CN1062003C - Modified high-molecular polyivnyl alcohol binding-agent and preparation method thereof - Google Patents
Modified high-molecular polyivnyl alcohol binding-agent and preparation method thereof Download PDFInfo
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- CN1062003C CN1062003C CN96117523A CN96117523A CN1062003C CN 1062003 C CN1062003 C CN 1062003C CN 96117523 A CN96117523 A CN 96117523A CN 96117523 A CN96117523 A CN 96117523A CN 1062003 C CN1062003 C CN 1062003C
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Abstract
The present invention relates to a modified high molecular polyivnyl alcohol (PVA) adhesive mainly used for the face adhesion of corrugated paper and a preparing method thereof. PVA generating aldolization under the acid condition is modified, an adopted M2 modifier is inorganic alkali metal silicate, and then, water impurities and salt impurities are removed. Finally, the modified PVA adhesive is obtained through neutralization treatment. The preparing method is convenient. The prepared adhesive has the advantages of favorable adhering strength, favorable storage stability, low cost and bright use prospect, and the water resisting property is enhanced obviously.
Description
The present invention relates to a kind of water-resistant adhesive, especially a kind of modified polyvinyl alcohol (PVA) tackiness agent that is mainly used in the fluting board veneer and preparation method thereof.
At present, the tackiness agent that domestic fluting board uses is generally based on milky white adhesive, but the main raw material Vinyl Acetate Monomer valency height of milky white adhesive, and cost occupies high-leveled and difficult following all the time.The producer that has for this reason voluntarily mounting production line prepare the PVA aqueous solution and piece together in order to reduce and use the glue cost.The water-soluble characteristic of PVA that can be wherein makes its water tolerance be difficult to improve, and especially this mixing is pieced together with tackiness agent has jelly in winter, summer cohesive strength to reach the disadvantage that humidity resistance descends inadequately and the exploitation of its new purposes is restricted.Yet well-known, PVA class tackiness agent is a kind of economic broad-spectrum tackiness agent, and is therefore, along with the fast development of paper article packaging industry, also just extremely urgent to adapt to new trend to the modification development of this tackiness agent.For many years, be noticeable abroad to improving PVA aqueous solution bond strength and water-proof research.As June 12 in 1980 everyday disclosure special permission communique clear No. 5578046 disclosed " constituents of filming " just reported the water-proof scheme of the raising PVA aqueous solution in detail, it is that spent ion exchange resin is handled alkalimetal silicate in advance, the lower concentration silicic acid that obtains is pieced together modification among the PVA, to reach the method that improves PVA water tolerance and cohesive strength.This has increased the complicacy of equipment and technology undoubtedly and has improved product cost, and the active height of the silicic acid that obtains by ion exchange resin and package stability is poor, only this a bit, just comparatively harsh to processing requirement.
The object of the present invention is to provide a kind of water tolerance to improve modified PVA tackiness agent and simple and convenient preparation method that bond strength and package stability are good.
Modified polyvinyl alcohol tackiness agent of the present invention, finished product contain (weight percent) 8～13% modified PVAs, 3～6% silicic acid and excess water, free aldehyde≤0.4%.
Further, modified polyvinyl alcohol tackiness agent of the present invention also contains tributyl phosphate defoamer, sanitas, 3～10% inanimate matter fillers.
In the present invention, described aldehyde can be industrial formol, acetaldehyde, propionic aldehyde, butyraldehyde and oxalic dialdehyde, can be used alone or two kinds of mixtures; Described acid can be sulfuric acid, phosphoric acid, hydrochloric acid, nitric acid, formic acid inorganic oxacid or oxygen-free acid, can be used alone or two kinds of mixtures; Described sanitas can be derosal, m-tetrachlorophthalodinitrile, phenylformic acid, Sodium Benzoate; Described inanimate matter water glass properties-correcting agent can be the alkalimetal silicate of sodium, potassium, lithium; Described inanimate matter filler can be light calcium carbonate, water-ground limestone, talcum powder, wilkinite, wollastonite powder, carclazyte.
