CN108384500A - Carbon dioxide-base reaction type polyurethane hot-melt adhesive and preparation method thereof - Google Patents

Carbon dioxide-base reaction type polyurethane hot-melt adhesive and preparation method thereof Download PDF

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CN108384500A
CN108384500A CN201810137490.8A CN201810137490A CN108384500A CN 108384500 A CN108384500 A CN 108384500A CN 201810137490 A CN201810137490 A CN 201810137490A CN 108384500 A CN108384500 A CN 108384500A
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carbon dioxide
melt adhesive
base
type polyurethane
polyurethane hot
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CN108384500B (en
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张红明
詹磊
王献红
王佛松
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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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
    • 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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    • 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
    • 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
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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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/18—Block or graft polymers
    • C—CHEMISTRY; METALLURGY
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    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/32—General preparatory processes using carbon dioxide
    • C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
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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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    • 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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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

A kind of carbon dioxide-base reaction type polyurethane hot-melt adhesive of present invention offer and preparation method thereof, belongs to field of adhesive technology.Solve the problems, such as that existing hot melt adhesive can not directly be bonded low polar material.The hot melt adhesive in parts by weight, is made of following raw material：60~80 parts of carbon dioxide-base dihydric alcohol, 5~10 parts of carbon dioxide-base tetrahydroxylic alcohol, 16~24 parts of diisocyanate, 8~15 parts of tackifying resin, 1~2 part of antioxidant, 0.01~0.05 part of catalyst；The structural formula of the carbon dioxide-base tetrahydroxylic alcohol is as shown in formula I.The present invention also provides a kind of preparation methods of carbon dioxide-base reaction type polyurethane hot-melt adhesive.Not only adhesive strength is high for the hot melt adhesive of the present invention, has the surface drying speed being exceedingly fast, and the hot melt colloid of crosslinking curing is easy to dispose from adhering part surface and noresidue, and has good heat resistance, bin stability and resistance to environmental aging.

Description

Carbon dioxide-base reaction type polyurethane hot-melt adhesive and preparation method thereof
Technical field
The invention belongs to field of adhesive technology, and in particular to a kind of carbon dioxide-base reaction type polyurethane hot-melt adhesive and its Preparation method.
Background technology
Traditional hot melt adhesive is non-reacted adhesive, is that thermoplastic polymer adds after being bonded exemplar by high temperature again After heat, hot melt colloid becomes again to be softened or melts again, to lose adhesive strength.And Reactive hot melt adhesive, it is especially wet Curing type polyurethane hot melt adhesive just overcomes these defects, is thermoplastic polymer before moisture is cured, heating can be with Melt, be bonded exemplar, the response type functional group in hot melt colloid after sizing will be handed over the moisture in air Connection solidification, reaches final adhesive strength, to form insoluble insoluble thermosetting polymer colloid, has reached excellent bonding Intensity and resistance to environmental aging.
In recent years, reaction type polyurethane hot-melt adhesive has obtained extensive research, 200910016844.4 disclosure of patent of invention A kind of reaction type polyurethane hot-melt adhesive and preparation method thereof, its main feature is that it is by polyester polyol, polyether polyol, attachment Power accelerating agent, chain extender, thermoplastic resin, tackifier, filler, stabilizer after mixing, be added isocyanates, catalyst, Sealer reacts under nitrogen protection；Due to adding adhesion promoter, reaction type polyurethane hot-melt adhesive adhesive force is excellent Different, the open hour are short and storage stability is excellent, low cost, and prepare simple.Patent of invention 201610834219.0 is public A kind of moisture-curable reaction type polyurethane hot-melt adhesive has been opened, has included mainly polyester polyol, polyether polyol, thermoplastic polymer Resin, isocyanates MDI, tackifying resin, filler, catalyst and coupling agent, said components polymerize under specific process conditions Reaction generates the moisture-curable reaction type polyurethane hot-melt adhesive haveing excellent performance.Patent of invention 201310625264.1 discloses one kind Reaction type polyurethane hot-melt adhesive is made of the raw material of following parts