CN110551479A - Preparation method of reactive moisture-curing polyurethane hot melt adhesive - Google Patents
Preparation method of reactive moisture-curing polyurethane hot melt adhesive Download PDFInfo
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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Abstract
The invention relates to a high-bonding-strength reactive moisture-curing polyurethane hot melt adhesive and a preparation method thereof. Adding ethyl acetate into a reaction bottle, magnetically stirring, adding Benzoyl Peroxide (BPO) initiator, dropwise adding a mixed solution of styrene, butyl acrylate, methyl methacrylate and acrylic acid-beta-hydroxyethyl ester in a certain mass ratio by using a constant-pressure funnel, reacting for 2 hours at the temperature of 90-95 ℃, synthesizing acrylic resin, and pouring out for later use. And adding polyether and polyester polyol into a reaction bottle, adding synthetic acrylic resin, dehydrating at the temperature of 100 ℃ and 120 ℃ for 2 h, cooling to 90 ℃, introducing N2 for protection, adding isocyanate for curing, and stopping the reaction when the-NCO value is not changed. The high-bonding-strength reaction type moisture-curing polyurethane hot melt adhesive has the advantages of narrow melting point range, no solvent, no toxicity, excellent bonding performance, especially initial bonding force, high bonding strength to various materials, particular suitability for bonding low-polarity plates and textiles, and wide application.
Description
Technical Field
the invention relates to preparation and application of a novel environment-friendly moisture-curing polyurethane hot melt adhesive, in particular to preparation of a building material low-polarity plate and a textile hot melt adhesive.
Background
Although the adhesive performance of the traditional hot melt adhesive basically meets the requirements of most fields, the traditional hot melt adhesive has poor heat resistance and poor solvent resistance, and is difficult to meet the requirements in some high-end industrial fields. The moisture-curing polyurethane hot melt adhesive is a solvent-free environment-friendly thermoplastic adhesive and is harmless to human bodies. The material melts with the rise of temperature in a certain temperature range, and the physical state changes with the change of temperature, while the chemical property is not changed. The adhesive is solid at normal temperature, is convenient to package, transport and store, is environment-friendly and nontoxic, has high added value, strong bonding force and the like, and is favored.
According to the invention, through the structural design of the whole polyurethane, an influence rule influencing the viscosity, the adhesive force and the molecular weight of the hot melt adhesive is obtained, and a production process which has excellent performance and is put into practical industrial production is researched and developed aiming at the surface structural characteristics of the PVC plate.
Disclosure of Invention
The invention aims to provide a preparation method of a novel moisture-curing polyurethane hot melt adhesive.
the invention also aims to provide application of the novel moisture-curing polyurethane hot melt adhesive to low-polarity plates such as PVC.
The invention aims to provide a preparation method of a novel environment-friendly moisture-curing polyurethane hot melt adhesive, which is tested on low-polarity plates such as PVC and the like, and has the advantages of excellent binding power, short curing time and good creep resistance.
A preparation method and steps of a novel moisture-curing polyurethane hot melt adhesive are as follows:
(1) The synthesis method of the acrylic resin (PAA) containing the hydroxyl active functional group comprises the following steps: adding ethyl acetate into a three-neck flask, magnetically stirring, adding a Benzoyl Peroxide (BPO) initiator, dropwise adding a mixed solution of styrene, butyl acrylate, methyl methacrylate and beta-hydroxyethyl acrylate according to a certain mass ratio, reacting for 2 hours at the temperature of 90-95 ℃, and synthesizing the acrylic resin.
(2) Preparing a moisture-curing polyurethane hot melt adhesive: adding polyether and polyester polyol into a three-neck flask, adding the synthesized acrylic resin, melting into liquid at 110-120 ℃ to be used as a solvent, magnetically stirring, and dehydrating in vacuum for 2 h, and simultaneously removing ethyl acetate in the acrylic resin. Cooling to 90 deg.C after dehydration, adding amine catalyst, stirring with machine, introducing N2and (3) protecting, adding a proper amount of isocyanate containing one or more of diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI) and 1, 6-Hexamethylene Diisocyanate (HDI), adding hydroxyl in polyether, polyester polyol and synthetic acrylic resin, reacting for 2-4 h, and stopping the reaction when the-NCO value is not changed. The reaction mechanism is as follows:
Note:Is an isocyanate, and is characterized in that,Polyether, polyester polyol and synthetic acrylic resin.
