CN102229791A - Environment-friendly type urea-formaldehyde resin adhesive and production method thereof - Google Patents
Environment-friendly type urea-formaldehyde resin adhesive and production method thereof Download PDFInfo
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- CN102229791A CN102229791A CN2011101577690A CN201110157769A CN102229791A CN 102229791 A CN102229791 A CN 102229791A CN 2011101577690 A CN2011101577690 A CN 2011101577690A CN 201110157769 A CN201110157769 A CN 201110157769A CN 102229791 A CN102229791 A CN 102229791A
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Abstract
An environment-friendly type urea-formaldehyde resin adhesive and a production method thereof. The method comprises the following steps: mixing glyoxal with urea in a container according to a certain mol ratio; adding a 10% polyvinyl alcoholic solution prepared in advance and urea under agitation, adjusting the pH value of the solution to be 7.5 to 8.5, and heating the solution to a temperature of 80 to 90 DEG C for reaction; adding a proper amount of urea for reaction for 40 minutes, adjusting the pH value of the solution to be 5 to 6, subjecting the solution to reaction at a temperature of 70 to 80 DEG C, and stopping the reaction when opacified sticky liquid appears or when cloudy sticky liquid appears under the condition that a droplet of the reaction solution is added into a glass with water at a temperature of 40 DEG C; cooling the solution to a temperature less than 40 DEG C and packaging the discharged products so as to obtain finished products. The adhesive provided in the invention belongs to excellent environment-friendly decoration materials, has remarkable adhesive properties, little smell, great initial adhesion, high final strength, good endurance and appropriate viscosity, is easy to paint and stable to store, and enables a glue film to be tough and tensile. Woodwork glued by the adhesive has no obvious glue lines, has excellent water tolerance, and produces no cracking in long-term usage.
Description
Technical field
The present invention relates to a kind of adhesive technology field, specifically a kind of environment friendly urea-formaldehyde resin adhesive and production method thereof.Be mainly used in bonding carpenter's furniture, various wood-based plates, integrated timber processing, senior solid wooden compound floor is bonding, and many-sides such as decorations have a wide range of applications.
Background technology
Along with the develop rapidly of China's timber industry, now become first big country of world's Wood-based Panel Production.Current domestic wood industry adopts urea-formaldehyde glue, phenolic glue, melamino-formaldehyde glue and polyvinyl acetate glue mostly with glue, their bonding strengths are poor, bonding plane is hard, crisp, immalleable, non-watertight, not durable etc., and poisonous, contaminate environment has peppery eye and pungent smell.That comes out at the top in various tackiness agent surely belongs to urea-formaldehyde resin adhesive, promptly by the UF resin adhesive of formaldehyde and urea synthesis.This tackiness agent has to be made simply, and curing speed is fast, and is cheap, and easy construction is widely used in creating card, glued board, and core-board, materials such as casting sand type connect, and become the industrial adhesive that has the call on the market.
But the shortcoming of UF tackiness agent maximum is the free formaldehyde content height, and this carcinogenic material not only contaminate environment also endangers the healthy of people.Transform poisonous UF tackiness agent and become the task of top priority.
Summary of the invention
The object of the present invention is to provide a kind of is formaldehydeless environment friendly urea-formaldehyde resin adhesive of main material production and production method thereof with oxalic dialdehyde.
The object of the present invention is achieved like this: it comprises that oxalic dialdehyde with the mol ratio of urea is
1.0-1.2:1, properties-correcting agent is above-mentioned mole total amount
1.0-2.5%Described properties-correcting agent is polyvinyl alcohol
1788, polyvinyl alcohol
2088, polyvinyl alcohol
1799, polyvinyl alcohol
1999, polyvinyl alcohol
2099
The preferable range of properties-correcting agent input amount is the 1.0-2.0 of oxalic dialdehyde with urea mole total amount
%
Purpose of the present invention also comprises: the production method that a kind of environment friendly urea-formaldehyde resin adhesive is provided.
