CN110804414A - Reactive polyurethane hot melt adhesive - Google Patents
Reactive polyurethane hot melt adhesive Download PDFInfo
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- CN110804414A CN110804414A CN201911167158.7A CN201911167158A CN110804414A CN 110804414 A CN110804414 A CN 110804414A CN 201911167158 A CN201911167158 A CN 201911167158A CN 110804414 A CN110804414 A CN 110804414A
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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
- C09J175/08—Polyurethanes from polyethers
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
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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
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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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
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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
- C08G18/44—Polycarbonates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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
- C08G18/48—Polyethers
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6622—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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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
- 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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- 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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- 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
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention provides a reactive polyurethane hot melt adhesive, which is prepared from the following raw materials: 10-40 parts of polyester diol, 20-50 parts of polyether diol, 8-25 parts of isocyanate and 5-25 parts of tackifying resin; 0.1-1.5 parts of antioxidant, 0.1-5 parts of carbon black, 0.1-2 parts of adhesion promoter, 1-5 parts of latent curing agent and 0.5-3 parts of damp-heat resistant agent. The polyurethane hot melt adhesive provided by the invention does not contain a catalyst, is safe and environment-friendly, has high curing speed, good aging resistance and excellent adhesion, and can be used as a hot melt adhesive for vehicle lamps.
Description
Technical Field
The invention relates to the technical field of polyurethane, in particular to a reactive polyurethane hot melt adhesive.
Background
The bonding and sealing of the lamp is an important part of the manufacturing process of the automobile lamp. The bonding of car light should be able to guarantee that the car light does not appear when using under various adverse circumstances and receives the problem such as the atress is come unstuck, infiltration oil impregnate and is oozed and discolour and haze. In conventional vehicular lamp bonding applications, ordinary hot melt adhesives and two-component silicone adhesives are commonly used; the traditional hot melt adhesive has the advantages of fast curing and good initial adhesion, and is mainly used for bonding the traditional vehicle lamp. However, the main component of the hot melt adhesive is thermoplastic polyolefin, which is very sensitive to temperature change, is easy to flow when heated, and is also very sensitive to the permeation of water and gasoline, so that the weight problems of water leakage, fogging and the like of the car lamp are caused in use, and even the whole car lamp is scrapped; on the other hand, the adhesive force between the polyolefin hot melt adhesive and the polycarbonate material of one of the car lamp structures is insufficient, and particularly, the polycarbonate is easy to open after surface hardening and wear-resistant treatment, so that the requirement of a user on the adhesive strength of the car lamp is difficult to meet. Although the two-component silicone adhesive has improved high and low temperature performance, the initial adhesion is poor, and the devices are often not movable after being placed for hours, occupying space and prolonging delivery time. Therefore, the development of new polyurethane hot melt adhesives for vehicle lamps has been a research and development focus.
The reactive polyurethane hot melt adhesive (PUR adhesive for short) is prepared by matching single-component solvent-free isocyanate-terminated prepolymer with corresponding auxiliary agent; the main component of the adhesive is an isocyanate-terminated prepolymer synthesized by polyester polyol and diisocyanate, and the adhesive can be quickly cured after being melted and sized and has better initial adhesive strength; in the post-curing process, moisture diffuses into the adhesive and reacts with isocyanate at the end group of the prepolymer to form urea, biuret and allophanate, so that linear prepolymer low molecules form a cross-linked macromolecular structure, and the hot melt adhesive has better high temperature resistance, solvent resistance and water resistance than the traditional hot melt adhesive. PUR is selected as the adhesive for the car lamp, and has the advantages of hot melt adhesive and single-component silica gel: similar to common hot melt adhesives, when the PUR adhesive is used, the PUR adhesive is heated, melted and coated on the automobile lamp through an adhesive melting machine, and is rapidly cooled and solidified to achieve higher initial bonding strength, and a bonded piece can be moved, assembled and the like; then, during the storage or transportation process of the product, the PUR adhesive can continuously react with moisture in the air, the curing degree is further increased, and the PUR adhesive becomes a colloid with high strength, temperature resistance and solvent corrosion resistance. The polyurethane car lamp adhesive has the advantages of the traditional hot melt adhesive and the double-component silicone adhesive, and can perfectly solve the contradiction between quick positioning and high-strength bonding in car lamp bonding, so that the polyurethane car lamp adhesive is an ideal substitute for the car lamp bonding adhesive.
