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CN111690118A - Waterborne polyurethane resin and preparation method thereof - Google Patents

Waterborne polyurethane resin and preparation method thereof Download PDF

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Publication number
CN111690118A
CN111690118A CN202010606035.5A CN202010606035A CN111690118A CN 111690118 A CN111690118 A CN 111690118A CN 202010606035 A CN202010606035 A CN 202010606035A CN 111690118 A CN111690118 A CN 111690118A
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CN
China
Prior art keywords
parts
polyurethane resin
glycol
isocyanate
aqueous polyurethane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN202010606035.5A
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Chinese (zh)
Inventor
徐晨昱
缪永进
罗婉贞
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Foshan Sanshui Lianmei Chemical Co ltd
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Foshan Sanshui Lianmei Chemical Co ltd
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Priority to CN202010606035.5A priority Critical patent/CN111690118A/en
Publication of CN111690118A publication Critical patent/CN111690118A/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • 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
    • C08G18/75—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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to the technical field of polyurethane, in particular to aqueous polyurethane resin and a preparation method thereof. The waterborne polyurethane resin is prepared from the following raw materials in parts by weight: 20-40 parts of polyether polyol, 10-30 parts of isocyanate, 15-40 parts of solvent, 1-10 parts of chain extender, 1-5 parts of neutralizer and 30-60 parts of water. The invention provides a waterborne polyurethane resin which is obtained by copolymerizing polyether polyol and isocyanate, and has the advantages of simple preparation method, mild reaction conditions, low requirements on reaction equipment and easy large-scale production; meanwhile, the waterborne polyurethane provided by the invention has better hydrolysis resistance and heat resistance.

Description

Waterborne polyurethane resin and preparation method thereof
Technical Field
The invention relates to the technical field of polyurethane, in particular to aqueous polyurethane resin and a preparation method thereof.
Background
Polyurethane (PU) is a short name for Polyurethane (Polyurethane) which is a high polymer containing a large number of urethane groups (-NHCOO-) in the main chain, and is an indispensable high polymer material in the development of socioeconomic industry because of its excellent physical and chemical properties. The polyurethane resin is classified into oil-based polyurethane resin obtained by dissolving high polymer polyurethane in an organic solvent such as dimethyl formamide (DMF), ketones, toluene, etc., and aqueous polyurethane resin obtained by dispersing high polymer polyurethane in water. Because the waterborne polyurethane has very excellent performances in the aspects of bonding strength, toughness, wear resistance, chemical resistance, water resistance and the like, the waterborne polyurethane is gradually developed in the fields of coatings, adhesives, leather finishing agents, pigment printing paste and printing ink, and has important influence on the development of the industries.
The oil-based polyurethane resin contains a large amount of organic solvents such as dimethyl formamide (DMF), ketones, toluene and the like, and causes damage to the surrounding environment and the physical health of field operators in the manufacturing process, and a large amount of solvent volatilization causes serious safety problems in the production process. The water-based polyurethane dispersion takes water as a dispersion medium, only water is volatilized into the atmosphere in the using process, no adverse effect is caused on the environment, and meanwhile, the water is taken as the dispersion medium, so that the water-based polyurethane dispersion has the characteristics of no toxicity, no odor, no combustion, no explosion and safety. In recent years, with the enhancement of environmental awareness and environmental regulations, aqueous polyurethane dispersions are vigorously developed and popularized. The aqueous polyurethane dispersion is widely applied as a green environment-friendly high polymer material, and is also trending to replace oil-based polyurethane resin.
However, the aqueous polyurethanes have the inherent disadvantage of poor water resistance, limiting their use, which may be due to the insertion of hydrophilic ionic groups in the structure, thus exhibiting high hydrophilicity compared to solvent-borne polyurethanes. In order to solve the problems, the invention provides the waterborne polyurethane with excellent hydrolysis resistance.
