CN115322726A - Low-density polyurethane hot melt adhesive and preparation method thereof - Google Patents
Low-density polyurethane hot melt adhesive and preparation method thereof Download PDFInfo
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
- C08G18/4202—Two or more polyesters of different physical or chemical nature
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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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4808—Mixtures of two or more polyetherdiols
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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
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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Abstract
The invention discloses a low-density polyurethane hot melt adhesive and a preparation method thereof, wherein the hot melt adhesive is prepared from the following raw materials in parts by weight: 9 to 20 portions of isocyanate, 20 to 45 portions of polyether diol, 10 to 40 portions of thermoplastic acrylic resin, 10 to 25 portions of poly-1, 6-hexanediol adipate diol, 3 to 10 portions of poly-neopentyl glycol adipate diol, 2 to 10 portions of poly-1, 6-hexanediol dodecacarbonate diol, 0.5 to 15 portions of hollow glass bead, 0.5 to 2 portions of silane coupling agent, 0.05 to 0.5 portion of antioxidant 1010, 0.01 to 0.1 portion of stabilizing agent and 0.01 to 0.5 portion of dimorpholinodiethyl ether. The invention has lower density, good hot melt fluidity, can realize roller coating, blade coating, spraying and spot coating sizing, and has excellent initial bonding strength and excellent final adhesion.
Description
Technical Field
The invention relates to the technical field of polyurethane hot melt adhesives, in particular to a low-density single-component moisture curing reaction type polyurethane hot melt adhesive and a preparation method thereof.
Background
The polyurethane hot melt adhesive is prepared by taking a polyurethane prepolymer or polyurethane resin as a main material and compounding a catalyst, an antioxidant, a filler, a thermoplastic resin and the like, has excellent chemical bonding force with various materials due to the fact that the polyurethane prepolymer or polyurethane resin contains isocyanate groups and urethane groups with strong polarity and high chemical activity, wherein the NCO-terminated single-component moisture curing reaction type polyurethane hot melt adhesive (HMPUR) has the capability of reacting with active hydrogen on the surface of a base material, has more excellent final chemical bonding capability, and is widely applied to bonding of industries such as automobile structures and parts, textile and shoemaking, book wireless binding, food packaging, wood processing, furniture, electronic and electric appliances and the like. The HPUR has excellent bonding property and belongs to an environment-friendly adhesive, the market demand and the national policy are met, and the market proportion is continuously and greatly increased.
The density of the polyurethane hot melt adhesive is generally 1.06-1.25 g/cm 3 The application of the adhesive in part of industries is limited due to the high density of the adhesive, and the application of the adhesive in the automobile industry is taken as an example, the requirements for light weight need to be met while composite and structural bonding are met, and the density specific gravity of most of the polyurethane hot melt adhesives can meet the requirements at present, but a large lifting space is still provided.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a low-density polyurethane hot melt adhesive and a preparation method thereof, wherein the low-density polyurethane hot melt adhesive has low density and good hot melt fluidity, can realize roller coating, blade coating, spraying and spot coating gluing, has excellent initial bonding strength and excellent final adhesion, and can well solve the technical problems in the prior art.
The purpose of the invention is realized by the following technical scheme:
a low-density polyurethane hot melt adhesive is prepared from the following raw materials in parts by weight:
the NCO% content of the polyurethane hot melt adhesive is 0.5% -4.0%.
Preferably, the polyether diol is polypropylene oxide ether glycol, and the hydroxyl value is 25-300 mgKOH/g.
Preferably, the acid value of the poly adipic acid-1, 6 hexanediol diol, the poly adipic acid-neopentyl glycol ester diol and the poly dodecane carbonic acid-1, 6 hexanediol diol is less than 1.2mgKOH/g, and the number average molecular weights are 1500-10000, 1000-4500 and 2500-5500 respectively.
Preferably, the thermoplastic acrylic resin synthetic monomers are methyl methacrylate and n-butyl methacrylate which are main monomers, the Tg point is 30-80 ℃, and the molecular weight is 20000-80000.