(3) The prepared moisture-curing polyurethane hot melt adhesive is heated to 90-120 ℃ to be melted, and is uniformly coated on a PVC polymer substrate plate with a base plate width of 7.0 cm by a 50-micrometer coater, and is adhered by an upper surface plate with a width of 4.0 cm. And (3) curing the bonded plate at 25 ℃ under the environment with the relative humidity of 50 ℃, testing the initial adhesion force for 12 hours, and testing the final adhesion force for 24 hours. The process flow is shown in figure 1.
The novel hot melt adhesive comprises the following raw materials in percentage by mass:
40 to 45 percent of polyester polyol
10 to 15 percent of polyether polyol
15 to 20 percent of synthetic acrylic resin
2 to 5 percent of ethylenediamine
0.1 to 1 percent of initiator
20 to 25 percent of isocyanate
Wherein the synthetic acrylic resin is copolymerized by synthetic acrylic resin, ethylenediamine, other aliphatic diamine, a chain initiator and a chain terminator, the viscosity of the synthetic acrylic resin is 900-1200 mpa.s/120 ℃, and the molecular weight is 3000-5000.
The novel hot melt adhesive is characterized in that raw materials and products are used as solvents, other solvents are not required to be added in the reaction process, and the products are environment-friendly and non-toxic.
The novel hot melt adhesive is characterized in that acrylic resin is removed, and the novel hot melt adhesive comprises the following components in percentage by mol: 25-35% of aliphatic polyester polyol, 15-25% of aliphatic polyether polyol and 5-10% of initiator, wherein the aliphatic polyester polyol is C15-C20Aliphatic polyester polyol, aliphatic polyether polyol is C3-C8An aliphatic polyether polyol.
The novel hot melt adhesive is characterized in that C15-C20the aliphatic polyester polyol is polyester compound polymerized by 1, 4-butanediol adipate, 1, 6-hexanediol adipate, glycol adipate, dibasic fatty acid such as adipic acid, terephthalic acid and the like and dihydric alcohol such as 1, 4-butanediol, propanediol and the like, and the hydroxyl value is 25-40 mgKOH/g.
The novel hot melt adhesive is characterized in that C3-C8The aliphatic polyether polyol is a copolymer among polypropylene glycol, polytetrahydrofuran ether glycol and dihydric aliphatic alcohol, and the hydroxyl value is 20-30 mgKOH/g.
The viscosity of the prepared novel hot melt adhesive is 20000-S/120 ℃ and the weight average molecular weight M isw8800 and 20000, and the melting temperature is 45-55 ℃.
The novel hot melt adhesive is characterized in that isocyanate is composed of one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and 1, 6-Hexamethylene Diisocyanate (HDI), and the isocyanate is industrial.
The polymer substrate board is one of a PVC board, a PC board, a PET board, a PP board or a PE board treated by a corona method.
the novel hot melt adhesive test method comprises the following performance indexes:
(1) Adhesive melt viscosity determination
Reference is made to standard HG/T3660-1999, measured with a digital viscometer. And (2) fully melting the adhesive in an oven environment of 120 ℃ for 30 minutes, quickly pouring the adhesive into a sleeve in a digital display viscometer, weighing about 10.0 g, setting the temperature at 120 ℃ and keeping the temperature for 10 minutes to uniformly heat the moisture-cured polyurethane hot melt adhesive, and measuring the viscosity by using the digital display viscometer.
(2) Measurement of peeling Strength
According to the standard GB 13022, a 90-degree tensile testing machine is adopted for testing, and the operation flow is as follows:
Bonding of base materials: two PVC plates, the width of the bottom plate is 7.0 cm, the width of the upper surface plate is 4.0 cm, the PVC plates are wiped by wet rags, the PVC plates are placed after water is dried, then the sealing glue bag and the coating rod are placed in a 120 ℃ oven, glue is melted, then the coating rod is used for gluing the PVC plates with the bottom plate, and then the upper surface plate is bonded.
And (3) according to the experimental requirements, placing the bonded plate in a constant temperature and humidity box or curing the bonded plate in a natural environment, and finally measuring the peel strength in different time periods, testing the initial adhesion force for 12 hours and testing the final adhesion force for 24 hours.
(3) Determination of tack-free time
According to the standard GB/T13477.5-2002, after a moisture-curing polyurethane hot melt adhesive prepolymer is heated to 120 ℃ and melted, a layer of adhesive with the thickness of 0.1 mm is quickly scraped out by a mould and coated on a smooth flat plate, and the time (min) from the coating start to the non-stickiness of the surface of the hot melt adhesive is recorded at the temperature of 25 ℃.
