CN114806489A - Waterborne polyurethane adhesive and preparation method and application thereof - Google Patents

Waterborne polyurethane adhesive and preparation method and application thereof Download PDF

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CN114806489A
CN114806489A CN202210551451.9A CN202210551451A CN114806489A CN 114806489 A CN114806489 A CN 114806489A CN 202210551451 A CN202210551451 A CN 202210551451A CN 114806489 A CN114806489 A CN 114806489A
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aqueous polyurethane
diisocyanate
sulfonate
polyurethane adhesive
preparation
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CN114806489B (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
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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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    • C08G18/00—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
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
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    • C08G18/30—Low-molecular-weight compounds
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    • 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
    • C08G18/675—Low-molecular-weight compounds
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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
    • 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
    • C08G18/70—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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    • 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
    • C08G18/70—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
    • 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
    • C08G18/70—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
    • 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
    • C08G18/7657—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

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

Description

Waterborne polyurethane adhesive and preparation method and application thereof
Technical Field
The invention belongs to the technical field of aqueous polyurethane adhesives, and particularly relates to an aqueous polyurethane adhesive as well as a preparation method and application thereof.
Background
The polyurethane can be obtained by the reaction of isocyanate and polyalcohol, the polyurethane adhesive is polyurethane with adhesive property, molecular chain of the polyurethane contains carbamate (-NHCOO-) or isocyanate (-NCO), the polyurethane adhesive shows high activity and polarity, and has excellent chemical adhesive force with porous materials such as foam, plastic, wood, leather, fabric, paper, ceramic and the like, and materials with smooth and clean surfaces such as metal, glass, rubber, plastic and the like. The method is widely applied to the preparation process of shoe bags, plastic runways and the like.
The polyurethane binder can be divided into a water-based polyurethane binder and a solvent-based polyurethane binder according to the difference of a dispersion system. Among them, the content of volatile organic compounds in the aqueous polyurethane binder is low, the pollution to the environment is less, and the harm to producers and users is very low, so the aqueous polyurethane binder is the current research and application trend.
However, the aqueous polyurethane adhesive has the performance problems of low curing speed, poor water resistance, poor mechanical property, no high temperature resistance and the like. And thus its use range is greatly limited.
Because the reactivity of the aromatic diisocyanate is significantly higher than that of the aliphatic diisocyanate, in order to increase the curing speed of the aqueous polyurethane adhesive, research attempts have been made to prepare the aqueous isocyanate adhesive by using the aromatic diisocyanate (such as TDI). Thus, there are three problems, namely, the reactivity of the aromatic diisocyanate with water is high, side reactions are likely to occur during the preparation and use of the binder, and carbon dioxide gas is generated to affect the use of the aqueous polyurethane binder 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 conclusion, the existing waterborne polyurethane adhesive is difficult to balance the curing speed and the yellowing resistance.
Disclosure of Invention
The present invention has been made to solve at least one of the above-mentioned problems occurring in the prior art. Therefore, the invention provides the waterborne polyurethane adhesive which optimizes the curing speed and does not lose the yellowing resistance.
The invention also provides a preparation method of the waterborne polyurethane adhesive.
The invention also provides application of the waterborne polyurethane adhesive.
According to one aspect of the invention, the waterborne polyurethane adhesive is prepared from the following raw materials in parts by weight:
Figure BDA0003655131960000021
the chain extender comprises at least one of glycerol monoacrylate (CAS: 5919-74-4) and sodium bis (hydroxymethyl) propionate;
the number average molecular weight of the sulfonate diol is 300-2000.
A preferred aqueous polyurethane binder according to the present invention has at least the following beneficial effects:
(1) the preparation raw materials adopted by the invention comprise fluorine-containing monomers with certain hydrophobic property, so that after the aqueous polyurethane adhesive is cured, the water resistance of the adhesive film is improved;
from the preparation raw materials adopted in the invention, the obtained aqueous polyurethane binder at least comprises acrylic acid segments (provided by acrylic acid monoglyceride and sodium bis (hydroxymethyl) propionate) and fluorine-containing segments (provided by fluorine-containing monomers). Due to the polarity difference between the two chain segments and other chain segments, in the curing process of the aqueous polyurethane adhesive, the acrylic acid chain segment and the fluorine-containing chain segment tend to migrate to the surface, and a film formed by the acrylic acid chain segment is more compact, which is equivalent to a compact protective film formed on the surface of a cured adhesive film, so that the water vapor is prevented from entering, and the water resistance of the aqueous polyurethane adhesive is improved.
