CN106118559A - A kind of soybean-based osseocolla sheet material adhesive and preparation method thereof - Google Patents
A kind of soybean-based osseocolla sheet material adhesive and preparation method thereof Download PDFInfo
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- CN106118559A CN106118559A CN201610656954.7A CN201610656954A CN106118559A CN 106118559 A CN106118559 A CN 106118559A CN 201610656954 A CN201610656954 A CN 201610656954A CN 106118559 A CN106118559 A CN 106118559A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H1/00—Macromolecular products derived from proteins
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- 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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a kind of soybean-based osseocolla sheet material adhesive, it is made up of the raw material of following weight parts: calcium lactobionate. 12, lauric acid amide of ethanol 0.7 1, osseocolla 68, naphthenic soap 0.6 1, diphenyl silanediol 34, zinc dibutyl dithiocarbamate 12, polyvinyl alcohol 24, defatted soybean flour 170 200, iron chloride 0.3 0.4, ferrous chloride 0.1 0.2, epoxychloropropane 0.8 1, N n-methylolacrylamide 23, styrene 16 20, potassium peroxydisulfate 0.1 0.2, hemicellulase 34, poly-methyl diphenylene diisocyanate 10 19, the hydrochloric acid solution 60 70 of 20 30%, isothiazolone 0.1 0.2, trisnonyl phenyl phosphite 0.8 1.The present invention is difficult to cause equipment corrosion, working life to deposit the features such as phase longer, formaldehydeless, residual monomer content is low, water-tolerant.
Description
Technical field
The present invention relates to adhesive technical field, particularly relate to a kind of soybean-based osseocolla sheet material adhesive and preparation side thereof
Method.
Background technology
Aldehyde system adhesive consumption in timber industry adhesive is maximum, but it exists shortcomings: primary raw material multi-source
In the non-renewable resources such as oil, coal;Produce and use process constantly distributes carcinogen (such as formaldehyde), can be good for by harmful to human
Health;Product non-degradable, easily pollutes environment.Therefore, biomass-based adhesive is researched and developed to substitute aldehyde system adhesive by the whole world
Pay much attention to.In various biological materials, Semen sojae atricolor (including genetically engineered soybean) has that yield is big, low cost, vegetable protein contain
Measure high feature, be good adhesive raw material;Research soybean-based adhesive so that it is all or part of petroleum replacing base gluing
Agent, to reduce depletion of non-renewable resources, ensure food safety the most significant, be outside Present Domestic research focus;
Adhesive the most nontoxic, free of contamination is applied to become trend, plant along with using the exploitation of reproducible biomass from producing to
The research of albumen adhesive causes the extensive concern of people.Wherein, utilizing soybean protein to prepare soybean-based adhesive is study hotspot,
Improving its resistance to water is then primary study content, and it is the most resistance to that oneself there are some researches show that adhesive prepared by soybean protein isolate has
Aqueous;But, SPI is isolatable from Semen sojae atricolor defatted soy flour, and the price of its costliness necessarily limits its application in terms of adhesive.Cause
This, the DSF of cost and low percentages of protein becomes the preferred raw materials preparing water-resistant soybean base adhesive;
SPI and DSF, SPI that after preparation soybean-based adhesive mainly uses soybean extract oil at present, defat bean cypress produces derive from
DSF, its soybean protein content is typically larger than 90%, it is easy to modified, the adhesive of preparation has good resistance to water.But SPI costliness
Its application in terms of adhesive of price limit.Therefore, the DSF of cost and low percentages of protein become preparation resistance to water big
The preferred material of bean base adhesive.A large amount of research methoies based on SPI adhesive are also used for modified DSF and prepare adhesive, and
Achieve certain effect, it is thus achieved that low resistance to water (cold water or humid air), medium resistance to water (63 DEG C of water) and enhanced water resistance
The modified soybean base adhesive formula of (boiling water);Wherein, enhanced water resistance soybean-based adhesive is mainly by excellent with boiling water resistance energy
Obtain after different synthetic resin mixing.But, DSF is complicated mixture, by the soybean protein of nearly 50%, the carbon hydrate of 40%
Thing and other micro constitutent form;
Current research method all lays particular emphasis on modified soybean protein therein, and is not directed to the carbohydrate of 40%, causes this
Resistance to water after adhesive is solidified by component is inoperative, even plays negative interaction, wastes raw material.Additionally, have resistance to boiling
Aqueous can be adhesive for making the precondition of outdoor cementing thing, if when with DSF glue so that it is in carbon hydrate
Thing converts the component that raising adhesive resistance to water rises positive interaction, in conjunction with Soybean Protein Modification method, prepares the bean of resistance to boiling water base
Adhesive, not only takes full advantage of raw material, can be also that a new way is opened up in the soybean-based adhesive research being applied to open air.