Disclosure of Invention
In order to solve the technical problems, the first aspect of the invention provides an aqueous polyurethane resin, which comprises the following raw materials in parts by weight: 20-40 parts of polyether polyol, 10-30 parts of isocyanate, 15-40 parts of solvent, 1-10 parts of chain extender, 1-5 parts of neutralizer and 30-60 parts of water.
As a preferred technical scheme of the invention, the number average molecular weight of the polyether polyol is 1000-5000.
In a preferred embodiment of the present invention, the polyether polyol has a hydroxyl value of 40 to 80 mgKOH/g.
In a preferred embodiment of the present invention, the isocyanate is a polyisocyanate containing a benzene ring or an aliphatic ring.
In a preferred embodiment of the present invention, the isocyanate is at least one selected from the group consisting of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, and methylcyclohexyl diisocyanate.
In a preferred embodiment of the present invention, the isocyanate is a combination of diphenylmethane diisocyanate and isophorone diisocyanate, and the weight ratio is 1: (1-2).
In a preferred embodiment of the present invention, the chain extender is at least one selected from the group consisting of ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 2, 3-butanediol, 1, 6-hexanediol, 1, 8-octanediol, neopentyl glycol, 2-methyl-1, 3-propanediol, glycerol, 1,2, 6-hexanetriol, 1,2, 4-butanetriol, triethylene glycol, tetraethylene glycol polyethylene glycol, dipropylene glycol, polypropylene glycol, diethylene glycol, pentaerythritol, glucitol, mannitol, dibutylene glycol, and polybutylene glycol.
As a preferable technical scheme of the invention, the chain extender is a combination of butanediol and ethylene glycol, and the weight ratio is (1-5): 1.
in a preferred embodiment of the present invention, the neutralizing agent is an amine compound.
The second aspect of the present invention provides a method for preparing the aqueous polyurethane resin, comprising at least the steps of:
(1) adding isocyanate, polyether polyol and a solvent into a reaction kettle, and heating to 40-60 ℃ while stirring; then adding a chain extender, heating to 60-80 ℃, and stirring for 4-6 h;
(2) and (2) adding a neutralizing agent into the step (1) for neutralization, then adding water for emulsification, cooling to 20-50 ℃, and stirring for 6-8 hours to obtain the emulsion.
Advantageous effects
The invention provides a waterborne polyurethane resin which is obtained by copolymerizing polyether polyol and isocyanate, and has the advantages of simple preparation method, mild reaction conditions, low requirements on reaction equipment and easy large-scale production; meanwhile, the waterborne polyurethane provided by the invention has better hydrolysis resistance and heat resistance.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
In order to solve the technical problems, the first aspect of the invention provides an aqueous polyurethane resin, which comprises the following raw materials in parts by weight: 20-40 parts of polyether polyol, 10-30 parts of isocyanate, 15-40 parts of solvent, 1-10 parts of chain extender, 1-5 parts of neutralizer and 30-60 parts of water.
In a preferred embodiment, the raw materials for preparing the aqueous polyurethane resin at least comprise the following components in parts by weight: 30 parts of polyether polyol, 15 parts of isocyanate, 30 parts of solvent, 4 parts of chain extender, 2 parts of neutralizer and 45 parts of water.
Polyether polyols
Polyether polyol (polyether for short) is prepared by the polyaddition reaction of an initiator (compound containing active hydrogen groups) and Ethylene Oxide (EO), Propylene Oxide (PO), Butylene Oxide (BO) and the like in the presence of a catalyst. The most productive polyether is the production of various general polyether polyols by using glycerol (glycerin) as an initiator and an epoxide (PO and EO are commonly used together) and changing the conditions of the PO and EO addition modes (mixed addition or separated addition), the addition ratio, the addition sequence and the like.
In the present invention, the number average molecular weight of the polyether polyol is 1000-.
The polymer is composed of a homologous mixture with the same chemical composition and different polymerization degrees, namely, the polymer is composed of high polymers with different Molecular chain lengths. The size of the molecules is usually characterized by the average molecular weight. The statistical average in terms of the number of molecules is referred to as the number average molecular weight, and the symbol is (Mn).
