CN108586720B - Alkyd prepolymer and preparation method and application thereof - Google Patents
Alkyd prepolymer and preparation method and application thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
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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
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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- 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
- C09J175/06—Polyurethanes from polyesters
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Abstract
The invention discloses an alkyd prepolymer and a preparation method and application thereof. The invention discloses an alkyd prepolymer prepared from dicarboxyl sulfonate and micromolecular dihydric alcohol through esterification reaction, wherein the alkyd prepolymer comprises three compounds with structural formulas. Also discloses a specific preparation method of the alkyd prepolymer and application of the alkyd prepolymer. The invention provides an alkyd prepolymer with an anionic sulfonic group and a nonionic hydrophilic group and used for manufacturing waterborne polyurethane. The water-soluble raw material can be used for preparing hydroxyl waterborne polyurethane resin, waterborne polyurethane curing agent and waterborne blocked polyurethane curing agent, and the finished product can have good water dispersibility, water solubility and storage stability only by adding a small amount.
Description
Technical Field
The invention relates to an alkyd prepolymer and a preparation method and application thereof.
Background
The polyurethane coating and the polyurethane adhesive have excellent performance and are widely applied to the fields of wood furniture, automobiles, buildings, flexible packages and the like. At present, the two products used in China are basically solvent-based, and mainly the existing water-based products have more complex processing technology and single hydrophilic raw material variety, so that the water-based products cannot completely replace solvent-based products. With the enhancement of environmental awareness of people and the increase of the execution force of national environmental regulations, the waterborne polyurethane becomes the urgent need for the transformation development of products of small and medium-sized enterprises, so that the research on hydrophilic raw materials convenient for processing is helpful for transforming the polyurethane coating and the polyurethane adhesive from a solvent type to a waterborne type.
The basic idea of the polyurethane industry, which is dedicated to the research of polyurethane water-based, is to introduce hydrophilic groups into the conventional polyurethane to modify the polyurethane so that the polyurethane can be easily emulsified and dispersed in water and maintain a certain stability, and therefore, some patent documents are published. The research method mainly comprises nonionic modification, anionic modification, cationic modification and mixed modification, each modification method has certain advantages and disadvantages, and compared with the method, the method has the advantages that the anionic sulfonic group is a hydrophilic group, is strong acid strong alkali salt, has high ionization degree, forms strong electrostatic repulsion between latex particles, prevents the latex particles from coagulating, and is easy to prepare the waterborne polyurethane with high solid content (more than 50 percent); it has good hydrophilicity, and can achieve satisfactory water dispersion effect with less addition amount. However, sulfonic acid compounds are aqueous compounds or non-aqueous solids, which are only soluble in water, insoluble in organic solvents, insoluble in diisocyanate, and incapable of reacting directly with isocyanate, and the sulfonic acid group is introduced into the intermediate link of the isocyanate structure requiring bridging, and the manufacturing process is relatively complicated. In order to simplify the process of introducing an anionic sulfonic group into an isocyanate main chain, CN1648151A discloses a water dispersible sulfonated polyester polyol, which can directly react with isocyanate in an organic assistant to simplify the processing steps, however, the viscosity of the water dispersible sulfonated polyester polyol is relatively high, the solid content of the product BY3306B (molecular weight 550) with the minimum molecular weight produced BY beijing baizai chemical limited is only 70%, the product contains 30% of diethylene glycol dimethyl ether solvent, the appearance is jelly-like, the product cannot be dissolved in common ester and ketone solvents, and the product is insoluble in water and can only be dispersed in water. CN103570915A discloses a method for preparing a high-solid hydroxyl-containing waterborne polyurethane resin by reacting water-dispersible sulfonated polyester glycol with polyester glycol, micromolecular glycol, polyol, dimethylol propionic acid and diisocyanate, wherein the added dimethylol propionic acid is a hydrophilic group, which indicates that the hydrophilicity of the sulfonated polyester glycol is not enough, other hydrophilic groups are required to be added, in addition, the carboxyl group contained in the waterborne resin is required to be neutralized by organic amine, and the problems of ammonia odor and yellowing of products exist.
How to obtain a hydrophilic raw material with better hydrophilicity, less addition amount and less influence on the performance of the product is urgent research on the water-based preparation of polyurethane.
