CN101191042B - Method for preparing urea-formaldehyde resin adhesive - Google Patents
Method for preparing urea-formaldehyde resin adhesive Download PDFInfo
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- CN101191042B CN101191042B CN200610104974XA CN200610104974A CN101191042B CN 101191042 B CN101191042 B CN 101191042B CN 200610104974X A CN200610104974X A CN 200610104974XA CN 200610104974 A CN200610104974 A CN 200610104974A CN 101191042 B CN101191042 B CN 101191042B
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Abstract
The invention discloses a preparation method for urea-formaldehyde resin adhesive. Ethyleneurea and melamine, or polyvinyl alcohol is taken as formaldehyde catching agent, and then added with carbamide, flour and lauxite to react to obtain the urea-formaldehyde resin adhesive. The invention with low formaldehyde content is low cost composite board adhesive that meets the requirements of environmental protection, ensures that all good performances of the urea-formaldehyde resin adhesive are kept and lowers the production cost, thus obtaining a pragmatic adhesive that can be afforded entirely by composite board processing enterprises.
Description
Technical field
The present invention relates to a kind of preparation method of environment friendly urea-formaldehyde resin adhesive, relate in particular to the method that compound formaldehyde-trapping agent is used to prepare urea-formaldehyde resin adhesive.
Background technology
China is the country of Shaolin, exists bigger contradiction between the timber supply and demand, and the important channel that solves this contradiction is production and the utilization that must greatly develop with the wood-based plate composite sheet that is the center.Produce 1 cubic metre of shaving board, the sheet material that can replace 3.1 cubic metres of logs to make with urea-formaldehyde resin adhesive; And produce 1 ton of fiberboard with urea-formaldehyde resin adhesive, can replace 5.6 cubic metres of former wood-based planets.Be that tackiness agent is significant to improving timber utilization rate; Simultaneously, timber industry also is huge to the consumption of tackiness agent, all will adopt a large amount of tackiness agent aspect the composite sheets such as wood-based plate, glued board, sandwich panel, cored slab, sewing machine table, wood plastic composite, wooden alloy sheets.For example: produce 10000 cubic metres of glued boards and need 1000 tons of tackiness agent.
This shows, in the production of composite sheet, to consume a large amount of tackiness agent, and use maximum in these are gluing is urea-formaldehyde resin adhesive, it has adhesiveproperties preferably, its sticking strong strength ratio animal and plant glue height, photostabilization is good and be applicable to the viscose glue production of composite sheets such as timber, glued board, veneer sheet and bamboo and wood products, the more important thing is that its price comparison is low and is widely used.And these composite sheet goods are widely used in places such as family that people hang up one's hat, live and office.But, exist a certain amount of free formaldehyde in these tackiness agent or the composite sheet goods, for example, free formaldehyde content in the urea-formaldehyde resin adhesive is up to 3-5%, because of it give off poisonous gas in process for processing and use---formaldehyde, severe contamination infringement people's is healthy, should be very restricted in the use.But, still also can't limit its use effectively at present, and develop into uncontrollable situation.Therefore, develop, application low formaldehyde content composite sheet sticks with glue agent or do not have the free formaldehyde composite sheet becomes the task of top priority, and seem very necessary.
China formulated GB18580-2001 " indoor decorating material wood-based plate and goods formaldehyde thereof discharge and limits the quantity of ", GB18583-2001 ten mandatory national standards such as " limits of harmful substances in the indoor decorating adhesive " December calendar year 2001, from compulsory execution on July 1 in 2002.New standard is very low to the free formaldehyde release restriction, and the wood-based plate that China produces at present still is difficult to the national standard requirement that reaches new, this mainly has been to use the cause of the high urea-formaldehyde resin adhesive of free formaldehyde content, also is present insoluble great technical barrier.And new standard does not reach the basic demand of protection HUMAN HEALTH yet to free formaldehyde release restriction, exist continue to reduce may or requirement.
Summary of the invention
The purpose of this invention is to provide a kind of burst size of methanal that reduces sheet material, improve the preparation method of urea-formaldehyde resin adhesive of the water resistance of sheet material.
Above-mentioned urea-formaldehyde resin adhesive is made by following steps:
One, in the container of 500ml, add content and be 1.90 parts in 36% formaldehyde, stir and add sodium hydroxide solution 0.01-0.1 part of 30% down, be warmed up to 40 ℃～60 ℃ then, add 0.56 part in urea, urea and formaldehyde mole ratio are 1: 2.45, be warmed up to 80 ℃～90 ℃ stirring reactions 60 minutes again, when being 6.5～7.5, the pH value of solution adds 0.19 part in urea again, urea and formaldehyde mole ratio are 1: 1.84, the temperature of solution is remained on 80 ℃～85 ℃ reactions 30 minutes, react the chlorination of adding 20% after 30 minutes and press solution 0.01-0.1 part, continuation remains on 80 ℃～85 ℃ reactions 60 minutes with the temperature of solution, when the pH value of solution is 5～6, adds sodium hydroxide solution 0.01-0.1 part of 30%, the temperature of solution is remained on 80 ℃～85 ℃ reactions 30 minutes, and the pH value that makes solution is 7 to make virgin rubber;
Two, in the virgin rubber that step 1 makes, under agitation add 0.17 part～0.23 part urea, urea and formaldehyde mole ratio are 1: 1.5～1.40, solution is warmed up to 90 ℃～96 ℃, kept this thermotonus 30 minutes, react after 30 minutes, solution is cooled to 80 ℃～85 ℃, kept this thermotonus 30 minutes, react after 30 minutes and to add 0.40 part～0.60 part in 0.12 part～0.18 part of formaldehyde-trapping agent and water, solution temperature is remained on 80 ℃～85 ℃ reactions 30 minutes;
Three, add 2.50 parts of urea-formaldehyde resin adhesives in the jelly that step 2 is made, 0.25 part～0.30 part in flour, and add ammonium chloride solution 0.01-0.1 part of 20%, stirring reaction is 30 minutes under the room temperature, makes urea-formaldehyde resin adhesive.