Namely, the fluorine-containing monomer and the special chain extender generate a synergistic effect, and the water resistance of the aqueous polyurethane adhesive is improved.
In addition, the fluorocarbon chain segment brought by the acrylic chain segment and the fluorine-containing monomer has stronger yellowing resistance. When the chain segments are transferred to the surface, the aromatic urethane generated by aromatic diisocyanate is equivalently protected, and the yellowing resistance is improved.
(2) Through the coordination between the molecular weight regulator and other preparation raw materials, the obtained waterborne polyurethane adhesive has narrower molecular weight distribution and better dispersibility. Meanwhile, the aromatic diisocyanate is introduced, so that the curing speed of the obtained waterborne polyurethane adhesive is higher.
(3) The preparation raw material provided by the invention comprises 150-200 parts of sulfonate dihydric alcohol, so that on one hand, enough sulfonate is provided, and the obtained waterborne polyurethane adhesive has good dispersibility in water. In addition, the invention adopts the sulfonate dihydric alcohol, compared with the traditional sulfonate dihydric alcohol, the acidity is reduced, so that a neutralizing agent is not required to be additionally added in the actual use process, and further, the side reaction of the neutralizing agent (mostly an amine neutralizing agent) and the aromatic diisocyanate in the traditional technology is avoided, and the side reaction of the obtained waterborne polyurethane adhesive in the preparation and curing processes is less.
The molecular weight of the sulfonate dihydric alcohol can influence the chain length of a soft segment in the molecular chain of the obtained waterborne polyurethane adhesive, and the chain length of the soft segment has a certain positive correlation with the flexibility of the obtained waterborne polyurethane adhesive and a certain inverse correlation with the heat resistance. Within the range of 300-2000 number average molecular weight, the obtained waterborne polyurethane adhesive has proper flexibility and heat resistance.
(4) The specific ratio of the aromatic diisocyanate to the aliphatic diisocyanate balances the curing speed of the aqueous diisocyanate binder.
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 kinds of aromatic diisocyanate have wide sources, and the two kinds of preparation raw materials are selected, so that the industrial production of the aqueous polyurethane adhesive is facilitated.
In some embodiments of the present 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 aromatic diisocyanate has a weight ratio of 2,4-TDI to 2,6-TDI of 75-85: 20.
In some further preferred embodiments of the present invention, the aromatic diisocyanate has a weight ratio of 2,4-TDI to 2,6-TDI of 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.
Wherein IPDI has a low reactivity but is excellent in yellowing resistance, and when IPDI is blended with other types of isocyanates, the obtained aqueous polyurethane binder is more excellent in yellowing resistance.
In some embodiments of the present invention, the weight ratio of IPDI to HDI in the aliphatic diisocyanate is 3:1 to 4.
In some preferred embodiments of the present invention, the weight ratio of IPDI to HDI in the aliphatic diisocyanate is 3:1 to 2.
In some embodiments of the invention, the sulfonate diol is the esterification product of a diol and a dicarboxy sulfonate. Therefore, sulfonate groups can be introduced into the sulfonate dihydric alcohol and further introduced into the molecular chain of the aqueous polyurethane adhesive, so that the hydrophilicity (dispersibility in water) of the obtained aqueous polyurethane adhesive is improved.
In some embodiments of the invention, the diols include 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), tetrahydrofuran diol (CAS: 25190-06-1), 1, 6-hexanediol (CAS: 629-11-8), trimethylpentanediol (CAS: 144-19-4), butylethylpropanediol (CAS: 115-84-4), 2-bis (4-hydroxyphenyl) propane (CAS: 80-05-7), dipropylene glycol (CAS: 25265-71-8), tripropylene glycol (CAS: 24800-44-0), and ethylhexanediol (CAS: 29656-68-6).