by weight：Polyether polyol, polyester polyol, isocyanates, thickening Resin, reactive plasticizer, latent curing agent, catalyst.Patent of invention 2015105220093 discloses a kind of reaction type polyurethane The synthetic method of hot melt adhesive uses methyl diphenylene diisocyanate and polyester diol, polycaprolactone glycol, PolyTHF Glycol carries out polymerisation, with the bis- Zhong Ding aminodiphenylmethanes of 4,4- for chain extender in reaction process, obtain it is a have it is high-strength Reaction type polyurethane hot-melt adhesive prepolymer is spent, this performed polymer is applied to reaction type polyurethane hot-melt adhesive, has stronger bonding strong Degree and long term storage stability.Hot melt adhesive applied to different field has also obtained in-depth study, patent of invention 201210538052.5 disclose a kind of reaction type polyurethane hot-melt adhesive for edge sealing in wood industry, and preparation method is by crystal type Polyester polyol, amorphous polyester polyalcohol, high-molecular-weight thermoplastic resin and diisocyanate carry out pre-polymerization, then, are added Plasticizer, inorganic filler, antioxidant and ultra-violet absorber are prepared.Patent of invention 201310248659.4 discloses one The method that kind can be applied to the reaction type polyurethane hot-melt adhesive composition of electrical apparatus industry, preparation method is added into reactor Polyester or polyether polyol and containing the living thermoplastic polymer resin for dialling hydrogen, then with polyisocyanate compound or isocyanide Acid esters group terminated prepolymer compound carries out polymerisation, reaches reaction type polyurethane hot-melt adhesive composition.Patent of invention 201410857083.6 disclosing another electronic apparatus reaction type polyurethane hot-melt adhesive and preparation method thereof, method is Polyester polyol, tackifying resin are placed in reaction kettle and are heated, multi isohydrocyanic ether is put into, carries out prepolymerization reaction under nitrogen protection, The adhesion promotor, catalyst, antioxidant that measure are put into after the completion of reaction successively to being uniformly mixed, discharging packs, system Obtain electronic apparatus reaction type polyurethane hot-melt adhesive.Patent of invention 2012102108026 discloses a kind of automobile lamp reaction The preparation method of type polyurethane hot melt adhesive.The reaction type polyurethane hot-melt adhesive of preparation is the reaction product of following product：At least one The crystalline polyester polyol that kind softening point is 70 DEG C or more, at least one liquid polyesters polyalcohol；At least one polyfunctionality Isocyanates.Patent of invention 201310711919.7 reports another car light moisture-curable polyurethane hot melt adhesive and its preparation Method, preparation method are that polyester polyol is placed in reaction kettle to heat, and are then carried out with methyl diphenylene diisocyanate pre- It is poly-, obtain car light moisture-curable polyurethane hot melt adhesive.Patent of invention 2011101973160 reports a kind of compound reaction of fabric The preparation method of type polyurethane hot melt adhesive, core are by polyester polyol, polyether polyol, chain extender, adhesion promoter With antioxidant heating mixing it is uniform after, carry out prepolymerization reaction under nitrogen protection with isocyanates, catalyst and silane coupling agent It forms.Patent of invention 2014108276005 discloses a kind of reaction type polyurethane hot-melt adhesive and preparation method thereof, the hot melt adhesive It is made of the raw material of following parts by weight：Polyester polyol, polyether polyol, isocyanates, reactive wax, tackifying resin, bonding Accelerating agent, latent curing agent and catalyst.
To reaction type polyurethane hot-melt adhesive correlative study above by carefully analyzing, it can be found that current reaction type polyurethane There is two common problems for hot melt adhesive：The first, price remains high always, second, hot melt adhesive can not be to the low pole such as polypropylene Property material, is directly bonded without flame treatment.Reaction type polyurethane hot-melt adhesive main raw material(s) is poly- Conjunction object polyalcohol and diisocyanate, and all polyester diols of polymer polyatomic alcohol and polyether Glycols, both groups Ratio point in hot melt adhesive component has been more than 60%, thus, price have become determine Reactive hot melt adhesive it is main because Element, currently, polyester and polyether Glycols are all from petroleum chemicals, higher price (ten thousand yuan/ton of 1.2-2.8), this is Lead to reaction type polyurethane hot-melt adhesive price high main cause always.Another question is, domestic and international hot melt adhesive The polyester and polyether Glycols that polymer diatomic alcohol all uses, hot melt adhesive performance all difference that this two classes dihydric alcohol is prepared Less, the bonding of the low polar material of polypropylene can not be all solved the problems, such as.
Invention content
The problem of low polar material can not being directly bonded the purpose of the present invention is to solve existing hot melt adhesive, And a kind of carbon dioxide-base reaction type polyurethane hot-melt adhesive is provided and preparation method thereof.