(4) curing time
And scraping the adhesive film on the plate material by using a plate cutter, wherein the adhesive film on the bottom layer can not be completely cured or cured if a blade is stuck or the blunt end of the blade can not be scraped by slight force, and the adhesive film is completely cured if the blade is not stuck or the blunt end of the blade cannot be scraped by slight force.
(5) Weight average molecular weight measurement
The gel chromatography was used, according to Agilent gpc.
The invention has the beneficial effects that: the invention provides a moisture-curing polyurethane hot melt adhesive synthesized by grafting hydroxyl-containing acrylic resin, wherein the addition amount of the resin is 15-20%, and the resin has good compatibility, high adhesive film curing speed, strong adhesive force and excellent initial adhesion. The product not only has all the advantages of the traditional polyurethane hot melt adhesive, namely, narrow melting point range, no solvent, no toxicity, good oil resistance and chemical resistance and good mechanical property, but also has higher bonding strength to various wood, metal and plastic materials, especially low-polarity PVC plates, and is widely applied.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings: FIG. 1 is a flow chart of a hot melt adhesive production process in an embodiment of the present invention; FIG. 2 is an infrared spectrum of a synthetic acrylic resin and an adhesive; FIG. 3 is data on the moisture-curing polyurethane hot melt adhesive performance.
Detailed Description
The present invention will be further described with reference to examples in order to facilitate understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example one
1. preparing a moisture-curing polyurethane hot melt adhesive:
(1) Preparation of acrylic resin (PAA): adding 25-30g of ethyl acetate into a 250 mL three-necked bottle, condensing and refluxing at 90 ℃, magnetically stirring, adding 0.05g of benzoyl peroxide, slowly dropwise adding a mixed solution (3.5 g of styrene, 7.0g of butyl acrylate, 3.5g of methyl methacrylate and 1.8g of acrylic acid-beta-hydroxyethyl) by using a constant-pressure funnel, keeping the temperature for reacting for 2 hours after dropwise adding, distilling off the ethyl acetate to obtain a transparent solution, and carrying out infrared characterization on the transparent solution, wherein the infrared characterization is shown in figure 1.
(2) Synthesizing a moisture-curing polyurethane hot melt adhesive: 15g of synthetic acrylic resin, 30g of poly adipic acid 1, 4-butanediol (PBA3000), 5g of poly adipic acid 1, 6-hexanediol (PHA2000), 15g of poly ethylene adipate (PEA2000) and 20g of poly isopropanol (PPG2000) are mixed, dehydrated at the temperature of 100 ℃ and 120 ℃ for 2 h, cooled to 90 ℃, added with 0.2g of triethylene diamine and 0.3g of leveling agent, mechanically stirred at the temperature of 250 revolutions per minute, added with 5g of Toluene Diisocyanate (TDI), 5g of diphenylmethane diisocyanate (MDI) and 5g of a mixture of 1, 6-Hexamethylene Diisocyanate (HDI), and reacted at the temperature of 90 ℃ for 2 h. The infrared characterization of the product structure is shown in FIG. 2.
from the infrared spectrum, the acrylic resin (PAA) is 3550--1The peak is wide, the absorption strength is medium, the peak is-O-H stretching vibration in the resin, and the length of the peak is 1700cm-1the left and the right are-C = O telescopic vibration, 3000 + 2840cm-1Is a C-H stretching vibration. 3350-3310cm in synthesized hot melt adhesive spectrogram-1A wide and weak absorption peak in the region is the stretching vibration of secondary amine-N-H, 2273--1Stretching vibration with peak of isocyanic acid radical-C = N-, 1700cm-1The left and right strong absorption peaks are-C = O stretching vibrations. 3500-3200cm from spectra of acrylic resin and hot melt adhesive-1peak characteristics and 2273-2000cm-1The characteristic peak of the isocyanic acid radical is known, and the-OH in the acrylic resin is completely reacted.
(3) The mixture was heated to 120 ℃ and poured out, and uniformly applied to a PVC substrate sheet using a 50 μm applicator.
2. Performance testing of moisture-curing polyurethane hot melt adhesive
The performance of the moisture-curing polyurethane hot melt adhesive was tested, and the results are shown in FIG. 3 below.