At present, performance reports about reactive polyurethane hot melt adhesives in a plurality of patents of reactive polyurethane hot melt adhesives for vehicle lamps mainly focus on improving heat resistance and adhesive property, and polyester polyol in raw materials is high in content and contains a catalyst; for example, Chinese patent with publication number CN108467702A discloses a moisture-curing polyurethane hot melt adhesive for vehicle lamps and a preparation method thereof, wherein the content of polyester polyol in a formula is 10-45%, and a catalyst is selected from dibutyltin dilaurate, stannous octoate, lead octoate and the like; chinese patent publication No. CN103740316A discloses a moisture-curable polyurethane hot melt adhesive for vehicle lamps and a preparation method thereof, wherein the content of polyester polyol is as high as 60-85%, and the catalyst is selected from dibutyltin dilaurate, stannous octoate and lead octoate. The high content of polyester polyol causes poor wet heat stability of the cured hot melt adhesive; on the other hand, the addition of the heavy metal catalyst organotin and organobismuth brings about serious biological toxicity.
After the polyurethane hot melt adhesive is assembled on the car lamp, the car lamp needs to be blown by wind and rain in the using process, so that the requirement on the weather resistance of the hot melt adhesive is very high; in the conventional formula of the polyurethane hot melt adhesive, the polyester content is high, so that the hot melt adhesive has poor damp-heat resistance stability, and no effective method for solving the damp-heat resistance stability of the polyurethane hot melt adhesive exists at present. On the other hand, the addition of heavy metal catalysts brings serious biological toxicity, and at present, only tertiary amine is used as a catalyst of the hot melt adhesive in patent reports, but the problems of surface foaming, slow deep layer curing, slow low-temperature curing in winter and the like are often existed. Therefore, at present, no catalyst-free reaction type polyurethane hot-melt car light adhesive is reported.
Disclosure of Invention
The invention solves the technical problem of providing a reactive polyurethane hot melt adhesive, and the reactive polyurethane hot melt adhesive formula provided by the application does not contain a catalyst, and has the characteristics of high curing speed and good bonding and aging resistance.
In view of the above, the application provides a reactive polyurethane hot melt adhesive, which is prepared from the following raw materials:
the structural formula of the latent curing agent is shown as the formula (I):
r is C2-C10 substituted alkyl or C2-C10 unsubstituted alkyl;
the R is1And R2Each independently selected from H, C1-C15 substituted hydrocarbyl or C1-C15 unsubstituted hydrocarbyl.
Preferably, the latent hardener is selected from one or more of incozol LV, incozol EH and incozol 4.
Preferably, the molecular weight of the polyester diol is 1000-4000, and the polyester diol is selected from one or two of polycaprolactone diol and polycarbonate diol.
Preferably, the molecular weight of the polyether diol is 600-2000, and the polyether diol is selected from one or two of polypropylene oxide diol and polytetrahydrofuran diol.
Preferably, the tackifying resin is selected from one or more of rosin resins, terpene resins, acrylic resins and polyurethane elastomers.
Preferably, the carbon black has a pH value of greater than 7.5 and a specific surface area of > 100m2/g。
Preferably, the content of the latent curing agent is 1.5-4.0 parts by weight.
Preferably, the isocyanate is selected from one or two of 4,4' -diphenylmethane diisocyanate and MDI-50; the adhesion promoter is selected from 3-mercaptopropyl-trimethoxysilane.
