CN110205080A - A kind of biomass combined environment-friendly water-based adhesive - Google Patents
A kind of biomass combined environment-friendly water-based adhesive Download PDFInfo
- Publication number
- CN110205080A CN110205080A CN201910519127.7A CN201910519127A CN110205080A CN 110205080 A CN110205080 A CN 110205080A CN 201910519127 A CN201910519127 A CN 201910519127A CN 110205080 A CN110205080 A CN 110205080A
- Authority
- CN
- China
- Prior art keywords
- solution
- alcohol
- water
- biomass
- aqueous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- 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
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
-
- 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
- C08G18/65—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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
- C08G18/683—Unsaturated polyesters containing cyclic groups
- C08G18/686—Unsaturated polyesters containing cyclic groups containing cycloaliphatic groups
-
- 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
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
-
- 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
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The present invention relates to a kind of biomass combined environment-friendly water-based adhesives, the adhesive is compounded by plurality of raw materials, it is formed including biomass water-based emulsion, aqueous binder material, oiliness binder, adhesion promoting component and auxiliary material, the adhesive is suitable for the bonding between plastics, the bonding being especially suitable between igelite and other polyolefin plastics, the adhesive has the advantages that good adhesive strength, also has bonding not degumming for a long time, environment friendly and pollution-free, can be widely applied to plastic bonding field.
Description
Technical field
The present invention relates to a kind of aqueous binders more particularly to a kind of using biomass as primary raw material, are applicable to wrap
Bonding in dress between plastics, with environment-friendly adhesive that is excellent sticky and can realizing prolonged adhesion not degumming.
Background technique
As the theory protected environment, treasure resource is increasingly rooted in the hearts of the people, the high solids content, solvent-free, water to adhesive
Property, the environmental-friendly factor such as photocuring and low-temperature setting, castoff regenerative the power-saving technologies such as utilize increasingly to pay attention to, and constantly plus
Big research and development dynamics.In flexible packaging industry, mainly no-solvent type used in the production of European and American developed countries' package compound
Adhesive and Aqueous Adhesives.Currently, the flexible package in 95% or more China is produced using solvent type adhesive, using most
More, performance is preferably solvent-type double-component adhesive for polyurethane.Since solvent type adhesive has excellent flexibility, low temperature resistant
And boiling resistance, ease for operation and extensive adaptability, and the dry complex equipment of domestic Flexible-Packaging Industry is only applicable at present
Solvent type adhesive.
Compared with solvent type adhesive, Aqueous Adhesives have solvent-free release, environmental-friendly, nontoxic, non-combustible, use
Safety, it is at low cost the advantages that, solid content may be up to 50%-60%, at present common aqueous polyurethane (PU) adhesive, third on the market
Olefin(e) acid lotion, EVA copolymer emulsion etc..But meanwhile aqueous binder is because there are still certain limitations in application for its performance characteristic
Property, if binding speed is slower, adhesive strength is lower, adhesion durability is poor, is easy mildew etc., limits it in automation
Glue field must apply.It is more to be particularly due to general water-soluble glue polar object, be more suitable between polar object as cardboard, timber it
Between bonding, and it is limited for the adhesiveness between the stronger plastics of nonpolarity.A kind of novel aqueous binder can such as be developed
Agent, partially deficiency more than improvement is realized between the weaker plastics of polarity especially in the substance for widening implementable bonding
Bonding will undoubtedly have very big market value.This patent will provide a kind of compound biomass environment-friendly aqueous binder, be
Non-polar plastic provides strong adhesive power, and can keep the lasting effects of bonding.
