CN102925102B - Modified soy protein adhesive and preparation method thereof - Google Patents
Modified soy protein adhesive and preparation method thereof Download PDFInfo
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- CN102925102B CN102925102B CN201210460187.4A CN201210460187A CN102925102B CN 102925102 B CN102925102 B CN 102925102B CN 201210460187 A CN201210460187 A CN 201210460187A CN 102925102 B CN102925102 B CN 102925102B
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- tackiness agent
- diisocyanate
- adhesive
- vulcabond
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Abstract
The invention discloses a modified soy protein adhesive and a method thereof. The modified soy protein adhesive is prepared by the following raw materials in weight part: 10-15 parts of SPI (Soybean Protein Isolate), 4-20 parts of urea, 8-13 parts of white emulsion and 0.5-3 parts of closed toluene 2, 4 diisocyanate in water. The preparation method comprises the following steps of dissolving the SPI into water, and then adding a pre-modifier for pre-modification; after the pre-modification is finished, adding the white emulsion for blending; after blending, adding the closed toluene 2, 4 diisocyanate for crosslinking; and after the crosslinking is finished, obtaining a finished product. The preparation process is simple, and the operation is convenient. The adhesive prepared by the formula has good water resistance and stability, and the dry-state shear bonding strength and the wet-state shear bonding strength are respectively 2.25 MPa and 1.05 MPa and are considerably larger than those of a general protein adhesive. The adhesive prepared by the formula can be widely applied to preparation of plywood and belongs to the field of the adhesive.
Description
Technical field:
The present invention relates to the preparation method of a kind of composite modified soy protein adhesive and tackiness agent, belong to adhesive area.
Background technology:
Current, prepare in tackiness agent at glued board that to use maximum be three-aldehyde glue stick, i.e. urea-formaldehyde resin, resol and terpolycyantoamino-formaldehyde resin.But these products in use constantly volatilize formaldehyde, have a strong impact on the health of people.On the other hand, because tackiness agent has very strong dependency to oil, along with the shortage of world petroleum resource, the rise of oil price, makes the market cost increase of tackiness agent, bogged down in crisis.Therefore, people more and more tend to use nontoxic, the renewable and aldehyde-free cement of wide material sources.Soy-protein tackiness agent is therefore by extensive concern.
Summary of the invention:
The object of the present invention is to provide a kind of prepare there is high strength and water tolerance and the composite modified soy protein adhesive of environmental protection cheapness.
Another object of the present invention is the method for the preparation modified soy protein adhesive described above providing a kind of simple low cost.
The invention provides a kind of modified soy protein adhesive, is be prepared from water by comprising following raw material:
Soybean protein isolate, i.e. SPI:10 ~ 15 part
Urea: 4 ~ 20 parts
White glue with vinyl: 8 ~ 13 parts
Close Toluene-2,4-diisocyanate, 4 vulcabond: 0.5 ~ 3 part
Described closed Toluene-2,4-diisocyanate, 4 vulcabond have formula 1 structural formula:
Formula 1
In formula 1, R is C
1 ~ 4alkoxyl formyl; R is preferably methoxycarbonyl base; In formula 1, R is preferably aligning structure.
Described tackiness agent viscosity 2 ~ 20Pas.
Described tackiness agent solid content is 40 ~ 65%..
Also add quality in described tackiness agent and be not more than the Sodium Benzoate of 3 parts as sanitas.
The present invention also provides a kind of preparation method of modified soy protein adhesive described above, after first soybean protein isolate is water-soluble, add urea and carry out pre-modification, white glue with vinyl is added blended after pre-modification completes, dead front type Toluene-2,4-diisocyanate is added after blended, 4-vulcabond is cross-linked, and has been cross-linked, and obtains product.
In above-mentioned production of adhesive process, pre-modification temperature controls in room temperature ~ 90 DEG C, and after pre-modification completes, control temperature DEG C carries out blended and crosslinking reaction in room temperature ~ 55.
Add urea in above-mentioned production of adhesive process and stir 0.5 ~ 3.0h, blended 0.5 ~ 2h after adding white glue with vinyl, adds dead front type Toluene-2,4-diisocyanate, reacts 0.5 ~ 3h after 4-vulcabond.
