CN112646529A - High-temperature-resistant single-component solvent-free polyurethane adhesive and preparation method and application thereof - Google Patents
High-temperature-resistant single-component solvent-free polyurethane adhesive and preparation method and application thereof Download PDFInfo
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- CN112646529A CN112646529A CN202011504442.1A CN202011504442A CN112646529A CN 112646529 A CN112646529 A CN 112646529A CN 202011504442 A CN202011504442 A CN 202011504442A CN 112646529 A CN112646529 A CN 112646529A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
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- 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
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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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
- C08G18/42—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
- C08G18/58—Epoxy resins
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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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C08G18/65—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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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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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- 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
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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 discloses a high-temperature-resistant single-component solvent-free polyurethane adhesive which is characterized in that an isocyanate prepolymer prepared from the following components in percentage by mass comprises the following components: 30 to 70 percent of special polyol; 20 to 60 percent of isocyanate; 0 to 10 percent of coupling agent; 0 to 10 percent of epoxy resin; 0-10% of micromolecular chain extender; 0 to 10 percent of catalyst; 0 to 10 percent of auxiliary agent. The invention also discloses a preparation method and application thereof. The high-temperature-resistant single-component solvent-free polyurethane adhesive provided by the invention can solve the problems of insufficient high-temperature-resistant strength and yellowing of products of the existing single-component solvent-free polyurethane adhesive.
Description
Technical Field
The invention relates to the field of preparation of single-component solvent-free polyurethane adhesives, in particular to a high-temperature-resistant single-component solvent-free polyurethane adhesive and a preparation method and application thereof.
Background
The solvent-free composite process is more and more known and applied by more composite film manufacturers due to the advantages of simplifying equipment process flow, reducing energy consumption, improving production efficiency and being green and environment-friendly.
At present, most composite film manufacturers in China gradually change the process of producing films from a simple dry compounding process into a multi-compounding process with a dry compounding process and a solvent-free compounding process. The gradual replacement of a dry compounding process by a solvent-free re-working process in the future is the development direction of the compounding process in the future and is a trend in the field of composite materials.
The solvent-free compounding process is a method for compounding two base materials together by adopting a solvent-free adhesive, and the used solvent-free adhesive mainly comprises a single-component polyurethane adhesive and a double-component polyester adhesive. The performance of the solvent-free adhesive is key to whether the composite process can be replaced in the compounding of different materials or not, and even optimization. Therefore, the improvement of the performance of the solvent-free adhesive is very important for expanding the application of the solvent-free composite process in the field of composite materials.
The single-component solvent-free polyurethane adhesive disclosed in Chinese patent application publication No. CN106883807A, the preparation method and the application thereof, and the single-component solvent-free polyurethane adhesive disclosed in Chinese patent application publication No. CN110922928A, the preparation method and the application thereof only mention that the single-component solvent-free polyurethane adhesive is prepared from an isocyanate-terminated polyurethane prepolymer and optional additives, the application is only directed at the normal temperature bonding performance of porous materials such as paper/plastic, paper/aluminum, non-woven fabrics and the like, and the high temperature resistance and yellowing resistance effects of the single-component solvent-free polyurethane adhesive prepared in the patent are not mentioned.
In addition, the single-component solvent-free polyurethane adhesive prepared according to the patent has the problems of obviously reduced performance and yellowing of products after compounding under the high-temperature condition.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a high-temperature-resistant single-component solvent-free polyurethane adhesive and a preparation method and application thereof. The problems of insufficient high-temperature resistance strength and yellowing of products of the existing single-component solvent-free polyurethane adhesive are solved.
In order to realize the purpose of the invention, the adopted technical scheme is as follows:
a high-temperature-resistant single-component solvent-free polyurethane adhesive is an isocyanate prepolymer prepared from the following components in percentage by mass, and comprises the following components:
in a preferred embodiment of the present invention, the special polyol is one or a mixture of any two or more of polyester polyol, polyether polyol, small molecule polyol or epoxy resin modified polyol with two or more functionalities: but at least includes any one or more of polyester polyol or epoxy resin modified polyol.
