CN112745492B - Polyester polyol for polyurethane hot melt adhesive and preparation method and application thereof - Google Patents
Polyester polyol for polyurethane hot melt adhesive and preparation method and application thereof Download PDFInfo
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- CN112745492B CN112745492B CN202110055116.5A CN202110055116A CN112745492B CN 112745492 B CN112745492 B CN 112745492B CN 202110055116 A CN202110055116 A CN 202110055116A CN 112745492 B CN112745492 B CN 112745492B
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
- C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
- C08G63/553—Acids or hydroxy compounds containing cycloaliphatic rings, e.g. Diels-Alder adducts
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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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
- C09J175/06—Polyurethanes from polyesters
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention provides a polyester polyol for polyurethane hot melt adhesive, and a preparation method and application thereof. The polyol is prepared from three components of dicarboxylic acid or anhydride containing unsaturated bond without polymerization reaction activity, dicarboxylic acid or anhydride containing unsaturated double bond or triple bond with polymerization reaction activity and dihydric alcohol. By introducing carboxylic acid monomer with rigid annular structure into the raw material, the initial adhesion strength of the hot melt adhesive can be obviously improved, and the positioning time of the hot melt adhesive can be shortened.
Description
Technical Field
The invention relates to the field of polyester polyol, in particular to polyester polyol for preparing moisture-curing polyurethane hot melt adhesive, and a preparation method and application thereof.
Background
The moisture-curing polyurethane hot melt adhesive is solvent-free environment-friendly, has the excellent performances of low use temperature, wide applicable base materials, solvent resistance, creep resistance and the like, and is widely applied to the fields of textile, woodworking, electronics, automobiles, white household appliances and the like. As environmental protection policies become more stringent, the application prospect of the moisture-curing polyurethane hot melt adhesive is wider.
The moisture-curable polyurethane hot melt adhesive is prepared by reacting polyol with isocyanate, has free isocyanate functional groups, and is chemically crosslinked by reacting the isocyanate functional groups with air and moisture on the surface of a substrate to form final adhesive strength, and the final adhesive strength is generally higher than that of the non-reactive hot melt adhesive. However, since the moisture-curable polyurethane hot melt adhesive is usually an oligomer, the initial adhesion strength is usually low, and the positioning time is long, so that the application of the moisture-curable polyurethane hot melt adhesive in various scenes with high requirements on the initial adhesion strength, such as carpentry coating, carpentry edge sealing and the like, is restricted, and the application is also an industry pain point for restricting the expansion of the application field of the moisture-curable polyurethane hot melt adhesive terminal. Patent CN109611043 devised a moisture curable adhesive that can be cured by uv, preparing a modified isocyanate from hydroxyalkyl acrylate reacted with excess isocyanate, then mixing with a diluent and an initiator; the synthesis step is divided into two steps, and the isocyanate needs to be added dropwise when synthesizing the modified isocyanate, the process route is complex, and the acrylate component in the hydroxyalkyl acrylate and the diluent has toxicity.
In summary, the important research direction in the field is to improve the initial adhesion strength of the moisture-curing polyurethane hot melt adhesive and shorten the positioning time of the hot melt adhesive, and the breakthrough of the technical difficulty can obviously improve the application performance of the moisture-curing polyurethane hot melt adhesive and expand the terminal application field of the moisture-curing polyurethane hot melt adhesive.
Disclosure of Invention
The invention provides a novel polyester polyol for preparing moisture-curing polyurethane hot melt adhesive, a preparation method thereof and application thereof in hot melt adhesive preparation, and aims to make up the defects of the prior art. By introducing carboxylic acid monomer with rigid annular structure into the raw material, the initial adhesion strength of the hot melt adhesive can be obviously improved, and the positioning time of the hot melt adhesive can be shortened.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a polyester polyol for polyurethane hot melt adhesive, which is prepared by mixing and reacting the following components in parts by mole:
a) 100 parts by mole of a dicarboxylic acid or acid anhydride having an unsaturated bond having no polymerization activity;
b) Dicarboxylic acids or anhydrides containing unsaturated double or triple bonds having polymerization activity, 5 to 500 parts by mole, preferably 10 to 300 parts by mole;
c) The diol is 110 to 700 parts by mole, preferably 120 to 550 parts by mole.