The research solving problem that aldehyde system adhesive exists and the based Wood Adhesives that instructs other similar biomass to be raw material is all anticipated by this
Justice is great;
Epoxy radicals is the polar group that a kind of work is dialled, and can form chemistry and be bonded with the radical reaction containing active oxygen, utilize containing epoxy
The compound on organism matter adhesive of group is modified improving research existing many reports of its performance, if therefore used
Containing epoxy compounds, it is modified, or access ring epoxide in the component containing these functional groups, necessarily can carry further
High Semen sojae atricolor base adhesive resistance to water.
Summary of the invention
The object of the invention is contemplated to make up the defect of prior art, it is provided that a kind of soybean-based osseocolla sheet material adhesive and
Preparation method.
The present invention is achieved by the following technical solutions:
A kind of soybean-based osseocolla sheet material adhesive, it is made up of the raw material of following weight parts:
Calcium lactobionate. 1-2, lauric acid amide of ethanol 0.7-1, osseocolla 6-8, naphthenic soap 0.6-1, diphenyl silanediol 3-4,
Zinc dibutyl dithiocarbamate 1-2, polyvinyl alcohol 2-4, defatted soybean flour 170-200, iron chloride 0.3-0.4, protochloride
Ferrum 0.1-0.2, epoxychloropropane 0.8-1, N hydroxymethyl acrylamide 2-3, styrene 16-20, potassium peroxydisulfate 0.1-0.2, half
Cellulase 3-4, the hydrochloric acid solution 60-70 of poly-methyl diphenylene diisocyanate 10-19,20-30%, isothiazolone 0.1-
0.2, trisnonyl phenyl phosphite 0.8-1.
The preparation method of a kind of described soybean-based osseocolla sheet material adhesive, comprises the following steps:
(1) by above-mentioned iron chloride, ferrous chloride mixing, join in the hydrochloric acid solution of 20-30%, stir, obtain iron salt molten
Liquid;
(2) above-mentioned osseocolla is joined in the deionized water of its weight 18-20 times, add lauric acid amide of ethanol, at 70-80
Insulated and stirred 4-7 minute at DEG C, obtains osseocolla emulsion;
(3) being joined by above-mentioned defatted soybean flour in the distilled water of its weight 20-27 times, add above-mentioned osseocolla emulsion, stirring is all
Even, add hemicellulase, enzymolysis 18-20 minute at 50-55 DEG C, reduce temperature and be 26-30 DEG C, add above-mentioned iron salt molten
Liquid, is incubated 30-35 minute, adds the sodium hydroxide of 3-5mol/l, and regulation pH is 5-6, adds above-mentioned epoxychloropropane, rises high temperature
Degree is 70-75 DEG C, insulated and stirred 30-35 minute, adds the sodium hydroxide of 3-5mol/l, and regulation pH is 10-11, and stirring is reacted
30-40 minute, obtain epoxide modified Semen sojae atricolor latex;
(4) above-mentioned isothiazolone is joined in the dehydrated alcohol of its weight 6-9 times, stir, add naphthenic soap, rise
High-temperature is 60-70 DEG C, adds above-mentioned epoxide modified Semen sojae atricolor latex, insulated and stirred 20-30 minute, ethanol is distilled off, obtains pre-
Process modified soybean latex;
(5) take above-mentioned pretreatment modification Semen sojae atricolor latex, be passed through nitrogen, rise high-temperature and be 70-75 DEG C, add above-mentioned N-methylol third
Acrylamide, drips acetic acid, and regulation pH is 5-6, and insulated and stirred 60-60 minute obtains acid amide-grafted epoxy soybean latex;