Example two
1. Preparing a moisture-curing polyurethane hot melt adhesive:
(1) Preparation of acrylic resin (PAA): an acrylic resin was prepared according to example one;
(2) synthesizing a moisture-curing polyurethane hot melt adhesive: mixing 15g of synthetic acrylic resin, 30g of poly adipic acid 1, 4-butanediol (PBA3000), 10g of poly adipic acid 1, 6-hexanediol (PHA2000), 10g of poly adipic acid ethylene glycol (PEA2000) and 20g of poly isopropanol (PPG2000), dehydrating at the temperature of 100 ℃ and 120 ℃ for 2 h, cooling to 90 ℃, adding 0.2g of triethylene diamine and 0.3g of flatting agent, mechanically stirring at the temperature of 250 rpm and 400 rpm, adding 5g of Toluene Diisocyanate (TDI), 5g of diphenylmethane diisocyanate (MDI) and 5g of a mixture of 1, 6-Hexamethylene Diisocyanate (HDI), and reacting at the temperature of 90 ℃ for 2 h;
(3) The mixture was heated to 120 ℃ and poured out, and uniformly applied to a PVC substrate sheet using a 50 μm applicator.
2. performance testing of moisture-curing polyurethane hot melt adhesive
The performance of the moisture-curing polyurethane hot melt adhesive was tested, and the results are shown in FIG. 3 below.
EXAMPLE III
1. Preparing a moisture-curing polyurethane hot melt adhesive:
(1) Preparation of acrylic resin (PAA): an acrylic resin was prepared according to example one;
(2) Synthesizing a moisture-curing polyurethane hot melt adhesive: mixing 15g of synthetic acrylic resin, 20g of poly adipic acid 1, 4-butanediol (PBA3000), 15g of poly adipic acid 1, 6-hexanediol (PHA2000), 15g of poly adipic acid ethylene glycol (PEA2000) and 20g of poly isopropanol (PPG2000), dehydrating at the temperature of 100 ℃ and 120 ℃ for 2 h, cooling to 90 ℃, adding 0.2g of triethylene diamine and 0.3g of flatting agent, mechanically stirring at the temperature of 250 rpm and 400 rpm, adding 5g of Toluene Diisocyanate (TDI), 5g of diphenylmethane diisocyanate (MDI) and 5g of a mixture of 1, 6-Hexamethylene Diisocyanate (HDI), and reacting at the temperature of 90 ℃ for 2 h;
(3) The mixture was heated to 120 ℃ and poured out, and uniformly applied to a PVC substrate sheet using a 50 μm applicator.
2. Performance testing of moisture-curing polyurethane hot melt adhesive
The performance test results of the moisture-curing polyurethane hot melt adhesive are shown in figure 3.
Example four
1. Preparing a moisture-curing polyurethane hot melt adhesive:
(1) Preparation of acrylic resin (PAA): an acrylic resin was prepared according to example one;
(2) Synthesizing a moisture-curing polyurethane hot melt adhesive: mixing 15g of synthetic acrylic resin, 30g of poly adipic acid 1, 4-butanediol (PBA3000), 7g of poly adipic acid 1, 6-hexanediol (PHA2000), 7g of poly adipic acid ethylene glycol (PEA2000) and 26g of poly isopropanol (PPG2000), dehydrating at the temperature of 100 ℃ and 120 ℃ for 2 h, cooling to 90 ℃, adding 0.2g of triethylene diamine and 0.3g of flatting agent, mechanically stirring at the temperature of 250 revolutions per minute, adding 5g of Toluene Diisocyanate (TDI), 5g of diphenylmethane diisocyanate (MDI) and 5g of a mixture of 1, 6-Hexamethylene Diisocyanate (HDI), and reacting at the temperature of 90 ℃ for 2 h;
(3) The mixture was heated to 120 ℃ and poured out, and uniformly applied to a PVC substrate sheet using a 50 μm applicator.
2. performance testing of moisture-curing polyurethane hot melt adhesive
The performance test results of the moisture-curing polyurethane hot melt adhesive are shown in figure 3.