In some preferred embodiments of the present invention, the diol comprises at least one of 3-methyl-1, 5-pentanediol, neopentyl glycol, 1, 5-pentanediol, diethylpentanediol, 1, 6-hexanediol, trimethylpentanediol, and ethylhexanediol.
Therefore, the molecular chain length of the dihydric alcohol is longer, the number of the dihydric alcohol molecules required for obtaining the sulfonate dihydric alcohol with the same molecular weight is less compared with that of ethylene glycol and the like, the number of ester groups in the sulfonate dihydric alcohol is less, the ester groups are easy to hydrolyze under high-temperature and high-humidity conditions, and the density of the ester groups has a certain inverse correlation with the water resistance and the heat resistance of the aqueous polyurethane adhesive. That is, the invention improves the water resistance and heat resistance of the aqueous polyurethane adhesive by selecting the type of the dihydric alcohol for preparing the sulfonate dihydric alcohol.
Furthermore, compared with multi-branched chain dihydric alcohol or straight chain (less-branched chain) dihydric alcohol with cyclic dihydric alcohol such as benzene ring and the like on the main chain, the flexibility of the obtained waterborne polyurethane adhesive can be further improved.
In some preferred embodiments of the present invention, the diol consists of 1, 6-hexanediol and 3-methyl-1, 5-pentanediol.
In some preferred embodiments of the present invention, the weight ratio of 1, 6-hexanediol to 3-methyl-1, 5-pentanediol in the diol is 1:0.8 to 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 diols is about 1:1.
In some embodiments of the invention, the dicarboxy sulfonate comprises sodium 5-sulfoisophthalate (CAS: 6362-79-4).
In some embodiments of the invention, the starting material for the preparation of the sulfonate diol further comprises a diacid. Therefore, the molecular weight, the stability and the uniformity of molecular weight distribution of the obtained sulfonate diol can be improved.
In some embodiments of the invention, the diacid includes 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 invention, in the preparation raw material of the sulfonate diol, the molar ratio of the diol to the dicarboxy sulfonate to the diacid is 2-2.5: 0.8-1.2.
Wherein the amount of said glycol is greater than the sum of the amounts of said dicarboxy sulfonate and diacid, thereby promoting the reaction of said dicarboxy sulfonate and diacid to be as complete as possible.
In some embodiments of the present invention, the sulfonate diol is used in an amount of 175 to 195 parts by weight.
In some embodiments of the present invention, the sulfonate diol has a number average molecular weight of 500 to 1200 parts by weight.
In some embodiments of the present invention, the polyol comprises a polyol having a functionality of 3 or more.
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 comprises 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 present invention, the polyol consists of pentaerythritol and trimethylolpropane.
In some preferred embodiments of the present invention, the polyol has a weight ratio of pentaerythritol to trimethylolpropane of 1:1 to 1.5.
In some embodiments of the invention, the fluoromonomer comprises at least one of 2,2,3,3,4,4,5, 5-octafluoro-1, 6-hexanediol (octafluoro-1, 6-hexanediol, CAS: 355-74-8), 2,2,3,3,4,4, 4-heptafluoro-1-butanol (perfluorobutanol, CAS: 375-01-9) and 1,1,2, 2-tetrahydroperfluoro-1-decanol (2-perfluorooctylethanol, CAS: 678-39-7). The fluorine-containing monomers have high fluorine content and moderate molecular chain length, and are beneficial to the 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, in the fluorine-containing monomer, the mass ratio of octafluoro-1, 6-hexanediol, perfluorobutanol, and 2-perfluorooctylethanol is 1:0.8 to 1.2.
In some preferred embodiments of the present invention, the weight ratio of octafluoro-1, 6-hexanediol, perfluorobutanol, and 2-perfluorooctylethanol in the fluoromonomer is about 1:1: 1.
In some embodiments of the invention, the sodium bis (hydroxymethyl) propionate in the chain extender is the product of the reaction of bis (hydroxymethyl) propionic acid (CAS: 4767-03-7) and sodium hydroxide in a molar ratio of about 1:1.
In some embodiments of the present 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 present invention, the chain extender further comprises an alcohol chain extender.
As isocyanic acid radical in the aromatic diisocyanate and amine substances have stronger reactivity, in order to reduce side reactions as much as possible, the chain extender is selected from alcohol chain extenders.