Preferably, the anti-damp-heat agent is selected from one or two of Stabaxol I and Stabaxol P200.
The application also provides the application of the reactive polyurethane hot melt adhesive in the hot melt adhesive for the car lamp.
The application provides a reactive polyurethane hot melt adhesive which is prepared from polyester diol, polyether diol, isocyanate, tackifying resin, an antioxidant, a bonding promoter, a latent curing agent, carbon black and a damp-heat resistant agent in a specific ratio; the application provides a latent curing agent that reaction type polyurethane hot melt adhesive adopted is oxazolidine tetrafunctional degree latent curing agent, it can improve curing speed and cross-linking density in the curing process, and preferentially react with water in the curing process and form two secondary amine functional groups and two hydroxyl functional groups, secondary amine reacts with isocyanate and forms the urea bond, the urea bond has higher ageing-resistant performance, simultaneously anti-hygrothermal agent has still been added in this application, consequently the reaction type polyurethane hot melt adhesive that the preparation obtained has excellent ageing-resistant performance.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In view of the influence of the catalyst on the polyurethane hot melt adhesive and the problem of poor aging resistance of the polyurethane hot melt adhesive in the prior art, the content of the raw materials is added and adjusted, so that the obtained polyurethane hot melt adhesive can be prepared under the condition of not adding the catalyst, and the polyurethane hot melt adhesive has good aging resistance. Specifically, the embodiment of the invention discloses a reactive polyurethane hot melt adhesive, which is prepared from the following raw materials:
the structural formula of the latent curing agent is shown as the formula (I):
r is C2-C10 substituted alkyl or C2-C10 unsubstituted alkyl;
the R is1And R2Each independently selected from H, C1-C15 substituted hydrocarbyl or C1-C15 unsubstituted hydrocarbyl.
The application provides a reactive polyurethane hot melt adhesive, which is prepared from polyester diol, polyether diol, isocyanate, tackifying resin, an antioxidant, a promoting adhesive, a latent curing agent and carbon black; the molecular weight of the polyester dihydric alcohol is 1000-4000, and the polyester dihydric alcohol can be one or two of polycaprolactone dihydric alcohol and polycarbonate dihydric alcohol. The content of the polyester diol is 10 to 40 parts by weight, in a specific embodiment, the content of the polyester diol is 20 to 35 parts by weight, and more specifically, the content of the polyester diol is 25 to 32 parts by weight. When the content of the polyester diol is reduced, the adhesiveness of the polyester diol to the surface of a substrate is affected.
The molecular weight of the polyether glycol is 600-2000; the polyether glycol described herein is selected from polyether glycols well known to those skilled in the art, and is not particularly limited in this application. In particular embodiments, the polyether glycol is selected from one or more of PPG800, PPG1000, and PPG 2000. The content of the polyether glycol is 20-50 parts by weight, in a specific embodiment, the content of the polyether glycol is 25-40 parts by weight, and more specifically, the content of the polyether glycol is 28-35 parts by weight. The viscosity of the polyurethane hot melt adhesive increases when the content of the polyether glycol is reduced, but the construction temperature increases.
The polyester diol and the polyether diol are used as the basis of the polyurethane hot melt adhesive, and directly influence the performance of the polyurethane hot melt adhesive.
The isocyanate is selected from one or two of 4,4' -diphenylmethane diisocyanate and MDI-50. The content of the isocyanate is 8 to 25 parts by weight, in a specific embodiment, the content of the isocyanate is 10 to 23 parts by weight, and more specifically, the content of the isocyanate is 15 to 20 parts by weight.
The antioxidant is an antioxidant well known to those skilled in the art, and is not particularly limited in this application, and exemplified by one or two selected from the group consisting of 2, 4-dimethyl-6-tert-butylphenol and HostanoxP-EPQ. The content of the antioxidant is 0.1-1.5 parts by weight.