Above-mentioned formaldehyde-trapping agent is ethylene group urea, trimeric cyanamide or polyvinyl alcohol.
The present invention has developed low content of free formaldehyde content, and the low-cost composite sheet tackiness agent of compliance with environmental protection requirements, and make it keep every premium properties of urea-formaldehyde resin adhesive, and reduce its production cost, make the practical tackiness agent that each composite sheet processing enterprise can bear fully.
The formation of urea-formaldehyde resin mainly is made up of two parts, i.e. polyaddition reaction and condensation polymerization reaction.Urea and formaldehyde carry out following reaction in weak alkaline medium:
H
2NCONH
2+CH
2O→H
2NCONHCH
2OH
H
2NCONHCH
2OH+CH
2O→HOH
2CNHCONHCH
2OH
Under slightly acidic condition, form various polycondensation intermediates earlier, after the initial stage intermediate formed, the heating and the polycondensation of dewatering in acidic medium formed the initial stage resin, and the polycondensation of further dewatering then forms the high synthetic resins of degree of crosslinking.
In initial reaction stage, formaldehyde is excessive to help generating the second light industry bureau methyl urea, the relational degree that increases resin there is bigger effect, but formaldehyde is excessive when too many, easily forms the ehter bond of less stable again, and ehter bond is when hot pressing, emit formaldehyde and change into the methyne key, and ehter bond is many more, and wetting ability is big more, causes water tolerance poorer.The method of the reduction burst size of methanal that therefore, proves effective most is: the free formaldehyde monomer of remained unreacted when reducing synthetic resins; Add the formaldehyde of formaldehyde-trapping agent in order in hot pressing or sheet material use, to discharge in conjunction with unsettled ehter bond.
Dimethylolurea is to form the crosslinked main body of synthetic resins, and therefore, for guaranteeing have enough dihydroxymethyls ureogenesis, tackiness agent should be between 1: 1.5～2.0 with the amount of substance ratio of urea in the glue and formaldehyde.Its amount of substance is when high, because it is many to generate dimethylolurea, degree of crosslinking is high high behind the curable synthetic resin, the consolidation strength height, and the resin stability in storage is good, but the free formaldehyde content height.Its amount of substance is when low, and dimethylolurea content is few, and monomethylolurea and the free urea of participating in reaction are many, causes degree of crosslinking to descend, and therefore influences the gluing quality and the stability in storage of tackiness agent.Like this, many producers in order to guarantee consolidation strength and stability in storage, often add excessive formaldehyde, make the free formaldehyde content severe overweight.Therefore it is most important to seek a kind of technology that can effectively reduce formaldehyde/urea drawback that mol ratio is brought.The present invention adopts low formaldehyde/urea mol ratio technology, from resin synthetic mechanism, has found out the top condition of this technology by experiment, and has selected the properties-correcting agent of suitable formaldehyde-trapping agent class, prepares the urea-formaldehyde resin adhesive of low content of free formaldehyde content.
The mol ratio of urea and formaldehyde is different to be had a significant impact condensation reaction speed, product structure and performance, free formaldehyde content, urea add the mol ratio that has changed each step of reaction in batches, also it is had very big influence.In the addition reaction stage originally, high molar ratio helps the formation of the second light industry bureau methyl urea, controls the carrying out that suitable mol ratio helps polycondensation afterwards, and the reaction later stage, low mol ratio helped reducing free formaldehyde content, and kept other performances.Formaldehyde-trapping agent is can produce chemical reaction with formaldehyde under certain condition to generate another kind of stable novel substance or absorb formaldehyde.Facts have proved that free formaldehyde content all has positive effect with reduction goods burst size of methanal in the resin liquid to reducing to use formaldehyde-trapping agent.Use different formaldehyde-trapping agents very big to the performance impact of urea-formaldehyde resin adhesive.