Preferably, the vacuum density of the hollow glass microspheres is 0.12-1.6 g/cm 3 The bulk density is 0.10-0.62 g/cm 3 And the particle diameter is 1-130 mu m.
Preferably, the silane coupling agent is at least one of primary amino, secondary amino silane and mercapto silane.
Preferably, the stabilizer is a compound formed by mixing phosphoric acid and polyphosphoric acid according to a mass ratio of 1-10.
Preferably, the isocyanate is at least one of diphenylmethane-4, 4-diisocyanate, diphenylmethane-2, 4-diisocyanate, 1, 5-naphthalene diisocyanate, p-toluenesulfonyl isocyanate, and 4, 4-dicyclohexylmethane diisocyanate.
A preparation method of a low-density polyurethane hot melt adhesive comprises the following steps:
step 1, weighing polyether diol, thermoplastic acrylate resin, poly (1, 6-hexanediol adipate) diol, poly (neopentyl glycol adipate) diol, poly (1, 6-hexanediol dodecanoate) diol, hollow glass microspheres, a silane coupling agent, an antioxidant 1010, a stabilizer, isocyanate and dimorpholine diethyl ether according to the raw material proportion of the polyurethane hot melt adhesive;
step 2, adding the polyether diol, the thermoplastic acrylate resin and the poly adipic acid-neopentyl glycol ester diol into a reaction kettle, starting vacuum to-0.05-0.095 Mpa, stirring for 1-2 hours at 120-160 ℃, and cooling to 80-120 ℃;
step 3, putting the poly-1, 6-hexanediol adipate glycol, the poly-1, 6-hexanediol dodecanoate glycol, the hollow glass microspheres, the antioxidant 1010 and the stabilizer into a reaction kettle, starting vacuum to-0.05-0.095 Mpa, stirring at 90-150 ℃ for 1-2 hours, and cooling to 80-120 ℃;
step 4, adding the isocyanate into a reaction kettle, and stirring for 0.5-2 hours at the temperature of 80-140 ℃ and the vacuum degree of-0.05-0.095 Mpa;
step 5, adding the silane coupling agent and dimorpholinyl diethyl ether into a reaction kettle, and stirring for 0.5-2 hours at 100-140 ℃ and under the vacuum degree of-0.05-0.095 Mpa;
thereby preparing the polyurethane hot melt adhesive.
Compared with the prior art, the low-density polyurethane hot melt adhesive provided by the invention takes the polyether glycol, the isocyanate, the polyester glycol, the hollow glass beads, the silane coupling agent, the antioxidant, the stabilizer and the dimorpholinyl diethyl ether in a specific proportion as raw materials, so that the prepared polyurethane hot melt adhesive has lower density and good hot melt fluidity, can realize roll coating, blade coating, spraying and spot coating glue application, has excellent initial bonding strength and excellent final adhesion.
Detailed Description
The technical scheme in the embodiment of the invention is clearly and completely described below; it should be understood that the described embodiments are only some of the embodiments of the present invention, not all of the embodiments, and are not intended to limit the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The terms that may be used herein are first described as follows:
the terms "comprising," "including," "containing," "having," or other similar terms of meaning should be construed as non-exclusive inclusions. For example: including a feature (e.g., material, component, ingredient, carrier, formulation, material, dimension, part, component, mechanism, device, process, procedure, method, reaction condition, processing condition, parameter, algorithm, signal, data, product, or article of manufacture), is to be construed as including not only the particular feature explicitly listed but also other features not explicitly listed as such which are known in the art.
The term "consisting of 823070 \8230composition" means to exclude any technical characteristic elements not explicitly listed. If used in a claim, the term shall render the claim closed except for the usual impurities associated therewith which do not include the technical features other than those explicitly listed. If the term occurs in only one clause of the claims, it is defined only to the elements explicitly recited in that clause, and elements recited in other clauses are not excluded from the overall claims.
The term "parts by weight" is intended to indicate the relationship of mass proportions between the various components, for example: if X parts by weight of the X component and Y parts by weight of the Y component are described, the mass ratio of the X component to the Y component is X: Y;1 part by weight may represent any mass, for example: 1 part by weight may be 1kg or 3.1415926 kg. The sum of the parts by weight of all components is not necessarily 100 parts and may be greater than 100 parts, less than 100 parts or equal to 100 parts. Unless otherwise indicated, parts, ratios, and percentages described herein are by mass.