The tackifying resin is selected from one or more of rosin resin, terpene resin, acrylic resin and polyurethane elastomer. The content of the tackifier resin is 5-25 parts by weight, and in a specific embodiment, the content of the tackifier resin is 8-22 parts by weight.
The adhesion promoter is used for further promoting the adhesion of the polyurethane hot melt adhesive; it may be chosen in particular from 3-mercaptopropyltrimethoxysilane. The content of the adhesion promoter is 0.1-2 parts by weight, and in a specific embodiment, the content of the adhesion promoter is 0.5-1.5 parts by weight.
The anti-damp heat agent is selected from one or two of Stabaxol I and Stabaxol P200 in specific embodiments. The content of the anti-damp and heat agent is 0.5-3 parts by weight, in a specific embodiment, the content of the anti-damp and heat agent is 0.6-2.0 parts by weight, and more specifically, the content of the anti-damp and heat agent is 0.8-1.8 parts by weight.
The carbon black has a pH value of > 7.5 and a specific surface area of > 100m2(ii)/g; the content of the carbon black is 0.1 to 5 parts by weight, in a specific embodiment, the content of the carbon black is 0.4 to 3.5 parts by weight, and more specifically, the content of the carbon black is 1.0 to 2.0 parts by weight. The content of the carbon black is reduced, so that the viscosity of the hot melt adhesive is reduced and the hot melt adhesive is easy to flow.
The latent curing agent is a tetrafunctional latent curing agent, and in particular embodiments, the latent curing agent is selected from one or more of incozol LV, incozol EH, and incozol 4. The content of the latent curing agent is 1-5 parts by weight, in a specific embodiment, the content of the latent curing agent is 1.5-4 parts by weight, and more specifically, the content of the latent curing agent is 2.5-3.5 parts by weight. The introduction of the latent curing agent can omit the addition of a catalyst, and the latent curing agent with four-functionality preferentially reacts with water in the curing process, so that the curing is accelerated, and the crosslinking effect of a system is ensured.
The preparation method of the reactive polyurethane hot melt adhesive is carried out according to a method well known by a person skilled in the art, namely, polyester polyol, polyether polyol, isocyanate, tackifying resin, an antioxidant, a bonding promoter, a latent curing agent, a damp-heat resistant agent and carbon black are mixed according to a proportion and then react to obtain the reactive polyurethane hot melt adhesive. In a specific embodiment, in order to fully react, the preparation method of the polyurethane hot melt adhesive for the vehicle lamp specifically comprises the following steps:
1) putting polyether polyol, polyester polyol and tackifying resin into a reaction kettle, heating to 100-130 ℃, and carrying out vacuum dehydration for 1.5-3 h under stirring, wherein the vacuum degree is less than-0.095 MPa;
2) cooling to 80-90 ℃, adding isocyanate into the mixture, and adding the isocyanate into the mixture in the presence of N2Heating to 93-98 ℃ under protection, stirring and reacting for 0.5-1 h; adding the anti-damp and heat agent and the carbon black to continue to react for 0.5 to 1 hour until the reaction is complete;
3) respectively adding a latent curing agent, an antioxidant and a bonding promoter, and stirring and dispersing at 90-95 ℃ under vacuum for reaction for 0.5-1.5 h; and obtaining the reactive polyurethane hot melt adhesive.
The polyurethane adhesive does not contain a catalyst, is safe and environment-friendly, has high crosslinking density after curing, good aging resistance and excellent adhesion, and can be used as a hot melt adhesive for vehicle lamps.