Present invention firstly provides a kind of carbon dioxide-base reaction type polyurethane hot-melt adhesives, in parts by weight, by following Raw material forms：
60~80 parts of carbon dioxide-base dihydric alcohol, 5~10 parts of carbon dioxide-base tetrahydroxylic alcohol, 16~24 parts of diisocyanate, 8~15 parts of tackifying resin, 1~2 part of antioxidant, 0.01~0.05 part of catalyst；
The structural formula of the carbon dioxide-base tetrahydroxylic alcohol is as shown in formula I：
In formula I, x, y, z, m, n, p be integer, 1≤x≤50,1≤y≤50,1≤z≤50,1≤m≤80,1≤n≤80, 1≤p≤80。
Preferably, the carbonate unit content of the carbon dioxide-base tetrahydroxylic alcohol is 45-75%, Mn=1500- 5000Da。
Preferably, the preparation method of the carbon dioxide-base tetrahydroxylic alcohol includes：
By reaction kettle at 50-80 DEG C, CO is filled through evacuating2Processing, and be cooled to room temperature, in CO2Protection under to reaction kettle Interior addition dmc catalyst and citric acid, obtain mixture；
It is evacuated to fill CO by reaction kettle at 50-80 DEG C2Processing, and be cooled to room temperature, it is added into reaction kettle above-mentioned Mixture and epoxide monomer, stirring, are passed through carbon dioxide into kettle, autoclave is set by pressurized carbon dioxide draught control mechanism Enter and carry out polymerisation in constant temperature bath, obtains carbon dioxide-base tetrahydroxylic alcohol.
Preferably, the structural formula of the carbon dioxide-base dihydric alcohol is as shown in formula II：
In formula II, a, b are integer, 1≤a≤60,1≤b≤60.
Preferably, the carbonate unit content of the carbon dioxide-base dihydric alcohol is 45-75%, Mn=1500- 5000Da。
Preferably, the diisocyanate is 2,4- toluene di-isocyanate(TDI)s, 4,4 '-diisocyanate of diphenyl-methane- Ester, naphthalene -1,5- diisocyanate, benzene dimethylene diisocyanate, 4,4 '-diphenyl-dimethylmethanediisocyanate, two Cyclohexyl-methane -4,4 '-diisocyanate, isophorone diisocyanate, hexamethylene -1,4- diisocyanate or hexane -1, 6- diisocyanate.
Preferably, the tackifying resin is rosin resin, Petropols (C5, C9) or terpene resin.
Preferably, the antioxidant is tea polyphenols, tocopherol, flavonoids, butylated hydroxy anisole, dibutyl hydroxyl Base toluene or tert-butyl hydroquinone.
Preferably, the antioxidant is antioxidant 1010, antioxidant 264, antioxidant 2112, antioxidant BHT, resists Oxygen agent 626, antioxidant 501, antioxidant AO-60 or antioxidant AO-50.
The present invention also provides a kind of preparation method of carbon dioxide-base reaction type polyurethane hot-melt adhesive, this method includes：
Step 1：Carbon dioxide-base dihydric alcohol, carbon dioxide-base tetrahydroxylic alcohol are added in reaction kettle, 100-110 DEG C of vacuum Dehydration 1-2.5 hours, is then cooled to 75-80 DEG C, and diisocyanate, while nitrogen charging gas shielded are added while stirring, reacts 2-3 Hour, obtain the first intermediate；
Step 2：Tackifying resin, antioxidant and catalyst are added into the first intermediate of step 1, in 110-130 Bubble-free appearance is evacuated under the conditions of DEG C, discharging obtains carbon dioxide-base reaction type polyurethane hot-melt adhesive.
Beneficial effects of the present invention
Present invention firstly provides a kind of carbon dioxide-base reaction type polyurethane hot-melt adhesives, in parts by weight, by following Raw material forms：60~80 parts of carbon dioxide-base dihydric alcohol, 5~10 parts of carbon dioxide-base tetrahydroxylic alcohol, 16~24 parts of diisocyanate, 8~15 parts of tackifying resin, 1~2 part of antioxidant, 0.01~0.05 part of catalyst；The knot of the carbon dioxide-base tetrahydroxylic alcohol Structure formula is as shown in formula I.It compares with the prior art, first, it is low to come from price for the carbon dioxide polylol that the present invention uses Honest and clean carbon dioxide gas, price are 600-800 yuan/ton, and the carbon dioxide polylol price of preparation is 1.1-1.3 ten thousand Yuan/ton, it is far below traditional polyester and polyether polyol, the price fall of the reaction type polyurethane hot-melt adhesive of preparation 25- 30%.Secondly, the synergistic effect of carbonic ester and ether in hot melt adhesive system of the invention in backbone structure substantially increases It is directly bonded without any flame treatment with the binding force of low polar polypropylene material, the present invention Hot melt adhesive not only adhesive strength is high, there is the surface drying speed being exceedingly fast, the hot melt colloid of crosslinking curing to be easy to from adhering part Surface is disposed and noresidue, and has good heat resistance, bin stability and resistance to environmental aging, will not cause valuable The destruction of electronic device is conducive to the recycling of precise electronic instrument device, it is each to can be widely applied to electronic enterprises The fixation of kind parts, bonding.