When concentrations, temperatures, pressures, dimensions, or other parameters are expressed as ranges of values, the ranges of values should be understood to specifically disclose all ranges formed by any pair of upper values, lower values, or preferred values within the range, regardless of whether the ranges are explicitly recited; for example, if a numerical range of "2 to 8" is recited, then that numerical range should be interpreted to include ranges such as "2 to 7," "2 to 6," "5 to 7," "3 to 4 and 6 to 7," "3 to 5 and 7," "2 and 5 to 7," and the like. Unless otherwise indicated, the numerical ranges recited herein include both the endpoints thereof and all integers and fractions within the numerical range.
The low-density polyurethane hot melt adhesive and the preparation method thereof provided by the invention are described in detail below. Details which are not described in detail in the embodiments of the invention belong to the prior art which is known to a person skilled in the art. Those not specifically mentioned in the examples of the present invention were carried out according to the conventional conditions in the art or conditions suggested by the manufacturer. The reagents and instruments used in the examples of the present invention are not specified by manufacturers, and are conventional products commercially available.
The invention provides a low-density polyurethane hot melt adhesive and a preparation method thereof, wherein the low-density polyurethane hot melt adhesive is a single-component moisture curing reaction type polyurethane hot melt adhesive and is prepared from the following raw materials in parts by weight:
the NCO% content of the polyurethane hot melt adhesive is 0.5% -4.0%.
Specifically, the polyurethane hot melt adhesive may comprise the following embodiments:
(1) The isocyanate is at least one of diphenylmethane-4, 4-diisocyanate, diphenylmethane-2, 4-diisocyanate, 1, 5-naphthalene diisocyanate, p-toluenesulfonyl isocyanate and 4, 4-dicyclohexylmethane diisocyanate. The isocyanates have high reaction activity, and the polyurethane materials synthesized by the alicyclic isocyanate and the aromatic isocyanate have high strength, wear resistance and heat resistance.
(2) The polyether diol is polypropylene oxide ether glycol, and the hydroxyl value is 25-300 mgKOH/g. Compared with HMPUR synthesized by polyethylene oxide dihydric alcohol, the poly propylene oxide ether glycol has higher initial adhesion and colloid strength, and has better dissolving power for thermoplastic acrylic resin compared with polyester dihydric alcohol, so that the colloid in a molten state has better fluidity.
(3) The acid values of the poly adipic acid-1, 6 hexanediol diol, the poly adipic acid-neopentyl glycol ester diol and the poly dodecane carbonic acid-1, 6 hexanediol diol are less than 1.2mgKOH/g, and the number average molecular weights are 1500-10000, 1000-4500 and 2500-5500 respectively. The poly-1, 6-hexanediol adipate diol and the poly-1, 6-hexanediol dodecanoate diol are high-crystallinity polyester diols, so that the opening time of HMPUR is shortened, and the initial bonding force can be improved; the small acid value is beneficial to improving the hydrolysis resistance of polyurethane products and adhesives, the initial bonding force and the cohesion of the polyurethane products and the adhesives can be improved by properly matching the molecular weight polyester diol in the range, and the synthesized polyurethane hot melt adhesive has good fluidity and wettability to base materials by matching the liquid polyester poly adipic acid-neopentyl glycol diol in the range, so that good spraying property, glue discharging smoothness and good bonding effect to the base materials can be realized.
(4) The Tg point of the thermoplastic acrylic resin is 30-80 ℃, the molecular weight is 20000-80000, the thermoplastic acrylic resin in the Tg range can provide good initial adhesion when being used together with dihydric alcohol, and the molecular weight is 20000-80000, so that the synthesized HMPUR has good fluidity. The thermoplastic acrylic resin synthetic monomer is copolymerized and synthesized by taking methyl methacrylate and n-butyl methacrylate as main monomers.