Disclosure of Invention
In order to overcome the defects of the prior art, one of the objects of the present invention is to provide an alkyd prepolymer which integrates the advantages of anionic sulfonic groups and nonionic hydrophilic groups, has good water dispersibility or water solubility, has high-activity hydroxyl and carboxyl groups, can directly react with isocyanate groups, and is a water-soluble raw material for preparing hydroxyl-type aqueous polyurethane resins and isocyanate-type aqueous curing agents. Another object of the present invention is to provide a process for the preparation of such alkyd prepolymers. It is a further object of the present invention to provide the use of such alkyd prepolymers.
The technical scheme adopted by the invention is as follows:
an alkyd prepolymer comprising compounds of the structures shown in formulas (1) to (3):
in the formulas (1) to (3), R represents a non-alcoholic hydroxyl structural group of the small molecular dihydric alcohol; m independently represents a monovalent alkali metal cation;
in the formula (1), m is 0-3; in the formula (2), n is 0 to 3; in the formula (3), z is 0-2;
the small molecule dihydric alcohol is dihydric alcohol with molecular weight less than 300.
The preparation method of the alkyd prepolymer takes dicarboxyl sulfonate and micromolecule dihydric alcohol as raw materials to prepare the alkyd prepolymer through esterification reaction.
The preparation method of the alkyd prepolymer comprises the following steps:
a) adding dicarboxyl sulfonate, micromolecular dihydric alcohol and water into a reactor, stirring, heating to 90-97 ℃, mixing and dissolving;
b) adding an antioxidant and a catalyst, sealing the reactor, introducing protective gas, heating the reactor to 100-180 ℃, and carrying out esterification reaction for 10-20 h;
c) adding a solvent into the reactor to dissolve the esterification product obtained in the step b), carrying out vacuum distillation and purification, and discharging to obtain the alkyd prepolymer.
In step a) of the preparation method, the mass ratio of the dicarboxyl sulfonate to the water is 1: (0.5 to 2.0); the molar ratio of the dicarboxyl sulfonate to the small-molecule dihydric alcohol is 1: (1.5 to 3).
In the step b) of the preparation method, the addition amount of the antioxidant is 0.01-0.5 percent of the total mass of the raw materials; the addition amount of the catalyst is 0.03-0.1% of the total mass of the raw materials.
In the step c) of the preparation method, the adding amount of the solvent is 20-200% of the sum of the mass of the dicarboxyl sulfonate and the mass of the micromolecular dihydric alcohol.
In step a) of the preparation method, the dicarboxyl sulfonate is dicarboxyl sulfonate alkali metal salt; the water is at least one of distilled water and deionized water.
In the step b) of the preparation method, the antioxidant is hindered phenol antioxidant; the catalyst is at least one of tetrabutyl titanate, antimony trioxide and zinc acetate.
In the step c) of the preparation method, the solvent is polyethylene glycol with the molecular weight of 220-800.
In step a) of the preparation method, the small molecule diol is at least one of 3-methyl-1, 5-pentanediol, neopentyl glycol, ethylene glycol, diethylene glycol, cyclohexanediol, methylpropanediol, TCD tricyclo glycol, 1, 3-propanediol, 1, 4-dimethylolcyclohexane, 1, 4-butanediol, 1, 3-butanediol, 1, 5-pentanediol, diethylpentanediol, 1, 2-propanediol, diethylene glycol, tetrahydrofuran diol, 1, 6-hexanediol, trimethylpentanediol, butylethylpropanediol, 2-bis (4-hydroxyphenyl) propane, dipropylene glycol, tripropylene glycol, or ethylhexanediol.
In the step b) of the preparation method, the reflux temperature of the water outlet of the condenser is maintained at 100-102 ℃ during the esterification reaction period, when the water yield approaches the water adding amount, the acid value of the esterification product is measured, and the reaction is stopped when the acid value reaches the designed value.
In step b) of the preparation method, the acid value of the esterified substance is in the range of 10mgKOH/g to 80 mgKOH/g.
In the step c) of the preparation method, the vacuum distillation and purification specifically comprise the following steps: vacuumizing to 0.09-0.093 MPa below 100 deg.C, distilling, heating to 150-180 deg.C when distillate is reduced, vacuumizing until no liquid drops are distilled, cooling to 110 deg.C, introducing protective gas to normal pressure, and cooling to below 70 deg.C.
The alkyd prepolymer is applied to the preparation of hydroxyl waterborne polyurethane resin or waterborne polyurethane curing agent.