The present invention also provides a kind of preparation method of carbon dioxide-base reaction type polyurethane hot-melt adhesive, preparation method letters Single, raw material is easy to get, and the hot melt adhesive being prepared has high initial and final adhesive strength, the experimental results showed that：The present invention's Hot melt adhesive initial 180 ° of peel strength >=60N/25mm, final 180 ° of peel strength >=900N/25mm, the short (＜ of surface drying time 60s), it trickles without softening, there is more excellent sizing temperature (120 DEG C) for 180 DEG C.
Description of the drawings
Fig. 1 is the infrared spectrogram for the carbon dioxide-base tetrahydroxylic alcohol that the embodiment of the present invention 1 is prepared；
Fig. 2 is the nucleus magnetic hydrogen spectrum figure for the carbon dioxide-base tetrahydroxylic alcohol that the embodiment of the present invention 1 is prepared.
Specific implementation mode
Present invention firstly provides a kind of carbon dioxide-base reaction type polyurethane hot-melt adhesives, in parts by weight, by following Raw material forms：
60~80 parts of carbon dioxide-base dihydric alcohol, 5~10 parts of carbon dioxide-base tetrahydroxylic alcohol, 16~24 parts of diisocyanate, 8~15 parts of tackifying resin, 1~2 part of antioxidant, 0.01~0.05 part of catalyst；Preferably：Carbon dioxide-base dihydric alcohol 65~ 75 parts, 7~9 parts of carbon dioxide-base tetrahydroxylic alcohol, 18~22 parts of diisocyanate, 10~13 parts of tackifying resin, antioxidant 1.5~ 1.8 parts, 0.02~0.04 part of catalyst.
The structural formula of the carbon dioxide-base tetrahydroxylic alcohol is as shown in formula I：
In formula I, x, y, z, m, n, p be integer, 1≤x≤50,1≤y≤50,1≤z≤50,1≤m≤80,1≤n≤80, 1≤p≤80。
According to the present invention, the carbonate unit content of the carbon dioxide-base tetrahydroxylic alcohol is 45-75%, Mn=1500- 5000Da。
According to the present invention, the preparation method of the carbon dioxide-base tetrahydroxylic alcohol is preferably as follows：
By reaction kettle at 50-80 DEG C, CO is filled through evacuating22h (inflation 6 times) is handled, and is cooled to room temperature, in CO2Guarantor Dmc catalyst and citric acid is added under shield into reaction kettle, obtains mixture；
It is evacuated to fill CO by reaction kettle at 50-80 DEG C22h is handled, and is cooled to room temperature, is added into reaction kettle Mixture and epoxide monomer are stated, stirs, carbon dioxide, autoclave is passed through into kettle by pressurized carbon dioxide draught control mechanism Polymerisation is carried out in (2-5MPa) merging constant temperature bath, the polymerization temperature is preferably 50-80 DEG C, and polymerization time is preferably 5- 30h, pressure carbon dioxide 4.0MPa obtain carbon dioxide-base tetrahydroxylic alcohol.The epoxide monomer is preferably epoxy third Alkane.
According to the present invention, the mass ratio of the dmc catalyst and citric acid is 0.05：20；The dmc catalyst is Y-DMC catalyst, specific preparation method application reference number are the patent of invention of 201210086834.X.The DMC catalysis The quality (mg) of agent：The volume (mL) of epoxide is 1：2.
According to the present invention, the structural formula of the carbon dioxide-base dihydric alcohol is as shown in formula II：
In formula II, a, b are integer, 1≤a≤60,1≤b≤60.The carbonate unit of the carbon dioxide-base dihydric alcohol Content is 45-75%, Mn=1500-5000Da.
According to the present invention, the diisocyanate includes aromatic series and aliphatic two major classes, wherein two isocyanide of aromatic series It is different that acid esters is preferably selected from 2,4 toluene diisocyanate (TDI), diphenyl-methane -4,4 '-diisocyanate (MDI), naphthalene -1,5- two Cyanate (NDI), benzene dimethylene diisocyanate (XDI) or 4,4 '-diphenyl-dimethylmethanediisocyanate；Fat (cyclo) aliphatic diisocyanates are preferably selected from dicyclohexyl methyl hydride -4,4 '-diisocyanate (H12MDI), isophorone diisocyanate (IPDI), hexamethylene -1,4- diisocyanate or hexane -1,6- diisocyanate (HDI).
