the invention comprises 150-200 parts of sulfonate dihydric alcohol, and enough sulfonate is provided, so that the obtained aqueous polyurethane binder has good dispersibility in water. In addition, the sulfonate dihydric alcohol is adopted, compared with the traditional sulfonate dihydric alcohol, the acidity is reduced, therefore, no neutralizing agent is required to be additionally added in the actual use process, and further, the side reaction of the neutralizing agent (mostly amine neutralizing agent) and the aromatic diisocyanate in the traditional technology is avoided, so that the side reaction of the obtained aqueous polyurethane adhesive in the preparation and curing processes is less.
The molecular weight of sulfonate dihydric alcohol can influence the chain length of a soft segment in the molecular chain of the obtained aqueous polyurethane binder, and the chain length of the soft segment has a certain positive correlation with the flexibility of the obtained aqueous polyurethane binder and a certain inverse correlation with heat resistance. In the number average molecular weight range of 300-2000, the obtained aqueous polyurethane adhesive has proper flexibility and heat resistance.
(4) The specific proportion of the aromatic diisocyanate and the aliphatic diisocyanate balances the curing speed of the aqueous diisocyanate adhesive.
In some embodiments of the invention, the aromatic diisocyanate comprises at least one of Toluene Diisocyanate (TDI) and diphenylmethane diisocyanate (MDI, CAS: 101-68-8). The two types of aromatic diisocyanate have wide sources, and the two preparation raw materials are selected, so that the industrial production of the aqueous polyurethane binder is facilitated.
In some embodiments of the invention, the toluene diisocyanate comprises at least one of 2, 4-toluene diisocyanate (2, 4-TDI, CAS: 584-84-9) and 2, 6-toluene diisocyanate (2, 6-TDI, CAS: 91-08-7).
In some preferred embodiments of the present invention, the weight ratio of 2,4-TDI to 2,6-TDI in the aromatic diisocyanate is 75 to 85:20.
In some further preferred embodiments of the present invention, the weight ratio of 2,4-TDI to 2,6-TDI in the aromatic diisocyanate is about 4:1.
In some embodiments of the present invention, the aliphatic diisocyanate comprises at least one of isophorone diisocyanate (IPDI, CAS: 4098-71-9) and hexamethylene diisocyanate (HDI, CAS: 822-06-0).
In some embodiments of the invention, the aliphatic diisocyanate consists of IPDI and HDI.
Among them, IPDI has a low reactivity, but has excellent yellowing resistance, and after it is blended with other types of isocyanate, the obtained aqueous polyurethane adhesive has more excellent yellowing resistance.
In some embodiments of the invention, the weight ratio of the IPDI to the HDI in the aliphatic diisocyanate is 3:1-4.
In some preferred embodiments of the invention, the weight ratio of IPDI to HDI in the aliphatic diisocyanate is 3:1-2.
In some embodiments of the invention, the sulfonate glycol is the esterification product of a glycol and a dicarboxyl sulfonate. Thus, sulfonate groups can be introduced into the sulfonate glycol, further into the molecular chain of the aqueous polyurethane binder, and the hydrophilicity (dispersibility in water) of the resulting aqueous polyurethane binder can be improved.
In some embodiments of the invention, the glycol comprises 3-methyl-1, 5-pentanediol (CAS: 4457-71-0), neopentyl glycol (CAS: 126-30-7), ethylene glycol (CAS: 107-21-1), cyclohexanediol (CAS: 1460-57-7), methylpropanediol (CAS: 2163-42-0), 1, 3-propanediol (CAS: 504-63-2), 1, 4-dimethylolcyclohexane (CAS: 105-08-8), 1, 4-butanediol (CAS: 110-63-4), 1, 3-butanediol (CAS: 107-88-0), 1, 5-pentanediol (CAS: 111-29-5), diethylpentanediol (CAS: 57987-55-0), 1, 2-propanediol (CAS: 57-55-6), diethylene glycol (CAS: 111-46-6), tetrahydrofurandiol (CAS: 25190-06-1), 1, 6-hexanediol (CAS: 629-11-8), trimethylpentanediol (CAS: 19-8), butylpropanediol (CAS: 35-80), and dipropylene glycol (CAS: 35-80-35-80) At least one of tripropylene glycol (CAS: 24800-44-0) and ethylhexyl glycol (CAS: 29656-68-6).