Summary of the invention
The purpose of the invention is to overcome aqueous binder poor adhesion in non-polar plastic material, viscosity it is not strong and
For a long time bond after easily degumming defect, provide it is a kind of using biomass as primary raw material, it is environmentally friendly, be applicable to plastics package
And the adhesive with excellent viscosity.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of biomass combined environment-friendly water-based adhesive, which is compounded by plurality of raw materials, including the aqueous cream of biomass
Liquid, aqueous binder material, oiliness binder, adhesion promoting component and auxiliary material；
Its mass fraction ratio are as follows:
Biomass water-based emulsion: 45-65 parts
Aqueous binder material: 10-18 parts
Oiliness binder: 12-20 parts
Adhesion promoting component: 4-8 parts
Auxiliary material: 2-4 parts
Further, the preparation of the biomass water-based emulsion are as follows:
(1) under nitrogen protection, maleopimaric acid polyester polyol, castor oil polyhydric alcohol, erythritol, isophorone two is different
Cyanate, catalyst dibutyltin dilaurylate are added in reaction vessel, and at a temperature of 60 DEG C -70 DEG C, 120rpm-180rpm turns
Speed is stirred to react 1.5 h -3h, obtains solution I；
Wherein, mole of maleopimaric acid polyester polyol, castor oil polyhydric alcohol, erythritol, isophorone diisocyanate
Than being Ma Laihai for the dosage of 2.2-2.8:1.4-2.2:0.6-0.96:2.5-3.2, the catalyst dibutyltin dilaurylate
Loose polyester polyols, castor oil polyhydric alcohol, erythritol, isophorone diisocyanate weight sum 0.05%-
0.10%；
(2) dimethyl acetamide, N-Methyl pyrrolidone, polyoxypropyleneglycol, laruyl alcohol, dihydroxy first are added into solution I
Base butyric acid reacts 0.5 h -1.0h at a temperature of 60 DEG C -70 DEG C, after be heated up to 70 DEG C -80 DEG C at a temperature of react 0.5 h -
1.0h obtains solution II；
Wherein, the addition of dimethyl acetamide, N-Methyl pyrrolidone, polyoxypropyleneglycol, laruyl alcohol, dimethylolpropionic acid
Amount is 2.4-4.2%, 1.4-2.1%, 1.6-2.1%, the 0.6-1.0% of isophorone diisocyanate weight in solution I,
2.6-4.2%；
(3) dimethyl acetamide, rosin polyester polyhydric-alcohol, trivinyl glycol are added to the container, at a temperature of 40 DEG C -50 DEG C
It stirs evenly, obtains solution III；
Wherein, dimethyl acetamide, rosin polyester polyhydric-alcohol, the additional amount of trivinyl glycol are polynary for castor oil in solution I
The 6.8-9.2% of alcohol weight, 4.6-7.4%, 8.7-12.5%；
(4) solution III is added in solvent II, a certain amount of two is added in mixed solution after 30min is stirred evenly at 30 DEG C
Methylacetamide reacts 0.5h-1h after being warming up to 70 DEG C -80 DEG C, obtains solution IV；
Wherein, the additional amount of dimethyl acetamide is the 3.2%-5.6% of solution II weight；
(5) solution IV is cooled to 35 DEG C -45 DEG C, triethylamine is added and reacts 0.5h-1.0h, obtains solution V；
Wherein, the molar ratio of triethylamine and dimethylolpropionic acid described in step (2) is 0.2-0.35:1.0；
(6) it at a temperature of 30-35 DEG C, disperses solution V in and is equivalent to 1-1.5 times of weight of solution V of water and the mixed liquor of ethyl alcohol
In, 500rpm-600rpm revolving speed stirs 30min, obtains solution VI；Wherein, the mass ratio of water and ethyl alcohol is between 1:1.5；
(7) solution VI is evaporated under reduced pressure, steams solvent, the rear anion that maleopimaric acid polyester polyol quality 5%-8% is added
Surfactant stirs 30min with 200-350rpm revolving speed, obtains biomass water-based emulsion.
Further, di-alcohols synthesis material used in the maleopimaric acid polyester polyol is that diethylene glycol (DEG) or three are sweet
Alcohol.
Further, the castor oil polyhydric alcohol is castor oil polyester polyol, and castor oil, small molecular alcohol, acid anhydrides can be used
For reactant preparation.
Further, the anionic surfactant preferably sodium dodecyl sulfate.
Further, the use ratio of the aqueous binder material and oiliness binder has certain rule, when binding tends to
The bonding such as bonding between igelite between polar plas, can be used aqueous binder material and accounts for larger proportion, work as bonding
Object tends to such as bonding between vinyon of the bonding between non-polar plastic, and oiliness binder can be used and account for larger ratio
Example.
Further, the aqueous binder material is glycidyl methacrylate graft modified soy-bean protein lotion and second
Alkene-acetate ethylene copolymer lotion mixing water-based emulsion, solid content is between 55%-60% in binder, wherein methyl-prop
The mass ratio of olefin(e) acid ethylene oxidic ester graft modification soybean protein and ethylene-vinyl acetate copolymer is between 1.2-1.8.