(6) take above-mentioned trisnonyl phenyl phosphite, join in diphenyl silanediol, rise high-temperature and be 60-65 DEG C, add two fourths
Base zinc dithiocarbamate, insulated and stirred 10-15 minute, obtain premix material;
(7) take above-mentioned acid amide-grafted epoxy soybean latex, add above-mentioned polyvinyl alcohol, rise high-temperature and be 76-80 DEG C, insulated and stirred
20-30 minute, adding the 20-25% of above-mentioned styrene weight, the 18-20% of above-mentioned potassium peroxydisulfate weight, stirring mixing 10-20 divides
Clock, drips remaining styrene, potassium peroxydisulfate, reduces temperature and is 40-45 DEG C, adds above-mentioned premix material, and insulation reaction 60-70 is divided
Clock, cooling, obtain Polystyrene grafting rubber made from soybean cake;
(8) above-mentioned Polystyrene grafting rubber made from soybean cake is mixed with remaining each raw material, stir, to obtain final product.
The invention have the advantage that using method:
During use, adhesive of the present invention 2-poly-with the firming agent of its weight 8-10% phenylmethane cyanate (PMDI) is mixed, stir
Mixing uniformly, be coated on plate surface, plate surface coating amount is 280 g/m2, and after gluing, room temperature Guan Bi ageing 10 min, are re-fed into
Press, sheeting process is: room temperature, 4.0 MPa, 40 min,.
First defatted soybean flour is used hemicellulose ferment treatment by the present invention, then by acid, alkali, salt Combined Treatment, can be by big
Soybean protein partial hydrolysis, destroys oxygen key, unfolds the chondritic of soybean protein so that it is active center is exposed, and improves in adhesive
The content of active function groups and reactivity, can form preferably crosslinking, thus improve its water resistance after causing its solidification,
And the Semen sojae atricolor latex after hemicellulose ferment treatment contains substantial amounts of active group, such as-NH2 ,-C00H ,-OH etc., can be with epoxy chlorine
Epoxy radicals generation chemical reaction in propane, is conducive to eliminating the hydrophilic radical in soybean-based adhesive, is cross-linked into said three-dimensional body
Type structure, improves the resistance to water after its solidification, then utilizes methylol and the epoxy soybean base gluing of N hydroxymethyl acrylamide
Agent contains the component reaction of these functional groups, forms grafting, and the vinyl in N hydroxymethyl acrylamide can be with styrene
Monomer forms stable copolymer, and after styrene copolymerized, vinyl residual quantity declines, the phenyl in polystyrene structure, alkane
Hydrocarbon methyl composition increases, and improves the stability of modified soybean base adhesive, and only containing phenyl, parent in styrene molecules structure
Aqueous is little;Meanwhile, the more preferable phenyl ring of a large amount of stability is introduced into modification by copolymerization soybean-based adhesive, causes its resistance to water to improve.
The styrene copolymerized modified soybean base adhesive of the present invention is difficult to cause equipment corrosion, working life to deposit, and the phase is longer, do not contain
The features such as formaldehyde, residual monomer content are low, the feature of environmental protection, water-tolerant
The osseocolla that the present invention adds can effectively improve adhesion strength and the pliability of finished product adhesive.