The preparation method of modified polyvinyl alcohol tackiness agent of the present invention comprises the steps:
1), with in 800 kilograms the uncovered reactor of tap water (1) adding, directly feed steam heating, when temperature rises to 70～80 ℃, start stirrer and stir the PVA-1799 that adds 80～100 liters of grams, continue to be warming up to 80～95 ℃, be incubated 60～120 minutes, use PVA fully to dissolve;
2), treat that PVA dissolves fully after, add 2～4 kilograms of sulfuric acid, 1～3 kilogram of phosphoric acid and 20～30 kilograms of industrial formols, the control pH value is in 1～2 scope, makes it keep carrying out in 40～100 minutes condensation reaction at 80～95 ℃;
3), after condensation reaction finishes,, must the water in advance latting drown be that concentration 10～18% backs add with 15～40 kilograms of water glass, under 80～95 ℃, stirred 5～20 minutes, treat its dehydration after, shutdown stops vapour and abandons isolated moisture content, salt and impurity;
4), start stirrer and add an amount of tap water (2) with after adjusting to user required solid part content and viscosity, add defoamer, the sanitass of 3～10 kilograms of ammoniacal liquor and 10～50 grams at last, adjust PH=6.5～8, shut down and filter and package warehouse-in.
Also can add the inanimate matter filler in the method for the invention.
The first step technological principle of tackiness agent of the present invention is to be undertaken by the specific acetalation of PVA, and it can make monoaldehyde and PVA intramolecule and intermolecular realization condensationization.This reaction has destroyed the molecular structure of PVA and with the group of going up the dissymmetry structure, the content that makes ethanoyl in the PVA molecule reduces and reduced the crystallinity of PVA, freeze-proof, water tolerance and initial bonding strength is improved, thereby further is fit to construction requirement.
Inanimate matter alkali metal silicate salt properties-correcting agent among the preparation method of tackiness agent of the present invention adds by limited means: the inanimate matter alkali metal silicate salt properties-correcting agent moment that is about to be diluted to lower concentration joins in the acid PVA aqueous solution of high density, make alkaline properties-correcting agent moment transfer to acidic side, obtain stable silicate solution, reach and in the PVA modifying and dewatering, remove salt, remaining free aldehyde and a part, most of silicic acid and part alkalimetal ion are retained in the isomerized PVA aqueous solution of molecule the alkali metal impurity of water sensitive.Owing to the hydrogen ion dissociation degree of the sulfuric acid that adopts, phosphoric acid is bigger than silicic acid, so can make the low molecular activity silicic acid stable performance that remains in the PVA solution.When the normal temperature construction is dry, the hydroxyl of PVA can produce the crosslinked dehydration of isostatic with the hydroxyl with active low molecularity silicic acid, the part alkalimetal silicate that remains has been converted into water-insoluble acidic water glass after sour modification, so the water tolerance of this tackiness agent cured article is significantly improved, its bond strength and package stability are good.
Tackiness agent of the present invention not only is used for the fluting board veneer, also is used for the bonding of kraft paper abnormity material etc.
The preparation method of tackiness agent of the present invention compares with day disclosure special permission communique clear No. 5578046 disclosed two-step processes on June 12nd, 1980, and the present invention is improved to single stage method, does not need silicic acid to store separately and has solved the silicic acid list and not store unsettled disease; Simultaneously work simplification is not extremely needed airtight cover reactor and vapor pressure boiler, only get final product, reduced production cost again with common life drinking water boiler and the uncovered retort direct heating of individual layer.
The invention will be further described below in conjunction with embodiment:
Product embodiments 1: in a kind of modified PVA tackiness agent 10000 grams, it contains modified PVA 900 grams, silicic acid 500 grams, water 8600 grams, free aldehyde 0.2%.
Product embodiments 2: in a kind of modified PVA tackiness agent 10000 grams, it contains modified PVA 850 grams, silicic acid 450 grams, tributyl phosphate 1 gram, Sodium Benzoate 48.5 grams, water 8650 grams, free aldehyde 0.2%.