The polyester polyol of the invention comprises a component A) which is one or more selected from dicarboxylic acids or anhydrides of C2-C20, preferably C6-C14, and comprises aliphatic dicarboxylic acids or anhydrides, aromatic dicarboxylic acids or anhydrides and dicarboxylic acids or anhydrides with partial hydrogen atoms replaced by halogen atoms, preferably one or more selected from adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, phthalic anhydride, 3-bromophthalic anhydride, tetrabromophthalic anhydride and the like; more preferably one or more of adipic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid and phthalic anhydride; further preferred is adipic acid.
The component B) of the dicarboxylic acid or anhydride containing unsaturated double bonds or triple bonds with polymerization activity is selected from cyclohexene dicarboxylic acid and derivatives thereof, tetrahydrophthalic anhydride and derivatives thereof, aliphatic chain alkene dicarboxylic acid and derivatives thereof;
preferably one or more of the structural compounds shown in the formula I or the formula II;
in the formula I, R 1 、R 2 Each independently selected from hydrogen, C1-C10 alkyl, branched alkyl or aryl, preferably hydrogen, methyl, ethyl, phenyl, 2-ethyloctyl, and the like, R 1 、R 2 May be the same or different, preferably both;
more preferably, the dicarboxylic acid containing an unsaturated double bond or triple bond having polymerization activity is dimethyl 4-cyclohexene-1, 2-dicarboxylate, and the dicarboxylic anhydride containing an unsaturated double bond or triple bond having polymerization activity is tetrahydrophthalic anhydride (structural compound shown in formula II).
The component C) of the polyester polyol is one or more selected from dihydric alcohols of C2-C20, preferably C2-C10, preferably one or more selected from ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, nonanediol, diethylene glycol and triethylene glycol; more preferably one or more of ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol; further preferred are 1, 4-butanediol and/or 1, 6-hexanediol.
The molar ratio C/(A+B) > 1, preferably 1 to 1.3, of component C) to the sum of component A) and component B) of the polyester polyol according to the invention.
The hydroxyl value of the polyester polyol according to the present invention is 10 to 200mg KOH/g, preferably 22 to 112mg KOH/g, and more preferably 28 to 112mg KOH/g.
The polyester polyol of the present invention has an acid value of 0.01 to 10mg KOH/g, preferably 0.01 to 5mg KOH/g, more preferably 0.01 to 2mg KOH/g.
The invention also provides a preparation method of the polyester polyol for preparing the polyurethane hot melt adhesive, which comprises the following steps: and mixing the component A), the component B) and the component C) according to the formula amount, and performing melt polycondensation to obtain the polyester polyol.
Preferably, the preparation method of the polyester polyol comprises the following steps:
mixing the component A), the component B) and the component C) under the protection of nitrogen, heating to 130-180 ℃, preferably 140-160 ℃ and reacting for 1-5 hours, preferably 1-3 hours at constant temperature; then continuously heating to 180-220 ℃ in 0.5-2 h, preferably 0.5-1 h, preferably 180-210 ℃, starting vacuum when the acid value is lower than 20mgKOH/g, removing water and micromolecular alcohol in the system, and continuously reacting until the acid value and the hydroxyl value are qualified, thus obtaining the polyester polyol for the polyurethane hot melt adhesive; cooling, discharging and packaging.
Preferably, the raw materials for preparing the polyester polyol further optionally comprise a catalyst, wherein the catalyst comprises one or more of antimony-based, titanium-based, germanium-based and tin-based catalysts, preferably one or more of antimony acetate, antimony trioxide, ethylene glycol antimony, tetraisobutyl titanate, tetraisopropyl titanate, germanium dioxide, stannous chloride, tin acetate and butyltin hydroxide, and further preferably, the catalyst is a titanium-based catalyst;
preferably, the catalyst is used in an amount of 0 to 600ppm, more preferably 40 to 300ppm, based on the total mass of component A), component B) and component C).