Detailed description of the invention
A kind of soybean-based osseocolla sheet material adhesive, it is made up of the raw material of following weight parts:
Calcium lactobionate. 1, lauric acid amide of ethanol 0.7, osseocolla 6, naphthenic soap 0.6, diphenyl silanediol 3, dibutyl two sulfur
For carbaminate 1, polyvinyl alcohol 2, defatted soybean flour 170, iron chloride 0.3, ferrous chloride 0.1, epoxychloropropane 0.8, N hydroxyl
Methacrylamide 2, styrene 16, potassium peroxydisulfate 0.1, hemicellulase 3, poly-methyl diphenylene diisocyanate 10,20%
Hydrochloric acid solution 60, isothiazolone 0.1, trisnonyl phenyl phosphite 0.8.
The preparation method of a kind of described soybean-based osseocolla sheet material adhesive, comprises the following steps:
(1) by above-mentioned iron chloride, ferrous chloride mixing, join in the hydrochloric acid solution of 20%, stir, obtain iron salt solutions;
(2) above-mentioned osseocolla is joined in the deionized water of its weight 18 times, add lauric acid amide of ethanol, protect at 70 DEG C
Temperature stirring 4 minutes, obtains osseocolla emulsion;
(3) above-mentioned defatted soybean flour is joined in the distilled water of its weight 20 times, adds above-mentioned osseocolla emulsion, stir,
Adding hemicellulase, enzymolysis 18 minutes at 50 DEG C, reducing temperature is 26 DEG C, adds above-mentioned iron salt solutions, is incubated 30 minutes,
Adding the sodium hydroxide of 3mol/l, regulation pH is 5, adds above-mentioned epoxychloropropane, and rising high-temperature is 70 DEG C, insulated and stirred 30 points
Clock, adds the sodium hydroxide of 3mol/l, and regulation pH is 10, stirring reaction 30 minutes, obtains epoxide modified Semen sojae atricolor latex;
(4) above-mentioned isothiazolone is joined in the dehydrated alcohol of its weight 6 times, stir, add naphthenic soap, raise
Temperature is 60 DEG C, adds above-mentioned epoxide modified Semen sojae atricolor latex, insulated and stirred 20 minutes, ethanol is distilled off, obtains pretreatment modification
Semen sojae atricolor latex;
(5) taking above-mentioned pretreatment modification Semen sojae atricolor latex, be passed through nitrogen, rising high-temperature is 70 DEG C, adds above-mentioned N methylol acryloyl
Amine, drips acetic acid, and regulation pH is 5, and insulated and stirred 60 minutes obtains acid amide-grafted epoxy soybean latex;
(6) taking above-mentioned trisnonyl phenyl phosphite, join in diphenyl silanediol, rising high-temperature is 60 DEG C, adds dibutyl
Zinc dithiocarbamate, insulated and stirred 10 minutes, obtain premix material;
(7) taking above-mentioned acid amide-grafted epoxy soybean latex, add above-mentioned polyvinyl alcohol, rising high-temperature is 76 DEG C, insulated and stirred 20
Minute, adding the 20% of above-mentioned styrene weight, the 18% of above-mentioned potassium peroxydisulfate weight, stirring mixes 10 minutes, drips remaining
Styrene, potassium peroxydisulfate, reducing temperature is 40 DEG C, adds above-mentioned premix material, insulation reaction 60 minutes, cooling, obtains polystyrene
Modified grafting rubber made from soybean cake;
(8) above-mentioned Polystyrene grafting rubber made from soybean cake is mixed with remaining each raw material, stir, to obtain final product.
Performance test:
Viscosity 4.94 Pa.s;
Bonding strength: 1.23 Mpa.