In some embodiments of the invention, the alcoholic 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 glycerol monoacrylate in the chain extender is 1:1 to 2.
In some embodiments of the invention, the weight ratio of the glycerol acrylate to the sodium bis (hydroxymethyl) propionate in the chain extender is 1: 1-2.
In some embodiments of the invention, the molecular weight regulator comprises at least one of tert-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 present 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 raw materials for preparing the aqueous polyurethane binder further include 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 invention, the organic solvent comprises at least one of acetone, ethyl acetate, and butyl acetate (CAS: 123-86-4). Therefore, the organic solvent can be dissolved with water to a certain degree, and provides a basis (dispersing in water) for the subsequent preparation of the aqueous polyurethane adhesive.
In some embodiments of the present invention, the raw materials for preparing the aqueous polyurethane binder further include a catalyst.
In some embodiments of the invention, the catalyst comprises at least one of tetramethylammonium bromide (CAS: 64-20-0) and triethylbenzylammonium chloride (CAS: 56-37-1).
In some embodiments of the present invention, the catalyst is added in an amount of 0.1 to 1 part by weight.
In some embodiments of the present invention, the raw materials for preparing the aqueous polyurethane binder further include water.
The water in the preparation raw materials is used for adjusting the solid content of the aqueous polyurethane adhesive.
In some embodiments of the present invention, the aqueous polyurethane binder has a solid content of 55 to 75 wt%.
In some preferred embodiments of the present invention, the solid content of the aqueous polyurethane binder is 58 to 60 wt%.
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 adjuvant comprises at least one of a thickener, a filler, a pigment, a leveling agent, and an antioxidant.
The additive can optimize the performances of the aqueous polyurethane adhesive such as appearance and the like to a certain extent, but has small influence on the essential performances such as the adhesive property, the water resistance and the like, and can be selectively added by a person skilled in the art according to the actual production requirement.
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 and reacting the mixture obtained in the step S1, the aliphatic diisocyanate and the rest of the sulfonate diol;
s3, reacting the polyol with the mixture obtained in the step S2 under the action of the molecular weight regulator;
and S4, reacting the mixture obtained in the step S3 with the chain extender and the fluorine-containing monomer in sequence.
The preparation method provided by the invention has the following mechanism:
in step S1, aromatic diisocyanate reacts with part of sulfonate diol to consume part of isocyanate group, for example, the difference of two isocyanate groups in TDI is large, and this step can consume the isocyanate group with large activity;
in step S2, adding aliphatic diisocyanate and the remaining sulfonate diol; because the concentration and activity of the isocyanic acid radical in the aromatic diisocyanate are reduced in the step S1, in the step S2, the newly added sulfonate diol, the aromatic diisocyanate and the aliphatic diisocyanate are possibly copolymerized, and the generated isocyanate prepolymer simultaneously comprises an aromatic diisocyanate chain segment, a sulfonate diol chain segment and an aliphatic diisocyanate chain segment; as is clear from the sequence of steps S1 and S2, at least a part of the sulfonate segment is located in the middle of the aqueous polyurethane binder molecule, and thus the water dispersibility is high.
In step S3, the polyol further reduces the content of free isocyanate in the isocyanate prepolymer and provides a certain crosslinking density; the mechanical property of the obtained waterborne polyurethane adhesive is improved; meanwhile, because the isocyanate prepolymer obtained in the step S2 contains aromatic diisocyanate and aliphatic diisocyanate, 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 even under the action of the molecular weight regulator; also provides a basis for obtaining the waterborne polyurethane adhesive with average molecular weight.
In the step, the polyol and the isocyanate prepolymer obtained in the step S2 react to generate a substance which has a hydrophilic chain segment and a hydrophobic chain segment; in the reaction process, molecular chains are wound and folded to form the condition that a hydrophilic group (a sulfonate group) faces to an organic solvent and a hydrophobic group (isocyanic acid radical) is wrapped by the molecular chains. Therefore, the isocyanate in the aromatic diisocyanate is equivalently protected.