In the present invention, the preparation method of modified soy protein adhesive is completed by following step: the total weight parts of following raw material is 100 parts, by SPI by weight 10 ~ 15 parts add in the there-necked flask be filled with water, after being uniformly dissolved completely, temperature is adjusted to room temperature ~ 55 DEG C, add 4 ~ 20 parts of pre-properties-correcting agent, stir 0.5 ~ 3.0h, add the white glue with vinyl 8 ~ 13 parts measured again, dead front type Toluene-2,4-diisocyanate is added after blended 0.5 ~ 2h, 4-vulcabond 0.5 ~ 3 part, stop stirring after reaction 0.5 ~ 3h, obtain thick liquid; (wherein water accounts for the surplus of above weight part).
Closed Toluene-2,4-diisocyanate of the present invention, 4 vulcabond can prepare in the following manner: close Toluene-2,4-diisocyanate in the present invention, the preparation method of 4-vulcabond is completed by following step: phenolic hydroxyl group benzoic ether is dissolved in polar solvent N by (1), in N '-dimethyl methane amide, acetone or tetrahydrofuran (THF), obtain phenolic hydroxyl group benzoic ether solution; (2) be 1.0 ~ 1.75:1.0(the best by the mol ratio of phenolic hydroxyl group and isocyanate group be at 1.2 ~ 1.5:1) by Toluene-2,4-diisocyanate; 4-vulcabond slowly adds in phenolic hydroxyl group benzoic ether solution; stir under nitrogen protection and be warming up to 40 ~ 95 ° of C; stirring reaction 1 ~ 6h(or also can by phenolic hydroxyl group benzoic ether and Toluene-2,4-diisocyanate; 0.1 ~ 3.5% of 4-vulcabond total mass adds catalyzer dibutyl tin dilaurate; reaction 1 ~ 6h); underpressure distillation go out solvent namely obtain can in the dead front type Toluene-2,4-diisocyanate of warm deblocking, 4-vulcabond.
Advantage of the present invention:
1, preparing in the formula of modified soy protein adhesive blended by introducing white glue with vinyl, re-using dead front type Toluene-2,4-diisocyanate, 4-vulcabond is cross-linked the water resistance and stability that improve rubber made from soybean cake stick.
2, the preparation technology of modified soy protein adhesive of the present invention is simple, easy to operate, not high to equipment requirements, is easy to suitability for industrialized production, and raw material is easy to get simultaneously, and environmental protection, price is relatively inexpensive, can wide popularization and application.
3, modified soy protein adhesive is respectively 2.25MPa and 1.05MPa for hot-press gluing plate according to their dry state of type Ⅰ plywood mensuration, hygrometric state shear bond strength.And under the same terms, do not add that blocked isocyanate makes dry state in the contrast experiment of linking agent, hygrometric state shear bond strength is respectively 1.39MPa and 0.53MPa.
Accompanying drawing illustrates:
[Fig. 1] is invention adhesive preparation technology schema.
[Fig. 2] is that the embodiment of the present invention 6 methyl p-hydroxybenzoate closes Toluene-2,4-diisocyanate, 4-vulcabond
13cNMR spectrogram: 51ppm is methoxyl group (CH
3o-) characteristic peak of carbon atom in; 167ppm is the characteristic peak of carbon atom in the ester group be connected with methoxyl group; 160ppm is the characteristic peak of carbon atom in the ester group be connected with amino; 114ppm, 121ppm, 131ppm are the charateristic avsorption band of carbon atom on phenyl ring.
[Fig. 3] is that the embodiment of the present invention 6 methyl p-hydroxybenzoate closes Toluene-2,4-diisocyanate, 4-vulcabond
1h NMR spectrogram: 3.89ppm is the characteristic peak of hydrogen atom on methoxyl group; 1.63ppm is the peak of hydrogen atom on the methyl that is connected with phenyl ring; 6.85 ~ 7.97ppm is the characteristic peak of hydrogen atom on phenyl ring.
Embodiment:
The embodiment of the present invention further illustrates of the present invention, instead of restriction the present invention.