In a preferred embodiment, the polyether polyol has a number average molecular weight of 2000-3000.
In a preferred embodiment, the polyether polyol has a hydroxyl value of from 40 to 80 mgKOH/g.
In a more preferred embodiment, the polyether polyol has a hydroxyl value of from 55 to 60 mgKOH/g.
In a most preferred embodiment, the acid number of the polyether polyol is not higher than 0.5 mgKOH/g.
In chemistry, the acid number (or neutralization number, acid number, acidity) represents the number of milligrams of potassium hydroxide (KOH) required to neutralize 1 gram of chemical. Acid number is a measure of the number of free carboxylic acid groups in a compound (e.g., fatty acid) or mixture. A typical measurement procedure is to dissolve a known aliquot of the sample in an organic solvent, titrate it with a known concentration of potassium hydroxide solution, and use the phenolphthalein solution as a color indicator. The acid value can be used as an index of the deterioration degree of the grease. Unit of acid value: (KOH)/(mg/g).
In the present invention, the source of the polyether polyol is not particularly limited, and may be referred to as Xuzhou City Thailand Biotechnology Limited, model JL-220, JL-330, etc.
Isocyanates
Isocyanates are a generic term for the various esters of isocyanic acid. When classified by the number of-NCO groups, the polyisocyanates include monoisocyanates R-N ═ C ═ O and diisocyanates O ═ C ═ N-R-N ═ C ═ O, polyisocyanates, and the like. Monoisocyanate is an important intermediate in organic synthesis, can be prepared into a series of carbamate pesticides, bactericides and herbicides, and is also used for improving the water resistance of plastics, fabrics, leather and the like. The isocyanate with two or more functional groups can be used for synthesizing a series of polyurethane foam plastics, rubber, elastic fibers, coatings, adhesives, synthetic leather, artificial wood and the like with excellent performance.
In the present invention, the isocyanate is a polyisocyanate containing a benzene ring or an aliphatic ring.
In a preferred embodiment, the isocyanate is selected from at least one of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, and methylcyclohexyl diisocyanate.
In a more preferred embodiment, the isocyanate is a combination of diphenylmethane diisocyanate and isophorone diisocyanate.
In a more preferred embodiment, the weight ratio of diphenylmethane diisocyanate to isophorone diisocyanate is 1: (0.5-1.5).
In a most preferred embodiment, the weight ratio of diphenylmethane diisocyanate to isophorone diisocyanate is 1: 1.
in the present invention, the source of the diphenylmethane diisocyanate is not particularly limited, and German Bayer may be mentioned.
In the present invention, the source of the isophorone diisocyanate is not particularly limited, and Haoyet chemical Co.
In the invention, the weight ratio of the polyether polyol to the isocyanate is (1-3): 1.
in a more preferred embodiment, the polyether polyol and isocyanate are present in a weight ratio of 2: 1.
the inventor finds that the hydrolysis resistance of the waterborne polyurethane can be effectively improved by compounding the diphenylmethane diisocyanate and the isophorone diisocyanate. The inventor thinks that the possible reasons are that the molecular structures of the diphenylmethane diisocyanate and the isophorone diisocyanate both contain benzene rings or fat rings with larger volumes, and the benzene rings or the fat rings with larger volumes react with the polyester polyol to generate a covalent bond mixed network structure to form a hybrid network structure, and the benzene rings and the fat rings with larger volumes are used as umbrella-shaped structures inside molecules to protect a main chain, so that the water resistance of the product is stably improved, and the service life of the product is effectively prolonged. Meanwhile, the bulky benzene ring or aliphatic ring structure in the isocyanate can weaken the chain winding among long chains, improve the resin washing capacity and improve the efficiency of eluting the organic solvent. The invention also selects polyether polyol with a hydroxyl value of 40-80mgKOH/g through the optimization and compounding of polyether polyol and isocyanate, not only enhances the compatibility of soft and hard sections in the structure and achieves high peel strength with better stability, but also avoids the problems of poor fluidity and difficult processing of common high peel resin at low temperature.