Preferably, a polymerization inhibitor is optionally added in the preparation process of the polyester polyol, wherein the polymerization inhibitor is selected from one of hypophosphorous acid, triethyl phosphite, phenyl phosphite and the like;
preferably, the polymerization inhibitor is added in an amount of 0.1 to 10.0%, preferably 0.1 to 5.0%, more preferably 0.3 to 2.0% based on the total mass of component A), component B) and component C).
Preferably, in the preparation process, when the vacuum is started, the vacuum degree is slowly reduced to be lower than 0.095MPa in 0.5-2 h, and the vacuum degree is controlled to be 0.09-0.095 MPa.
Preferably, the acid value at the end of the reaction is in the range of 0.01 to 10mg KOH/g, and the hydroxyl value is in the range of 10 to 200mg KOH/g.
The invention also provides an application of the polyester polyol in the field of polyurethane hot melt adhesive preparation.
According to the application, a moisture-curing polyurethane hot melt adhesive is provided, which is prepared by mixing and reacting the polyester polyol and isocyanate:
the molar ratio of the polyester polyol to isocyanate is 1:2 to 3, preferably 1:2.2 to 2.5.
Preferably, the isocyanate is a diisocyanate selected from the group consisting of diphenylmethane diisocyanate (MDI), toluene Diisocyanate (TDI), isophthalone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI), naphthalene Diisocyanate (NDI), dicyclohexylmethane diisocyanate (HMDI), cyclohexane diisocyanate (CHDI), and the like, preferably diphenylmethane diisocyanate (MDI), toluene Diisocyanate (TDI).
Preferably, the reaction temperature is 80-150 ℃, preferably 100-130 ℃; the reaction time is 30-120 min, preferably 60-90 min, until the NCO content reaches the theoretical value;
preferably, the hot melt adhesive is kept at a constant temperature of 120-130 ℃ for standby;
preferably, the moisture-curable polyurethane hot melt adhesive has curing conditions of: the moisture curing reaction is carried out under the condition of ultraviolet/electron radiation, wherein the ultraviolet/electron radiation condition is that a mercury lamp irradiates for 10 to 120 seconds, and the moisture curing process is 25 ℃/30 to 50 percent of humidity.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
according to the invention, carboxylic acid/anhydride monomer with a specific rigid annular structure is introduced into the polyester polyol formula, so that the molecular structure of the polyurethane hot melt adhesive has lower degree of free rotation, and the cohesive force of the hot melt adhesive is enhanced, thereby obviously enhancing the initial adhesion strength of the hot melt adhesive, and the moisture-cured polyurethane hot melt adhesive prepared from the polyester polyol can rapidly undergo a crosslinking reaction under the condition of ultraviolet/electron radiation, so that the initial adhesion strength and mechanical property of the hot melt adhesive are further enhanced.
In addition, the carboxylic acid/anhydride monomer with a specific rigid annular structure introduced by the invention also improves the crystallinity of the polyurethane hot melt adhesive, and the crystallinity and the radiation crosslinking reaction are combined to obviously shorten the positioning time of the hot melt adhesive and improve the production efficiency.
Detailed Description
For a better understanding of the technical solution of the present invention, the following examples are further described below, but the present invention is not limited to the following examples.
The main raw materials used in the examples or comparative examples are described below:
adipic acid: henan Shenma Corp;
phthalic anhydride: korean love company;
dimethyl 4-cyclohexene 1, 2-dicarboxylate, diethyl 4-cyclohexene 1, 2-dicarboxylate: jinan Yinchun company;
tetrahydrophthalic anhydride: taiwan south asia corporation;
butenedioic acid: shanghai Taitan technologies Co;
ethylene glycol, diethylene glycol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol: basf corporation;
MDI, TDI: wanhua chemistry;
unless otherwise stated, other materials are commercially available as common reagents.