(5) The vacuum density of the hollow glass beads is 0.12-1.6 g/cm 3 The bulk density is 0.10-0.62 g/cm 3 And the particle diameter is 1-130 mu m. The hollow glass beads are borosilicate glass formed at high temperature, have high chemical stability, do not react with other chemical substances when being used as a filler, have a spherical shape similar to a micro ball bearing, and are flaky, acicular or irregularThe filler with the characteristics has better fluidity, and the interior of the glass beads is vacuum thin gas, so that the product density can be effectively reduced, and the product with extremely low density can be manufactured.
(6) The silane coupling agent is at least one of primary amino, secondary amino silane and mercapto silane. The silane coupling agent with active hydrogen reacts with isocyanate group to form a silane end-capping structure, so that the adhesive capacity to inorganic materials can be improved, and the hydrolysis resistance and high temperature resistance of the colloid can be improved.
(7) The stabilizer is a compound formed by mixing phosphoric acid and polyphosphoric acid according to the mass ratio of 1-10. The stabilizer is adopted, and phosphoric acid in the stabilizer can more effectively enable the polyurethane synthesis reaction to be stably carried out, inhibit the reaction from being carried out too violently, and has small smell and extraction resistance.
(8) The content of NCO% in the polyurethane hot melt adhesive provided by the invention is 0.5% -4.0%, and the specific content of NCO% can avoid excessive CO generated in the curing process of an adhesive layer due to overhigh NCO% 2 More air bubbles are formed in the adhesive layer, and the lower limit value set by the NCO% can ensure that the adhesive layer has enough NCO groups to react and crosslink with moisture in the air and hydroxyl on the surface of the base material, so that the final higher adhesive layer body strength and the final higher bonding strength can be achieved by forming enough chemical bonds with the base material.
Further, the invention also provides a preparation method of the polyurethane hot melt adhesive, which comprises the following steps:
step 1, weighing polyether diol, thermoplastic acrylate resin, poly adipic acid-1, 6 hexanediol, poly adipic acid-neopentyl glycol ester diol, poly dodecane acid-1, 6 hexanediol, hollow glass microspheres, a silane coupling agent, an antioxidant 1010, a stabilizer, isocyanate and dimorpholine diethyl ether according to the raw material ratio of the polyurethane hot melt adhesive;
step 2, adding the polyether diol, the thermoplastic acrylate resin and the poly adipic acid-neopentyl glycol ester diol into a reaction kettle, starting vacuum to-0.05-0.095 Mpa, stirring for 1-2 hours at 120-160 ℃, and cooling to 80-120 ℃;
step 3, putting the poly adipic acid-1, 6 hexanediol ester diol, the poly dodecane carbonic acid-1, 6 hexanediol ester diol, the hollow glass microspheres, the antioxidant 1010 and the stabilizer into the reaction kettle after the reaction in the step 2, starting vacuum to-0.05-0.095 Mpa, stirring for 1-2 hours at 90-150 ℃, and cooling to 80-120 ℃;
step 4, adding the isocyanate into the reaction kettle reacted in the step 3, and stirring for 0.5-2 hours at the temperature of 80-140 ℃ and the vacuum degree of-0.05-0.095 Mpa;
step 5, adding the silane coupling agent and dimorpholinyl diethyl ether into a reaction kettle, and stirring for 0.5-2 hours at the temperature of 100-140 ℃ and the vacuum degree of-0.05-0.095 Mpa; discharging, and carrying out nitrogen protection packaging or vacuum packaging to obtain the polyurethane hot melt adhesive.
Compared with the prior art, the low-density polyurethane hot melt adhesive and the preparation method provided by the invention at least have the following advantages:
(1) Compared with the common polyurethane hot melt adhesive, the low-density polyurethane hot melt adhesive provided by the invention has lower density and is more suitable for light-weight products.
(2) The low-density polyurethane hot melt adhesive provided by the invention has low density and good hot melt fluidity, and can realize various glue applying modes such as roller coating, blade coating, spraying, glue dispensing and the like;
(3) The low-density polyurethane hot melt adhesive provided by the invention has low density and good initial bonding strength and final adhesion.