Meanwhile, the reason why polyurethane prepared by aromatic diisocyanate is easy to yellow is that aromatic amine and benzene ring generated by decomposition of aromatic urethane after ultraviolet irradiation are in resonance rearrangement; in the preparation method provided by the invention, the folding of the molecular chain just protects the chain segment which is easy to decompose, and the chain segment with stronger ultraviolet resistance faces to illumination. Thereby improving the yellowing resistance of the obtained waterborne polyurethane adhesive.
In the step, the molecular weight regulator is also used as a chain transfer agent to regulate the reaction probability of the isocyanic acid radicals with different activities and the polyhydric alcohols, thereby playing a role in regulating the molecular weight. On the other hand, as an oily substance, an intermediate product containing isocyanate is coated to a certain extent, and the side reaction of the isocyanate is further inhibited. Finally, the waterborne polyurethane adhesive with high curing speed and less side reaction can be obtained.
In step S4, chain extension and crosslinking reactions are performed, and at the same time, due to the influence of the addition sequence, the fluorine-containing monomer tends to be introduced into the end of the aqueous polyurethane binder, so that the migration of the acrylic acid segment and the fluorine-containing segment in the chain extender is less limited, and the above-mentioned water resistance is more favorably exerted.
In some preferred embodiments of the present 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 adjustment of the step sequence and the feeding sequence, the comprehensive performances of yellowing resistance, water resistance and the like of the aqueous polyurethane adhesive can be improved to a certain extent.
In some embodiments of the present invention, in step S1, the temperature of the mixing reaction is 70-90 ℃. The difference of the reactivity of different aromatic diisocyanates is large at normal temperature, but is reduced when the temperature is raised to more than 70 ℃, so that the mixing reaction rate is moderate, and the aqueous isocyanate binder with uniform molecular weight can be obtained more favorably.
In some embodiments of the present invention, in step S1, the mixing reaction is performed for 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 in the absence of air; specifically, the gas may be replaced with nitrogen or an inert gas for protection.
The reason for isolating air is that the aromatic diisocyanate has a higher activity of side reaction with water, etc., and the isocyanate group thereon is not protected in step S1, which reduces 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 rest in step S2 is 1: 0.25-0.35.
In some preferred embodiments of the present invention, the mass ratio of the portion in step S1 to the remainder in step S2 is 1: 0.3. Within the proportion range, the reaction probability of the aromatic diisocyanate and the aliphatic diisocyanate and the sulfonate dihydric alcohol is adjusted, the molecular weight distribution of the obtained isocyanate prepolymer is more concentrated, and the consistency and the caking property of the obtained waterborne polyurethane binding agent are higher.
In some embodiments of the present invention, in step S2, the temperature of the mixing reaction is 40 to 60 ℃.
In some embodiments of the present invention, in step S2, the mixing reaction is performed for 1 to 2 hours.
In some embodiments of the present invention, in step S3, the molecular weight regulator and the polyol are added by: after the molecular weight modifier is dissolved in the polyol, the mixture obtained in step S2 is added dropwise. Therefore, the dispersion uniformity of the molecular weight regulator can be improved, and the effect of the molecular weight regulator can be better played.
In some embodiments of the present invention, the dropping speed is 1-2 mL/min.
In some embodiments of the present invention, during the dropping, the mixture obtained in step S2 is stirred at a speed of 150 to 400 rpm. At this speed, the homogenization speed can be increased and the breaking of the molecular chains of the intermediate product obtained can also be avoided.
In some preferred embodiments of the present invention, the stirring speed is 180 to 200 rpm.
In some embodiments of the present invention, in step S3, the temperature of the reaction is 70 to 90 ℃.
In some embodiments of the present invention, in step S3, the reaction time is 0.5-4 h.
In some preferred embodiments of the present invention, in step S3, the reaction time is 1.5 to 2.5 hours.
Under the conditions of the temperature and the time, the folding and winding functions of the molecular chain of the intermediate product are more sufficient, so that better yellowing resistance can be obtained, and the protection function on isocyanic acid radical in the aromatic diisocyanate is more sufficient.
In some embodiments of the present invention, in step S4, the temperature of the reaction is 70 to 90 ℃.
In some embodiments of the present invention, in step S4, the reaction time is 1-3 h.
In some embodiments of the invention, in step S4, the feedstock for the reaction further comprises the catalyst.