The polyester polyol acid value test method comprises the following steps: reference HG/T2709-1995;
the hydroxyl value test method comprises the following steps: reference HG/T2708-1995;
the moisture testing method comprises the following steps: reference GB/T6283-2008;
the initial adhesion strength test method of the polyurethane hot melt adhesive comprises the following steps:
in a constant temperature and humidity laboratory with 50% humidity/25 ℃, hot melt adhesive is brushed on PVC strips with the thickness of 4cm x 25cm, a mercury lamp is used for irradiating for 1min, then another PVC strip with the same size is overlapped and bonded with the glued strips, and the bonded strips are placed on a gas compressor to be maintained for 5min under the pressure of 10MPa so that two strips are fully bonded; and (3) carrying out 180-degree peel strength test on the prepared adhesive tape on a tensile machine, wherein the tensile rate is 20mm/min, and recording peel strength data.
The method for testing the positioning time of the polyurethane hot melt adhesive comprises the following steps:
in a constant temperature and humidity laboratory at 50% humidity/25 ℃, hot melt adhesive was brushed onto 10cm x 10cm blocks, irradiated with a mercury lamp for 1min, then another block of the same size was laminated over the glued block, and pressed with a 2kg die. The time from the attachment of the wood block to the failure to screw by hand was recorded as the positioning time.
The tensile strength and elongation at break test method of the polyurethane hot melt adhesive comprises the following steps:
the hot melt adhesive was prepared into a 2mm thick film in a constant temperature and humidity laboratory at 50% humidity/25 ℃ and left to stand in the constant temperature and humidity laboratory for 7 days, and tensile strength and elongation at break were tested with reference to standard ASTM D412.
Examples 1 to 10
The preparation method of the polyester polyol A-J for preparing the polyurethane hot melt adhesive comprises the following steps:
under the protection of nitrogen, sequentially adding the component A), the component B) and the component C), a tetraisopropyl titanate catalyst, a polymerization inhibitor hypophosphorous acid into a 5L reaction kettle, wherein the raw material preparation ratio is shown in table 1; the temperature of the system is raised to 140-160 ℃, and the reaction is carried out for 1.0h at the constant temperature (example 1-8:150 ℃, example 9:140 ℃, example 10:160 ℃); the temperature of the system is increased to 180-210 ℃ in 1h (example 1-8: 210 ℃, example 9:200 ℃ and example 10:180 ℃), the acid value and the hydroxyl value are monitored, a vacuum system is started when the acid value is lower than 20mgKOH/g, the vacuum degree is slowly reduced to-0.095 MPa in 0.5h, the vacuum degree is controlled to be 0.09-0.095 MPa, the moisture and the small molecular alcohol in the system are removed, the vacuum is stopped when the acid value and the hydroxyl value reach the standard, and the temperature is reduced and the material is discharged. The resulting product was designated as polyester polyol A-J.
The performance index test of the obtained polyester polyol is shown in Table 2.
Table 1 examples 1-10 raw material ratios
Comparative example 1
The process for preparing polyester polyol was as described in example 1, except that no tetrahydrophthalic anhydride of component B was added to the starting material, designated as polyester polyol A1, and the performance index test is shown in Table 2.
Comparative example 2
The process for preparing polyester polyols was as described in example 1, except that no adipic acid component A was added to the starting materials, designated as polyester polyol A2, and the performance index test is shown in Table 2.
Comparative example 3
The process for preparing polyester polyols is described with reference to example 5, except that no adipic acid component A is added to the starting materials, designated as polyester polyol E1, and the performance index test is shown in Table 2.
TABLE 2 results of polyol tests prepared in examples 1-10 and comparative examples 1-3
Examples 11 to 20
Synthesis of polyurethane hot melt adhesive
Under the protection of nitrogen, adding the polyester polyol A-J and isocyanate prepared in preparation examples 1-10 into a 2L three-neck round bottom flask, stirring and reacting until the NCO content reaches a theoretical value, stopping experiment, vacuum defoaming, and keeping the obtained hot melt adhesive at a constant temperature of 130 ℃ for later use, wherein the raw material proportion and the reaction condition are shown in Table 3.