Further, the grafting degree of the glycidyl methacrylate graft modified soy-bean protein is calculated as mass fraction
Between 12% -24%.
Further, the mass fraction of vinyl acetate is greater than 50% in the ethene-vinyl acetate.
Further, the oiliness binder is the mixed of aqueous Bisphenol-a Epoxy Resin lotion and aqueous EP rubbers lotion
Lotion is closed, solid content is between 45%-50% in binder, and wherein the mass ratio of Bisphenol-a Epoxy Resin and EP rubbers is situated between
Between 2.5-3.5.
Further, a small amount of emulsifier can be added in oiliness binder to improve the emulsion stability of mixed emulsion.
Further, the adhesion promoting component is aqueous terpene resin, and solid content is between 42%-64%.
Further, the auxiliary material is one of antioxidant, plasticizer, diluent, thixotropic agent or several combinations.
Specific embodiment
Illustrative embodiment of the invention described in detail below.But these implementation methods are only exemplary purpose, and
The invention is not limited thereto.
Embodiment 1
A kind of biomass combined environment-friendly water-based adhesive, which is compounded by plurality of raw materials, including the aqueous cream of biomass
Liquid, aqueous binder material, oiliness binder, adhesion promoting component and auxiliary material；
Its mass fraction ratio are as follows:
Biomass water-based emulsion: 50 parts
Aqueous binder material: 16 parts
Oiliness binder: 13 parts
Adhesion promoting component: 6 parts
Auxiliary material: 2.5 parts
Further, the preparation of the biomass water-based emulsion are as follows:
(1) under nitrogen protection, maleopimaric acid polyester polyol, castor oil polyhydric alcohol, erythritol, isophorone two is different
Cyanate, catalyst dibutyltin dilaurylate are added in reaction vessel, and at a temperature of 65 DEG C, 120rpm-180rpm revolving speed is stirred
Reaction 2h is mixed, solution I is obtained；
Wherein, mole of maleopimaric acid polyester polyol, castor oil polyhydric alcohol, erythritol, isophorone diisocyanate
Than for 2.6:1.8:0.82:2.8, the dosage of the catalyst dibutyltin dilaurylate be maleopimaric acid polyester polyol,
Castor oil polyhydric alcohol, erythritol, isophorone diisocyanate weight sum 0.08%；
(2) dimethyl acetamide, N-Methyl pyrrolidone, polyoxypropyleneglycol, laruyl alcohol, dihydroxy first are added into solution I
Base butyric acid reacts 0.8h at a temperature of 65 DEG C, after be heated up to react 0.6h at 75 DEG C, obtain solution II；
Wherein, the addition of dimethyl acetamide, N-Methyl pyrrolidone, polyoxypropyleneglycol, laruyl alcohol, dimethylolpropionic acid
Amount is 3.4% of isophorone diisocyanate weight in solution I, 1.8%, 1.8%, 0.7%, 3.6%；
(3) dimethyl acetamide, rosin polyester polyhydric-alcohol, trivinyl glycol are added to the container, are stirred at a temperature of 45 DEG C
Uniformly, solution III is obtained；
Wherein, dimethyl acetamide, rosin polyester polyhydric-alcohol, the additional amount of trivinyl glycol are polynary for castor oil in solution I
The 7.8% of alcohol weight, 6.2%, 10.4%；
(4) solution III is added in solvent II, a certain amount of two is added in mixed solution after 30min is stirred evenly at 30 DEG C
Methylacetamide reacts 0.6h after being warming up to 75 DEG C, obtains solution IV；
Wherein, the additional amount of dimethyl acetamide is the 3.2%-5.6% of solution II weight；
(5) solution IV is cooled to 40 DEG C, triethylamine is added and reacts 0.8h, obtains solution V；
Wherein, the molar ratio of triethylamine and dimethylolpropionic acid described in step (2) is 0.25:1.0；
(6) it at a temperature of 32 DEG C, disperses solution V in the mixed liquor of the water and ethyl alcohol that are equivalent to 1.2 times of solution V weight,
550rpm revolving speed stirs 30min, obtains solution VI；Wherein, the mass ratio of water and ethyl alcohol is 1:1.2；
(7) solution VI is evaporated under reduced pressure, steams solvent, the rear anion table that 6.5% mass of maleopimaric acid polyester polyol is added
Face activating agent stirs 30min with 250rpm revolving speed, obtains biomass water-based emulsion.