Due to the protection of isocyanate group in step S3, even if a catalyst is added in step S4, the probability of side reaction is not increased.
In some embodiments of the present invention, the method for preparing the aqueous polyurethane binder further comprises adding water for dilution and evaporation after step S4.
In some embodiments of the invention, the water dilution and evaporation comprises stirring; the rotating speed of the stirring is 300-800 rpm.
In some preferred embodiments of the invention, the water dilution and evaporation comprises stirring; the rotating speed of the stirring is 500-600 rpm.
In some embodiments of the invention, the effect of the dilution and evaporation with water comprises: adjusting the viscosity, removing the organic solvent added in the preparation process, and shearing and emulsifying.
In some embodiments of the invention, the temperature for the dilution and evaporation with water is 50-60 ℃.
According to a third aspect of the present invention, the use of the aqueous polyurethane adhesive for the preparation of plastic racetracks and shoes is proposed.
The waterborne polyurethane adhesive provided by the invention has excellent adhesive property, curing speed, water resistance, heat resistance and compatibility, so that when the waterborne polyurethane adhesive is used for preparing plastic runways and shoes, the preparation period can be obviously shortened, the service period can be prolonged, and the service environment (high-humidity environment) can be widened.
Unless otherwise specified, "about" in the present invention means an allowable error of ± 2%.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The embodiment prepares the waterborne polyurethane adhesive, and the specific process is as follows:
s1, mixing aromatic diisocyanate and partial sulfonate diol for reaction for 3 hours at 80 ℃ in the atmosphere of nitrogen protection;
s2, mixing the mixture obtained in the step S1, aliphatic diisocyanate and the residual sulfonate diol at 50 ℃ and reacting for 1 h; the mass ratio of the sulfonate diol used in the step S1 is 0.3: 1;
s3, mixing the molecular weight regulator and the polyhydric alcohol at 75 ℃, and then dropwise adding the mixture into the mixture obtained in the step S2 at the speed of 1mL/min, wherein the mixture obtained in the step S2 is stirred at the rotating speed of 200 rpm; after the dropwise addition is finished, the reaction is continued 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 75 ℃, and continuing to react for 1h after the addition is finished;
s5, adding water into the mixture obtained in the step S4 at 55 ℃, and stirring and evaporating the organic solvent in the mixture at the rotating speed of 500 rpm.
The information on the preparation raw materials used in this example is shown in Table 1.
Example 2
The embodiment prepares a waterborne polyurethane adhesive, and the specific process is different from the embodiment 1 in that:
the preparation raw materials are different, and specific preparation raw materials are shown in table 1.
Comparative examples 1-3 prepared a waterborne polyurethane adhesive respectively, the specific process difference with example 1 was:
the preparation raw materials are different, and specific preparation raw materials are shown in table 1.
Comparative example 4
This comparative example prepared an aqueous polyurethane binder, differing from example 1 in that:
in step S1, all of the sulfonate diol is added.
Comparative example 5
This comparative example prepared an aqueous polyurethane binder, differing from example 1 in that:
(1) the preparation raw materials do not contain polyol;
(2) the specific operation of step S3 is: after mixing a molecular weight regulator and an organic solvent (see examples for specific mixture ratio, the amount is equal to that of the polyol in the examples) at 75 ℃, the mixture obtained in the step S2 is added dropwise at a speed of 1mL/min, and the mixture obtained in the step S2 is stirred at a rotation speed of 200 rpm; after the completion of the dropwise addition, the reaction was continued for 2 hours.
TABLE 1 preparation raw materials (parts by weight) used in examples 1 to 2 and comparative examples 1 to 3
Figure BDA0003655131960000131
Figure BDA0003655131960000141
If not stated otherwise, the preparation method of the sulfonate diol in Table 1 is as follows: mixing 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, sodium 5-isophthalate and sebacic acid in water according to a molar ratio of 1:1.2:1.2:0.8 at 95 ℃, performing esterification reaction, stopping the reaction when the number average molecular weight is about 900, and distilling to remove unreacted dihydric alcohol, dibasic acid and water, wherein the solid content is 99.9 wt%.