According to the present invention, the tackifying resin is preferably rosin resin, Petropols (C5, C9) or terpene resin.
According to the present invention, the antioxidant is preferably tea polyphenols (TP), tocopherol, flavonoids, butylhydroxy fennel Ether (BHA), dibutyl hydroxy toluene (BHT) or tert-butyl hydroquinone (TBHQ), more preferably antioxidant 1010, antioxidant 264, antioxidant 2112, antioxidant BHT, antioxidant 626, antioxidant 501, antioxidant AO-60 or antioxidant AO-50.
According to the present invention, the catalyst is organo-tin compound or bismuth organic compound.The organotin chemical combination Object is preferably selected from dibutyltin diacetate, stannous octoate, two fourths of dibutyl tin laurate, tin dilaurate dioctyl tin or oxidation Ji Xi；The bismuth organic compound is preferably selected from Bismuth Octoate, bismuth neodecanoate or 8-hydroxyquinoline bismuth.
The present invention also provides a kind of preparation method of carbon dioxide-base reaction type polyurethane hot-melt adhesive, this method includes：
Step 1：Carbon dioxide-base dihydric alcohol, carbon dioxide-base tetrahydroxylic alcohol are added in reaction kettle, 100-110 DEG C of vacuum Dehydration 1-2.5 hours, is then cooled to 75-80 DEG C, and diisocyanate, while nitrogen charging gas shielded are added while stirring, reacts 2-3 Hour, obtain the first intermediate；
Step 2：Tackifying resin, antioxidant and catalyst are added into the first intermediate of step 1, in 110-130 Bubble-free appearance is evacuated under the conditions of DEG C, discharging obtains carbon dioxide-base reaction type polyurethane hot-melt adhesive.
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit Determine the scope of the present invention.Involved in embodiment to raw material be commercially available.
Embodiment 1
By measuring cup at 80 DEG C, CO is filled through evacuating2Gas disposal 2h (inflation 6 times), and be cooled to room temperature, then claimed with this Measuring bottle weighs the Y-DMC (embodiment 1 of patent of invention 201210086834.X) of 50.0mg, and in CO2To weighing under gas shielded 20.0g citric acids are added in bottle and make chain-transferring agent；The mixture of the Y-DMC and citric acid is added in advance at 80 DEG C, warp CO is filled in evacuation2Gas disposal 2h (inflation 6 times), and in the 500mL autoclaves being cooled to room temperature, it is then act through catalyst weighing Bottle connection 100mL propylene oxide is added into kettle, start stirring (500rpm), run through pressurized carbon dioxide draught control mechanism to It is passed through carbon dioxide in kettle, polymerisation, the pressure carbon dioxide 4.0MPa of polymerization, polymerization are carried out in autoclave merging constant temperature bath 80 DEG C, polymerization reaction time 5h of reaction temperature obtains poly- (carbonic ester-ether) dihydric alcohol 110g.Using GPC prepared by the present embodiment Poly- (carbonic ester-ether) tetrahydroxylic alcohol be detected, the number-average molecular weight of poly- (carbonic ester-ether) tetrahydroxylic alcohol is 2300g/mol, point Son amount is distributed as 1.35.
Fig. 1 is the infrared spectrogram for the carbon dioxide-base tetrahydroxylic alcohol that the embodiment of the present invention 1 is prepared；It can be with from spectrogram Find out, in 1745 and 1260cm-1Absorption peak be respectively belonging to the C=O in carbonate unit and C (O)-O absorption peaks. 1074cm-1The absorption peak at place is ether section absorption peak, and show has continuous PO to be inserted into copolyreaction generates ether section.3500cm-1 The absorption peak at place then belongs to the terminal hydroxyl absorption peak of polymer, shows in resulting polymers main chain by carbonate unit and ether Unit is constituted, and end group is hydroxyl.
Fig. 2 is the nucleus magnetic hydrogen spectrum figure for the carbon dioxide-base tetrahydroxylic alcohol that the embodiment of the present invention 1 is prepared.It can be with from spectrogram Find out, nuclear-magnetism peak belongs to the CH and CH being connected with carbonate group in polymer chain at 5.0 and 4.2ppm2Group, 3.5ppm Peak belongs to CH and CH in ether section2Group.