In a preferred embodiment of the present invention, the polyester polyol having two or more functionalities includes any one or more of a polyester polyol prepared by a polycondensation esterification reaction of a dibasic acid with a polyhydric alcohol, a polyester polyol prepared by a ring-opening polymerization of caprolactone, or a polyester polyol prepared by transesterification of a small-molecular diol as an initiator with dimethyl carbonate or diphenyl carbonate.
Wherein the dibasic acid is one or the mixture of more than two of phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid and sebacic acid;
the polyhydric alcohol is one or the mixture of more than two of ethylene glycol, diethylene glycol, triethylene glycol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, trimethylolethane or trimethylolpropane; the small molecular diol is one or the mixture of more than two of ethylene glycol, diethylene glycol, butanediol or hexanediol.
In a preferred embodiment of the present invention, the polyether polyol with two or more functionalities comprises one or a mixture of any two or more of polypropylene glycol, polyglycerol, polyethylene glycol or polytetrahydrofuran glycol.
In a preferred embodiment of the present invention, the small molecule polyol is one or a mixture of any two or more of ethylene glycol, diethylene glycol, triethylene glycol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, trimethylolethane, and trimethylolpropane.
In a preferred embodiment of the present invention, the epoxy resin modified polyol is a modified polyol obtained by ring-opening polymerization of an epoxy compound initiated by a hydroxyl compound.
In a preferred embodiment of the present invention, the isocyanate is one or any mixture of two or more of 4,4 '-diphenylmethane diisocyanate, 2, 4' -diphenylmethane diisocyanate, carbodiimide liquefied diphenylmethane diisocyanate, hexamethylene diisocyanate trimer, isophorone diisocyanate or dicyclohexylmethane diisocyanate.
In a preferred embodiment of the present invention, the coupling agent is one or a mixture of any two or more of vinyl silane, amino silane, epoxy silane, acyloxy silane, hydrogen-containing silane, alkyl silane, phenyl silane, sulfur-containing silane, or isocyanate silane.
In a preferred embodiment of the present invention, the epoxy resin is a mixture of any one of bisphenol a polyol, bisphenol F polyol and bisphenol S polyol and one or more of propylene oxide and ethylene oxide polycondensation products.
In a preferred embodiment of the present invention, the small molecule chain extender is one or a mixture of any two or more of ethylene glycol, diethylene glycol, triethylene glycol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, trimethylolethane, or trimethylolpropane.
In a preferred embodiment of the present invention, the catalyst is a metal organic acid salt or a bimetallic complex including one or a mixture of two or more of zinc, iron, tin, bismuth, cobalt or nickel.
In a preferred embodiment of the present invention, the auxiliary agent is one or a mixture of any two or more of a water removal agent, a leveling agent, a defoaming agent, a surfactant, an adhesion promoter, a substrate wetting agent, an antioxidant, an ultraviolet light absorber, and a yellowing resistant agent.
A preparation method of a high-temperature-resistant single-component solvent-free polyurethane adhesive comprises the following steps:
a pretreatment step:
adding the special polyol component into a reaction kettle, heating to 110-120 ℃, and dehydrating under the condition that the vacuum degree is more than 0.09MPa (preferably, the dehydration time is 1-2 h);
then cooling to a temperature not higher than 60 ℃, adding the coupling agent, and uniformly stirring to obtain a dehydrated mixed product of the polyol and the coupling agent;
a prepolymerization reaction step:
adding the isocyanate into the dehydrated mixed product for reaction, controlling the reaction temperature to be between 80 and 100 ℃, and reacting to generate a polyurethane prepolymer (preferably, the reaction time is 1 to 2 hours);
chain extension reaction:
after the prepolymerization reaction is finished, adding the epoxy resin and the micromolecule chain extender into a reaction kettle, controlling the reaction temperature to be between 100 and 120 ℃, and reacting to generate a polyurethane prepolymer with the required molecular weight (preferably, the reaction time is 0.5 to 2 hours);
adding an auxiliary agent:
after the prepolymer with the required molecular weight is prepared, the temperature is reduced to 60-100 ℃, and the catalyst or the rest of the auxiliary agent is added to obtain the high-temperature resistant single-component solvent-free polyurethane adhesive.