Solvent(s)
The solvent is a liquid (gas or solid) capable of dissolving a solid, liquid or gaseous solute (the solvent and solute can be solid, liquid or gas), and then becomes a solution. The most common solvent in daily life is water. The organic solvent is an organic compound containing carbon atoms. Solvents generally possess a relatively low boiling point and are readily volatile. Or can be removed by distillation, leaving a dissolved material. Thus, the solvent may not chemically react with the solute. They must be inert. The solvent may extract soluble compounds from the mixture, the most common example being brewing coffee or tea with hot water. Solvents are generally clear, colorless liquids, most of which have a distinctive odor.
In the present invention, the solvent is not particularly limited, and ketones, alcohols, esters, ethers, hydrocarbons, nitrogen-or sulfur-containing compounds, and the like can be mentioned.
In a preferred embodiment, the solvent is a ketone solvent.
In a more preferred embodiment, the ketone solvent has a boiling point of less than 100 ℃.
In a most preferred embodiment, the solvent is acetone.
In the present invention, the source of acetone is not particularly limited, and Shenzhen Xiangxing chemical Co.
Chain extender
The chain extender, also called chain extender, is a substance that can react with functional groups on the linear polymer chain to extend the molecular chain and increase the molecular weight. Is often used for improving the mechanical property and the processing property of products such as polyurethane, polyester and the like.
In the present invention, the chain extender is not particularly limited, and a small molecule alcohol containing a di-or poly-hydroxyl group, an amino group-containing, imino compound or an ether alcohol may be mentioned.
In a preferred embodiment, the chain extender is a di-or poly-hydroxyl small molecule alcohol.
In a preferred embodiment, the chain extender is selected from at least one of ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 2, 3-butanediol, 1, 6-hexanediol, 1, 8-octanediol, neopentyl glycol, 2-methyl-1, 3-propanediol, glycerol, 1,2, 6-hexanetriol, 1,2, 4-butanetriol, triethylene glycol, tetraethylene glycol polyethylene glycol, dipropylene glycol, polypropylene glycol, diethylene glycol, pentaerythritol, glucitol, mannitol, dibutylene glycol, and polytetramethylene glycol.
In a more preferred embodiment, the chain extender is a combination of butanediol and ethylene glycol.
In a more preferred embodiment, the weight ratio of butanediol to ethylene glycol is (1-5): 1.
in a more preferred embodiment, the weight ratio of butanediol to ethylene glycol is 2: 1.
in the present invention, the sources of the butanediol and the ethylene glycol are not particularly limited, and Haoyet chemical company may be mentioned.
Neutralizing agent
The neutralizing agent is a substance for adjusting the pH value of the medium by the interaction of acid (acid salt) and alkali (basic salt). It has a great influence on emulsion polymerization, acetalization, curing of resin, storage of latex, etc. Organic or inorganic basic/acidic substances which can form salts with-COOH or-OH groups can be used as neutralizing agents, but the neutralization effects of different basic/acidic substances are very different. The neutralizing agent is usually sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium acetate, sodium pyrophosphate, sodium carbonate, ammonia water, hydrochloric acid, phosphoric acid, formic acid, acetic acid, AMP95, diethanolamine, triethanolamine, glycine, etc.
In the present invention, the neutralizing agent is an alkaline substance.
In a preferred embodiment, the neutralizing agent is an amine compound.
As the amine compound, there may be mentioned isophoronediamine, triethylamine, di-n-butylamine and the like.
In a preferred embodiment, the neutralizing agent is isophoronediamine.
In the present invention, the source of the isophoronediamine is not particularly limited, and Wuyi chemical Co., Ltd.
Water (W)
In the present invention, the water is not particularly limited, and deionized water, distilled water and the like can be mentioned.
In a preferred embodiment, the water is deionized water.