The evaluation data after curing of the polyurethane hot melt adhesive are shown in Table 4 below.
TABLE 3 examples 11-20 raw material ratios and reaction conditions
Comparative examples 4 to 6
Polyurethane hot melt adhesives were prepared by the method described in example 11, except that the polyester polyol A was replaced with the polyols A1-2, E1 prepared in comparative examples 1-3 in that order.
The evaluation data after curing of the polyurethane hot melt adhesive are shown in Table 4 below.
Table 4 evaluation results of examples 11 to 20 and comparative examples 4 to 6
As can be seen from the experimental data of examples 11 to 20 and comparative examples 4 to 6, the initial adhesion strength of the polyurethane hot melt adhesives synthesized from the polyester polyols prepared according to the present invention is significantly improved. As can be seen from the experimental data of comparative example 4, the adhesive does not have the ability to crosslink under irradiation without the addition of component B, and thus has lower initial tack strength, longer positioning time, and lower mechanical properties than in example 11. As can be seen from the experimental data of comparative examples 5 and 6, when component a is not added, the initial adhesive strength of the prepared hot melt adhesive is poor because the crosslinking degree is too high, the shrinkage rate of the adhesive after curing is high, and the adhesion to the substrate is deteriorated; in addition, the adhesive cannot bond the wood substrate used in the test experiment due to high cure shrinkage, so the positioning time cannot be tested. Experimental data for examples 13 and 14 shows that increasing the level of unsaturated carboxylic acid monomer helps to increase the initial tack strength of the polyurethane hot melt adhesive. As can be seen from the experimental data of example 19, when component B does not contain a rigid ring structure, the positioning time of the hot melt adhesive is significantly increased compared with that of example 13, and the initial adhesion strength is also reduced.
Claims (36)
1. The polyester polyol for the polyurethane hot melt adhesive is characterized by being prepared by mixing and reacting the following components in parts by mole:
a) 100 parts by mole of a dicarboxylic acid or acid anhydride having an unsaturated bond having no polymerization activity;
b) 5-500 parts by mol of dicarboxylic acid or anhydride containing unsaturated double bonds or triple bonds with polymerization activity;
c) 110-700 mole parts of dihydric alcohol;
the component B) dicarboxylic acid or anhydride containing unsaturated double bond or triple bond with polymerization reaction activity is one or more of compounds with a structure shown in a formula I or a formula II;
in the formula I, R 1 、R 2 Each independently selected from hydrogen, C1-C10 alkyl, branched alkyl or aryl, R 1 、R 2 The same or different.
2. The polyester polyol according to claim 1, wherein the polyester polyol is prepared by mixing and reacting components comprising the following molar parts:
a) 100 parts by mole of a dicarboxylic acid or acid anhydride having an unsaturated bond having no polymerization activity;
b) 10-300 parts by mol of dicarboxylic acid or anhydride containing unsaturated double bonds or triple bonds with polymerization activity;
c) 20-550 mole parts of dihydric alcohol.
3. The polyester polyol according to claim 1, wherein component a) is one or more selected from the group consisting of C2 to C20 dicarboxylic acids or anhydrides, including aliphatic dicarboxylic acids or anhydrides, aromatic dicarboxylic acids or anhydrides, and dicarboxylic acids or anhydrides in which a part of the hydrogen atoms is substituted with a halogen atom.
4. A polyester polyol according to claim 3, wherein component a) is selected from one or more of the group consisting of C6 to C14 dicarboxylic acids or anhydrides.
5. A polyester polyol according to claim 3 wherein component a) is selected from one or more of adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, phthalic anhydride, 3-bromophthalic anhydride, tetrabromophthalic anhydride.
6. The polyester polyol according to claim 1, wherein in formula I, R 1 、R 2 Each independently selected from hydrogen, methyl, ethyl, phenyl, 2-ethyloctyl.