The application of the high-temperature-resistant single-component solvent-free polyurethane adhesive is to prepare a high-temperature-resistant flame-retardant material, wherein the material needs to be subjected to corona treatment.
In a preferred embodiment of the invention, the high temperature resistant and flame retardant material is any one or a mixture of more than two of PET, PA, PBT, PPO, PPA, PPS, PI or AR high temperature resistant fibers.
In a preferred embodiment of the invention, the application is coating and compounding at 80-120 ℃, and the coating amount is 1.0-10.0 g/m2。
The invention has the beneficial effects that:
the high-temperature-resistant single-component solvent-free polyurethane adhesive provided by the invention can solve the problems of insufficient high-temperature-resistant strength and yellowing of products of the existing single-component solvent-free polyurethane adhesive.
Detailed Description
The temperature resistance is mainly as follows:
1. increasing product crosslinking, i.e. adding a small molecule polyol (comparative examples 1, 2, 3)3 functionality TMP is better than 2 functionality DEG than without the addition of product.
2. The temperature-resistant polycaprolactone polyol is adopted to replace general polyester polyol (the heat resistance of the lactone diol polyester is superior to that of the hexanediol polyester)
The yellowing resistance of the product is mainly achieved by: 2, 4-diphenylmethane diisocyanate which is easy to yellow is replaced, and isophorone diisocyanate which is not yellow is adopted.
The present invention is described in detail below with reference to specific examples, but the scope of the present invention is not limited to the specific examples.
Example 1 (without addition of Small molecule polyol)
Firstly, 40 parts of polyester polyol PDA2000 and 15 parts of polycarbonate polyol PCDL2000 are added into a reaction kettle and heated to 110-120 ℃, and dehydration is carried out for 1-2 h under the condition that the vacuum degree is more than 0.09 MPa; cooling to below 60 ℃, adding 5 parts of aminosilane coupling agent, and uniformly stirring to obtain a dehydrated mixed product of polyol and the coupling agent;
adding 35 parts of 2, 4-diphenylmethane diisocyanate, controlling the reaction temperature to rise to 80-100 ℃, and reacting for 1-2 h to generate a polyurethane prepolymer;
after the prepolymerization reaction is finished, 2 parts of epoxy resin E12 are added into a reaction kettle, the reaction temperature is controlled to be between 100 and 120 ℃, and the reaction is carried out for 0.5 to 2 hours to generate a polyurethane prepolymer with the required molecular weight;
cooling to 60-100 ℃, adding 0.5 part of organic zincate catalyst and 0.5 part of silane modified polyether surfactant, and discharging to obtain isocyanate-terminated polyurethane prepolymer P1.
Example 2 (lower functionality of polyol added with small molecule)
Firstly, 40 parts of polyester polyol PDA2000 and 15 parts of polycarbonate polyol PCDL2000 are added into a reaction kettle and heated to 110-120 ℃, and dehydration is carried out for 1-2 h under the condition that the vacuum degree is more than 0.09 MPa; cooling to below 60 ℃, adding 5 parts of aminosilane coupling agent, and uniformly stirring to obtain a dehydrated mixed product of polyol and the coupling agent;
adding 35 parts of 2, 4-diphenylmethane diisocyanate, controlling the reaction temperature to rise to 80-100 ℃, and reacting for 1-2 h to generate a polyurethane prepolymer;
after the prepolymerization reaction is finished, 2 parts of epoxy resin E12 and 2 parts of ethylene glycol DEG are added into a reaction kettle, the reaction temperature is controlled to be between 100 and 120 ℃, and the reaction is carried out for 0.5 to 2 hours to generate a polyurethane prepolymer with the required molecular weight;
cooling to 60-100 ℃, adding 0.5 part of organic zincate catalyst and 0.5 part of silane modified polyether surfactant, and discharging to obtain isocyanate-terminated polyurethane prepolymer P2.