In conclusion, the embodiments of the present invention have low density, good hot melt flowability, good initial adhesion strength, and good final adhesion.
In order to more clearly show the technical solutions and the technical effects provided by the present invention, the following detailed description of the low-density polyurethane hot melt adhesive and the preparation method provided by the embodiments of the present invention are provided by specific examples.
The starting materials used in the following examples are first described as follows:
MDI-100: diphenylmethane-4, 4-diisocyanate;
PPG: polypropylene oxide ether glycol
PHA2000: 1, 6-hexanediol polyadipate diol having a number average molecular weight of 2000;
PHA8500: 1,6 hexanediol polyadipate diol having a number average molecular weight of 8500;
PNA3000: poly (neopentyl glycol adipate) glycol having a number average molecular weight of 3000;
PE3500: 1,6 hexanediol polydodecacarbonate having a number average molecular weight of 3500;
a stabilizer: a compound formed by mixing phosphoric acid and polyphosphoric acid according to the mass ratio of 1-10;
example 1
A preparation method of the low-density polyurethane hot melt adhesive comprises the following steps:
step A1, adding 100kg of PPG1000, 200kg of PPG2000, 220kg of acrylic resin BR-113 and 50kg of PNA3000 into a reaction kettle, starting vacuum to-0.05-0.095 Mpa, stirring for 1-2 hours at 120-160 ℃, and cooling to 80-120 ℃;
step A2, putting 160kg of PHA2000, 50kg of PHA8500, 70kg of PE3500, 60kg of hollow glass microsphere, 2kg of antioxidant 1010 and 0.2kg of stabilizer into a reaction kettle, starting vacuum to-0.05-0.095 Mpa, stirring for 1-2 hours at 90-150 ℃, and cooling to 80-120 ℃; in the step, the stabilizer is prepared from phosphoric acid and polyphosphoric acid in a mass ratio of 1:1 mixed formulation
Step A3, adding 145kg of MDI-100 into the reaction kettle reacted in the step A2, and stirring for 0.5-2 hours at the temperature of 80-140 ℃ and the vacuum degree of-0.05-0.095 Mpa;
and A4, adding 5kg of silane coupling agent and 1kg of dimorpholinyl diethyl ether into a reaction kettle, stirring for 0.5 to 2 hours at the temperature of between 100 and 140 ℃ and under the vacuum degree of between-0.05 and 0.095Mpa, discharging, and carrying out nitrogen protection packaging or vacuum packaging to obtain 1060kg of single-component moisture-curing polyurethane hot melt adhesive.
Example 2
A preparation method of the low-density polyurethane hot melt adhesive comprises the following steps:
step B1, adding 100kg of PPG1000, 200kg of PPG2000, 220kg of acrylic resin BR-113 and 50kg of PNA3000 into a reaction kettle, starting vacuum to-0.05-0.095 Mpa, stirring for 1-2 hours at 120-160 ℃, and cooling to 80-120 ℃;
step B2, putting 160kg of PHA2000, 50kg of PHA8500, 70kg of PE3500, 80kg of hollow glass microspheres, 2kg of antioxidant 1010 and 0.25kg of stabilizer into a reaction kettle, starting vacuum to-0.05-0.095 Mpa, stirring at 90-150 ℃ for 1-2 hours, and cooling to 80-120 ℃; in the step, the mass ratio of phosphoric acid to polyphosphoric acid adopted as a stabilizer is 4: 1;
step B3, adding 145kg of MDI-100 into the reaction kettle, and stirring for 0.5-2 hours at the temperature of 80-140 ℃ and the vacuum degree of-0.05-0.095 Mpa;
and step B4, adding 5kg of silane coupling agent and 1kg of dimorpholinyl diethyl ether into a reaction kettle, stirring for 0.5 to 2 hours at the temperature of between 100 and 140 ℃ and under the vacuum degree of between-0.05 and 0.095Mpa, discharging, and packaging under the protection of nitrogen or under vacuum to obtain 1080kg of single-component moisture-cured polyurethane hot melt adhesive.