In some preferred embodiments of the present invention, the glycol comprises at least one of 3-methyl-1, 5-pentanediol, neopentyl glycol, 1, 5-pentanediol, diethylpentanediol, 1, 6-hexanediol, trimethylpentanediol, and ethylhexanediol.
Thus, the molecular chain length of the diol is longer, the number of molecules of the diol required for obtaining the sulfonate diol with the same molecular weight is smaller than that of ethylene glycol and the like, further, the number of ester groups in the sulfonate diol is smaller, the ester groups are easy to hydrolyze under the conditions of high temperature and high humidity, and the density of the ester groups has a certain inverse relation with the water resistance and the heat resistance of the aqueous polyurethane adhesive. That is, the water resistance and heat resistance of the aqueous polyurethane binder are improved by selecting the kind of glycol from which the sulfonate glycol is prepared.
Further, compared with a branched chain or a main chain of a cyclic diol such as benzene ring, the flexibility of the obtained aqueous polyurethane adhesive can be further improved.
In some preferred embodiments of the present invention, the glycol consists of 1, 6-hexanediol and 3-methyl-1, 5-pentanediol.
In some preferred embodiments of the present invention, the weight ratio of the 1, 6-hexanediol to 3-methyl-1, 5-pentanediol in the glycol is 1:0.8-1.2.
In some preferred embodiments of the present invention, the weight ratio of 1, 6-hexanediol to 3-methyl-1, 5-pentanediol in the glycol is about 1:1.
In some embodiments of the invention, the dicarboxy sulfonate comprises sodium isophthalic acid-5-sulfonate (CAS: 6362-79-4).
In some embodiments of the invention, the sulfonate glycol preparation feedstock further comprises a diacid. Thus, the molecular weight, stability and uniformity of molecular weight distribution of the obtained sulfonate glycol can be improved.
In some embodiments of the invention, the dibasic acid comprises at least one of sebacic acid (CAS: 111-20-6), succinic acid (CAS: 110-15-6), and glutaric acid (CAS: 110-94-1).
In some embodiments of the present invention, the molar ratio of diol, dicarboxyl sulfonate, and diacid in the starting materials for the preparation of the sulfonate diol is 2-2.5:0.8-1.2:0.8-1.2.
Wherein the amount of the diol is greater than the sum of the amounts of the dicarboxylic sulfonate and diacid, thereby promoting the dicarboxylic sulfonate and diacid to react as completely as possible.
In some embodiments of the invention, the sulfonate glycol is used in an amount of 175 to 195 parts by weight.
In some embodiments of the invention, the sulfonate glycol has a number average molecular weight of 500 to 1200 in parts by weight.
In some embodiments of the invention, the polyol comprises a polyol having a functionality of 3 or greater.
In some embodiments of the invention, the polyol comprises at least one of a triol and a tetraol.
In some embodiments of the invention, the polyol includes at least one of pentaerythritol (CAS: 115-77-5), trimethylolpropane (CAS: 77-99-6), and glycerol (CAS: 56-81-5).
In some preferred embodiments of the invention, the polyol consists of pentaerythritol and trimethylolpropane.
In some preferred embodiments of the present invention, the weight ratio of pentaerythritol to trimethylolpropane in the polyol is from 1:1 to 1.5.
In some embodiments of the present invention, the fluoromonomer comprises 2,3, 4, 5-octafluoro-1, 6-hexanediol (octafluoro-1, 6-hexanediol, CAS: 355-74-8), 2,3, 4-heptafluoro-1-butanol (abbreviated as perfluorobutanol, CAS: 375-01-9) and 1, 2-tetrahydroperfluoro-1-decanol (abbreviated as 2-perfluorooctylethanol, CAS: 678-39-7). The fluorine-containing monomers have high fluorine content and moderate molecular chain length, and are beneficial to migration of fluorine-containing chain segments to the surface.