Example 3 (higher functionality of Small molecule polyol added)
Firstly, 40 parts of polyester polyol PDA2000 and 15 parts of polycarbonate polyol PCDL2000 are added into a reaction kettle and heated to 110-120 ℃, and dehydration is carried out for 1-2 h under the condition that the vacuum degree is more than 0.09 MPa; cooling to below 60 ℃, adding 5 parts of aminosilane coupling agent, and uniformly stirring to obtain a dehydrated mixed product of polyol and the coupling agent;
adding 35 parts of 2, 4-diphenylmethane diisocyanate, controlling the reaction temperature to rise to 80-100 ℃, and reacting for 1-2 h to generate a polyurethane prepolymer;
after the prepolymerization reaction is finished, 2 parts of epoxy resin E12 and 2 parts of trimethylolpropane TMP are added into a reaction kettle, the reaction temperature is controlled to be 100-120 ℃, and the reaction is carried out for 0.5-2 h to generate a polyurethane prepolymer with the required molecular weight;
cooling to 60-100 ℃, adding 0.5 part of organic zincate catalyst and 0.5 part of silane modified polyether surfactant, and discharging to obtain isocyanate-terminated polyurethane prepolymer P3.
Example 4 (polyester polyol is replaced by polycaprolactone having better Heat resistance)
Firstly, adding 40 parts of polycaprolactone polyol PCL2000 and 15 parts of polycarbonate polyol PCDL2000 into a reaction kettle, heating to 110-120 ℃, and dehydrating for 1-2 hours under the condition that the vacuum degree is more than 0.09 MPa; cooling to below 60 ℃, adding 5 parts of aminosilane coupling agent, and uniformly stirring to obtain a dehydrated mixed product of polyol and the coupling agent;
adding 35 parts of 2, 4-diphenylmethane diisocyanate, controlling the reaction temperature to rise to 80-100 ℃, and reacting for 1-2 h to generate a polyurethane prepolymer;
after the prepolymerization reaction is finished, 2 parts of epoxy resin E12 and 2 parts of trimethylolpropane TMP are added into a reaction kettle, the reaction temperature is controlled to be 100-120 ℃, and the reaction is carried out for 0.5-2 h to generate a polyurethane prepolymer with the required molecular weight;
cooling to 60-100 ℃, adding 0.5 part of organic zincate catalyst and 0.5 part of silane modified polyether surfactant, and discharging to obtain isocyanate-terminated polyurethane prepolymer P4.
Example 5 (replacement of yellowing-prone 2, 4-diphenylmethane diisocyanate by non yellowing-prone isophorone diisocyanate IPDI)
Firstly, adding 40 parts of polycaprolactone polyol PCL2000 and 15 parts of polycarbonate polyol PCDL2000 into a reaction kettle, heating to 110-120 ℃, and dehydrating for 1-2 hours under the condition that the vacuum degree is more than 0.09 MPa; cooling to below 60 ℃, adding 5 parts of aminosilane coupling agent, and uniformly stirring to obtain a dehydrated mixed product of polyol and the coupling agent;
adding 40 parts of isophorone diisocyanate, controlling the reaction temperature to rise to 80-100 ℃, and reacting for 1-2 h to generate a polyurethane prepolymer;
after the prepolymerization reaction is finished, 2 parts of epoxy resin E12 and 2 parts of trimethylolpropane TMP are added into a reaction kettle, the reaction temperature is controlled to be 100-120 ℃, and the reaction is carried out for 0.5-2 h to generate a polyurethane prepolymer with the required molecular weight;
cooling to 60-100 ℃, adding 0.5 part of organic zincate catalyst and 0.5 part of silane modified polyether surfactant, and discharging to obtain isocyanate-terminated polyurethane prepolymer P5.