Test examples
The test examples tested the performance of the aqueous polyurethane binders prepared in examples 1-2 and comparative examples 1-5. Wherein:
the test method of the bonding strength comprises the following steps: the method provided in the standard document with reference number GBT7124-2008 was carried out using, in particular, a 6061 aluminum sheet with a bonding face size of 12.5mm × 25 mm. After the waterborne polyurethane adhesive obtained in the embodiment and the comparative example is coated and activated at 80 ℃ for 3min, an aluminum sheet is adhered, constant pressure is applied, the aluminum sheet is placed in an oven at 80 ℃ for 3h, the aluminum sheet is immediately tested on a computerized tensile sample machine after being cooled, the tensile speed is 5mm/min, 5 samples are tested in each group, and the arithmetic mean value is calculated to obtain the initial adhesive strength. Standing at room temperature for 3 days, testing on a computerized tensile specimen machine at a tensile speed of 5mm/min, testing 5 specimens per group, and calculating the arithmetic mean value to obtain the final bonding strength.
The water resistance test method comprises the steps of preparing a sample plate by the same method as the bonding strength, soaking the sample plate in 65 ℃ water, and testing the bonding strength of the sample after 24 hours.
The yellowing resistance was measured by pouring the aqueous polyurethane binders obtained in the examples and comparative examples into a 8mm deep mold, curing at 80 ℃ for 3 hours to form a test block with a thickness of 8mm, placing one of the test blocks in a HZ-3017 type bulb-type yellowing resistance test chamber, irradiating for 24 hours under a 300W ultraviolet lamp at a distance of 25cm from the bulb and a temperature of about 60 ℃ in the exposure chamber, and after 7 days of irradiation, observing the yellowing resistance and comparing the color with that of a blank sample on a gray card.
The temperature resistance was measured by preparing a sample in the same manner as the yellowing resistance and measuring the time during which the sample remained uncracked at 80 ℃.
The testing temperature of the surface drying time is 50 ℃, the thickness of the waterborne polyurethane adhesive is 8mm, and the specific method is a cotton blowing ball method.
The tensile strength and the elongation at break were performed according to the method provided by the standard document with the number GB/T36246-2018, and the sample was prepared by mixing the aqueous polyurethane binder and the ethylene propylene diene rubber particles (purchased from Guangdong Feng energy science and technology Co., Ltd.) provided in the examples and the comparative examples at the mass ratio of 1:6, spreading the mixture on a polytetrafluoroethylene plate, curing the mixture under the conditions, and then preparing the sample.
The test results are shown in table 2.
TABLE 2 Performance results of aqueous polyurethane binders obtained in examples 1-2 and comparative examples 1-4
Figure BDA0003655131960000161
From the results shown in table 2, it can be seen that the aqueous polyurethane adhesive obtained by the method and parameter ranges of the present invention has excellent adhesive properties, temperature resistance, water resistance, yellowing resistance, open time and mechanical properties. In examples 1 to 2, the types and contents of isocyanates were largely changed, but the surface drying times of the obtained aqueous isocyanate adhesives were the same as explained below:
the reaction activity difference of two isocyanic acid radicals in 2,4-TDI and 2,6-TDI is large, the reaction activity of the two isocyanic acid radicals in MDI is relatively equivalent, and the activity is positioned between the two isocyanic acid radicals in TDI; thus, when the first isocyanate group of 2,4-TDI or 2,6-TDI is consumed, the activity of the remaining isocyanate group is lower than that of MDI. In the process of the present invention for preparing the aqueous isocyanate binder, a portion of the isocyanate groups in the aromatic diisocyanate have 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 the case of aliphatic diisocyanates, IPDI is less reactive and the tack-free time of example 2 decreases somewhat after increasing the IPDI content.
And the standard file specifies that if the table-drying time is less than or equal to 30min, recording according to the multiple of 5 min. Therefore, the actual tack-free of example 1 and example 2 is somewhat different, but similar, and both results are 15min using the standard time recording method. It can be seen from the results of comparative example 1 and comparative example 1 that, if the raw materials for preparation do not include aromatic diisocyanate (ensuring that the content of isocyanate is unchanged and the content of aliphatic diisocyanate is increased in equal proportion), the properties of the obtained waterborne polyurethane adhesive are reduced to some extent except the elongation at break and the yellowing resistance, and the reason for increasing the elongation at break is that after all the aliphatic diisocyanate is used, the content of rigid ring-packaged groups (such as benzene rings) in the molecules of the obtained waterborne polyurethane adhesive is reduced, and the molecular form of chain is more beneficial to improving the flexibility and elongation at break.