7. The polyester polyol according to claim 1, wherein the dicarboxylic acid having an unsaturated double bond or triple bond having a polymerization activity is dimethyl 4-cyclohexene-1, 2-dicarboxylate, and the dicarboxylic acid anhydride having an unsaturated double bond or triple bond having a polymerization activity is tetrahydrophthalic anhydride.
8. The polyester polyol according to claim 1, wherein component C) is one or more selected from the group consisting of C2-C20 diols.
9. The polyester polyol according to claim 1, wherein component C) is one or more selected from the group consisting of C2-C10 diols.
10. The polyester polyol according to claim 8, wherein component C) is selected from one or more of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, nonanediol, diethylene glycol, triethylene glycol.
11. The polyester polyol according to claim 1, wherein the molar ratio C/(A+B) > 1 of component C) to the sum of component A) and component B).
12. The polyester polyol according to claim 11, wherein the molar ratio C/(A+B) of component C) to the sum of component A) and component B) is 1 to 1.3.
13. The polyester polyol according to claim 1, wherein the hydroxyl value is 10 to 200mg KOH/g; and/or
The acid value is 0.01-10 mg KOH/g.
14. The polyester polyol according to claim 13, wherein the hydroxyl number is 22 to 112mg KOH/g.
15. The polyester polyol according to claim 14, wherein the hydroxyl number is 28 to 112mg KOH/g.
16. The polyester polyol according to claim 13, wherein the acid value is 0.01 to 5mg KOH/g.
17. The polyester polyol according to claim 16, wherein the acid value is 0.01 to 2mg KOH/g.
18. A process for the preparation of the polyester polyol according to any of claims 1 to 17, comprising: comprises mixing component A), component B) and component C), and melt-polycondensing.
19. The method of preparing as claimed in claim 18, wherein the steps comprise: under the protection of nitrogen, mixing the component A), the component B) and the component C), heating to 130-180 ℃ and reacting for 1-5 h at constant temperature; then continuously heating to 180-220 ℃ within 0.5-2 h, starting vacuum when the acid value is lower than 20mgKOH/g, removing water and micromolecular alcohol in the system, and continuously reacting until the acid value and the hydroxyl value are qualified, thus obtaining the polyester polyol for the polyurethane hot melt adhesive.
20. The method of preparing as claimed in claim 19, wherein the steps comprise: under the protection of nitrogen, mixing the component A), the component B) and the component C), heating to 140-160 ℃ and reacting for 1-3 h at constant temperature; then continuously heating to 180-210 ℃ within 0.5-1 h, starting vacuum when the acid value is lower than 20mgKOH/g, removing water and micromolecular alcohol in the system, and continuously reacting until the acid value and the hydroxyl value are qualified, thus obtaining the polyester polyol for the polyurethane hot melt adhesive.
21. The method of claim 18, comprising a catalyst comprising one or more combinations of antimony, titanium, germanium, and tin based catalysts.
22. The method of claim 21, wherein the catalyst is selected from one or more of antimony acetate, antimony trioxide, antimony glycol, tetraisobutyl titanate, tetraisopropyl titanate, germanium dioxide, stannous chloride, tin acetate, and butyltin hydroxide oxide.
23. The process according to claim 21, wherein the catalyst is used in an amount of 0 to 600ppm based on the total mass of component A), component B) and component C).
24. The process according to claim 23, wherein the catalyst is used in an amount of 40 to 300ppm based on the total mass of component a), component B) and component C).
25. The method according to claim 18, comprising a polymerization inhibitor selected from one of hypophosphorous acid, triethyl phosphite, and phenyl phosphite.
26. The process according to claim 25, wherein the polymerization inhibitor is added in an amount of 0.1 to 10.0% based on the total mass of component A), component B) and component C).
27. The process according to claim 26, wherein the polymerization inhibitor is added in an amount of 0.1 to 5.0% based on the total mass of component A), component B) and component C).
28. The process according to claim 27, wherein the polymerization inhibitor is added in an amount of 0.3 to 2.0% based on the total mass of component A), component B) and component C).