Di-alcohols synthesis material used in the maleopimaric acid polyester polyol is diethylene glycol (DEG).
The castor oil polyhydric alcohol is castor oil polyester polyol, uses castor oil, small molecular alcohol, acid anhydrides for reactant system
It is standby.
The anionic surfactant is lauryl sodium sulfate.
The aqueous binder material is glycidyl methacrylate graft modified soy-bean protein lotion and ethyl vinyl acetate second
The mixing water-based emulsion of alkene copolymer lotion, solid content is 57% in binder, and wherein glycidyl methacrylate graft changes
Property soybean protein and ethylene-vinyl acetate copolymer mass ratio be 1.5.
The oiliness binder is the mixed emulsion of aqueous Bisphenol-a Epoxy Resin lotion and aqueous EP rubbers lotion,
Solid content is 48% in binder, and wherein the mass ratio of Bisphenol-a Epoxy Resin and EP rubbers is 3.2.
The grafting degree of the glycidyl methacrylate graft modified soy-bean protein is as mass fraction
16.3%。
The mass fraction of vinyl acetate is 54% in the ethene-vinyl acetate.
The adhesion promoting component is aqueous terpene resin, solid content 46%.
The auxiliary material is the arbitrary proportion combination of antioxidant, plasticizer, diluent.
The adhesive be suitable for polyvinyl chloride and other with the bonding between certain polar plas.
Embodiment 2
A kind of biomass combined environment-friendly water-based adhesive, which is compounded by plurality of raw materials, including the aqueous cream of biomass
Liquid, aqueous binder material, oiliness binder, adhesion promoting component and auxiliary material；
Its mass fraction ratio are as follows:
Biomass water-based emulsion: 55 parts
Aqueous binder material: 12 parts
Oiliness binder: 18 parts
6.5 parts of adhesion promoting component
Auxiliary material: 2.5 parts
Further, the preparation of the biomass water-based emulsion are as follows:
(1) under nitrogen protection, maleopimaric acid polyester polyol, castor oil polyhydric alcohol, erythritol, isophorone two is different
Cyanate, catalyst dibutyltin dilaurylate are added in reaction vessel, and at a temperature of 68 DEG C, 160rpm revolving speed is stirred to react
2.2h obtains solution I；
Wherein, mole of maleopimaric acid polyester polyol, castor oil polyhydric alcohol, erythritol, isophorone diisocyanate
Than for 2.5:1.8:0.82:2.8, the dosage of the catalyst dibutyltin dilaurylate be maleopimaric acid polyester polyol,
Castor oil polyhydric alcohol, erythritol, isophorone diisocyanate weight sum 0.07%；
(2) dimethyl acetamide, N-Methyl pyrrolidone, polyoxypropyleneglycol, laruyl alcohol, dihydroxy first are added into solution I
Base butyric acid reacts 0.8h at a temperature of 65 DEG C, after be heated up to 78 DEG C at a temperature of react 0.9h, obtain solution II；
Wherein, the addition of dimethyl acetamide, N-Methyl pyrrolidone, polyoxypropyleneglycol, laruyl alcohol, dimethylolpropionic acid
Amount is 2.4-4.2%, 1.4-2.1%, 1.6-2.1%, the 0.6-1.0% of isophorone diisocyanate weight in solution I,
2.6-4.2%；
(3) dimethyl acetamide, rosin polyester polyhydric-alcohol, trivinyl glycol are added to the container, are stirred at a temperature of 48 DEG C
Uniformly, solution III is obtained；
Wherein, dimethyl acetamide, rosin polyester polyhydric-alcohol, the additional amount of trivinyl glycol are polynary for castor oil in solution I
The 8.4% of alcohol weight, 6.6%, 10.2%；
(4) solution III is added in solvent II, a certain amount of two is added in mixed solution after 30min is stirred evenly at 30 DEG C
Methylacetamide reacts 0.6h after being warming up to 75 DEG C, obtains solution IV；
Wherein, the additional amount of dimethyl acetamide is the 4.6% of solution II weight；
(5) solution IV is cooled to 42 DEG C, triethylamine is added and reacts 0.8h, obtains solution V；
Wherein, the molar ratio of triethylamine and dimethylolpropionic acid described in step (2) is 0.28:1.0；
(6) it at a temperature of 33 DEG C, disperses solution V in the mixed liquor of the water and ethyl alcohol that are equivalent to 1.3 times of solution V weight,
550rpm revolving speed stirs 30min, obtains solution VI；Wherein, the mass ratio position 1:1.3 of water and ethyl alcohol；
(7) solution VI is evaporated under reduced pressure, steams solvent, the rear anion table that 6.5% mass of maleopimaric acid polyester polyol is added
Face activating agent stirs 30min with 280rpm revolving speed, obtains biomass water-based emulsion.