For further understanding of the present invention, the reactive polyurethane hot melt adhesive provided by the present invention is described in detail below with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Example 1
Adding PPG1000, Yingchuang polyester polyol Dynacoll7130 and Yingchuang acrylic resin AC1920 into a reaction kettle according to the formula amount, heating to 115-120 ℃, dehydrating for 2h under the condition that the vacuum degree is less than or equal to-0.095 MPa until the water content is less than or equal to 500ppm, then cooling to 80 ℃, adding MDI (diphenylmethane diisocyanate) according to the formula amount, heating to 95 ℃ for reaction for 1h, then adding the anti-damp-heat agent and the carbon black, and continuing stirring for 0.5-1 h; finally, adding the latent curing agent, the antioxidant and the adhesion promoter in a formula amount, and stirring and dispersing at 90-95 ℃ for reaction for 1h under vacuum; and (3) uniformly dispersing to obtain the reactive polyurethane hot melt adhesive. The formula amounts of the raw materials used in this example are shown in table 1.
TABLE 1 data table of the raw material formulation of this example
The curing speed of the reactive hot melt adhesive prepared in this example was tested under standard conditions, and the strength of the adhesive cured under conventional conditions for 14 days and under conditions of dual 85 curing for 14 days was tested by using a PP flame treated substrate and a PC substrate as an adhesive module, and the data are shown in Table 9.
Example 2
Adding Dynacol7150, polyether glycol PPG2000 and acrylic resin into a reaction kettle according to the formula amount, heating to 115-120 ℃, dehydrating for 2 hours under the condition that the vacuum degree is less than or equal to-0.095 MPa until the water content is less than or equal to 500ppm, then cooling to 80 ℃, adding MDI-50 according to the formula amount, heating to 95 ℃ for reaction for 1 hour, then adding a damp-heat resistant agent and carbon black, and stirring and reacting for 0.5-1 hour at 90-100 ℃ under vacuum; finally, adding the latent curing agent, the antioxidant and the adhesion promoter in a formula amount, and stirring and dispersing at 90-95 ℃ for reaction for 1h under vacuum; and (3) uniformly dispersing to obtain the reactive polyurethane hot melt adhesive. The formula amounts of the raw materials used in this example are shown in Table 2.
TABLE 2 data table of the formulation of the raw materials used in this example
| Raw materials | Input amount |
| PPG2000 | 35 |
| Dynacoll7150 | 25 |
| Acrylic resin AC1920 | 24 |
| MDI-50 | 11 |
| Anti-damp-heat agent (Stabaxol P200) | 0.6 |
| Antioxidant (HostanoxP-EPQ) | 0.5 |
| Carbon Black HIBLACK 30 | 2 |
| Latent curing agent Incozol IV | 1.5 |
| Adhesion promoter | 0.4 |
The curing speed of the reactive hot melt adhesive prepared in this example was tested under standard conditions, and the strength of the adhesive cured under conventional conditions for 14 days and under conditions of dual 85 curing for 14 days was tested by using a PP flame treated substrate and a PC substrate as an adhesive module, and the data are shown in Table 9.
Example 3
Adding Dynacol7380, polytetrahydrofuran dihydric alcohol and tackifying resin pearlond 500 into a reaction kettle according to the formula amount, heating to 115-120 ℃, dehydrating for 2 hours under the condition that the vacuum degree is less than or equal to-0.095 MPa until the water content is less than or equal to 500ppm, then cooling to 80 ℃, adding MDI-50 according to the formula amount, heating to 95 ℃ for reaction for 1 hour, then adding a damp-heat resistant agent and carbon black, and stirring and reacting for 0.5-1 hour at 90-100 ℃ under vacuum; finally, adding the latent curing agent, the antioxidant and the adhesion promoter in a formula amount, and stirring and dispersing at 90-95 ℃ for reaction for 1h under vacuum; and (3) uniformly dispersing to obtain the reactive polyurethane hot melt adhesive. The formula amounts of the raw materials used in this example are shown in Table 3.
TABLE 3 data table of the formulation of the raw materials used in this example
| Raw materials | Input amount |
| PTMEG (molecular weight 1000) | 25 |
| Dynacoll7380 | 36 |
| pearlbond 500 | 15 |
| MDI | 15.5 |
| Anti-damp-heat agent (stabaxol I) | 1.2 |
| Antioxidant (HostanoxP-EPQ) | 1.2 |
| Carbon black | 1.2 |
| Latent curing agent | 3.5 |
| Adhesion promoter | 1.4 |
The curing speed of the reactive hot melt adhesive prepared in this example was tested under standard conditions, and the strength of the adhesive cured under conventional conditions for 14 days and under conditions of dual 85 curing for 14 days was tested by using a PP flame treated substrate and a PC substrate as an adhesive module, and the data are shown in Table 9.