Application example 1
The cured PET/AR material compounded with the isocyanate-terminated polyurethane prepolymer P1, the isocyanate-terminated polyurethane prepolymer P2, the isocyanate-terminated polyurethane prepolymer P3, the isocyanate-terminated polyurethane prepolymer P4 and the isocyanate-terminated polyurethane prepolymer P5 was aged at 200 ℃ for 40min to test appearance and peel strength of the sample.
The material peel test criteria are shown in table 1 in the order determined as material failure:
| example 1 | Peeling, delamination of two materials |
| Example 2 | Peeling, delamination of the two materials for the most part |
| Example 3 | Peeling, slight delamination of the two materials |
| Example 4 | Peeling, no delamination, slight yellow |
| Example 5 | Peeling, no delamination, no yellowing |
Peel Strength test Standard
Wherein, the PET/AR compounded by the isocyanate-terminated polyurethane prepolymer P1 has obvious yellowing of the material, the AR fiber material is not transferred to the PET, the isocyanate-terminated polyurethane prepolymer P1 is decomposed at high temperature, and the PET and the AR fiber material are delaminated;
the PET/AR compounded by the isocyanate-terminated polyurethane prepolymer P2 has obvious yellowing of materials, a small amount of AR fiber materials are transferred to the PET, the isocyanate-terminated polyurethane prepolymer P2 is decomposed at high temperature, and most of the PET and AR fiber materials are separated;
the PET/AR compounded by the isocyanate-terminated polyurethane prepolymer P3 has light yellowing of materials, most of AR fiber materials are transferred to the PET, the isocyanate-terminated polyurethane prepolymer P3 is partially decomposed at high temperature, and the PET and the AR fiber materials are partially separated;
the PET/AR compounded by the isocyanate-terminated polyurethane prepolymer P4 has light yellowing of materials, the AR fiber materials are basically and completely transferred to the PET, and the AR fiber materials are peeled and damaged;
the material of the PET/AR compounded by the isocyanate-terminated polyurethane prepolymer P5 is not yellowed, the AR fiber material is basically and completely transferred to the PET, and the AR fiber material is peeled and damaged;
it can be found that the isocyanate-terminated polyurethane prepolymer prepared by the method of the present invention has more excellent high temperature resistance and yellowing resistance.
Example 1 is different from examples 2 and 3 in that examples 2 and 3 are added with small molecular weight polyol, and example 1 is not added with small molecular weight polyol. The small molecule polyol added in example 3 has a higher functionality, while the small molecule polyol added in example 2 has a lower functionality.
By comparison, it can be seen that the final strength of example 3 is significantly greater than the final strength of example 2 than the final peel strength of example 1.
Examples 1 and 3 are different from example 4 in that example 4 is added with polycaprolactone polyol having better heat resistance. Examples 1 and 3 used general polyester polyols.
By comparison, it can be seen that the final strength of example 4 is significantly greater than the final strength of example 3 is greater than the final peel strength of example 1.
Example 4 differs from example 5 in that example 5 uses isophorone diisocyanate and example 4 uses 2, 4-diphenylmethane diisocyanate. The comparison revealed that example 5 is superior in yellowing resistance.
Claims (10)
1. The high-temperature-resistant single-component solvent-free polyurethane adhesive is characterized in that an isocyanate prepolymer prepared from the following components in percentage by mass comprises the following components:
2. the high temperature resistant single component solvent-free polyurethane adhesive of claim 1, wherein the special polyol is one or a mixture of any two or more of polyester polyol, polyether polyol, small molecule polyol or epoxy resin modified polyol with two or more functionalities: but at least includes any one or more of polyester polyol or epoxy resin modified polyol.