In some preferred embodiments of the present invention, the fluoromonomer consists of octafluoro-1, 6-hexanediol, perfluorobutanol, and 2-perfluorooctylethanol.
In some preferred embodiments of the present invention, the mass ratio of the octafluoro-1, 6-hexanediol, perfluorobutanol, and 2-perfluorooctyl ethanol in the fluoromonomer is 1:0.8-1.2:0.8-1.2.
In some preferred embodiments of the present invention, the mass ratio of octafluoro-1, 6-hexanediol, perfluorobutanol, and 2-perfluorooctyl ethanol in the fluoromonomer is about 1:1:1.
In some embodiments of the present invention, the sodium bis-methylol propionate is the product of a reaction of bis-methylol propionic acid (CAS: 4767-03-7) and sodium hydroxide in a molar ratio of about 1:1.
In some embodiments of the invention, the chain extender further comprises at least one of an amine chain extender and an alcohol chain extender.
In some preferred embodiments of the invention, the chain extender further comprises an alcohol chain extender.
As the isocyanate radical in the aromatic diisocyanate has stronger reactivity with amine substances, the chain extender is selected from alcohol chain extenders in order to reduce side reactions as much as possible.
In some embodiments of the invention, the alcohol chain extender comprises at least one of ethylene glycol, propylene glycol, and 1, 4-butanediol.
In some embodiments of the invention, the weight ratio of the alcohol chain extender to the monoglyceride acrylate is 1:1-2.
In some embodiments of the invention, the weight ratio of the monoglyceride to sodium dimethylolpropionate in the chain extender is 1:1-2.
In some embodiments of the invention, the molecular weight regulator includes at least one of t-dodecyl mercaptan (CAS: 25103-58-6), n-dodecyl mercaptan (CAS: 7773-83-3) and 1, 3-propane sultone (CAS: 1120-71-4).
In some embodiments of the invention, the molecular weight regulator consists of 1, 3-propane sultone and n-dodecyl mercaptan.
In some embodiments of the invention, the weight ratio of the 1, 3-propane sultone to n-dodecyl mercaptan in the molecular weight regulator is 1:1 to 1.5.
In some embodiments of the present invention, the aqueous polyurethane binder is prepared from a raw material further comprising an organic solvent.
In some embodiments of the present invention, the organic solvent is added in an amount of 50 to 80 parts by weight.
In some preferred embodiments of the present invention, the organic solvent is added in an amount of 55 to 80 parts by weight.
In some embodiments of the present invention, the organic solvent includes at least one of acetone, ethyl acetate, and butyl acetate (CAS: 123-86-4). Therefore, the used organic solvent can be compatible with water to a certain extent, and provides a basis for the subsequent preparation of the aqueous polyurethane adhesive (dispersion in water).
In some embodiments of the invention, the aqueous polyurethane binder is prepared from a raw material further comprising a catalyst.
In some embodiments of the invention, the catalyst comprises at least one of tetramethyl ammonium bromide (CAS: 64-20-0) and triethyl benzyl ammonium chloride (CAS: 56-37-1).
In some embodiments of the invention, the catalyst is added in an amount of 0.1 to 1 part by weight.
In some embodiments of the invention, the aqueous polyurethane binder is prepared from a raw material that also includes water.
The water in the preparation raw materials has the function of adjusting the solid content of the aqueous polyurethane binder.
In some embodiments of the invention, the aqueous polyurethane binder has a solids content of 55 to 75wt%.
In some preferred embodiments of the present invention, the aqueous polyurethane binder has a solids content of 58 to 60wt%.
In some preferred embodiments of the present invention, the raw materials for preparing the aqueous polyurethane binder further include an auxiliary agent.
In some embodiments of the invention, the auxiliary agent comprises at least one of a thickener, a filler, a pigment, a leveling agent, and an antioxidant.
The auxiliary agent can optimize performances such as appearance and the like of the aqueous polyurethane adhesive to a certain extent, but has little influence on essential performances such as cohesiveness, water resistance and the like, and can be selectively added according to actual production requirements by a person skilled in the art.