The second aspect of the present invention provides a method for preparing the aqueous polyurethane resin, comprising at least the steps of:
(1) adding isocyanate, polyether polyol and a solvent into a reaction kettle, and heating to 40-60 ℃ while stirring; then adding a chain extender, heating to 60-80 ℃, and stirring for 4-6 h;
(2) and (2) adding a neutralizing agent into the step (1) for neutralization, then adding water for emulsification, cooling to 20-50 ℃, and stirring for 6-8 hours to obtain the emulsion.
In a preferred embodiment, the preparation method of the aqueous polyurethane resin at least comprises the following steps:
(1) adding isocyanate, polyether polyol and a solvent into a reaction kettle, and heating to 50 ℃ while stirring; then adding a chain extender, heating to 70 ℃, and stirring for 6 hours;
(2) and (2) adding a neutralizing agent into the step (1) for neutralization, then adding water for emulsification, cooling to 30 ℃, and stirring for 8 hours to obtain the emulsion.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
Example 1
Embodiment 1 provides a raw material for preparing an aqueous polyurethane resin, which at least comprises the following components in parts by weight: 30 parts of polyether polyol, 15 parts of isocyanate, 30 parts of solvent, 4 parts of chain extender, 2 parts of neutralizer and 45 parts of water.
The polyether polyol has the number average molecular weight of 2000-3000, the hydroxyl value of 55-60mgKOH/g and the acid value of not higher than 0.5mgKOH/g, and is purchased from Xuzhou city, China national Tai Biotechnology Limited official, model JL-220; the isocyanate is the combination of diphenylmethane diisocyanate and isophorone diisocyanate, and the weight ratio is 1: 1; the diphenylmethane diisocyanate is selected from Bayer Germany; the isophorone diisocyanate is purchased from Hao Yi chemical company; the solvent is acetone, and is purchased from Xiangxing chemical Co., Ltd, Shenzhen city; the chain extender is a combination of butanediol and ethylene glycol, and the weight ratio is 2: 1; the butanediol and the ethylene glycol are purchased from Hao Yi chemical company Limited; the neutralizer is isophorone diamine and is purchased from Wuyi chemical Co.Ltd.
The preparation method of the waterborne polyurethane resin at least comprises the following steps:
(1) adding isocyanate, polyether polyol and a solvent into a reaction kettle, and heating to 50 ℃ while stirring; then adding a chain extender, heating to 70 ℃, and stirring for 6 hours;
(2) and (2) adding a neutralizing agent into the step (1) for neutralization, then adding water for emulsification, cooling to 30 ℃, and stirring for 8 hours to obtain the emulsion.
Example 2
Embodiment 2 provides a raw material for preparing an aqueous polyurethane resin, which at least comprises the following components in parts by weight: 20 parts of polyether polyol, 10 parts of isocyanate, 15 parts of solvent, 1 part of chain extender, 1 part of neutralizer and 30 parts of water.
The polyether polyol has the number average molecular weight of 2000-3000, the hydroxyl value of 55-60mgKOH/g and the acid value of not higher than 0.5mgKOH/g, and is purchased from Xuzhou city, China national Tai Biotechnology Limited official, model JL-220; the isocyanate is the combination of diphenylmethane diisocyanate and isophorone diisocyanate, and the weight ratio is 1: 0.5; the diphenylmethane diisocyanate is selected from Bayer Germany; the isophorone diisocyanate is purchased from Hao Yi chemical company; the solvent is acetone, and is purchased from Xiangxing chemical Co., Ltd, Shenzhen city; the chain extender is a combination of butanediol and ethylene glycol, and the weight ratio is 1: 1; the butanediol and the ethylene glycol are purchased from Hao Yi chemical company Limited; the neutralizer is isophorone diamine and is purchased from Wuyi chemical Co.Ltd.