The invention has the beneficial effects that:
the present invention provides an alkyd prepolymer for the production of aqueous polyurethane having anionic sulfonic acid groups and nonionic hydrophilic groups, which is a solvent-free flowable liquid (the viscosity of the alkyd prepolymer of examples 1 to 3 at 25 ℃ is 6800Pa · s to 9100mPa · s). The water-soluble raw material can be used for preparing hydroxyl waterborne polyurethane resin, waterborne polyurethane curing agent and waterborne blocked polyurethane curing agent, and the finished product can have good water dispersibility, water solubility and storage stability only by adding a small amount.
The method comprises the following specific steps:
1) the alkyd prepolymer disclosed by the invention is good in hydrophilicity, and can be dissolved in water to form colorless and transparent liquid.
2) The alkyd prepolymer disclosed by the invention is low in viscosity, is a flowable liquid when the solid content is 100%, and is favorable for the subsequent modification reaction of isocyanate.
3) The molecular weight of the alkyd prepolymer can be calculated by detecting the acid value and the hydroxyl value of a product, the molecular weight is smaller, the activity of functional groups is high, the modified isocyanate can have good water solubility or water dispersibility only by using a smaller adding amount, the adding amount of the modified hydrophilic raw material is small, the consumed-NCO in the preparation process is small, the reserved-NCO is high, and the strength performance and the water resistance of a final product are high.
4) Hydroxyl and carboxyl of the alkyd prepolymer and hydroxyl of polyethylene glycol used as a solvent can be chemically reacted with isocyanate, and the polyisocyanate is mixed and modified by anionic and nonionic hydrophilic monomers, so that beads formed by the modified isocyanate in water are protected by a double-layer surfactant, and the water dispersibility, water solubility and storage stability of the waterborne polyurethane can be effectively improved.
5) The reactivity of hydroxyl contained in the alkyd prepolymer is higher than that of carboxyl, and the reaction speed has high and low selectivity when the alkyd prepolymer reacts with diisocyanate with a symmetrical structure, so that the reaction is controlled; when the isocyanate reacts with the aromatic diisocyanate with high activity and symmetrical structure, the hydroxyl with high activity reacts firstly, and the carboxyl with low activity reacts later to form orderly reaction speed in the system, thereby solving the problem that the chemical reaction speed is difficult to control due to the high activity of the aromatic diisocyanate with symmetrical structure. In the application example 3 of the invention, 4 '-MDI and alkyd prepolymer are used for preparing the waterborne pouring sealant, although the two-NCO of the 4, 4' -MDI has the same activity and very high activity, the reaction can be carried out stably when the two-NCO reacts with hydroxyl and carboxyl with different activities, and implosion can not occur, so the high-quality waterborne pouring sealant is prepared.
6) The alkyd prepolymer has wide acid value range, can be adjusted, and is convenient to prepare raw materials suitable for various performance requirements.
7) Neither the waterborne polyurethane resin prepared by the alkyd prepolymer of the invention nor the waterborne polyurethane curing agent needs amine neutralization, and the problem of negative quality of products caused by neutralization with amine substances after chain extension by adding dimethylol carboxylic acid in the prior art is solved because carboxyl groups are removed after reaction with isocyanate.
8) The method can reduce the chemical synthesis steps for producing the waterborne polyurethane, and brings better economic benefit for the enterprises producing the polyurethane to carry out product transformation.
Drawings
FIG. 1 is a schematic representation of the reaction equation for preparing an alkyd prepolymer according to the present invention.
Detailed Description
An alkyd prepolymer comprising compounds of the structures shown in formulas (1) to (3):
in the formulas (1) to (3), R represents a non-alcoholic hydroxyl structural group of the small molecular dihydric alcohol; m independently represents a monovalent alkali metal cation;
in the formula (1), m is 0-3; in the formula (2), n is 0 to 3; in the formula (3), z is 0-2;
the small molecule dihydric alcohol is dihydric alcohol with molecular weight less than 300.
Further, in the formulas (1) to (3), R represents a group of a non-alcoholic hydroxyl group structure of the small molecule diol refers to a remaining part of the small molecule diol structure excluding an alcoholic hydroxyl group.
Preferably, in the formulae (1) to (3), M represents Na independently+Or K+。
Further, formula (1) indicates that both carboxyl groups of the dicarboxy sulfonate are esterified, and formulas (2) and (3) indicate that one carboxyl group of the dicarboxy sulfonate is esterified and the other carboxyl group remains unesterified. This prepolymer is soluble in low molecular weight polyethylene glycols.