Example 3
A preparation method of the low-density polyurethane hot melt adhesive comprises the following steps:
step C1, adding 150kg of PPG1000, 150kg of PPG2000, 220kg of acrylic resin BR-113 and 60kg of PNA3000 into a reaction kettle, starting vacuum to-0.05-0.095 Mpa, stirring for 1-2 hours at 120-160 ℃, and cooling to 80-120 ℃;
step C2, putting 160kg of PHA2000, 50kg of PHA8500, 50kg of PE3500, 60kg of hollow glass microsphere, 2kg of antioxidant 1010 and 0.3kg of stabilizer into a reaction kettle, starting vacuum to-0.05-0.095 Mpa, stirring for 1-2 hours at 90-150 ℃, and cooling to 80-120 ℃; in the step, the mass ratio of phosphoric acid to polyphosphoric acid adopted as a stabilizer is 1: 1;
step C3, adding 155kg of MDI-100 into a reaction kettle, and stirring for 0.5-2 hours at the temperature of 80-140 ℃ and the vacuum degree of-0.05-0.095 Mpa;
and step C4, adding 5kg of silane coupling agent and 1kg of dimorpholinyl diethyl ether into a reaction kettle, stirring for 0.5-2 hours at the temperature of 100-140 ℃ and the vacuum degree of-0.05-0.095 Mpa, discharging, and carrying out nitrogen protection packaging or vacuum packaging to obtain 1060kg of single-component moisture curing polyurethane hot melt adhesive.
Comparative example 1
The commercial flex bond8971S one-component moisture-curing polyurethane hot melt adhesive applied to the bonding of automobile exterior trimming parts such as new energy automobile door trim panels, front bumpers, spoilers and the like by Beijing GaoUnion New materials Ltd is selected as a comparative example 1.
Comparative example 2
The Flexibond8990 one-component moisture-curing polyurethane hot melt adhesive applied to the bonding of household electrical appliance materials by the new materials of Beijing Gai Union, which is commercially available, was selected as the comparative example 2.
Performance detection
The following performance tests were performed on the above-described inventive example 1, inventive example 2, inventive example 3, comparative example 1, and comparative example 2:
(1) Rotational viscosity: rotational viscosity at 120 ℃ was measured using brookfield viscometer # 27 spindle; the flowability is characterized.
(2) Opening time: sticker test, characterized by the time of nonstick kraft paper.
(3) Colloid density: and (3) testing by using an MDJ-300A densitometer.
(4) And (3) glue discharging fluency: a hot melt glue gun is matched with a 1.0mm gun head, the temperature is set at 150 ℃, and the air pressure of 0.4Mpa, so that the glue beating fluency and continuity are tested; smooth and continuous glue discharge is required.
(5) Shear force: the prepared hot melt adhesive ABS substrates are mutually adhered in an environment (RT: 23 ℃, RH: 50%), the shearing force is tested for 3min, 10min and 72h after the adhesion, 5 samples are tested, and the average value is taken after the test.
Summary of test results table:
in conclusion, the low-density polyurethane hot melt adhesive disclosed by the embodiment of the invention has the advantages of lower density, good hot melt fluidity, good initial bonding strength and final adhesion.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (9)
1. The low-density polyurethane hot melt adhesive is characterized by being prepared from the following raw materials in parts by weight:
2. the low-density polyurethane hot melt adhesive as claimed in claim 1, wherein the polyether diol is propylene oxide ether diol, and the hydroxyl value is 25-300 mgKOH/g.
3. The low-density polyurethane hot melt adhesive according to claim 1 or 2, wherein the poly 1, 6-hexanediol adipate diol, the poly-neopentyl glycol adipate diol and the poly-1, 6-hexanediol dodecacarbonate diol each have an acid value of less than 1.2mgKOH/g, and number average molecular weights of 1500 to 10000, 1000 to 4500 and 2500 to 5500, respectively.
4. The low-density polyurethane hot melt adhesive according to claim 1 or 2, wherein the thermoplastic acrylic resin has a Tg point of 30 to 80 ℃ and a molecular weight of 20000 to 80000, and the synthetic monomer of the thermoplastic acrylic resin comprises at least one of methyl methacrylate and n-butyl methacrylate.