The preparation method of the waterborne polyurethane resin at least comprises the following steps:
(1) adding isocyanate, polyether polyol and a solvent into a reaction kettle, and heating to 50 ℃ while stirring; then adding a chain extender, heating to 70 ℃, and stirring for 6 hours;
(2) and (2) adding a neutralizing agent into the step (1) for neutralization, then adding water for emulsification, cooling to 30 ℃, and stirring for 8 hours to obtain the emulsion.
Example 2
Embodiment 2 provides a raw material for preparing an aqueous polyurethane resin, which at least comprises the following components in parts by weight: 40 parts of polyether polyol, 30 parts of isocyanate, 40 parts of solvent, 5 parts of chain extender, 5 parts of neutralizer and 60 parts of water.
The polyether polyol has the number average molecular weight of 2000-3000, the hydroxyl value of 55-60mgKOH/g and the acid value of not higher than 0.5mgKOH/g, and is purchased from Xuzhou city, China national Tai Biotechnology Limited official, model JL-220; the isocyanate is the combination of diphenylmethane diisocyanate and isophorone diisocyanate, and the weight ratio is 1: 1.5; the diphenylmethane diisocyanate is selected from Bayer Germany; the isophorone diisocyanate is purchased from Hao Yi chemical company; the solvent is acetone, and is purchased from Xiangxing chemical Co., Ltd, Shenzhen city; the chain extender is a combination of butanediol and ethylene glycol, and the weight ratio is 5: 1; the butanediol and the ethylene glycol are purchased from Hao Yi chemical company Limited; the neutralizer is isophorone diamine and is purchased from Wuyi chemical Co.Ltd.
The preparation method of the waterborne polyurethane resin at least comprises the following steps:
(1) adding isocyanate, polyether polyol and a solvent into a reaction kettle, and heating to 50 ℃ while stirring; then adding a chain extender, heating to 70 ℃, and stirring for 6 hours;
(2) and (2) adding a neutralizing agent into the step (1) for neutralization, then adding water for emulsification, cooling to 30 ℃, and stirring for 8 hours to obtain the emulsion.
Example 3
Embodiment 3 provides a raw material for preparing an aqueous polyurethane resin, which at least comprises the following components in parts by weight: 40 parts of polyether polyol, 30 parts of isocyanate, 40 parts of solvent, 10 parts of chain extender, 5 parts of neutralizer and 60 parts of water.
The polyether polyol has the number average molecular weight of 2000-3000, the hydroxyl value of 55-60mgKOH/g and the acid value of not higher than 0.5mgKOH/g, and is purchased from Xuzhou city, China national Tai Biotechnology Limited official, model JL-220; the isocyanate is the combination of diphenylmethane diisocyanate and isophorone diisocyanate, and the weight ratio is 1: 1.5; the diphenylmethane diisocyanate is selected from Bayer Germany; the isophorone diisocyanate is purchased from Hao Yi chemical company; the solvent is acetone, and is purchased from Xiangxing chemical Co., Ltd, Shenzhen city; the chain extender is a combination of butanediol and ethylene glycol, and the weight ratio is 5: 1; the butanediol and the ethylene glycol are purchased from Hao Yi chemical company Limited; the neutralizer is isophorone diamine and is purchased from Wuyi chemical Co.Ltd.
The preparation method of the waterborne polyurethane resin at least comprises the following steps:
(1) adding isocyanate, polyether polyol and a solvent into a reaction kettle, and heating to 50 ℃ while stirring; then adding a chain extender, heating to 70 ℃, and stirring for 6 hours;
(2) and (2) adding a neutralizing agent into the step (1) for neutralization, then adding water for emulsification, cooling to 30 ℃, and stirring for 8 hours to obtain the emulsion.
Example 4
Example 4 differs from example 1 in that the isocyanate is hexamethylene diisocyanate.
Example 5
Example 5 differs from example 1 in that the isocyanate is lysine diisocyanate.