3. The high temperature resistant one-component solvent-free polyurethane adhesive according to claim 1, wherein the polyester polyol having two or more functionalities comprises any one or more of polyester polyol prepared by polycondensation esterification of dibasic acid and polyol, polyester polyol prepared by ring-opening polymerization of caprolactone, or polyester polyol prepared by transesterification of small molecular diol as initiator with dimethyl carbonate or diphenyl carbonate;
the polyether polyol with two or more functionalities comprises one or a mixture of more than two of polypropylene glycol, polyglycerol, polyethylene glycol or polytetrahydrofuran glycol;
one or more than two of small molecular polyol ethylene glycol, diethylene glycol, triethylene glycol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, trimethylolethane or trimethylolpropane;
the epoxy resin modified polyol is prepared by initiating ring-opening polymerization reaction of an epoxy compound by a hydroxyl compound.
4. The high temperature resistant one-component solvent-free polyurethane adhesive of claim 1, wherein the isocyanate is one or more of 4,4 '-diphenylmethane diisocyanate, 2, 4' -diphenylmethane diisocyanate, carbodiimide liquefied diphenylmethane diisocyanate, hexamethylene diisocyanate trimer, isophorone diisocyanate, and dicyclohexylmethane diisocyanate.
5. The high temperature resistant one-component solvent-free polyurethane adhesive of claim 1, wherein the coupling agent is one or a mixture of any two or more of vinyl silane, amino silane, epoxy silane, acyloxy silane, hydrogen silane, alkyl silane, phenyl silane, sulfur silane, and isocyanate silane.
6. The high temperature resistant single component solvent-free polyurethane adhesive of claim 1, wherein the epoxy resin is a mixture of any one of bisphenol a polyol, bisphenol F polyol, bisphenol S polyol and one or more of propylene oxide or ethylene oxide polycondensation product.
7. The high temperature resistant single component solvent-free polyurethane adhesive as claimed in claim 1, wherein the small molecule chain extender is one or a mixture of any two or more of ethylene glycol, diethylene glycol, triethylene glycol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, trimethylolethane or trimethylolpropane.
8. The high temperature resistant single component solvent-free polyurethane adhesive of claim 1, wherein the catalyst is a metal organic acid salt or a bimetallic complex, and the bimetallic complex comprises one or a mixture of more than two of zinc, iron, tin, bismuth, cobalt or nickel;
the auxiliary agent is one or the mixture of more than two of a water removing agent, a flatting agent, a defoaming agent, a surfactant, an adhesion promoter, a base material wetting agent, an antioxidant, an ultraviolet light absorber or an anti-yellowing agent.
9. The method for preparing a high temperature resistant one-component solvent-free polyurethane adhesive according to any one of claims 1 to 8, comprising the steps of:
a pretreatment step:
adding the special polyol component into a reaction kettle, heating to 110-120 ℃, and dehydrating under the condition that the vacuum degree is more than 0.09 MPa;
then cooling to a temperature not higher than 60 ℃, adding the coupling agent, and uniformly stirring to obtain a dehydrated mixed product of the polyol and the coupling agent;
a prepolymerization reaction step:
adding the isocyanate into the dehydrated mixed product for reaction, and controlling the reaction temperature to be between 80 and 100 ℃ to generate polyurethane prepolymer;
chain extension reaction:
after the prepolymerization reaction is finished, adding the epoxy resin and the micromolecule chain extender into a reaction kettle, controlling the reaction temperature to be between 100 and 120 ℃, and reacting to generate a polyurethane prepolymer with the required molecular weight;
adding an auxiliary agent:
after the prepolymer with the required molecular weight is prepared, the temperature is reduced to 60-100 ℃, and the catalyst or the rest of the auxiliary agent is added to obtain the high-temperature resistant single-component solvent-free polyurethane adhesive.
10. The use of the high temperature resistant one-component solvent-free polyurethane adhesive according to any one of claims 1 to 8 for the preparation of high temperature resistant flame retardant materials which require corona treatment.
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