Embodiment 2
By measuring cup at 80 DEG C, CO is filled through evacuating2Gas disposal 2h (inflation 6 times), and be cooled to room temperature, then claimed with this Measuring bottle weighs the Y-DMC (embodiment 1 of patent of invention 201210086834.X) of 50.0mg, and in CO2To weighing under gas shielded 20.0g citric acids are added in bottle and make chain-transferring agent；The mixture of the Y-DMC and citric acid is added in advance at 80 DEG C, warp CO is filled in evacuation2Gas disposal 2h (inflation 6 times), and in the 500mL autoclaves being cooled to room temperature, it is then act through catalyst weighing Bottle connection 100mL propylene oxide is added into kettle, start stirring (500rpm), run through pressurized carbon dioxide draught control mechanism to It is passed through carbon dioxide in kettle, polymerisation, the pressure carbon dioxide 4.0MPa of polymerization, polymerization are carried out in autoclave merging constant temperature bath 70 DEG C, polymerization reaction time 10h of reaction temperature obtains poly- (carbonic ester-ether) tetrahydroxylic alcohol 118g.Using GPC to the present embodiment system Standby poly- (carbonic ester-ether) tetrahydroxylic alcohol is detected, and the number-average molecular weight of poly- (carbonic ester-ether) tetrahydroxylic alcohol is 3000g/mol, Molecular weight distribution is 1.35.
Embodiment 3
By measuring cup at 80 DEG C, CO is filled through evacuating2Gas disposal 2h (inflation 6 times), and be cooled to room temperature, then claimed with this Measuring bottle weighs the Y-DMC (embodiment 1 of patent of invention 201210086834.X) of 50.0mg, and in CO2To weighing under gas shielded 20.0g citric acids are added in bottle and make chain-transferring agent；The mixture of the Y-DMC and citric acid is added in advance at 80 DEG C, warp CO is filled in evacuation2Gas disposal 2h (inflation 6 times), and in the 500mL autoclaves being cooled to room temperature, it is then act through catalyst weighing Bottle connection 100mL propylene oxide is added into kettle, start stirring (500rpm), run through pressurized carbon dioxide draught control mechanism to It is passed through carbon dioxide in kettle, polymerisation, the pressure carbon dioxide 4.0MPa of polymerization, polymerization are carried out in autoclave merging constant temperature bath 50 DEG C, polymerization reaction time 30h of reaction temperature obtains poly- (carbonic ester-ether) tetrahydroxylic alcohol 64g.Using GPC prepared by the present embodiment Poly- (carbonic ester-ether) tetrahydroxylic alcohol be detected, using GPC to the number of poly- (carbonic ester-ether) tetrahydroxylic alcohol manufactured in the present embodiment Average molecular weight is 3500g/mol, molecular weight distribution 1.30.
Embodiment 4
By 60g carbon dioxide-bases dihydric alcohol, (carbonate unit content is 45%, Mn=1500Da.), 10g carbon dioxide-bases (carbonate unit content is 45%, Mn=1500Da to tetrahydroxylic alcohol.) be added in reaction kettle, 100 DEG C of vacuum dehydration 2.5 hours, so 2, the 4- toluene di-isocyanate(TDI)s (TDI) of 16g, while nitrogen charging gas shielded is added to 75 DEG C in postcooling while stirring, and reaction 2 is small When；The C5 Petropols of 8g, the antioxidant 1010 of 1g and 0.01g stannous octoates are added, is evacuated under the conditions of 110 DEG C Bubble-free occurs, and discharging, airtight package obtains carbon dioxide-base reaction type polyurethane hot-melt adhesive.The heat that embodiment 4 is prepared Melten gel performance data is as shown in table 1.
Embodiment 5
By 80g carbon dioxide-bases dihydric alcohol, (carbonate unit content is 75%, Mn=5000Da.), 5g carbon dioxide-bases (carbonate unit content is 75%, Mn=5000Da to tetrahydroxylic alcohol.) be added in reaction kettle, 110 DEG C of vacuum dehydration 1 hour, then 80 DEG C are cooled to, diphenyl-methane -4 24g, 4 '-diisocyanate (MDI), while nitrogen charging gas shielded, reaction 3 are added while stirring Hour；The C9 Petropols, 2g antioxidants 264 and 0.05g tin dilaurate dioctyl tins for adding 14.5g, in 130 DEG C of conditions Under be evacuated to bubble-free appearance, discharging, airtight package obtains carbon dioxide-base reaction type polyurethane hot-melt adhesive.Embodiment 5 is made Standby obtained hot melt adhesive performance data is as shown in table 1.