Example 4
Adding UH-CARB300 polycarbonate polyol, polytetrahydrofuran dihydric alcohol, PPG2000 and tackifying resin SYLVALITERE100L into a reaction kettle according to the formula amount, heating to 115-120 ℃, dehydrating for 2 hours under the condition that the vacuum degree is less than or equal to-0.095 MPa until the water content is less than or equal to 500ppm, then cooling to 80 ℃, adding MDI-50 according to the formula amount, heating to 95 ℃ for reaction for 1 hour, then adding a damp-heat resistant agent and carbon black, and stirring and reacting for 0.5-1 hour at 90-100 ℃ under vacuum; finally, adding the latent curing agent, the antioxidant and the adhesion promoter in a formula amount, and stirring and dispersing at 90-95 ℃ for reaction for 1h under vacuum; and (3) uniformly dispersing to obtain the reactive polyurethane hot melt adhesive. The formula amounts of the raw materials used in this example are shown in Table 4.
TABLE 4 data table of the formulation of the raw materials used in this example
| Raw materials | Input amount |
| PTMEG | 8 |
| PPG2000 | 30 |
| UH-CARB300 | 30 |
| SYLVALITE RE100L | 12 |
| MDI | 14 |
| Anti-damp-heat agent (stabaxol I) | 0.7 |
| Antioxidant (2, 4-dimethyl-6-tert-butylphenol) | 0.3 |
| Carbon black | 0.4 |
| Latent curing agent Incozol EH | 4 |
| Adhesion promoter | 0.6 |
The curing speed of the reactive hot melt adhesive prepared in this example was tested under standard conditions, and the strength of the adhesive cured under conventional conditions for 14 days and under conditions of dual 85 curing for 14 days was tested by using a PP flame treated substrate and a PC substrate as an adhesive module, and the data are shown in Table 9.
Comparative example 1
Adding hexanediol adipate, polyether polyol and an antioxidant into a reaction kettle according to the formula amount, heating to 80 ℃, adding acrylic resin 2740 according to the formula amount, heating to 115-120 ℃, dehydrating for 2 hours under the condition that the vacuum degree is less than or equal to-0.095 MPa until the water content is less than or equal to 500ppm, cooling to 80 ℃, adding MDI according to the formula amount, heating to 95 ℃ for reaction for 1 hour, adding 1, 4-butanediol for continuous reaction for 1 hour until the reaction is complete, finally adding carbon black and a catalyst DMDEE according to the formula amount, defoaming for 0.5-1 hour in vacuum, taking out the glue after uniformly stirring and dispersing, and filling to obtain the reactive polyurethane hot melt adhesive. The formulation amounts of the raw materials used in this comparative example are shown in table 5.
TABLE 5 formulation data Table of raw materials used in this comparative example
The hot melt adhesive for vehicle lamps prepared according to the comparative example was tested for curing speed under standard conditions, and the strength after curing under conventional conditions for 14 days and under conditions of dual 85 curing for 14 days was tested by using a PP flame treated substrate and a PC substrate as a bonding module, and the data are shown in Table 9.
Comparative example 2
Adding PPG1000 polyether diol, Yingchuang Dynacoll7365 polyester diol and acrylic resin into a reaction kettle according to the formula amount, heating to 115-120 ℃, dehydrating for 2h under the condition that the vacuum degree is less than or equal to-0.095 MPa until the water content is less than or equal to 500ppm, then cooling to 80 ℃, adding MDI according to the formula amount, heating to 95 ℃ for reaction for 1h, adding a damp-heat resistant agent and carbon black, and finally adding a latent curing agent, an antioxidant, an adhesion promoter and a catalyst according to the formula amount, stirring and dispersing for reaction for 0.5-1 h at 90-95 ℃ under vacuum; obtaining the reactive polyurethane hot melt adhesive. The formulation amounts of the raw materials used in this comparative example are shown in table 6.