Product embodiments 3: in a kind of modified PVA tackiness agent 10000 grams, it contains modified PVA 850 grams, silicic acid 450 grams, talcum powder 300 grams, derosal 0.5 gram, water 8400 grams, free aldehyde 0.2%.
Product embodiments 4: in a kind of modified PVA tackiness agent 10000 grams, it contains modified PVA 1000 grams, silicic acid 500 grams, tributyl phosphate 0.5 gram, light calcium carbonate 250 grams, water 8250 grams, free aldehyde 2.5%.
Product embodiments 5: in a kind of modified PVA tackiness agent 10000 grams, it contains modified PVA 1200 grams, silicic acid 350 grams, phenylformic acid 20 grams, water 8450 grams, free aldehyde 3%.
Certainly, the inanimate matter filler that adds according to user's needs in these products can also be water-ground limestone, talcum powder, wilkinite, wollastonite powder, carclazyte etc.
Method embodiment: at first take by weighing starting material by following formula rate:
Tap water 70～80%, PVA 7～12%, industrial formol 2～4%, phosphoric acid 0.2～0.4%, sulfuric acid 0.1～0.3%, inanimate matter water glass properties-correcting agent 1.5～4%, defoamer 0.01%, sanitas 0.01%, ammoniacal liquor 0.2%, tap water is an amount of.
Wherein the model of PVA is that home products such as 1799,1788 get final product:
Industrial formol can also with oxalic dialdehyde, one or both mixed aldehydes such as acetaldehyde, propionic aldehyde, butyraldehyde replace;
Inorganic oxacid or oxygen-free acid replacements such as the also available hydrochloric acid of sulfuric acid, phosphoric acid, nitric acid, formic acid;
Inanimate matter alkali metal silicate sodium properties-correcting agent can also use potassium, soda metal silicate to replace;
Defoamer is a tributyl phosphate, uses according to the foaming situation, also can;
Also interchangeable alkali in blocks of ammoniacal liquor or liquid caustic soda that neutralizing treatment is used;
Sanitas: derosal, m-tetrachlorophthalodinitrile, phenylformic acid, Sodium Benzoate etc.;
Tap water is used to adjust product viscosity, and will discard 30～50% when dehydration, mends tap water (2), is to be adjusted to desired solids content and viscosity.
Below in conjunction with example method is further elaborated:
1, with in 800 kilograms the uncovered reactor of tap water (1) adding, directly feed steam heating, when temperature rises to 70～80 ℃, start stirrer and stir the PVA-1799 that adds 80～100 liters of grams, continue to be warming up to 80～95 ℃, be incubated 60～120 minutes, use PVA fully to dissolve;
2, treat that PVA dissolves fully after, add 2～4 kilograms of sulfuric acid, 1～3 kilogram of phosphoric acid and 20～30 kilograms of industrial formols, the control pH value is in 1～2 scope, makes it keep carrying out in 40～100 minutes condensation reaction at 80～95 ℃;
3, after condensation reaction is finished, with 15～40 kilograms of water glass, must water in advance latting drown be that concentration 10～18% backs add, under 80～95 ℃, stirred 5～20 minutes, treat its dehydration after, shutdown stops vapour and abandons isolated moisture content, salt and impurity;
4, start stirrer and add an amount of tap water (2), add defoamer, the sanitass of 3～10 kilograms of ammoniacal liquor and 10～50 grams at last, adjust PH=6.5～8, shut down and filter and package warehouse-in with after adjusting to user required solid part content and viscosity.
In order to increase filling effect, also can add the inanimate matter filler, when adding the inanimate matter filler, should be with filled water in advance dispersion moistening, to improve the dispersion effect of filler in PVA.
Claims (6)
1, a kind of modified polyvinyl alcohol tackiness agent is characterized in that finished product contains (weight percent) 8～13% modified PVAs, 3～6% silicic acid and excess water, free aldehyde≤0.4%.
2, modified polyvinyl alcohol tackiness agent as claimed in claim 1 is characterized in that also containing tributyl phosphate defoamer, sanitas, 3～10% inanimate matter fillers.