According to a second aspect of the present invention, there is provided a method for preparing the aqueous polyurethane binder, comprising the steps of:
s1, mixing and reacting the aromatic diisocyanate and part of the sulfonate dihydric alcohol;
s2, mixing the mixture obtained in the step S1, the aliphatic diisocyanate and the rest sulfonate dihydric alcohol for reaction;
s3, reacting the polyol with the mixture obtained in the step S2 under the action of the molecular weight regulator;
s4, sequentially reacting the mixture obtained in the step S3 with the chain extender and the fluorine-containing monomer.
The preparation method provided by the invention has the following mechanism:
in the step S1, the aromatic diisocyanate reacts with part of sulfonate dihydric alcohol to consume part of isocyanate, for example, the two isocyanate groups in TDI have larger activity difference, and the step can consume the isocyanate groups with larger activity;
in step S2, adding aliphatic diisocyanate and the rest sulfonate dihydric alcohol; because the concentration and activity of isocyanate groups in the aromatic diisocyanate are reduced in the step S1, the newly added sulfonate glycol, the aromatic diisocyanate and the aliphatic diisocyanate may be copolymerized in the step S2, and the generated isocyanate prepolymer simultaneously comprises an aromatic diisocyanate segment, a sulfonate glycol segment and an aliphatic diisocyanate segment; and the implementation sequence of the step S1 and the step S2 can be known, at least a part of sulfonate chain segments are positioned in the middle of the water-based polyurethane binder molecules, so that the water dispersibility is high.
In step S3, the polyol further reduces the free isocyanate content in the isocyanate prepolymer and simultaneously provides a certain crosslinking density; the mechanical property of the obtained aqueous polyurethane adhesive is improved; meanwhile, the isocyanate prepolymer obtained in the step S2 contains aromatic diisocyanate and aliphatic diisocyanate, so that the reaction probability of each isocyanate prepolymer and the polyol is similar, and the molecular weight distribution of the product obtained in the step is relatively average; and also provides a basis for obtaining the waterborne polyurethane adhesive with average molecular weight.
In the step, the polyol reacts with the isocyanate prepolymer obtained in the step S2, and the generated substance has both a hydrophilic chain segment and a hydrophobic chain segment; in the reaction process, the molecular chain is entangled and folded, so that the situation that hydrophilic groups (sulfonate groups) face to the organic solvent and hydrophobic groups (isocyanate groups) are wrapped by the molecular chain is formed. This is equivalent to protecting isocyanate groups in aromatic diisocyanates.
Meanwhile, the polyurethane prepared from the aromatic diisocyanate is easy to generate yellowing because aromatic amine and benzene ring generated by decomposing aromatic urethane after ultraviolet irradiation are subjected to resonance rearrangement; in the preparation method provided by the invention, the chain segment which is easy to decompose is just protected by folding the molecular chain, so that the chain segment with strong ultraviolet resistance is irradiated. Therefore, the yellowing resistance of the obtained aqueous polyurethane adhesive is improved.
In this step, the molecular weight regulator also serves as a chain transfer agent to regulate the reaction probability of isocyanate groups and polyols of different activities, thereby playing a role in regulating molecular weight. On the other hand, as the oily substance, the intermediate product containing isocyanate groups is wrapped to some extent, and the side reaction of isocyanate groups is further suppressed. Finally, the aqueous polyurethane adhesive with high curing speed and less side reaction can be obtained.
In step S4, chain extension and crosslinking reactions are performed, and meanwhile, due to the influence of the addition sequence, the fluorine-containing monomer tends to be introduced into the end part of the aqueous polyurethane binder, so that the migration of the acrylic acid chain segment and the fluorine-containing chain segment in the chain extender is less limited, and the water resistance is more beneficial to be exerted.
In some preferred embodiments of the invention, the preparation method has at least the following beneficial effects:
the preparation method provided by the invention is simple to operate and easy for industrial production.
Through the step sequence and the adjustment of the feeding sequence, the comprehensive properties of yellowing resistance, water resistance and the like of the obtained aqueous polyurethane adhesive can be improved to a certain extent.