Di-alcohols synthesis material used in the maleopimaric acid polyester polyol is triethylene glycol.
The castor oil polyhydric alcohol is castor oil polyester polyol, uses castor oil, small molecular alcohol, acid anhydrides for reactant system
It is standby.
The anionic surfactant is lauryl sodium sulfate.
The aqueous binder material is glycidyl methacrylate graft modified soy-bean protein lotion and ethyl vinyl acetate second
The mixing water-based emulsion of alkene copolymer lotion, solid content is 57% in binder, and wherein glycidyl methacrylate graft changes
Property soybean protein and ethylene-vinyl acetate copolymer mass ratio be 1.5.
The oiliness binder is the mixed emulsion of aqueous Bisphenol-a Epoxy Resin lotion and aqueous EP rubbers lotion,
Solid content is 46% in binder, and wherein the mass ratio of Bisphenol-a Epoxy Resin and EP rubbers is 3, is added in oiliness binder
Entering quality is the odium stearate of Bisphenol-a Epoxy Resin 3.5% to promote to emulsify.
Further, the adhesion promoting component is aqueous terpene resin, solid content 48%.
Further, the auxiliary material is any combination of plasticizer, diluent, thixotropic agent.
Further, bonding effect of the adhesive between polyethylene and non-polar plastic is best.
Claims (6)
1. a kind of biomass combined environment-friendly water-based adhesive, which is compounded by plurality of raw materials, including biomass is aqueous
Lotion, aqueous binder material, oiliness binder, adhesion promoting component and auxiliary material；
Its mass fraction ratio are as follows:
Biomass water-based emulsion: 45-65 parts
Aqueous binder material: 10-18 parts
Oiliness binder: 12-20 parts
Adhesion promoting component: 4-8 parts
Auxiliary material: 2-4 parts
It is further characterized in that: the preparation of the biomass water-based emulsion are as follows:
(1) under nitrogen protection, maleopimaric acid polyester polyol, castor oil polyhydric alcohol, erythritol, isophorone two is different
Cyanate, catalyst dibutyltin dilaurylate are added in reaction vessel, and at a temperature of 60 DEG C -70 DEG C, 120rpm-180rpm turns
Speed is stirred to react 1.5 h -3h, obtains solution I；
Wherein, mole of maleopimaric acid polyester polyol, castor oil polyhydric alcohol, erythritol, isophorone diisocyanate
Than being Ma Laihai for the dosage of 2.2-2.8:1.4-2.2:0.6-0.96:2.5-3.2, the catalyst dibutyltin dilaurylate
Loose polyester polyols, castor oil polyhydric alcohol, erythritol, isophorone diisocyanate weight sum 0.05%-
0.10%；
(2) dimethyl acetamide, N-Methyl pyrrolidone, polyoxypropyleneglycol, laruyl alcohol, dihydroxy first are added into solution I
Base butyric acid reacts 0.5 h -1.0h at a temperature of 60 DEG C -70 DEG C, after be heated up to 70 DEG C -80 DEG C at a temperature of react 0.5 h -
1.0h obtains solution II；
Wherein, the addition of dimethyl acetamide, N-Methyl pyrrolidone, polyoxypropyleneglycol, laruyl alcohol, dimethylolpropionic acid
Amount is 2.4-4.2%, 1.4-2.1%, 1.6-2.1%, the 0.6-1.0% of isophorone diisocyanate weight in solution I,
2.6-4.2%；
(3) dimethyl acetamide, rosin polyester polyhydric-alcohol, trivinyl glycol are added to the container, at a temperature of 40 DEG C -50 DEG C
It stirs evenly, obtains solution III；
Wherein, dimethyl acetamide, rosin polyester polyhydric-alcohol, the additional amount of trivinyl glycol are polynary for castor oil in solution I
The 6.8-9.2% of alcohol weight, 4.6-7.4%, 8.7-12.5%；
(4) solution III is added in solvent II, a certain amount of two is added in mixed solution after 30min is stirred evenly at 30 DEG C
Methylacetamide reacts 0.5h-1h after being warming up to 70 DEG C -80 DEG C, obtains solution IV；
Wherein, the additional amount of dimethyl acetamide is the 3.2%-5.6% of solution II weight；
(5) solution IV is cooled to 35 DEG C -45 DEG C, triethylamine is added and reacts 0.5h-1.0h, obtains solution V；