TABLE 6 formulation data Table of raw materials used in this comparative example
| Raw materials | Input amount |
| PPG1000 | 40 |
| Dynacoll 7365 | 15 |
| Acrylic resin AC1630 | 12 |
| MDI | 15 |
| Damp-heat resisting agent | 0.6 |
| Antioxidant agent | 0.8 |
| Carbon black HIBLACK49L | 13 |
| Latent curing agent BH (aldehyde imine type) | 2 |
| Adhesion promoter | 1.5 |
| Catalyst DMDEE | 0.1 |
The hot melt adhesive for vehicle lamps prepared according to the comparative example was tested for curing speed under standard conditions, and the strength after curing under conventional conditions for 14 days and under conditions of dual 85 curing for 14 days was tested by using a PP flame treated substrate and a PC substrate as a bonding module, and the data are shown in Table 9.
Comparative example 3
Putting Polyoxypropylene Glycol (PPG), polybutylene adipate glycol (PBA) and rosin resin into a reaction kettle according to a formula amount, heating to 110 ℃, and carrying out vacuum dehydration for 2 hours under stirring, wherein the vacuum degree is-0.085 MPa; cooling to 80 deg.C, adding 2MDI-50 (mixture of 2, 4-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate), and adding into the reactor2Stirring and reacting for 1-3 hours at 80 ℃ under protection; adding 3-hydroxyethyl-1, 3-oxazolidine in N2Stirring and reacting for 1 hour at 80 ℃ under protection; finally, hydroxyl-terminated polyethylene wax and 3- [3- (trimethoxysilyl) propyl group are added in sequence]Isocyanurate, dibutyltin dilaurate, dibutyltin diacetate in N2Stirring and reacting for 0.6 hour at 80 ℃ under protection; and (3) heating to 110 ℃, vacuumizing until no bubbles appear, discharging, and sealing and packaging to obtain the PUR adhesive, wherein the formula amount of the raw materials used in the comparative example is shown in Table 7.
TABLE 7 data table of the formulation of the raw materials used in this comparative example
| Raw materials | Input amount |
| Polyether diol PPG2000 | 98 |
| Dynacoll 7360 | 2 |
| Rosin resin | 3.9 |
| MDI-50 | 29.6 |
| 3-hydroxyethyl-1, 3-oxazolidines | 5 |
| Hydroxyl-terminated polyethylene wax | 1 |
| 3- [3- (trimethoxysilyl) propyl]Isocyanurates | 1 |
| Dibutyl tin dilaurate | 0.2 |
| Dibutyl tin diacetate | 0.1 |
The hot melt adhesive for vehicle lamps prepared according to the comparative example was tested for curing speed under standard conditions, and the strength after curing under conventional conditions for 14 days and under conditions of dual 85 curing for 14 days was tested by using a PP flame treated substrate and a PC substrate as a bonding module, and the data are shown in Table 9.
Comparative example 4
Adding PPG1000, Yingchuang polyester polyol Dynacoll7130 and Yingchuang acrylic resin AC1920 into a reaction kettle according to the formula amount, heating to 115-120 ℃, dehydrating for 2h under the condition that the vacuum degree is less than or equal to-0.095 MPa until the water content is less than or equal to 500ppm, then cooling to 80 ℃, adding MDI (diphenylmethane diisocyanate) according to the formula amount, heating to 95 ℃ for reaction for 1h, then adding the anti-damp-heat agent and the carbon black, and continuing stirring for 0.5-1 h; finally, adding the antioxidant and the adhesion promoter in a formula amount, and stirring and dispersing at 90-95 ℃ for reaction for 1h under vacuum; and (3) uniformly dispersing to obtain the reactive polyurethane hot melt adhesive. The formulation amounts of the raw materials used in this comparative example are shown in table 8.