EXAMPLE five
1. Preparing a moisture-curing polyurethane hot melt adhesive:
(1) preparation of acrylic resin (PAA): an acrylic resin was prepared according to example one;
(2) Synthesizing a moisture-curing polyurethane hot melt adhesive: mixing 15g of acrylic resin, 30g of poly adipic acid 1, 4-butanediol (PBA3000), 10g of poly adipic acid 1, 6-hexanediol (PHA2000), 10g of poly adipic acid ethylene glycol (PEA2000) and 20g of poly isopropanol (PPG2000), dehydrating at the temperature of 100 ℃ and 120 ℃ for 2 h, cooling to 90 ℃, adding 0.2g of triethylene diamine and 0.3g of flatting agent, mechanically stirring at the temperature of 250 ℃ per minute and 400 turns, adding 4g of Toluene Diisocyanate (TDI), 4g of diphenylmethane diisocyanate (MDI) and 4g of a mixture of 1, 6-Hexamethylene Diisocyanate (HDI), and reacting at the temperature of 90 ℃ for 2 h;
(3) The mixture was heated to 120 ℃ and poured out, and uniformly applied to a PVC substrate sheet using a 50 μm applicator.
2. Performance testing of moisture-curing polyurethane hot melt adhesive
the performance test results of the moisture-curing polyurethane hot melt adhesive are shown in figure 3.
In comparison with examples 1, 2, 3 and 4, under the same process conditions, the polyester raw material in the formula has high energy, improves the binding power and viscosity, and shortens the surface drying time and the curing time, mainly because of strong hydrogen bond, high crystallinity and high melting point of esters; in comparison with examples 4 and 5, the increase in isocyanate resulted in an increase in viscosity and a decrease in cohesive strength, mainly due to the fact that when the amount of isocyanate was small, the molecular weight of the adhesive produced was large and the isocyanate content in the raw material was small.
The technical solutions provided by the present invention are described in detail above, and those skilled in the art can make corresponding adjustments in the specific implementation and application ranges according to the conditions of the embodiments of the present invention.
Claims (9)
1. A novel reactive moisture-curing polyurethane hot melt adhesive comprises the following raw materials in percentage by mass:
40 to 45 percent of polyester polyol
10 to 15 percent of polyether polyol
15 to 20 percent of synthetic acrylic resin
2 to 5 percent of ethylenediamine
0.1 to 1 percent of initiator
20 to 25 percent of isocyanate
Wherein the synthetic acrylic resin is copolymerized by synthetic acrylic resin, ethylenediamine, other aliphatic diamine, a chain initiator and a chain terminator.
2. The novel hot melt adhesive of claim 1, wherein: the raw materials are used as solvents and participate in the reaction, volatile components do not exist at the temperature of below 100 ℃, other solvents do not need to be added in the reaction process, and the product is environment-friendly and non-toxic.
3. The novel hot melt adhesive of claim 1, wherein the acrylic resin-removed, in mole percent, comprises the following components: 25-35% of aliphatic polyester polyol, 15-25% of aliphatic polyether polyol and 5-10% of initiator, wherein the aliphatic polyester polyol is C15-C20Aliphatic polyester polyol, aliphatic polyether polyol is C3-C8An aliphatic polyether polyol.
4. the novel hot melt adhesive of claim 1, wherein C is15-C20The aliphatic polyester polyol is a polyAdipic acid 1, 4-butanediol ester, poly adipic acid 1, 6-hexanediol ester, poly adipic acid ethylene glycol ester, and polyester compound polymerized by dibasic fatty acid such as adipic acid, terephthalic acid and the like and dihydric alcohol such as 1, 4-butanediol, propylene glycol and the like, and the hydroxyl value is 25-40 mgKOH/g.
5. the novel hot melt adhesive of claim 1, wherein C is3-C8The aliphatic polyether polyol is a copolymer among polypropylene glycol, polytetrahydrofuran ether glycol and dihydric aliphatic alcohol, and the hydroxyl value is 20-30 mgKOH/g.
6. The novel hot melt adhesive as claimed in claim 1, wherein the synthetic acrylic resin contains hydroxyl functional groups, has a molecular weight of 3000-5000 and a viscosity of 900-1200 mPas (120 ℃).
7. the synthetic acrylic resin according to claim 6, which is not an inert component and can participate in the synthetic reaction.
8. The novel hot melt adhesive as claimed in claim 1, wherein the isocyanate is one or more selected from the group consisting of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and hexamethylene 1,6 diisocyanate (HDI).
9. the novel hot melt adhesive as claimed in claim 1, which has a viscosity of 20000-50000 (mpa-s/120 ℃), and a weight-average molecular weight Mw8800 and 20000, and the melting temperature is 45-55 ℃.
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Application publication date: 20191210 |