In some embodiments of the invention, in step S1, the temperature of the mixing reaction is 70 to 90 ℃. The reactivity difference of different aromatic diisocyanates at normal temperature is large, but when the temperature is raised to more than 70 ℃, the difference is reduced, so that the rate of the mixing reaction is moderate, and the aqueous isocyanate binder with uniform molecular weight is more favorable to be obtained.
In some embodiments of the invention, in step S1, the duration of the mixing reaction is 3 to 4 hours.
In some embodiments of the invention, in step S1, the mixing reaction is performed in the organic solvent.
In some embodiments of the invention, in step S1, the mixing reaction is performed under air-insulated conditions; the gas replacement and protection can be specifically performed by nitrogen or inert gas.
The reason for the isolation of air is that the aromatic diisocyanate has higher activity of side reaction with water, etc., while in step S1, the isocyanate groups thereon are not protected yet, the activity is higher, and the isolation of air can reduce the probability of side reaction of the aromatic diisocyanate.
In some embodiments of the present invention, the mass ratio of the part in step S1 to the remainder in step S2 is 1:0.25-0.35.
In some preferred embodiments of the present invention, the mass ratio of the part in step S1 to the remainder in step S2 is 1:0.3. Within this ratio range, the reaction probabilities of the aromatic diisocyanate and the aliphatic diisocyanate with the sulfonate diol are adjusted, the molecular weight distribution of the obtained isocyanate prepolymer is more concentrated, and the consistency and the cohesiveness of the obtained aqueous polyurethane binder are higher.
In some embodiments of the invention, in step S2, the temperature of the mixing reaction is 40 to 60 ℃.
In some embodiments of the invention, in step S2, the duration of the mixing reaction is 1-2 hours.
In some embodiments of the present invention, in step S3, the method of adding the molecular weight regulator and the polyol is: after dissolving the molecular weight regulator into the polyol, it is added dropwise to the mixture obtained in step S2. Therefore, the dispersion uniformity of the molecular weight regulator can be improved, and the molecular weight regulator is more beneficial to play a role.
In some embodiments of the invention, the rate of addition is 1 to 2mL/min.
In some embodiments of the present invention, the mixture obtained in step S2 is stirred simultaneously during the dropping, and the stirring speed is 150 to 400rpm. At this speed, the homogenization speed can be increased, and also the breaking of the molecular chain of the resulting intermediate product can be avoided.
In some preferred embodiments of the present invention, the stirring speed is 180 to 200rpm.
In some embodiments of the invention, in step S3, the temperature of the reaction is 70-90 ℃.
In some embodiments of the invention, in step S3, the duration of the reaction is between 0.5 and 4 hours.
In some preferred embodiments of the invention, in step S3, the duration of the reaction is 1.5 to 2.5 hours.
Under the conditions of the temperature and the time, the folding and winding actions of the molecular chain of the obtained intermediate product are more sufficient, so that better yellowing resistance can be obtained, and the protection action on isocyanate groups in aromatic diisocyanate is also more sufficient.
In some embodiments of the invention, in step S4, the temperature of the reaction is 70-90 ℃.
In some embodiments of the invention, in step S4, the duration of the reaction is 1 to 3 hours.
In some embodiments of the invention, in step S4, the starting materials for the reaction further comprise the catalyst.
Due to the protection of isocyanate groups in step S3, the probability of side reactions is not increased even if a catalyst is added in step S4.
In some embodiments of the present invention, the method for preparing an aqueous polyurethane binder further includes diluting with water and evaporating after step S4.
In some embodiments of the invention, the water dilution and evaporation comprises stirring; the stirring speed is 300-800 rpm.
In some preferred embodiments of the invention, the water dilution and evaporation comprises stirring; the stirring speed is 500-600 rpm.
In some embodiments of the invention, the dilution with water and evaporation comprises: adjusting viscosity, removing organic solvent added in the preparation process, and shearing and emulsifying.
In some embodiments of the invention, the dilution with water and evaporation temperature is 50-60 ℃.
According to a third aspect of the invention, the use of the aqueous polyurethane adhesive for the preparation of plastic tracks and shoes is proposed.