Wherein, the molar ratio of triethylamine and dimethylolpropionic acid described in step (2) is 0.2-0.35:1.0；
(6) it at a temperature of 30-35 DEG C, disperses solution V in and is equivalent to 1-1.5 times of weight of solution V of water and the mixed liquor of ethyl alcohol
In, 500rpm-600rpm revolving speed stirs 30min, obtains solution VI；Wherein, the mass ratio of water and ethyl alcohol is between 1:1.5；
(7) solution VI is evaporated under reduced pressure, steams solvent, the rear anion that maleopimaric acid polyester polyol quality 5%-8% is added
Surfactant stirs 30min with 200-350rpm revolving speed, obtains biomass water-based emulsion.
2. a kind of biomass combined environment-friendly water-based adhesive as described in claim 1, it is characterised in that: the aqueous binder material is
The aqueous cream of the mixing of glycidyl methacrylate graft modified soy-bean protein lotion and ethylene-vinyl acetate copolymer emulsion
Liquid, solid content is between 55%-60% in binder, wherein glycidyl methacrylate graft modified soy-bean protein and second
Alkene-acetate ethylene copolymer mass ratio is between 1.2-1.8.
3. a kind of biomass combined environment-friendly water-based adhesive as described in claim 1, it is characterised in that: the oiliness binder is
The mixed emulsion of aqueous Bisphenol-a Epoxy Resin lotion and aqueous EP rubbers lotion, solid content is between 45%-50% in binder
Between, wherein the mass ratio of Bisphenol-a Epoxy Resin and EP rubbers is between 2.5-3.5.
4. a kind of biomass combined environment-friendly water-based adhesive as described in claim 1, it is characterised in that: the adhesion promoting component is water
Property terpene resin, solid content is between 42%-64%.
5. a kind of biomass combined environment-friendly water-based adhesive as described in claim 1, it is characterised in that: the auxiliary material is anti-oxidant
One of agent, plasticizer, diluent, thixotropic agent or several combinations.
6. a kind of biomass combined environment-friendly water-based adhesive as described in claim 1, it is characterised in that: the maleopimaric acid
Binary alcohol composition used in polyester polyol is diethylene glycol (DEG) or triethylene glycol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910519127.7A CN110205080A (en) | 2019-06-17 | 2019-06-17 | A kind of biomass combined environment-friendly water-based adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910519127.7A CN110205080A (en) | 2019-06-17 | 2019-06-17 | A kind of biomass combined environment-friendly water-based adhesive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110205080A true CN110205080A (en) | 2019-09-06 |
Family
ID=67793012
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910519127.7A Pending CN110205080A (en) | 2019-06-17 | 2019-06-17 | A kind of biomass combined environment-friendly water-based adhesive |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110205080A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111117527A (en) * | 2019-12-31 | 2020-05-08 | 河南省中凌煜新材料科技有限公司 | Water-based adhesive |
| CN111117552A (en) * | 2019-12-31 | 2020-05-08 | 河南省中凌煜新材料科技有限公司 | Dual-responsiveness composite adhesive and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618202A (en) * | 2012-04-01 | 2012-08-01 | 江阴市诺科科技有限公司 | Water-based polyurethane composite adhesive for tanning and preparation method and application of composite adhesive |
| CN104263252A (en) * | 2014-09-25 | 2015-01-07 | 朱羽涵 | Egg white-based wood adhesive |
| CN104974696A (en) * | 2015-07-29 | 2015-10-14 | 湖南工业大学 | Biomass environment-friendly water-based adhesive |
| CN105440972A (en) * | 2015-07-31 | 2016-03-30 | 湖南工业大学 | Nano-compound biomass waterborne adhesive |
| CN106675424A (en) * | 2016-12-29 | 2017-05-17 | 郑州佰沃生物质材料有限公司 | Biomass synthetic resin and method for producing coconut palm mattress by use of biomass synthetic resin as adhesive |