Comparing the results of example 1 and comparative example 2, it can be seen that if the raw materials do not include the fluorine-containing monomer (the sum of the contents of the chain extender and the fluorine-containing monomer is kept unchanged, and the content of the chain extender is increased in equal proportion), the water resistance of the obtained aqueous polyurethane adhesive is reduced to half of that of example 1, the fluorocarbon segment is not protected, the yellowing resistance of the obtained aqueous polyurethane adhesive is remarkably reduced, and other properties are also slightly reduced.
Comparing the results obtained in example 1 and comparative example 3, it can be seen that if the raw materials for preparation do not include acrylic acid monoglyceride and sodium bis (hydroxymethyl) propionate (the amount of 1, 4-butanediol is increased to ensure the amount of chain extender is not changed), the obtained results are equivalent to those obtained in comparative example 2, i.e. the water resistance and yellowing resistance are obviously reduced, and other properties are also slightly reduced.
It can be seen from the results obtained in comparative example 1 and comparative example 4 that, if all of the sulfonate diol is added in step S1, that is, the sulfonate diol tends to react with the aromatic diisocyanate, the molecular weight uniformity of the resulting isocyanate prepolymer is poor, and thus, the properties of the resulting aqueous polyurethane binder, particularly the yellowing resistance and elongation at break, are significantly reduced.
The results of comparative example 5 show that, if polyol is not included in the preparation raw materials, molecular chain folding cannot be formed in step S3, that is, during the emulsification process with water in step S5, isocyanate groups in the aromatic diisocyanate rapidly undergo side reaction with water to generate bubbles (carbon dioxide), and the resulting aqueous polyurethane binder is not usable due to the solid agglomeration phenomenon.
According to the results, each preparation raw material in the aqueous polyurethane binder provided by the invention has specific action, and simultaneously has synergistic action with other preparation raw materials, if any one preparation raw material is absent or replaced, each performance of the obtained aqueous polyurethane binder is reduced to a certain extent, and even the aqueous polyurethane binder cannot be used.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the embodiments, and various changes can be made without departing from the gist of the present invention within the knowledge of those skilled in the art. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.

Claims (10)

1. The water-based polyurethane adhesive is characterized by comprising the following preparation raw materials in parts by weight:
Figure FDA0003655131950000011
the chain extender comprises at least one of glycerol acrylate and sodium bis (hydroxymethyl) propionate;
the number average molecular weight of the sulfonate diol is 300-2000.
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 sulfonate diol is an esterification product of a diol and a dicarboxy sulfonate.
5. The aqueous polyurethane binder of claim 1, wherein the fluoromonomer comprises at least one of 2,2,3,3,4,4,5, 5-octafluoro-1, 6-hexanediol, 2,2,3,3,4,4, 4-heptafluoro-1-butanol, and 1,1,2, 2-tetrahydroperfluoro-1-decanol.
6. 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.
7. The preparation method of the aqueous polyurethane binder as claimed in any one of claims 1 to 6, comprising the steps of:
s1, mixing and reacting the aromatic diisocyanate and part of the sulfonate dihydric alcohol;
s2, mixing and reacting the mixture obtained in the step S1, the aliphatic diisocyanate and the rest of the sulfonate diol;
s3, reacting the polyol with the mixture obtained in the step S2 under the action of the molecular weight regulator;
and S4, reacting the mixture obtained in the step S3 with the chain extender and the fluorine-containing monomer in sequence.
8. The method according to claim 7, wherein the mass ratio of the fraction obtained in step S1 to the remainder obtained in step S2 is 1:0.25 to 0.35.
9. The method according to claim 7 or 8, wherein the reaction temperature in step S3 is 70-90 ℃.
10. Use of the aqueous polyurethane binder of any one of claims 1 to 6 for the preparation of plastic tracks and shoes.
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