FIG. 1 is a schematic representation of the reaction equation for preparing an alkyd prepolymer according to the present invention. The preparation of an alkyd prepolymer composed of structural compounds represented by the formulae (1) to (3) according to the present invention is further illustrated with reference to FIG. 1 as follows: the product of the reaction formula (1) has hydroxyl groups at both ends, and both carboxyl groups of the dicarboxysulfonate are esterified; the product of the reaction formula (2) has a carboxyl group at one end and a hydroxyl group at the other end, and the product of the reaction formula (3) has carboxyl groups at both ends, both of which indicate that one carboxyl group of the dicarboxy sulfonate is esterified and the other carboxyl group is not esterified and remained. The carboxyl groups of the dicarboxyl sulfonate are not completely esterified in the invention, and the purpose is to obtain an esterified product partially terminated by the carboxyl groups, wherein the carboxyl group termination means that the sulfonic acid group content of esterified molecules is high, and means that the esterified molecules are relatively small. The sulfonic acid group content is high, the hydrophilicity is good, the amount of hydrophilic substances added in the subsequent preparation of the aqueous polyurethane resin and the aqueous polyurethane curing agent is small, and the consumption of effective functional groups is low; the esterified molecules have small viscosity, and are beneficial to subsequent processing. The alkyd prepolymer disclosed by the invention has structural characteristics of hydroxyl and carboxyl, is different from sulfonated polyester polyol disclosed in the prior art CN1648151A, and is also different from micromolecule dihydric alcohol with the molecular weight of 350-1000 and containing sulfonic acid groups disclosed in the prior art CN 106366291A.
The molecular structure of the alkyd prepolymer is in three forms, the ends of the alkyd prepolymer all have hydroxyl and carboxyl, the ends of the low molecular weight polyethylene glycol used as a solvent also have hydroxyl, and the low molecular weight polyethylene glycol and the hydroxyl can react with isocyanate to introduce anionic sulfonic acid groups and nonionic hydrophilic groups into an isocyanate structure, so that the alkyd prepolymer provided by the invention is a water-soluble raw material with the anionic sulfonic acid groups and the nonionic hydrophilic groups and used for preparing waterborne polyurethane.
The preparation method of the alkyd prepolymer takes dicarboxyl sulfonate and micromolecule dihydric alcohol as raw materials to prepare the alkyd prepolymer through esterification reaction.
Further, the preparation method of the alkyd prepolymer comprises the following steps:
a) adding dicarboxyl sulfonate, micromolecular dihydric alcohol and water into a reactor, stirring, heating to 90-97 ℃, mixing and dissolving;
b) adding an antioxidant and a catalyst, sealing the reactor, introducing protective gas, heating the reactor to 100-180 ℃, and carrying out esterification reaction for 10-20 h;
c) adding a solvent into the reactor to dissolve the esterification product obtained in the step b), carrying out vacuum distillation and purification, and discharging to obtain the alkyd prepolymer.
Preferably, in step a) of the preparation method, the mass ratio of the dicarboxyl sulfonate to the water is 1: (0.5 to 2.0); the molar ratio of the dicarboxyl sulfonate to the small-molecule dihydric alcohol is 1: (1.5 to 3).
Preferably, in the step b) of the preparation method, the addition amount of the antioxidant is 0.01-0.5% of the total mass of the raw materials; the addition amount of the catalyst is 0.03-0.1% of the total mass of the raw materials. The starting materials mentioned here are all the starting materials added in step a) of the preparation process.
Preferably, in the step c) of the preparation method, the addition amount of the solvent is 20-200% of the sum of the mass of the dicarboxyl sulfonate and the mass of the small molecular diol.
Preferably, the dicarboxylic acid sulfonate is an alkali metal salt of dicarboxylic acid; further preferably, the dicarboxyl sulfonate is at least one of a dicarboxyl sulfonic acid sodium salt and a dicarboxyl sulfonic acid potassium salt; still more preferably, the dicarboxy sulfonate is sodium 5-sulfoisophthalate. The sodium 5-sulfoisophthalate on the market has sufficient supply and low price, and is suitable for hydrophilic substances preferably aqueous polyurethane.
Preferably, the small molecule diol is at least one of 3-methyl-1, 5-pentanediol, neopentyl glycol, ethylene glycol, diethylene glycol, cyclohexanediol, methylpropanediol, TCD tricyclo diol, 1, 3-propanediol, 1, 4-dimethylolcyclohexane, 1, 4-butanediol, 1, 3-butanediol, 1, 5-pentanediol, diethylpentanediol, 1, 2-propanediol, diethylene glycol, tetrahydrofuran diol, 1, 6-hexanediol, trimethylpentanediol, butylethylpropanediol, 2-bis (4-hydroxyphenyl) propane, dipropylene glycol, tripropylene glycol, or ethylhexanediol; still more preferably, the small molecule diol is at least one of diethylene glycol, 1, 4-butanediol, 1, 2-propanediol, methyl propanediol and neopentyl glycol.