The aqueous polyurethane binder provided by the invention has relatively excellent binding property, curing speed, water resistance, heat resistance and compatibility, so that when the aqueous polyurethane binder is used for preparing plastic tracks and shoes, the preparation period can be remarkably reduced, the service period can be prolonged, and the service environment (high-humidity environment) can be widened.
The term "about" in the present invention means that the allowable error is within + -2% unless otherwise specified.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
Example 1
The embodiment prepares the aqueous polyurethane binder, which comprises the following specific processes:
s1, mixing and reacting aromatic diisocyanate and partial sulfonate dihydric alcohol for 3 hours under the atmosphere of 80 ℃ and nitrogen protection;
s2, mixing and reacting the mixture obtained in the step S1, aliphatic diisocyanate and residual sulfonate dihydric alcohol for 1h at 50 ℃; the mass ratio of the sulfonate dihydric alcohol used in the step and the step S1 is 0.3:1;
s3, after mixing the molecular weight regulator and the polyol at the temperature of 75 ℃, dropwise adding the mixture obtained in the step S2 at the speed of 1mL/min, and stirring the mixture obtained in the step S2 at the speed of 200 rpm; after the dripping is completed, continuing to react for 2 hours;
s4, sequentially adding a catalyst, a chain extender and a fluorine-containing monomer into the mixture obtained in the step S3 at the temperature of 75 ℃, and continuing to react for 1h after the addition is completed;
s5, adding water into the mixture obtained in the step S4 at 55 ℃, and stirring and evaporating the organic solvent at a rotation speed of 500 rpm.
The information on the raw materials used in the preparation of this example is shown in Table 1.
Example 2
The specific process of the aqueous polyurethane binder prepared in this example differs from that of example 1 in that:
the preparation materials are different, and the specific preparation materials are shown in table 1.
Comparative examples 1 to 3 each prepared an aqueous polyurethane binder, and the specific procedure was different from example 1 in that:
the preparation materials are different, and the specific preparation materials are shown in table 1.
Comparative example 4
This comparative example produced an aqueous polyurethane binder, which differs from example 1 in that:
in step S1, all of the sulfonate glycol is added.
Comparative example 5
This comparative example produced an aqueous polyurethane binder, which differs from example 1 in that:
(1) The preparation raw materials do not comprise polyhydric alcohol;
(2) The specific operation of step S3 is: after mixing the molecular weight regulator and the organic solvent (see example for specific proportions, equal amounts of polyol used in the example) at 75 ℃, the mixture was added dropwise to the mixture obtained in step S2 at a rate of 1mL/min, during which the mixture obtained in step S2 was stirred at a speed of 200 rpm; after the completion of the dropwise addition, the reaction was continued for 2 hours.
Table 1 examples 1 to 2 and comparative examples 1 to 3 were prepared as raw materials (parts by weight)
Figure BDA0003655131960000131
Figure BDA0003655131960000141
If not specified, the sulfonate glycol of Table 1 was prepared by the following method: and (3) mixing 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, isophthalic acid-5-sodium sulfonate and sebacic acid in water according to a molar ratio of 1:1.2:1.2:0.8, performing esterification reaction, stopping the reaction when the number average molecular weight is monitored to be about 900, and distilling to remove unreacted complete diol, diacid and water to obtain the aqueous emulsion with the solid content of 99.9 weight percent.
Test examples
This test example tests the properties of the aqueous polyurethane binders prepared in examples 1 to 2 and comparative examples 1 to 5. Wherein:
the bonding strength test method comprises the following steps: the method provided in the standard document with reference GBT7124-2008 is carried out, in particular with 6061 aluminium sheet, with bonding surface dimensions of 12.5mm x 25mm. After the aqueous polyurethane adhesives obtained in examples and comparative examples were applied and activated at 80℃for 3 minutes, aluminum sheets were adhered and subjected to constant pressure, and placed in an oven at 80℃for 3 hours, immediately after cooling, were tested on a computerized tensile tester at a tensile speed of 5mm/min, 5 samples were tested per group, and an arithmetic average was calculated to obtain the initial adhesive strength. The mixture was left at room temperature for 3 days, tested on a computerized tensile tester at a tensile speed of 5mm/min, 5 samples were tested per group, and an arithmetic average was calculated to give the final bond strength.