Embodiment 1
In present embodiment, the preparation method of modified soy protein adhesive is completed by following step: 1, in there-necked flask by soluble in water for 35.29g SPI, after being uniformly dissolved completely, temperature is adjusted to 30 DEG C; 2, in system, add 9g urea, stir 1h; 3, the white glue with vinyl 23.5g measured is added again, blended 1h; 4, add linking agent dead front type Toluene-2,4-diisocyanate, 4-vulcabond 6.09g, reaction adds Sodium Benzoate 0.5g after stirring 1.5h, stops stirring, obtain thick liquid after stirring 30min---composite modified soy protein adhesive.Note keeping SPI mass concentration to be 15%.This viscosity is 10.8Pas, solid content 52.4%, and suppressing dry state shear bond strength after three layers of glued board is 2.25MPa, and measuring its hygrometric state shear bond strength according to type Ⅰ plywood is 1.05MPa.
Embodiment 2
In present embodiment, the preparation method of modified soy protein adhesive can also be completed by following step: 1, in there-necked flask by soluble in water for 35.29g SPI, after being uniformly dissolved completely, temperature is adjusted to 30 DEG C; 2, in system, add 12g urea, stir 1h; 3, the white glue with vinyl 29.41g measured is added again, blended 0.5h; 4, add linking agent dead front type Toluene-2,4-diisocyanate, 4-vulcabond 3.65g, reaction adds Sodium Benzoate 0.8g after stirring 2.0h, stops stirring, obtain thick liquid after stirring 30min---composite modified soy protein adhesive.Note keeping SPI mass concentration to be 13%.This viscosity is 8.09Pas, solid content 46.7%, and suppressing dry state shear bond strength after three layers of glued board is 2.15MPa, and measuring its hygrometric state shear bond strength according to type Ⅰ plywood is 1.05MPa.
Embodiment 3
In present embodiment, the preparation method of modified soy protein adhesive can also be completed by following step: 1, in there-necked flask by soluble in water for 35.29g SPI, after being uniformly dissolved completely, temperature is adjusted to 30 DEG C; 2, in system, add 9.5g urea, stir 1h; 3, the white glue with vinyl 23.53g measured is added again, add linking agent dead front type Toluene-2,4-diisocyanate after blended 1.0h, 4-vulcabond 3.65g, reaction adds Sodium Benzoate 1.0g after stirring 2.0h, stop stirring after stirring 30min, obtain thick liquid---composite modified soy protein adhesive.Note keeping SPI mass concentration to be 15%.This viscosity is 12.6Pas, solid content 56.3%, and suppressing dry state shear bond strength after three layers of glued board is 2.10MPa, and measuring its hygrometric state shear bond strength according to type Ⅰ plywood is 1.10MPa.
Embodiment 4
In present embodiment, the preparation method of modified soy protein adhesive can also be completed by following step: 1, in there-necked flask by soluble in water for 35.29g SPI, after being uniformly dissolved completely, temperature is adjusted to 30 DEG C; 2, in system, add 15g urea, stir 1h; 3, the white glue with vinyl 32.14g measured is added again, add linking agent dead front type Toluene-2,4-diisocyanate after blended 1h, 4-vulcabond 6.09g, reaction adds Sodium Benzoate 4.0g after stirring 1.5h, stop stirring after stirring 30min, obtain thick liquid---composite modified soy protein adhesive.Note keeping SPI mass concentration to be 12%.This viscosity is 5.8Pas, solid content 49.4%, and suppressing dry state shear bond strength after three layers of glued board is 2.05MPa, and measuring its hygrometric state shear bond strength according to type Ⅰ plywood is 0.98MPa.
Embodiment 5
In present embodiment, the preparation method of modified soy protein adhesive can also be completed by following step: 1, in there-necked flask by soluble in water for 35.29g SPI, after being uniformly dissolved completely, temperature is adjusted to 30 DEG C; 2, in system, add 15g urea, stir 1h; 3, white glue with vinyl 42.14g is added again, add linking agent dead front type Toluene-2,4-diisocyanate after blended 1h, 4-vulcabond 9.13g, reaction adds Sodium Benzoate 1.0g after stirring 2.0h, stop stirring after stirring 30min, obtain thick liquid---composite modified soy protein adhesive.Note keeping SPI mass concentration to be 15%.This viscosity is 14.7Pas, solid content 58.0%, and suppressing dry state shear bond strength after three layers of glued board is 2.08MPa, and measuring its hygrometric state shear bond strength according to type Ⅰ plywood is 0.98MPa.