-
2019
- 2019-06-17 CN CN201910519127.7A patent/CN110205080A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618202A (en) * | 2012-04-01 | 2012-08-01 | 江阴市诺科科技有限公司 | Water-based polyurethane composite adhesive for tanning and preparation method and application of composite adhesive |
| CN104263252A (en) * | 2014-09-25 | 2015-01-07 | 朱羽涵 | Egg white-based wood adhesive |
| CN104974696A (en) * | 2015-07-29 | 2015-10-14 | 湖南工业大学 | Biomass environment-friendly water-based adhesive |
| CN105440972A (en) * | 2015-07-31 | 2016-03-30 | 湖南工业大学 | Nano-compound biomass waterborne adhesive |
| CN106675424A (en) * | 2016-12-29 | 2017-05-17 | 郑州佰沃生物质材料有限公司 | Biomass synthetic resin and method for producing coconut palm mattress by use of biomass synthetic resin as adhesive |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111117527A (en) * | 2019-12-31 | 2020-05-08 | 河南省中凌煜新材料科技有限公司 | Water-based adhesive |
| CN111117552A (en) * | 2019-12-31 | 2020-05-08 | 河南省中凌煜新材料科技有限公司 | Dual-responsiveness composite adhesive and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102433052B (en) | Aqueous polyurethane modified silicon-acrylate multifunctional waterproof heat-insulation elastic paint and preparation method thereof | |
| CN101362929B (en) | Emulsion type adhesive for paper and plastics and preparation method thereof | |
| CN100381531C (en) | Composite adhesive for soft wrapper and its preparation method | |
| CN104974696B (en) | A kind of biomass environment-friendly water-base cement | |
| CN110205080A (en) | A kind of biomass combined environment-friendly water-based adhesive | |
| CN101928529B (en) | EVA (Ethylene-Vinyl Acetate) composite emulsion type low temperature-resistant and environmentally-friendly all-purpose adhesive and preparation method thereof | |
| CN106458755A (en) | High performance water-based adhesion compositions and applications | |
| CN101580682B (en) | Waterborne compound adhesive and preparation method and application thereof | |
| CN103242787A (en) | Acrylic acid modified water-based polyurethane adhesive and preparation method thereof | |
| CN105176457B (en) | A kind of environment-friendly water-based adhesive | |
| CN101955742A (en) | Self-crosslinking aqueous laminating adhesive and preparation method thereof | |
| CN105440972A (en) | Nano-compound biomass waterborne adhesive | |
| CN102134466A (en) | Reactive water-borne adhesive and preparation method thereof | |
| CN105440982B (en) | Packing box used and wood-leather base material used environmentally-friendly aqueous binder | |
| CN106634720B (en) | A kind of water-fast glue bond of paper products of room temperature quickstick and preparation method thereof | |
| CN102134463A (en) | Water-based dry-type complex film adhesive and preparation method thereof | |
| CN105189580B (en) | Acrylic emulsion resin having excellent adhesive property and preparation method therefor | |
| CN105419681A (en) | Aqueous binder suitable for binding leather and flannelet | |
| CN109609080A (en) | A kind of isocyanates used for shaving board (environment-friendly type) adhesive and preparation method thereof | |
| CN105482738B (en) | One kind is applied to the special paper bonding aqueous binder of high speed gluing machine | |
| CN106634785B (en) | A kind of preparation method of strong water resistance Aqueous Polyurethane Adhesives | |
| CN110172312A (en) | A kind of environment-friendly water-based composite adhesive | |
| CN107189723A (en) | Waterborne dry-type laminated adhesive and preparation method thereof | |
| CN106085288A (en) | A kind of environment-friendly type mounts paper-hanging and preparation method thereof | |
| CN109294494A (en) | A kind of high-performance environment protection type neoprene adhesive by compound grafting |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190906 |
|
| WD01 | Invention patent application deemed withdrawn after publication |