Claims (2)
1. a soybean-based osseocolla sheet material adhesive, it is characterised in that it is made up of the raw material of following weight parts:
Calcium lactobionate. 1-2, lauric acid amide of ethanol 0.7-1, osseocolla 6-8, naphthenic soap 0.6-1, diphenyl silanediol 3-4,
Zinc dibutyl dithiocarbamate 1-2, polyvinyl alcohol 2-4, defatted soybean flour 170-200, iron chloride 0.3-0.4, protochloride
Ferrum 0.1-0.2, epoxychloropropane 0.8-1, N hydroxymethyl acrylamide 2-3, styrene 16-20, potassium peroxydisulfate 0.1-0.2, half
Cellulase 3-4, the hydrochloric acid solution 60-70 of poly-methyl diphenylene diisocyanate 10-19,20-30%, isothiazolone 0.1-
0.2, trisnonyl phenyl phosphite 0.8-1.
2. the preparation method of a soybean-based osseocolla sheet material adhesive as claimed in claim 1, it is characterised in that include following
Step:
(1) by above-mentioned iron chloride, ferrous chloride mixing, join in the hydrochloric acid solution of 20-30%, stir, obtain iron salt molten
Liquid;
(2) above-mentioned osseocolla is joined in the deionized water of its weight 18-20 times, add lauric acid amide of ethanol, at 70-80
Insulated and stirred 4-7 minute at DEG C, obtains osseocolla emulsion;
(3) being joined by above-mentioned defatted soybean flour in the distilled water of its weight 20-27 times, add above-mentioned osseocolla emulsion, stirring is all
Even, add hemicellulase, enzymolysis 18-20 minute at 50-55 DEG C, reduce temperature and be 26-30 DEG C, add above-mentioned iron salt molten
Liquid, is incubated 30-35 minute, adds the sodium hydroxide of 3-5mol/l, and regulation pH is 5-6, adds above-mentioned epoxychloropropane, rises high temperature
Degree is 70-75 DEG C, insulated and stirred 30-35 minute, adds the sodium hydroxide of 3-5mol/l, and regulation pH is 10-11, and stirring is reacted
30-40 minute, obtain epoxide modified Semen sojae atricolor latex;
(4) above-mentioned isothiazolone is joined in the dehydrated alcohol of its weight 6-9 times, stir, add naphthenic soap, rise
High-temperature is 60-70 DEG C, adds above-mentioned epoxide modified Semen sojae atricolor latex, insulated and stirred 20-30 minute, ethanol is distilled off, obtains pre-
Process modified soybean latex;
(5) take above-mentioned pretreatment modification Semen sojae atricolor latex, be passed through nitrogen, rise high-temperature and be 70-75 DEG C, add above-mentioned N-methylol third
Acrylamide, drips acetic acid, and regulation pH is 5-6, and insulated and stirred 60-60 minute obtains acid amide-grafted epoxy soybean latex;
(6) take above-mentioned trisnonyl phenyl phosphite, join in diphenyl silanediol, rise high-temperature and be 60-65 DEG C, add two fourths
Base zinc dithiocarbamate, insulated and stirred 10-15 minute, obtain premix material;
(7) take above-mentioned acid amide-grafted epoxy soybean latex, add above-mentioned polyvinyl alcohol, rise high-temperature and be 76-80 DEG C, insulated and stirred
20-30 minute, adding the 20-25% of above-mentioned styrene weight, the 18-20% of above-mentioned potassium peroxydisulfate weight, stirring mixing 10-20 divides
Clock, drips remaining styrene, potassium peroxydisulfate, reduces temperature and is 40-45 DEG C, adds above-mentioned premix material, and insulation reaction 60-70 is divided
Clock, cooling, obtain Polystyrene grafting rubber made from soybean cake;
(8) above-mentioned Polystyrene grafting rubber made from soybean cake is mixed with remaining each raw material, stir, to obtain final product.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN112143436A (en) * | 2020-09-28 | 2020-12-29 | 钟雨玲 | Preparation method of high-temperature and high-humidity resistant polyurethane adhesive |
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2016
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112143436A (en) * | 2020-09-28 | 2020-12-29 | 钟雨玲 | Preparation method of high-temperature and high-humidity resistant polyurethane adhesive |
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Application publication date: 20161116 |