The method feature of invention is achieved in that getting concentration is
40-45%Glyoxal water solution place in the reaction vessel, under agitation add the urea total amount
65-80%And concentration exists
8-20%Modifier aqueous solution, be warming up to
48-52 ℃After, by alkaline conditioner reaction vessel internal reaction liquid is transferred to
PHValue is
7.5 ~ 8.5, when being warming up to
80 ~ 90 ℃Afterreaction
40-45Minute; And then with remainder
20-35%Urea add wherein, continue reaction
40-50Minute, by acid regulator reaction vessel internal reaction liquid is transferred to again
PHFor
5.5 ~ 6.5, and in
70 ~ 80 ℃Internal reaction is added dropwise to the thick shape liquid of oyster white occurring or extract reaction solution one
40 ℃Stir when presenting cloud in the cup of water and be reaction end, again reaction solution is transferred to by alkaline conditioner
PHValue is
7.0 ~ 8.0, be cooled to
40 ℃To be finished product after the bottom discharge packing;
Oxalic dialdehyde with the mol ratio of urea is
1.0-1.2:1, properties-correcting agent is oxalic dialdehyde with urea mole total amount
1.0-2.5%;Described properties-correcting agent and aforementioned identical.
Described alkaline conditioner is: sodium hydroxide, potassium hydroxide, yellow soda ash, six formaldehyde tetramines or ammoniacal liquor.
The preferred composition of alkaline conditioner is: sodium hydroxide or six formaldehyde tetramines
Described acid regulator is:: hydrochloric acid, sulfuric acid, oxalic acid, formic acid, acetate, propionic acid, oxalic acid, phenylformic acid, Phenylsulfonic acid or ammonium chloride.
The preferred composition of acid regulator is: hydrochloric acid, oxalic acid or formic acid.
Advantage of the present invention and characteristics comprise:
It is big that product of the present invention has a bonding force, stable performance, and easy construction, comparing with the urea-formaldehyde resin adhesive that traditional formaldehyde and urea reaction generate is genuine environment-friendly type renewal product.Present method is genuine high-tech environmentfriendly products, and not only domestic innovation in the world wide yet and do not find relevant report.
Urea-formaldehyde resin adhesive of the present invention has good high strength, splendid water resistance is arranged, resistance to frost, strong adhesion, cohesive strength height, good weatherability and ageing resistance excellence, is nontoxic, harmless environmental type high-tech product innovation.Of many uses on wood working, be the upgraded product of ideal import substitution product and domestic furniture industry tackiness agent.The starting material that this product adopted are nontoxic, harmless, do not have the objectionable impurities formaldehyde that country prohibites employing, objectionable impuritiess such as benzene and derivative, amine, and nontoxic during production, pollution-free, the no three wastes are handled.Product starting material wide material sources, cost are low, and material cost is compared with similar products at home and abroad, and cost reduces more than 50 ~ 60%.So the economic benefit height, Application Areas is wide.Bondingly be penetrated into every field as a kind of technology, all need adhesive technology from aerospace, machine, traffic, building, chemical industry, decorations, wood working etc., and finish bonding material is exactly tackiness agent, therefore adhesives industries has become world's development mutually unexpectedly, and keeps one of industry of the fastest rate of growth.
This product is applicable to furniture, high level plywood, decorative sheet and other woodworks.This product also can be used for the bonding and compound of paper, leather, decorations etc.
This environment-friendly type high-tech patent environmental protection glue series product are not only outstanding environmental protection decoration materials, and have remarkable adhesiveproperties, and smell is minimum, and color is tempting, brushing is easy, the big whole intensity height of initial bonding strength, and weather resistance is good, the thickness appropriateness, brushing is easy, and glued membrane is tough and tensile, shelf-stable.Cementitious woodwork does not have tangible glue-line, the water tolerance excellence, and life-time service does not ftracture.Owing to adopted novel material, new preparation process, do not have any waste discharge, and the preparation method is simple, operating environment is good.
To be described in further detail the present invention by example below, but following example only is the present invention's example wherein, the rights protection scope of not representing the present invention and being limited, the scope of the present invention is as the criterion with claims.
Embodiment
Example 1
Oxalic dialdehyde 175 gram of getting 40% content places 1000 milliliters there-necked flask, under agitation adds urea 45 grams and 10% polyvinyl alcohol, 2088 solution, 15 grams, is warming up to 50 ℃ and stops heating, divides by methyl tetramine accent pH value to be for six times
7.5 ~ 8.5, reaction is 40 minutes when being warmed up to 80 ~ 90 ℃.Remaining then 25% urea, 15 grams add, and continue reaction 40 minutes, transfer PH to be with formic acid then
5.5 ~ 6.5And in
70 ~ 80Being added dropwise to stir in the cup of 40 ℃ of water and being terminal point when presenting cloud the thick shape liquid of oyster white appears or extracts reaction solution one in ℃ reaction.Transfer PH to be with NaOH again
7.0 ~ 8.0, be cooled to 40 ℃ to be finished product after the bottom discharge packing.