The water resistance test method is that a sample plate is prepared by adopting the same method with the bonding strength, and is soaked in water at 65 ℃ for 24 hours, and then the bonding strength of the sample is tested.
The test method of yellowing resistance comprises pouring the aqueous polyurethane adhesives obtained in the examples and the comparative examples into a mold with the depth of 8mm, curing at 80 ℃ for 3 hours to form a test block with the thickness of 8mm, placing one block into a HZ-3017 bulb type yellowing resistance experiment box, irradiating for 24 hours under a 300W ultraviolet lamp, keeping the distance between a sample and a bulb at 25cm, irradiating for 7 days at the temperature of about 60 ℃ in an exposure box, observing the yellowing property, and comparing the yellowing property with a blank sample on a gray color card.
The temperature resistance test method is to prepare a sample plate by adopting the same method with yellowing resistance, and measure the duration of keeping the sample plate at 80 ℃ without cracking.
The test temperature of the surface drying time is 50 ℃, the thickness of the aqueous polyurethane binder is 8mm, and the specific method is a cotton ball blowing method.
The tensile strength and elongation at break were carried out according to the method provided by the standard document with the number of GB/T36246-2018, and the preparation method of the sample comprises the steps of mixing the aqueous polyurethane binder provided by the examples and the aqueous polyurethane binder provided by the comparative examples and ethylene propylene diene monomer rubber particles (purchased from Guangdong Feng energy technology Co., ltd.) in a mass ratio of 1:6, spreading the mixture on a polytetrafluoroethylene plate, curing the mixture under the condition, and preparing the sample.
The test results are shown in Table 2.
Table 2 results of Properties of the aqueous polyurethane binders obtained in examples 1 to 2 and comparative examples 1 to 4
Figure BDA0003655131960000161
As can be seen from the results obtained in Table 2, the aqueous polyurethane adhesive has excellent effects on adhesion performance, temperature resistance, water resistance, yellowing resistance, surface drying time and mechanical properties in the method and parameter ranges provided by the invention. Regarding examples 1 to 2, the types and contents of isocyanates vary greatly, but the explanation of the same tack-free time of the aqueous isocyanate adhesive obtained is as follows:
the reactivity difference of two isocyanic acid groups in 2,4-TDI and 2,6-TDI is larger, the reactivity of two isocyanic acid groups in MDI is equivalent, and the activity is positioned between the two isocyanic acid groups of TDI; thus, when the first isocyanate of 2,4-TDI or 2,6-TDI is consumed, the remaining one isocyanate activity is instead lower than the reactivity of MDI. In the process of the present invention for preparing an aqueous isocyanate binder, part of the isocyanate groups in the aromatic diisocyanate has been consumed by the sulfonate diol, and it appears that the open time of example 2 should be greater than that of example 1.
However, in aliphatic diisocyanates, the reactivity of IPDI was small, and the open time of example 2 was somewhat reduced after increasing the content of IPDI.
In addition, the standard document prescribes that if the surface time is less than or equal to 30min, recording is carried out according to the multiple of 5min. Therefore, the actual tack-free values of example 1 and example 2 differ somewhat, but are similar, showing 15 minutes for each result, using standard time-recording methods. As is clear from the results obtained in comparative examples 1 and 1, if the preparation raw materials do not include aromatic diisocyanate (the isocyanate content is kept unchanged, the content of aliphatic diisocyanate is increased in equal proportion), the properties of the obtained aqueous polyurethane adhesive are reduced to a certain extent except for the elongation at break and yellowing resistance, and the elongation at break is increased because the content of rigid ring-shaped groups (such as benzene rings) in the molecules of the obtained aqueous polyurethane adhesive is reduced after the aliphatic diisocyanate is fully adopted, and the chain-shaped molecular morphology is more favorable for improving the flexibility and the elongation at break.