Preferably, in step a) of the preparation method, the water is at least one of distilled water and deionized water.
Preferably, in the step b) of the preparation method, the antioxidant is a hindered phenol antioxidant; more preferably, in step b) of the preparation method, the antioxidant is at least one of antioxidants 1010, 1076 and 3114.
Preferably, in step b) of the preparation method, the catalyst is at least one of tetrabutyl titanate, antimony trioxide and zinc acetate.
Preferably, in the step c) of the preparation method, the solvent is polyethylene glycol with a molecular weight of 220-800.
Preferably, in step b) of the preparation method, the esterification temperature is 110 to 160 ℃.
Preferably, in step b) of the preparation method, the reflux temperature at the water outlet of the condenser is maintained at 100-102 ℃ during the esterification reaction until the water yield is the same as the added water amount, the acid value of the esterification product is measured, and the reaction is stopped when the acid value reaches the designed value.
Further, in step b) of the preparation method, the acid value of the esterified substance is in the range of 10mgKOH/g to 80 mgKOH/g.
Preferably, in step c) of the preparation method, the vacuum distillation purification specifically comprises: vacuumizing to 0.09-0.093 MPa below 100 deg.C, distilling, heating to 150-180 deg.C when distillate is reduced, vacuumizing until no liquid drops are distilled, cooling to 110 deg.C, introducing protective gas to normal pressure, and cooling to below 70 deg.C.
Preferably, in the preparation method, the protective gas is one of nitrogen, argon, neon and helium.
The esterification reaction method is different from the preparation method of sulfonated polyester diol disclosed by CN1648151A in the prior art, mainly the esterification reaction temperature is lower, and the esterification reaction temperature in the prior art is higher (160-230 ℃). The invention only needs to carry out partial esterification reaction and keeps a certain acid value, thus being capable of preparing products with smaller molecular weight and lower viscosity and being beneficial to the reaction of the subsequent procedure and the polyisocyanate.
The alkyd prepolymer is applied to the preparation of hydroxyl waterborne polyurethane resin or waterborne polyurethane curing agent.
The present invention will be described in further detail with reference to specific examples. The starting materials used in the examples are, unless otherwise specified, commercially available from conventional sources.
In the following examples, the detection method is illustrated as follows:
1. the viscosity was measured according to the national Standard GB/T2794-1995 determination of the viscosity of the adhesive.
2. The detection of the solid content is carried out according to the national standard GB/T2793-1995 determination of the content of the adhesive non-volatile matter.
3. The hydroxyl value was measured according to the Standard of chemical industry "determination of resin value of HG/T2709-95".
4. Detecting the acid value according to the determination of the acid value of the unsaturated polyester resin GB/T2895-2008 of the national Standard
Example 1:
a) adding 214g of distilled water, 168g of 1, 4-butanediol and 200g of isophthalic acid-5-sodium sulfonate into a reactor, stirring, heating to 90-97 ℃, and mixing and dissolving;
b) adding 0.4g of antioxidant 1010 and 0.2g of tetrabutyl titanate, sealing the reactor, introducing nitrogen, increasing the steam quantity when the temperature in the kettle rises to 107 ℃, controlling the reflux temperature of the water outlet of the condenser to be 100-102 ℃, continuously raising the temperature in the reactor to be 120-130 ℃, carrying out esterification reaction for 15 hours, maintaining the reflux temperature of the water outlet of the condenser to be 100-102 ℃ during the esterification reaction, controlling the water outlet rate of condensed water, starting to measure the acid value when the water outlet quantity is close to the water adding quantity, stopping the reaction when the set acid value is reached, and stopping the cooling water of the condenser;
c) adding 122g of polyethylene glycol (molecular weight is 400) into the reactor, stirring to dissolve the esterified materials, starting to vacuumize, slowly increasing the vacuum degree to 0.092MPa below 100 ℃, increasing the temperature to 150 ℃ when the distillate is reduced, continuing to vacuumize until no liquid drops are distilled out, cooling to 110 ℃, introducing nitrogen to normal pressure, cooling to 70 ℃, and discharging to obtain the alkyd prepolymer of the example 1.