The correlated performance index of urea glyoxal resin tackiness agent:
The title index
The pale brown look inclusion-free of outward appearance liquid
PH value 7.0 ~ 8.0
Solid content/% 50 ~ 60
Viscosity/Pas 0.55 ~ 1.10
Cohesive strength/Mpa 2.0 ~ 3.0
Example 2:
Get 40% oxalic dialdehyde 200 gram and place 1000 milliliters there-necked flask, under agitation add and stop heating after urea 54 grams and 10% polyvinyl alcohol, 2099 solution, 35 grams are warmed up to 50 ℃, be with hexamethylenetetramine accent pH value
7.5 ~ 8.5Be warming up to then
80 ~ 90℃ time reaction 40 minutes, remaining 30% urea 23 grams continue to add, and reacts after 40 minutes usefulness
1:1Hydrochloric acid transfer PH to be
5.5 ~ 6.5, and in
70 ~ 80Being added dropwise to stir in the cup of 40 ℃ of water and being terminal point when presenting cloud the thick shape liquid of oyster white appears or extracts reaction solution one in ℃ reaction.Transfer PH to be with sodium hydroxide again
7.0 ~ 8.0, be cooled to 40 ℃ to be finished product after the bottom discharge packing.
This is identical for using method and correlation technique parameter and aforementioned phase, the Therefore, omited it.
Claims (7)
1. environment friendly urea-formaldehyde resin adhesive is characterized in that: it comprises that oxalic dialdehyde is 1.0-1.2:1 with the mol ratio of urea, and properties-correcting agent is the 1.0-2.5% of above-mentioned mole total amount; Described properties-correcting agent is polyvinyl alcohol 1788, polyvinyl alcohol 2088, polyvinyl alcohol 1799, polyvinyl alcohol 1999, polyvinyl alcohol 2099.
2. environment friendly urea-formaldehyde resin adhesive according to claim 1 is characterized in that: properties-correcting agent is the 1.0-2.0% of oxalic dialdehyde with urea mole total amount.
3. the production method of a kind of environment friendly urea-formaldehyde resin adhesive according to claim 1, its production method is:
The glyoxal water solution of getting concentration and be 40-45% places in the reaction vessel, under agitation add the 65-80% of urea total amount and concentration modifier aqueous solution at 8-20%, after being warming up to 48-52 ℃, by alkaline conditioner reaction vessel internal reaction liquid being transferred to pH value is 7.5 ~ 8.5, when being warming up to 80 ~ 90 ℃ of afterreaction 40-45 minutes; And then the urea of the 20-35% of remainder added wherein, continue reaction 40-50 minute, by acid regulator reaction vessel internal reaction liquid being transferred to PH again is 5.5 ~ 6.5, and be added dropwise to stir in the cup of 40 ℃ of water and be reaction end when presenting cloud to the thick shape liquid of oyster white occurring or extract reaction solution one in 70 ~ 80 ℃ of internal reactions, reaction solution being transferred to pH value again by alkaline conditioner is 7.0 ~ 8.0, is cooled to 40 ℃ to be finished product after the bottom discharge packing;
Described properties-correcting agent is: polyvinyl alcohol 1788, polyvinyl alcohol 2088, polyvinyl alcohol 1799, polyvinyl alcohol 1999 or polyvinyl alcohol 2099;
Oxalic dialdehyde is 1.0-1.2:1 with the mol ratio of urea, and properties-correcting agent is the 1.0-2.5% of oxalic dialdehyde with urea mole total amount.
4. the production method of environment friendly urea-formaldehyde resin adhesive according to claim 3, it is characterized in that: described alkaline conditioner is: sodium hydroxide, potassium hydroxide, yellow soda ash, six formaldehyde tetramines or ammoniacal liquor.
5. the production method of environment friendly urea-formaldehyde resin adhesive according to claim 4, it is characterized in that: described alkaline conditioner is: sodium hydroxide or six formaldehyde tetramines.
6. the production method of environment friendly urea-formaldehyde resin adhesive according to claim 3, it is characterized in that: described acid regulator is: hydrochloric acid, sulfuric acid, oxalic acid, formic acid, acetate, propionic acid, oxalic acid, phenylformic acid, Phenylsulfonic acid or ammonium chloride.