Embodiment 6
By 70g carbon dioxide-bases dihydric alcohol, (carbonate unit content is 55%, Mn=2000Da.), 8g carbon dioxide-bases (carbonate unit content is 55%, Mn=2000Da to tetrahydroxylic alcohol.) be added in reaction kettle, 105 DEG C of vacuum dehydration 1.5 hours, so Postcooling is added dicyclohexyl methyl hydride -4 20g, 4 '-diisocyanate (H12MDI), while inflated with nitrogen and protects while stirring to 78 DEG C Shield is reacted 2.5 hours；10g rosin resins, 1.5g antioxidants 2112 and 0.03g dibutyl tin laurates are added, Bubble-free appearance, discharging are evacuated under the conditions of 120 DEG C, airtight package obtains carbon dioxide-base reaction type polyurethane hot-melt adhesive. The hot melt adhesive performance data that embodiment 6 is prepared is as shown in table 1.
Embodiment 7
By 65g carbon dioxide-bases dihydric alcohol, (carbonate unit content is 60%, Mn=3000Da.), 7g carbon dioxide-bases (carbonate unit content is 60%, Mn=3000Da to tetrahydroxylic alcohol.) be added in reaction kettle, 110 DEG C of vacuum dehydration 2 hours, then 80 DEG C are cooled to, 22g, isophorone diisocyanate (IPDI), while nitrogen charging gas shielded are added while stirring, reacts 3 hours； 13g terpene resins, 1.8g antioxidant BHTs and 0.04g dibutyltin oxides are added, nothing is evacuated under the conditions of 125 DEG C Bubble occurs, and discharging, airtight package obtains carbon dioxide-base reaction type polyurethane hot-melt adhesive.The hot melt that embodiment 7 is prepared Glue performance data is as shown in table 1.
Embodiment 8
By 75g carbon dioxide-bases dihydric alcohol, (carbonate unit content is 65%, Mn=4000Da.), 5g carbon dioxide-bases (carbonate unit content is 65%, Mn=4000Da to tetrahydroxylic alcohol.) be added in reaction kettle, 100 DEG C of vacuum dehydration 2 hours, then 75 DEG C are cooled to, 18g hexanes -1,6- diisocyanate (HDI), while nitrogen charging gas shielded are added while stirring, reacts 2 hours； The C5 Petropols, 1.6g antioxidants 626 and 0.02g Bismuth Octoates for adding 10g, no gas is evacuated under the conditions of 130 DEG C It bubbles out now, discharging, airtight package obtains carbon dioxide-base reaction type polyurethane hot-melt adhesive.The hot melt adhesive that embodiment 8 is prepared Performance data is as shown in table 1.
Embodiment 9
By 65g carbon dioxide-bases dihydric alcohol, (carbonate unit content is 70%, Mn=4500Da.), 9g carbon dioxide-bases (carbonate unit content is 70%, Mn=4500Da to tetrahydroxylic alcohol.) be added in reaction kettle, 105 DEG C of vacuum dehydration 1.5 hours, so Diphenyl-methane -4 20g, 4 '-diisocyanate (MDI), while nitrogen charging gas shielded, reaction is added to 80 DEG C in postcooling while stirring 3 hours；12g terpene resins, 1.6g antioxidant AO-60 and 0.03g bismuth neodecanoates are added, is vacuumized under the conditions of 120 DEG C Occur to bubble-free, discharging, airtight package obtains carbon dioxide-base reaction type polyurethane hot-melt adhesive.What embodiment 9 was prepared Hot melt adhesive performance data is as shown in table 1.
The hot melt adhesive that embodiment 4-9 is prepared is coated in after melting on ABS PP plastic skeletons, PVC skins, nonwoven It is not coated by hot melt adhesive above the fabrics such as cloth, foam, within the open hour, fabric is fitted on plastic skeleton.After 72 hours, into Row correlated performance is tested.
Peel strength measures：
It on cupping machine, is tested, is tested when being destroyed at its adhering components with the tensile speed of 10mm/min Adhesive strength when maximum bonding force and destruction.Melt viscosity is tested by GB/T10247-2008, is surveyed by ASTM 4497-2004 The open hour are tried, tensile strength is tested by GB/T 528-2009, (sample is 85 by GB/T 7124-2008 tests high temperature and humidity DEG C/95%RH under conditions of place 72 hours after tested) tensile shear strength of sample afterwards, test result is as shown in table 1.