The product of example 1 was tested for a solids content of 99.8%, a viscosity of 9100mPa · s (25 ℃), an acid value of 43.5mgKOH/g, a hydroxyl value of 180.8mgKOH/g, and the calculated molecular weight was 500.
Example 2:
a) adding 230g of distilled water, 127.2g of diethylene glycol, 104.2g of neopentyl glycol and 200g of sodium m-phthalate-5-sulfonate into a reactor, stirring, heating to 90-97 ℃, and mixing and dissolving;
b) adding 0.5g of antioxidant 1010 and 0.3g of tetrabutyl titanate, sealing the reactor, introducing nitrogen, increasing the steam quantity when the temperature in the kettle rises to 107 ℃, controlling the reflux temperature of the water outlet of the condenser to be 100-102 ℃, continuously raising the temperature in the reactor to 160-170 ℃, carrying out esterification reaction for 17 hours, maintaining the reflux temperature of the water outlet of the condenser to be 100-102 ℃ during the esterification reaction, controlling the water outlet rate of condensed water, starting to measure the acid value when the water outlet quantity is close to the water adding quantity, stopping the reaction when the set acid value is reached, and stopping the cooling water of the condenser;
c) adding 135g of polyethylene glycol (molecular weight is 400) into the reactor, stirring to dissolve the esterified materials, starting vacuumizing, slowly increasing the vacuum degree to 0.092MPa below 100 ℃, increasing the temperature to 180 ℃ when the distillate is reduced, continuing vacuumizing until no liquid drops are distilled out, cooling to 110 ℃, introducing nitrogen to the normal pressure, cooling to 70 ℃, discharging, and obtaining the alkyd prepolymer of example 2.
The product of example 2 was tested to have a solids content of 99.8%, a viscosity of 7500mPa · s (25 ℃), an acid value of 21.5mgKOH/g, a hydroxyl value of 194.2mgKOH/g, and the calculated molecular weight of the product was 520.
Example 3:
a) adding 220g of distilled water, 134.2g of methyl propylene glycol and 200g of isophthalic acid-5-sodium sulfonate into a reactor, stirring, heating to 90-97 ℃, and mixing and dissolving;
b) adding 0.4g of antioxidant 1010 and 0.2g of tetrabutyl titanate, sealing the reactor, introducing nitrogen, increasing the steam quantity when the temperature in the kettle rises to 107 ℃, controlling the reflux temperature of the water outlet of the condenser to be 100-102 ℃, continuously raising the temperature in the reactor to be 120-130 ℃, carrying out esterification reaction for 14 hours, maintaining the reflux temperature of the water outlet of the condenser to be 100-102 ℃ during the esterification reaction, controlling the water outlet rate of condensed water, starting to measure the acid value when the water outlet quantity is close to the water adding quantity, stopping the reaction when the set acid value is reached, and stopping the cooling water of the condenser;
c) adding 100g of polyethylene glycol (molecular weight is 400) into the reactor, stirring to dissolve the esterified materials, starting vacuumizing, slowly increasing the vacuum degree to 0.092MPa below 100 ℃, increasing the temperature to 150 ℃ when the distillate is reduced, continuing vacuumizing until no liquid drops are distilled out, cooling to 110 ℃, introducing nitrogen to the normal pressure, cooling to 70 ℃, discharging to obtain the alkyd prepolymer of the embodiment 3.
The product of example 3 was found to have a solid content of 99.6%, a viscosity of 6800 mPas (25 ℃), an acid value of 35.1mgKOH/g, a hydroxyl value of 184.6mgKOH/g, and a molecular weight of 519.
Application example 1:
1) preparation of hydroxyl-containing aqueous polyurethane resin
200g of poly adipic acid-1, 2-propylene glycol-1, 4-butanediol ester diol (molecular weight is 2000), 44g of N-methyl pyrrolidone, 44g of propylene glycol monomethyl ether acetate and 36g of the alkyd prepolymer obtained in example 1 are added into a No. 1 reactor, uniformly stirred, 29g of MDI is added, the mixture is reacted for 0.5 hour at room temperature, the temperature is increased to 60-70 ℃ for 3 hours, the mixture is further increased to 75-85 ℃ for 6 hours, the temperature is reduced to 60 ℃ for discharging, and the hydroxyl-containing waterborne polyurethane resin is obtained, wherein the solid content of the waterborne resin is detected to be 75%, the hydroxyl value is 15.6mgKOH/g, and the viscosity is 5500 mPas (25 ℃).