Embodiment 6
Close Toluene-2,4-diisocyanate, the preparation method of 4-vulcabond is completed by following step: 1,13.0345g methyl p-hydroxybenzoate is dissolved in 125ml N, in N '-dimethyl methane amide, obtains methyl p-hydroxybenzoate solution; 2, by 5g Toluene-2,4-diisocyanate; 4-vulcabond slowly adds in methyl p-hydroxybenzoate solution; then 0.18g catalyst dibutyltin dilaurylate is added; stir with 300r/min speed under nitrogen protection and be warming up to 80 DEG C; at 80 DEG C of stirring reaction 3h; underpressure distillation goes out solvent and namely obtains methyl p-hydroxybenzoate and close Toluene-2,4-diisocyanate, 4-vulcabond.
Claims (6)
1. a modified soy protein adhesive, is characterized in that, is to be prepared from water by comprising following raw material:
Soybean protein isolate, i.e. SPI:10 ~ 15 part
Urea: 4 ~ 20 parts
White glue with vinyl: 8 ~ 13 parts
Close Toluene-2,4-diisocyanate, 4 vulcabond: 0.5 ~ 3 part
Described closed Toluene-2,4-diisocyanate, 4 vulcabond have formula 1 structural formula:
In formula 1, R is methoxycarbonyl base, and R is aligning structure;
Described modified soy protein adhesive prepares by the following method: after first soybean protein isolate is water-soluble, add urea and carry out pre-modification, white glue with vinyl is added blended after pre-modification completes, dead front type Toluene-2,4-diisocyanate is added after blended, 4-vulcabond is cross-linked, be cross-linked, obtained product.
2. tackiness agent as claimed in claim 1, is characterized in that, the viscosity 2 ~ 20Pas of described tackiness agent.
3. tackiness agent as claimed in claim 1, it is characterized in that, the solid content of described tackiness agent is 40 ~ 65%.
4. tackiness agent as claimed in claim 1, is characterized in that, also add the Sodium Benzoate that mass parts is not more than 3 parts in described tackiness agent.
5. tackiness agent as claimed in claim 1, it is characterized in that, in production of adhesive process, pre-modification temperature controls in room temperature ~ 90 DEG C, and after pre-modification completes, control temperature DEG C carries out blended and crosslinking reaction in room temperature ~ 55.
6. tackiness agent as claimed in claim 1, it is characterized in that, add the pre-modification 0.5 ~ 3.0h of urea, blended 0.5 ~ 2h after adding white glue with vinyl, adds dead front type Toluene-2,4-diisocyanate, reacts 0.5 ~ 3h after 4-vulcabond.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210460187.4A CN102925102B (en) | 2012-11-15 | 2012-11-15 | Modified soy protein adhesive and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210460187.4A CN102925102B (en) | 2012-11-15 | 2012-11-15 | Modified soy protein adhesive and preparation method thereof |
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| CN102925102A CN102925102A (en) | 2013-02-13 |
| CN102925102B true CN102925102B (en) | 2015-03-25 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107116658A (en) * | 2017-05-15 | 2017-09-01 | 中国林业科学研究院林产化学工业研究所 | It is a kind of that the method for preparing dregs of beans glue fibre board is combined based on two-component dregs of beans adhesive/isocyanates |
| CN109294487A (en) * | 2018-09-08 | 2019-02-01 | 佛山朝鸿新材料科技有限公司 | A kind of preparation method of high stable water-resistant type white glue with vinyl |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130678A (en) * | 2006-08-22 | 2008-02-27 | 贺宏彬 | Aquosity polymer isocyanic ester adhesion agent of soy protein, preparing method and application of the same |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130678A (en) * | 2006-08-22 | 2008-02-27 | 贺宏彬 | Aquosity polymer isocyanic ester adhesion agent of soy protein, preparing method and application of the same |
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