The results obtained in comparative examples 1 and 2 show that if the preparation raw materials do not include the fluoromonomer (the sum of the content of the chain extender and the content of the fluoromonomer is kept unchanged, the content of the chain extender is increased in equal proportion), the water resistance of the obtained aqueous polyurethane adhesive is reduced to half that of example 1, the yellowing resistance of the obtained aqueous polyurethane adhesive is obviously reduced without the protection of fluorocarbon segments, and other properties are slightly reduced.
The results obtained in comparative examples 1 and 3 revealed that, if the raw materials for preparation did not include monoglyceride acrylate and sodium bis (hydroxymethyl) propionate (the amount of 1, 4-butanediol was increased to ensure that the amount of the chain extender was unchanged), the obtained results were comparable to those obtained in comparative example 2, i.e., the water resistance and yellowing resistance were remarkably lowered, and the other properties were slightly lowered.
As is clear from the results obtained in comparative examples 1 and 4, when all of the sulfonate diol is added in step S1, that is, the sulfonate diol tends to react with the aromatic diisocyanate, the resultant isocyanate prepolymer has poor molecular weight uniformity, and thus the respective properties of the resultant aqueous polyurethane adhesive are significantly lowered, particularly, yellowing resistance and elongation at break are significantly lowered.
The result of comparative example 5 shows that if the polyol is not included in the raw material for preparation, folding of the molecular chain cannot be formed in step S3, that is, isocyanate groups in the aromatic diisocyanate and water rapidly undergo side reaction to generate bubbles (carbon dioxide) in the process of emulsification by adding water in step S5, and the obtained aqueous polyurethane binder exhibits a solid agglomeration phenomenon and cannot be used.
According to the results, each preparation raw material has a specific effect, and meanwhile, a synergistic effect is generated between the preparation raw materials and other preparation raw materials, and if any one of the preparation raw materials is default or replaced, each performance of the obtained aqueous polyurethane adhesive is reduced to a certain extent, and even the aqueous polyurethane adhesive cannot be used.
While the embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.

Claims (8)

1. The aqueous polyurethane binder is characterized by comprising the following preparation raw materials in parts by weight:
Figure FDA0004178208750000011
the chain extender comprises acrylic acid monoglyceride and sodium bis (hydroxymethyl) propionate;
the number average molecular weight of the sulfonate dihydric alcohol is 300-2000; is the esterification product of dihydric alcohol and dicarboxyl sulfonate;
the polyol includes at least one of pentaerythritol, trimethylolpropane, and glycerol;
the aqueous polyurethane binder is prepared by a preparation method comprising the following steps:
s1, mixing and reacting the aromatic diisocyanate and part of the sulfonate dihydric alcohol;
s2, mixing the mixture obtained in the step S1, the aliphatic diisocyanate and the rest sulfonate dihydric alcohol for reaction;
s3, reacting the polyol with the mixture obtained in the step S2 under the action of the molecular weight regulator;
s4, sequentially reacting the mixture obtained in the step S3 with the chain extender and the fluorine-containing monomer.
2. The aqueous polyurethane binder of claim 1 wherein the aromatic diisocyanate comprises at least one of toluene diisocyanate and diphenylmethane diisocyanate.
3. The aqueous polyurethane binder of claim 1 wherein the aliphatic diisocyanate comprises at least one of isophorone diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane diisocyanate.
4. The aqueous polyurethane binder of claim 1, wherein the aqueous polyurethane binder comprises, the fluorine-containing monomer comprises 2,3, 4, 5-octafluoro-1, 6-hexanediol 2,3, 4-heptafluoro-1-butanol and 1, 2-at least one of the tetrahydro perfluoro-1-decanols.
5. The aqueous polyurethane binder of claim 1 wherein the molecular weight regulator comprises at least one of t-dodecyl mercaptan, n-dodecyl mercaptan, and 1, 3-propane sultone.
6. The aqueous polyurethane binder according to claim 1, wherein the mass ratio of the part in step S1 to the remainder in step S2 is 1:0.25-0.35.
7. The aqueous polyurethane binder according to claim 1 or 6, wherein the reaction temperature in step S3 is 70 to 90 ℃.
8. Use of the aqueous polyurethane binder according to any one of claims 1 to 7 for the preparation of plastic tracks and shoes.
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