2) Preparation of aqueous HDI trimer curing agent
Adding 200g of HDI trimer into a No. 2 reactor, adding 20g of the water-soluble alkyd prepolymer obtained in the example 1, stirring and mixing, reacting at room temperature for 1 hour, raising the temperature to 60 ℃ for reacting for 1 hour, raising the temperature to 80-90 ℃ for reacting for 9.5 hours, sampling and detecting the NCO content, stopping heating when the NCO content is reduced to be stable, cooling to 60 ℃ and discharging to obtain the water-based HDI trimer curing agent, wherein the NCO% of the curing agent is detected to be 15.4%.
3) Applications of
Uniformly mixing 300g of the waterborne polyurethane resin with hydroxyl obtained in the step 1) and 30g of the waterborne HDI trimer curing agent obtained in the step 2) to prepare a two-component waterborne polyurethane adhesive for bonding a PVC film and a solid wood board, and carrying out a 180-DEG C peel strength test on a rigid material according to an adhesive 180-DEG C peel strength test method GB/T2790-.
Application example 2:
1) preparation of hydroxyl-containing aqueous polyurethane resin
Adding 200g of poly adipic acid-sebacic acid-neopentyl glycol-1, 4-butanediol glycol ester diol (molecular weight is 2000), 46g of N-methyl pyrrolidone, 45g of propylene glycol monomethyl ether acetate and 40g of the alkyd prepolymer obtained in the example 2 into a No. 1 reactor, uniformly stirring, adding 34g of MDI, heating to 60-70 ℃, reacting for 3 hours, heating to 75-85 ℃, reacting for 5 hours, cooling to 60 ℃, discharging to obtain the waterborne polyurethane resin with hydroxyl, wherein the solid content of the resin is 75%, the hydroxyl value is 12.5mgKOH/g, and the viscosity is 6200mPa & s (25 ℃).
2) Preparation of aqueous HDI trimer curing agent
Adding 300g of IPDI trimer (solid content is 70%, NCO%: 12.3%) into a reactor No. 2, adding 30g of the water-soluble alkyd prepolymer obtained in the embodiment 2, stirring and mixing, reacting at room temperature for 1 hour, raising the temperature to 60 ℃ for reaction for 1 hour, raising the temperature to 80-90 ℃ for reaction for 10 hours, sampling and detecting the NCO content, stopping heating when the NCO content is reduced to be stable, cooling to 60 ℃ and discharging to obtain the water-based IPDI trimer curing agent, wherein the solid content of the curing agent is 72.6% and the NCO% is 9.1% through detection.
3) Applications of
Uniformly mixing 300g of the waterborne polyurethane resin with hydroxyl obtained in the step 1) and 60g of the waterborne IPDI trimer curing agent obtained in the step 2) to obtain a two-component waterborne polyurethane coating, preparing a test piece, and curing for 48 hours at 50 ℃ to obtain a paint film with the following properties: gloss (60 °): more than or equal to 88 percent; hardness: shore D50; impact strength: 46KJ/m2(ii) a Adhesion force: grade 1; flexibility: 1 mm.
The detection method comprises the following steps: the gloss is in accordance with GB9754-88, the hardness is in accordance with GB1730-79, the impact strength is in accordance with GB/T2571-1995, the adhesion is in accordance with GB1720-89, and the flexibility is in accordance with GB1731-79 standard.
Application example 3:
1) preparation of single-component moisture-curing polyurethane adhesive-water-based pouring sealant
Adding 300g of baked 4, 4-MDI into a reactor, starting stirring, adding 219g of the water-soluble alkyd prepolymer obtained in the embodiment 3, reacting for 1 hour at room temperature, raising the temperature to 60 ℃ for reacting for 1 hour, raising the temperature to 70-80 ℃ for reacting for 2 hours, reacting for 1-2 hours at 80-90 ℃, sampling and detecting the NCO content, stopping the reaction when the NCO content is reduced to be stable, cooling to 60 ℃, discharging, and obtaining the solvent-free moisture-curable polyurethane adhesive, namely the water-based pouring sealant. The appearance of the water-based pouring sealant is detected to be light yellow transparent viscous liquid, the viscosity is 8900mPa & s, and the NCO percent is 11.8 percent.
2) Applications of
The water-based pouring sealant is mainly used for leaking stoppage construction in a humid environment, and because the sealant has hydrophilic sulfonic acid groups and has good affinity to water molecules, the water in the construction environment does not influence the adhesive force to a base material; the 4, 4' -MDI has a symmetrical double-benzene-ring molecular structure, so that the waterborne pouring sealant can be endowed with high strength, and can be used for underwater building construction.