3, as claim 1,2 described modified polyvinyl alcohol tackiness agents, it is characterized in that described aldehyde can be industrial formol, acetaldehyde, propionic aldehyde, butyraldehyde and oxalic dialdehyde, can be used alone or two kinds of mixtures.
4,, it is characterized in that described sanitas can be derosal, m-tetrachlorophthalodinitrile, phenylformic acid and Sodium Benzoate as claim 1,2 described modified polyvinyl alcohol tackiness agents.
5,, it is characterized in that described inanimate matter filler can be light calcium carbonate, water-ground limestone, talcum powder, wilkinite, wollastonite powder and carclazyte as claim 1,2 described modified polyvinyl alcohol tackiness agents.
6, as the preparation method of claim 1,2 described modified polyvinyl alcohol tackiness agents, it is characterized in that comprising the steps:
1), with in 800 kilograms the uncovered reactor of tap water (1) adding, directly feed steam heating, when temperature rises to 70～80 ℃, start stirrer and stir the PVA-1799 that adds 80～100 liters of grams, continue to be warming up to 80～95 ℃, be incubated 60～120 minutes, use PVA fully to dissolve;
2), treat that PVA dissolves fully after, add 2～4 kilograms of sulfuric acid, 1～3 kilogram of phosphoric acid and 20～30 kilograms of industrial formols, the control pH value is in 1～2 scope, makes it keep carrying out in 40～100 minutes condensation reaction at 80～95 ℃;
3), after condensation reaction finishes,, must the water in advance latting drown be that concentration 10～18% backs add with 15～40 kilograms of water glass, under 80～95 ℃, stirred 5～20 minutes, treat its dehydration after, shutdown stops vapour and abandons isolated moisture content, salt and impurity;
4), start stirrer and add an amount of tap water (2) with after adjusting to user required solid part content and viscosity, add defoamer, the sanitass of 3～10 kilograms of ammoniacal liquor and 10～50 grams at last, adjust PH=6.5～8, shut down and filter and package warehouse-in.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96117523A CN1062003C (en) | 1996-04-10 | 1996-04-10 | Modified high-molecular polyivnyl alcohol binding-agent and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96117523A CN1062003C (en) | 1996-04-10 | 1996-04-10 | Modified high-molecular polyivnyl alcohol binding-agent and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1162000A CN1162000A (en) | 1997-10-15 |
| CN1062003C true CN1062003C (en) | 2001-02-14 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN96117523A Expired - Fee Related CN1062003C (en) | 1996-04-10 | 1996-04-10 | Modified high-molecular polyivnyl alcohol binding-agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102504452B (en) * | 2011-10-21 | 2013-09-25 | 广东海洋大学 | Pinctada martensii nucleated pearl interlayer gap filling agent and preparation method thereof |
| CN107805460A (en) * | 2017-10-25 | 2018-03-16 | 成都森钰泓绿化工程有限公司 | A kind of Environment-friendlyadhesive adhesive for timber processing |
| CN107793935A (en) * | 2017-10-25 | 2018-03-13 | 成都森钰泓绿化工程有限公司 | A kind of preparation method of Environment-friendlyadhesive adhesive for timber processing |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4096121A (en) * | 1977-03-04 | 1978-06-20 | Blount David H | Process for the production of resinous products by chemically reacting silicic acid with poly(vinyl acetate) polymer |
| JPH04306269A (en) * | 1989-12-29 | 1992-10-29 | D & D Kk | Antifouling paint |
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1996
- 1996-04-10 CN CN96117523A patent/CN1062003C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4096121A (en) * | 1977-03-04 | 1978-06-20 | Blount David H | Process for the production of resinous products by chemically reacting silicic acid with poly(vinyl acetate) polymer |
| JPH04306269A (en) * | 1989-12-29 | 1992-10-29 | D & D Kk | Antifouling paint |
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| Publication number | Publication date |
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| CN1162000A (en) | 1997-10-15 |
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