Example 6
Example 6 differs from example 1 in that the isocyanate is a combination of diphenylmethane diisocyanate and hexamethylene diisocyanate in a weight ratio of 1: 1.
example 7
Example 7 differs from example 1 in that the polyether polyol has a hydroxyl value of 260mgKOH/g, a number average molecular weight of 400 and is selected from the group of Dow under the trade name VORANOL 220-.
Performance testing
And (3) testing water resistance: the test was carried out according to the GB/T1733-93 standard.
Calculating the formula:
∩＝(M2-M1)/M1x 100%, wherein the water absorption of ∩ -waterborne polyurethane, M1Original mass g, M of the aqueous polyurethane2Mass g of the aqueous polyurethane after soaking.
And (4) testing standard: the water absorption rate is 0-2%, and is recorded as good; the water absorption is 2-10%, and is recorded as general; the water absorption was greater than 10%, and is reported as poor.
The test results are shown in Table 1.
TABLE 1 Water resistance test results of the aqueous polyurethane resins obtained in examples 1 to 7
Figure BDA0002559045330000111
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.

Claims (10)

1. The waterborne polyurethane resin is characterized by comprising the following raw materials in parts by weight: 20-40 parts of polyether polyol, 10-30 parts of isocyanate, 15-40 parts of solvent, 1-10 parts of chain extender, 1-5 parts of neutralizer and 30-60 parts of water.
2. The aqueous polyurethane resin as described in claim 1, wherein the polyether polyol has a number average molecular weight of 1000-5000.
3. The aqueous polyurethane resin according to claim 1, wherein the polyether polyol has a hydroxyl value of 40 to 80 mgKOH/g.
4. The aqueous polyurethane resin according to claim 1, wherein the isocyanate is a polyisocyanate having a benzene ring or an aliphatic ring.
5. The aqueous polyurethane resin according to claim 4, wherein the isocyanate is at least one selected from the group consisting of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, and methylcyclohexyl diisocyanate.
6. The aqueous polyurethane resin according to claim 5, wherein the isocyanate is a combination of diphenylmethane diisocyanate and isophorone diisocyanate in a weight ratio of 1: (1-2).
7. The aqueous polyurethane resin according to claim 1, wherein the chain extender is at least one member selected from the group consisting of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butylene glycol, 2, 3-butylene glycol, 1, 6-hexanediol, 1, 8-octanediol, neopentyl glycol, 2-methyl-1, 3-propanediol, glycerin, 1,2, 6-hexanetriol, 1,2, 4-butanetriol, triethylene glycol, tetraethylene glycol polyethylene glycol, dipropylene glycol, polypropylene glycol, diethylene glycol, pentaerythritol, glucitol, mannitol, dibutylene glycol, and polybutylene glycol.
8. The aqueous polyurethane resin according to claim 7, wherein the chain extender is a combination of butanediol and ethylene glycol in a weight ratio of (1-5): 1.
9. the aqueous polyurethane resin according to claim 1, wherein the neutralizing agent is an amine compound.
10. A method for preparing the aqueous polyurethane resin according to any one of claims 1 to 9, characterized by comprising at least the steps of:
(1) adding isocyanate, polyether polyol and a solvent into a reaction kettle, and heating to 40-60 ℃ while stirring; then adding a chain extender, heating to 60-80 ℃, and stirring for 4-6 h;
(2) and (2) adding a neutralizing agent into the step (1) for neutralization, then adding water for emulsification, cooling to 20-50 ℃, and stirring for 6-8 hours to obtain the emulsion.
CN202010606035.5A 2020-06-29 2020-06-29 Waterborne polyurethane resin and preparation method thereof Withdrawn CN111690118A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114940735A (en) * 2021-06-18 2022-08-26 佛山市三水联美化工有限公司 High-water-solubility PU resin and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114940735A (en) * 2021-06-18 2022-08-26 佛山市三水联美化工有限公司 High-water-solubility PU resin and preparation method thereof
CN114940735B (en) * 2021-06-18 2023-09-15 佛山市三水联美化工有限公司 High-solubility water-based PU resin and preparation method thereof

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Application publication date: 20200922