Claims (9)
1. An alkyd prepolymer, characterized by: which comprises compounds having the structures shown in formulas (1) to (3):
in the formulas (1) to (3), R represents a non-alcoholic hydroxyl structural group of the small molecular dihydric alcohol; m independently represents a monovalent alkali metal cation;
in the formula (1), m is 0-3; in the formula (2), n is 0 to 3; in the formula (3), z is 0-2;
the small molecular diol is diol with molecular weight less than 300, specifically at least one of 3-methyl-1, 5-pentanediol, neopentyl glycol, ethylene glycol, diethylene glycol, cyclohexanediol, methylpropanediol, TCD tricyclo diol, 1, 3-propanediol, 1, 4-dimethylolcyclohexane, 1, 4-butanediol, 1, 3-butanediol, 1, 5-pentanediol, diethylpentanediol, 1, 2-propanediol, diethylene glycol, tetrahydrofuran diol, 1, 6-hexanediol, trimethylpentanediol, butylethylpropanediol, 2-bis (4-hydroxyphenyl) propane, dipropylene glycol, tripropylene glycol or ethylhexanediol;
the alkyd prepolymer is prepared by taking dicarboxyl sulfonate and micromolecular dihydric alcohol as raw materials through esterification reaction; the acid value of the esterified product obtained by the esterification reaction is within the range of 10mgKOH/g to 80 mgKOH/g.
2. A process for preparing an alkyd prepolymer according to claim 1, wherein: dicarboxyl sulfonate and micromolecule dihydric alcohol are used as raw materials, and the alcohol acid prepolymer is prepared through esterification reaction.
3. The method of preparing an alkyd prepolymer according to claim 2, wherein: the method comprises the following steps:
a) adding dicarboxyl sulfonate, micromolecular dihydric alcohol and water into a reactor, stirring, heating to 90-97 ℃, mixing and dissolving;
b) adding an antioxidant and a catalyst, sealing the reactor, introducing protective gas, heating the reactor to 100-180 ℃, and carrying out esterification reaction for 10-20 h;
c) adding a solvent into the reactor to dissolve the esterification product obtained in the step b), carrying out vacuum distillation and purification, and discharging to obtain the alkyd prepolymer.
4. The method of preparing an alkyd prepolymer according to claim 3, wherein: in step a), the mass ratio of the dicarboxyl sulfonate to the water is 1: (0.5 to 2.0); the molar ratio of the dicarboxyl sulfonate to the small-molecule dihydric alcohol is 1: (1.5-3); in the step b), the addition amount of the antioxidant is 0.01-0.5 percent of the total mass of the raw materials; the addition amount of the catalyst is 0.03-0.1% of the total mass of the raw materials; in the step c), the adding amount of the solvent is 20-200% of the sum of the mass of the dicarboxyl sulfonate and the mass of the micromolecule dihydric alcohol.
5. The method of preparing an alkyd prepolymer according to claim 4, wherein: the dicarboxyl sulfonate is dicarboxyl sulfonic acid alkali metal salt; the water is at least one of distilled water and deionized water; the antioxidant is hindered phenol antioxidant; the catalyst is at least one of tetrabutyl titanate, antimony trioxide and zinc acetate; the solvent is polyethylene glycol with the molecular weight of 220-800.
6. The method of preparing an alkyd prepolymer according to claim 4, wherein: in the step b), the reflux temperature of the water outlet of the condenser is maintained at 100-102 ℃ during the esterification reaction period, when the water yield approaches the water adding amount, the acid value of the esterification product is measured, and the reaction is stopped when the acid value reaches the designed value.
7. The method of preparing an alkyd prepolymer according to claim 6, wherein: in step b), the acid value of the esterified substance is in the range of 10mgKOH/g to 80 mgKOH/g.
8. The method of preparing an alkyd prepolymer according to claim 4, wherein: in the step c), the vacuum distillation purification specifically comprises the following steps: vacuumizing to 0.09-0.093 MPa below 100 deg.C, distilling, heating to 150-180 deg.C when distillate is reduced, vacuumizing until no liquid drops are distilled, cooling to 110 deg.C, introducing protective gas to normal pressure, and cooling to below 70 deg.C.
9. Use of an alkyd prepolymer according to claim 1 in the preparation of a hydroxyl-based waterborne polyurethane resin or waterborne polyurethane curing agent.
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