5. The low-density polyurethane hot melt adhesive according to claim 1 or 2, wherein the true density of the hollow glass beads is 0.12-1.6 g/cm 3 The bulk density is 0.10-0.62 g/cm 3 The particle size is 1 to 130 μm.
6. The low-density polyurethane hot melt adhesive as claimed in claim 1 or 2, wherein the silane coupling agent is at least one of primary amino, secondary amino silane and mercapto silane.
7. The low-density polyurethane hot melt adhesive according to claim 1 or 2, wherein the stabilizer is a compound formed by mixing phosphoric acid and polyphosphoric acid according to a mass ratio of 1-20.
8. The low-density polyurethane hot melt adhesive according to claim 1 or 2, wherein at least one of the isocyanates diphenylmethane-4, 4-diisocyanate, diphenylmethane-2, 4-diisocyanate, 1, 5-naphthalene diisocyanate, p-toluenesulfonyl isocyanate, and 4, 4-dicyclohexylmethane diisocyanate.
9. A preparation method of a low-density polyurethane hot melt adhesive is characterized by comprising the following steps:
step 1, weighing polyether diol, thermoplastic acrylate resin, poly (1, 6-hexanediol adipate) diol, poly (neopentyl glycol adipate) diol, poly (1, 6-hexanediol dodecanoate) diol, hollow glass microspheres, a silane coupling agent, an antioxidant 1010, a stabilizer, isocyanate and dimorpholine diethyl ether according to the raw material proportion of the low-density polyurethane hot melt adhesive disclosed by any one of the claims 1 to 8;
step 2, adding the polyether diol, the thermoplastic acrylate resin and the poly adipic acid-neopentyl glycol ester diol into a reaction kettle, starting vacuum to-0.05-0.095 Mpa, stirring for 1-2 hours at 120-160 ℃, and cooling to 80-120 ℃;
step 3, putting the poly adipic acid-1, 6 hexanediol ester diol, the poly dodecane carbonic acid-1, 6 hexanediol ester diol, the hollow glass microspheres, the antioxidant 1010 and the stabilizer into the reaction kettle after the reaction in the step 2, starting vacuum to-0.05-0.095 Mpa, stirring for 1-2 hours at 90-150 ℃, and cooling to 80-120 ℃;
step 4, adding the isocyanate into the reaction kettle reacted in the step 3, and stirring for 0.5 to 2 hours at the temperature of between 80 and 140 ℃ and under the vacuum degree of between-0.05 and 0.095 Mpa;
and 5, adding the silane coupling agent and dimorpholinyl diethyl ether into the reaction kettle reacted in the step 4, and stirring at 100-140 ℃ and a vacuum degree of-0.05-0.095 Mpa for 0.5-2 hours to obtain the low-density polyurethane hot melt adhesive as claimed in any one of claims 1 to 8.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107987778A (en) * | 2017-12-08 | 2018-05-04 | 杭州之江有机硅化工有限公司 | A kind of household electrical appliances reaction type polyurethane hot-melt adhesive and preparation method thereof |
| CN108587551A (en) * | 2018-04-12 | 2018-09-28 | 浙江中特化工有限公司 | A kind of polyurethane hot melt and preparation method thereof with low temperature modulus high strength |
| US20200299554A1 (en) * | 2017-11-27 | 2020-09-24 | Yantai Darbond Technology Co.,Ltd. | Method of Preparing Polyurethane Hot Melt Adhesive with High Temperature Resistance |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20200299554A1 (en) * | 2017-11-27 | 2020-09-24 | Yantai Darbond Technology Co.,Ltd. | Method of Preparing Polyurethane Hot Melt Adhesive with High Temperature Resistance |
| CN107987778A (en) * | 2017-12-08 | 2018-05-04 | 杭州之江有机硅化工有限公司 | A kind of household electrical appliances reaction type polyurethane hot-melt adhesive and preparation method thereof |
| CN108587551A (en) * | 2018-04-12 | 2018-09-28 | 浙江中特化工有限公司 | A kind of polyurethane hot melt and preparation method thereof with low temperature modulus high strength |
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