Table 8 data table of the raw material formulation of this comparative example
| Raw materials | Input amount |
| PPG1000 | 35 |
| Dynaco ll7 130 | 25 |
| Acrylic resin AC1920 | 19 |
| MDI | 15 |
| Damp-heat resisting agent | 0.6 |
| Antioxidant agent | 0.8 |
| Carbon Black HIBLACK49L | 1.5 |
| Adhesion promoter | 0.6 |
The hot melt adhesive for vehicle lamps prepared according to the comparative example was tested for curing speed under standard conditions, and the strength after curing under conventional conditions for 14 days and under conditions of dual 85 curing for 14 days was tested by using a PP flame treated substrate and a PC substrate as a bonding module, and the data are shown in Table 9.
TABLE 9 data table of 90 ℃ extrudability, adhesiveness and hardness after complete curing of hot melt adhesives prepared in the examples of the invention and comparative examples
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A reactive polyurethane hot melt adhesive is prepared from the following raw materials:
the structural formula of the latent curing agent is shown as the formula (I):
r is C2-C10 substituted alkyl or C2-C10 unsubstituted alkyl;
the R is1And R2Each independently selected from H, C1-C15 substituted hydrocarbyl or C1-C15 unsubstituted hydrocarbyl.
2. The reactive polyurethane hot melt adhesive of claim 1, wherein the latent curing agent is selected from one or more of incozol LV, incozol EH, and incozol 4.
3. The reactive polyurethane hot melt adhesive according to claim 1, wherein the molecular weight of the polyester diol is 1000-4000, and the polyester diol is one or two of polycaprolactone diol and polycarbonate diol.
4. The reactive polyurethane hot melt adhesive according to claim 1, wherein the molecular weight of the polyether diol is 600-2000, and the polyether diol is one or two of polypropylene oxide diol and polytetrahydrofuran diol.
5. The reactive polyurethane hot melt adhesive of claim 1, wherein the tackifying resin is selected from one or more of rosin resins, terpene resins, acrylic resins, and polyurethane elastomers.
6. The reactive polyurethane hot melt adhesive according to claim 1, wherein the carbon black has a pH value of more than 7.5 and a specific surface area of more than 100m2/g。
7. The reactive polyurethane hot melt adhesive according to claim 1, wherein the content of the latent curing agent is 1.5-4.0 parts by weight.
8. The reactive polyurethane hot melt adhesive according to claim 1, wherein the isocyanate is selected from one or two of 4,4' -diphenylmethane diisocyanate and MDI-50; the adhesion promoter is selected from 3-mercaptopropyl-trimethoxysilane.
9. The reactive polyurethane hot melt adhesive of claim 1, wherein the moisture and heat resistant agent is selected from one or both of Stabaxol I and Stabaxol P200.
10. The application of the reactive polyurethane hot melt adhesive as claimed in any one of claims 1 to 9 in a hot melt adhesive for vehicle lamps.
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| CN111303824A (en) * | 2020-04-20 | 2020-06-19 | 常州威斯敦粘合材料有限责任公司 | Moisture-curing polyurethane hot melt adhesive, preparation method and application thereof, and steel member |
| CN111826117A (en) * | 2020-08-17 | 2020-10-27 | 山东乐邦化工科技有限公司 | Two-component polyurethane sealing heat-insulating glue |
| CN113698909A (en) * | 2021-09-15 | 2021-11-26 | 杭州之江新材料有限公司 | High-temperature-resistant polyurethane hot melt adhesive and preparation method thereof |
| CN115353494A (en) * | 2022-08-31 | 2022-11-18 | 苏州湘园新材料股份有限公司 | Dioxazolidine latent curing agent and preparation method thereof |
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