7. the production method of environment friendly urea-formaldehyde resin adhesive according to claim 6, it is characterized in that: described acid regulator is: hydrochloric acid, oxalic acid or formic acid.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011101577690A CN102229791A (en) | 2011-06-14 | 2011-06-14 | Environment-friendly type urea-formaldehyde resin adhesive and production method thereof |
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|---|---|---|---|
| CN2011101577690A CN102229791A (en) | 2011-06-14 | 2011-06-14 | Environment-friendly type urea-formaldehyde resin adhesive and production method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838956A (en) * | 2012-07-04 | 2012-12-26 | 湖北省宏源药业有限公司 | Environment-friendly urea resin adhesive and preparation method thereof |
| CN102989995A (en) * | 2012-05-25 | 2013-03-27 | 辉煌水暖集团有限公司 | Sand core material used for casting copper part and preparation method thereof |
| CN103305168A (en) * | 2013-07-02 | 2013-09-18 | 西南林业大学 | Resin adhesive free from formaldehyde release as well as preparation method and application thereof |
| CN103333651A (en) * | 2013-07-02 | 2013-10-02 | 西南林业大学 | Hyperbranched resin adhesive with low formaldehyde release rate as well as preparation method and application of hyperbranched resin adhesive |
| CN103509165A (en) * | 2012-12-21 | 2014-01-15 | 北京林业大学 | Preparation method of timber dipping reinforcing agent |
| CN103909210A (en) * | 2012-05-25 | 2014-07-09 | 辉煌水暖集团有限公司 | Preparation method for sand core material for casting copper part |
| CN104789174A (en) * | 2015-04-29 | 2015-07-22 | 王学谦 | Environment-friendly urea formaldehyde resin adhesive and production method thereof |
| CN105400468A (en) * | 2015-12-18 | 2016-03-16 | 太仓康盛化工有限公司 | Preparation method of high-bonding-strength low-formaldehyde-emission adhesive used for glued boards |
| CN105400467A (en) * | 2015-12-18 | 2016-03-16 | 太仓康盛化工有限公司 | High-bonding-strength low-formaldehyde-emission adhesive for glued boards |
| CN104710366B (en) * | 2013-12-17 | 2017-04-19 | 上海雅运纺织助剂有限公司 | Improved preparation method of dimethylol dihydroxy ethylene urea |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102989995A (en) * | 2012-05-25 | 2013-03-27 | 辉煌水暖集团有限公司 | Sand core material used for casting copper part and preparation method thereof |
| CN103909210B (en) * | 2012-05-25 | 2020-10-27 | 辉煌水暖集团有限公司 | Preparation method of sand core material for casting copper parts |
| CN103909210A (en) * | 2012-05-25 | 2014-07-09 | 辉煌水暖集团有限公司 | Preparation method for sand core material for casting copper part |
| CN102989995B (en) * | 2012-05-25 | 2014-10-08 | 辉煌水暖集团有限公司 | Sand core material used for casting copper part |
| CN102838956A (en) * | 2012-07-04 | 2012-12-26 | 湖北省宏源药业有限公司 | Environment-friendly urea resin adhesive and preparation method thereof |
| CN103509165B (en) * | 2012-12-21 | 2015-06-24 | 北京林业大学 | Preparation method of timber dipping reinforcing agent |
| CN103509165A (en) * | 2012-12-21 | 2014-01-15 | 北京林业大学 | Preparation method of timber dipping reinforcing agent |
| CN103333651A (en) * | 2013-07-02 | 2013-10-02 | 西南林业大学 | Hyperbranched resin adhesive with low formaldehyde release rate as well as preparation method and application of hyperbranched resin adhesive |
| CN103333651B (en) * | 2013-07-02 | 2014-11-05 | 西南林业大学 | Hyperbranched resin adhesive with low formaldehyde release rate as well as preparation method and application of hyperbranched resin adhesive |
| CN103305168A (en) * | 2013-07-02 | 2013-09-18 | 西南林业大学 | Resin adhesive free from formaldehyde release as well as preparation method and application thereof |
| CN104710366B (en) * | 2013-12-17 | 2017-04-19 | 上海雅运纺织助剂有限公司 | Improved preparation method of dimethylol dihydroxy ethylene urea |
| CN104789174A (en) * | 2015-04-29 | 2015-07-22 | 王学谦 | Environment-friendly urea formaldehyde resin adhesive and production method thereof |
| CN105400468A (en) * | 2015-12-18 | 2016-03-16 | 太仓康盛化工有限公司 | Preparation method of high-bonding-strength low-formaldehyde-emission adhesive used for glued boards |
| CN105400467A (en) * | 2015-12-18 | 2016-03-16 | 太仓康盛化工有限公司 | High-bonding-strength low-formaldehyde-emission adhesive for glued boards |
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Application publication date: 20111102 |