The reaction type polyurethane hot-melt adhesive correlated performance test result of 1 embodiment 4-9 of table

Claims (10)

1. a kind of carbon dioxide-base reaction type polyurethane hot-melt adhesive, which is characterized in that in parts by weight, by following raw material group At：
60~80 parts of carbon dioxide-base dihydric alcohol, 5~10 parts of carbon dioxide-base tetrahydroxylic alcohol, 16~24 parts of diisocyanate, thickening 8~15 parts of resin, 1~2 part of antioxidant, 0.01~0.05 part of catalyst；
The structural formula of the carbon dioxide-base tetrahydroxylic alcohol is as shown in formula I：
In formula I, x, y, z, m, n, p are integer, 1≤x≤50,1≤y≤50,1≤z≤50,1≤m≤80,1≤n≤80,1≤p ≤80。
2. a kind of carbon dioxide-base reaction type polyurethane hot-melt adhesive according to claim 1, which is characterized in that described two The carbonate unit content for aoxidizing carbon-based tetrahydroxylic alcohol is 45-75%, Mn=1500-5000Da.
3. a kind of carbon dioxide-base reaction type polyurethane hot-melt adhesive according to claim 1, which is characterized in that the dioxy The preparation method for changing carbon-based tetrahydroxylic alcohol includes：
By reaction kettle at 50-80 DEG C, CO is filled through evacuating2Processing, and be cooled to room temperature, in CO2Protection under into reaction kettle plus Enter dmc catalyst and citric acid, obtains mixture；
It is evacuated to fill CO by reaction kettle at 50-80 DEG C2Processing, and be cooled to room temperature, above-mentioned mixing is added into reaction kettle Object and epoxide monomer, stirring are passed through carbon dioxide into kettle by pressurized carbon dioxide draught control mechanism, and autoclave merging is permanent Polymerisation is carried out in warm bath, obtains carbon dioxide-base tetrahydroxylic alcohol.
4. a kind of carbon dioxide-base reaction type polyurethane hot-melt adhesive according to claim 1, which is characterized in that described two The structural formula of carbon-based dihydric alcohol is aoxidized as shown in formula II：
In formula II, a, b are integer, 1≤a≤60,1≤b≤60.
5. a kind of carbon dioxide-base reaction type polyurethane hot-melt adhesive according to claim 1, which is characterized in that described two The carbonate unit content for aoxidizing carbon-based dihydric alcohol is 45-75%, Mn=1500-5000Da.
6. a kind of carbon dioxide-base reaction type polyurethane hot-melt adhesive according to claim 1, which is characterized in that described two Isocyanates is 2,4 toluene diisocyanate, diphenyl-methane -4,4 '-diisocyanate, naphthalene -1,5- diisocyanate, benzene two Methylene diisocyanate, 4,4 '-diphenyl-dimethylmethanediisocyanate, dicyclohexyl methyl hydride -4,4 '-diisocyanate Ester, isophorone diisocyanate, hexamethylene -1,4- diisocyanate or hexane -1,6- diisocyanate.
7. a kind of carbon dioxide-base reaction type polyurethane hot-melt adhesive according to claim 1, which is characterized in that the increasing Viscosity resin is rosin resin, Petropols or terpene resin.
8. a kind of carbon dioxide-base reaction type polyurethane hot-melt adhesive according to claim 1, which is characterized in that described is anti- Oxidant is tea polyphenols, tocopherol, flavonoids, butylated hydroxy anisole, dibutyl hydroxy toluene or tert-butyl hydroquinone.
9. a kind of carbon dioxide-base reaction type polyurethane hot-melt adhesive according to claim 1, which is characterized in that described is anti- Oxidant is antioxidant 1010, antioxidant 264, antioxidant 2112, antioxidant BHT, antioxidant 626, antioxidant 501, antioxidant AO-60 or antioxidant AO-50.
10. a kind of preparation side of carbon dioxide-base reaction type polyurethane hot-melt adhesive according to claim 1-9 any one Method, which is characterized in that this method includes：
Step 1：Carbon dioxide-base dihydric alcohol, carbon dioxide-base tetrahydroxylic alcohol are added in reaction kettle, 100-110 DEG C of vacuum dehydration 1-2.5 hours, it is then cooled to 75-80 DEG C, diisocyanate, while nitrogen charging gas shielded are added while stirring, reaction 2-3 is small When, obtain the first intermediate；
Step 2：Tackifying resin, antioxidant and catalyst are added into the first intermediate of step 1, in 110-130 DEG C of item Bubble-free appearance is evacuated under part, discharging obtains carbon dioxide-base reaction type polyurethane hot-melt adhesive.
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