29. The moisture-curing polyurethane hot melt adhesive is characterized by being prepared by mixing and reacting polyester polyol and isocyanate, wherein the molar ratio of the polyester polyol to the isocyanate is 1:2 to 3;
the polyester polyol is the polyester polyol of any of claims 1-17 or the polyester polyol prepared by the process of any of claims 18-28.
30. The moisture curable polyurethane hot melt adhesive of claim 29, wherein the molar ratio of polyester polyol to isocyanate is 1:2.2 to 2.5.
31. The moisture-curable polyurethane hot melt adhesive of claim 29, wherein the isocyanate is selected from the group consisting of diphenylmethane diisocyanate, toluene diisocyanate, isoparaffin diisocyanate, hexamethylene diisocyanate, naphthalene diisocyanate, dicyclohexylmethane diisocyanate, and cyclohexane diisocyanate.
32. The moisture curable polyurethane hot melt adhesive of claim 29, wherein the reaction temperature is 80 to 150 ℃ for 30 to 120 minutes until the NCO content reaches a theoretical value.
33. The moisture curable polyurethane hot melt adhesive of claim 32, wherein the reaction temperature is 100 to 130 ℃ for 60 to 90 minutes.
34. The moisture curable polyurethane hot melt adhesive of claim 29, wherein the hot melt adhesive is maintained at a constant temperature of 120 to 130 ℃ for use.
35. The moisture-curable polyurethane hot melt adhesive of claim 29, wherein the moisture-curable polyurethane hot melt adhesive undergoes a moisture-curing reaction under uv/electron radiation.
36. The moisture-curable polyurethane hot melt adhesive of claim 35, wherein the ultraviolet/electron radiation condition is mercury lamp irradiation for 10 to 120 seconds and the moisture curing process is 25 ℃/30 to 50% humidity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110055116.5A CN112745492B (en) | 2021-01-15 | 2021-01-15 | Polyester polyol for polyurethane hot melt adhesive and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110055116.5A CN112745492B (en) | 2021-01-15 | 2021-01-15 | Polyester polyol for polyurethane hot melt adhesive and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112745492A CN112745492A (en) | 2021-05-04 |
| CN112745492B true CN112745492B (en) | 2023-07-14 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6774154B2 (en) * | 2002-04-08 | 2004-08-10 | Crompton Corporation | Semiflexible and flexible polyurethanes foams having low fogging characteristics and improved physical properties |
| MX2011013703A (en) * | 2009-07-01 | 2012-02-22 | Bayer Materialscience Ag | Method for the production of a polyurethane polymer comprising polyester polyols that contain terminal secondary hydroxyl groups. |
| CN102827343B (en) * | 2012-09-21 | 2014-06-04 | 肇庆福田化学工业有限公司 | Polyurethane unsaturated polyester resin and photocuring coating containing same |
| CN103012746A (en) * | 2012-12-31 | 2013-04-03 | 东莞英铭化工有限公司 | Method for synthesizing freeze-proof unsaturated coating polyester resin |
| CN103497318B (en) * | 2013-10-21 | 2015-11-18 | 肇庆福田化学工业有限公司 | A kind of Methylhexahydrophthaanhydride anhydride type high-solid low-viscosity resin |
| CN105906793A (en) * | 2016-06-25 | 2016-08-31 | 成都杰晟蜀邦新材料科技有限公司 | Water-based unsaturated polyester resin and preparation method thereof |
| CN108503756B (en) * | 2017-02-28 | 2020-12-18 | 常州华科聚合物股份有限公司 | Vinyl monomer modified polyester resin, low shrinkage agent and preparation method |
| CN107522854A (en) * | 2017-09-27 | 2017-12-29 | 浙江天和树脂有限公司 | A kind of preparation method of high flexibility unsaturated polyester resin |
| CN109553766B (en) * | 2018-09-28 | 2021-11-02 | 长兴材料工业（广东）有限公司 | Modified polyester polyol and preparation method and application thereof |
| CN111662540B (en) * | 2020-07-31 | 2023-03-31 | 肇庆福田化学工业有限公司 | Amino modified unsaturated polyester resin |
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