Contain poly-hydroxy in the flour, they can form acetal with free formaldehyde, thereby prevent that free formaldehyde from discharging into air, reduce and pollute.Simultaneously, C in the glucose unit in hydroxyl in the urea-formaldehyde resin and flour or the flour molecular structure
6On aldehyde radical, in the hot-press solidifying stage of board materials production, reaction generates hemiacetal and acetal, forms crosslinked three dimensional structure, so can increase the bond strength and the water tolerance of glue.In addition, it can also act in the filler adding glue, and its filling effect can reduce the volumetric shrinkage of glue-line, shrinks the pressure that produces thereby reduce with volume.And can improve the solid content of product, and remove the vacuum hydro-extraction operation in the former technology, make raw material consumption and process cost reduce simultaneously.
Polyvinyl alcohol can obtain polyvinyl formal with formaldehyde reaction under acidic conditions, the polyvinyl alcohol in the reaction system, and one side becomes the trapping agent of formaldehyde, can reduce free formaldehyde content; On the other hand, itself all has glueability polyvinyl alcohol and polyvinyl formal, makes urea-formaldehyde resin adhesive have good tack.Having the trimeric cyanamide of ring texture and formaldehyde reaction becomes the formaldehyde Pu and catches agent, can reduce its free formaldehyde content; The content of free methylol in the condensation product can be reduced simultaneously, thereby the water resistance and the package stability of urea-formaldehyde resin adhesive can be improved.The ethylene group urea contains 2 amidos and formaldehyde reaction generates polymkeric substance, except that reducing free formaldehyde content, urea-formaldehyde resin adhesive is had good modifying function.
In the process that reduces the urea-formaldehyde resin adhesive free formaldehyde, can use micromolecular compound, it has impregnability preferably, and the internal-response that can enter product falls the formaldehyde of content.Also available more macromolecular compound or low-molecular-weight resin, it can also be as the properties-correcting agent of its tackiness agent except that having the effect that reduces free formaldehyde.They all should have better water solubility, and well compatible, can reach more satisfactory effect, help applying glue and curing simultaneously.
Embodiment
Embodiment 1
One, in the container of 500ml, add content and be 36% formaldehyde 190g, stir the sodium hydroxide solution 1g of adding 30% down, be warmed up to 40 ℃ then, add urea 56g, urea and formaldehyde mole ratio are 1: 2.45, be warmed up to 80 ℃ of stirring reactions 60 minutes again, when being 6.5, the pH value of solution adds urea 19g again, urea and formaldehyde mole ratio are 1: 1.84, the temperature of solution is remained on 80 ℃ of reactions 30 minutes, react the ammonium chloride solution 1g of adding 20% after 30 minutes, continuation remains on 80 ℃ of reactions 60 minutes with the temperature of solution, when the pH value of solution is 5, adds 30% sodium hydroxide solution knob, the temperature of solution is remained on 80 ℃ of reactions 30 minutes, and the pH value that makes solution is 7 to make virgin rubber;
Two, in the virgin rubber that step 1 makes, under agitation add 17g urea, urea and formaldehyde mole ratio are 1: 1.5-1.40, solution is warmed up to 90 ℃, kept this thermotonus 30 minutes, react after 30 minutes, solution is cooled to 80 ℃, kept this thermotonus 30 minutes, react adding ethylene group urea 129g and water 40g after 30 minutes, solution temperature is remained on 80 ℃ of reactions 30 minutes;
Three, add urea-formaldehyde resin adhesive 250g in the jelly that step 2 is made, flour 25g, and add 20% chlorination by solution 1g, stirring reaction is 30 minutes under the room temperature, makes urea-formaldehyde resin adhesive.
Embodiment 2
One, in the container of 500ml, add content and be 36% formaldehyde 190g, stir the sodium hydroxide solution 1g of adding 30% down, be warmed up to 60 ℃ then, add urea 56g, urea and formaldehyde mole ratio are 1: 2.45, be warmed up to 90 ℃ of stirring reactions 60 minutes again, when being 7.5, the pH value of solution adds urea 19g again, urea and formaldehyde mole ratio are 1: 1.84, the temperature of solution is remained on 85 ℃ of reactions 30 minutes, react the ammonium chloride solution 1g of adding 20% after 30 minutes, continuation remains on 85 ℃ of reactions 60 minutes with the temperature of solution, when the pH value of solution is 6, adds 30% sodium hydroxide solution 1g, the temperature of solution is remained on 85 ℃ of reactions 30 minutes, and the pH value that makes solution is 7 to make virgin rubber;
Two, in the virgin rubber that step 1 makes, under agitation add 23g urea, urea and formaldehyde mole ratio are 1: 1.5～1.40, solution is warmed up to 96 ℃, kept this thermotonus 30 minutes, react after 30 minutes, solution is cooled to 85 ℃, kept this thermotonus 30 minutes, react adding trimeric cyanamide 18g and water 60g after 30 minutes, solution temperature is remained on 85 ℃ of reactions 30 minutes;
Three, add urea-formaldehyde resin adhesive 250g in the jelly that step 2 is made, flour 30g, and add 20% ammonium chloride solution 1g, stirring reaction is 30 minutes under the room temperature, makes urea-formaldehyde resin adhesive.
Embodiment 3
One, in the container of 500ml, add content and be 36% formaldehyde 190g, stir the sodium hydroxide solution 1g of adding 30% down, be warmed up to 40 ℃ then, add urea 56g, urea and formaldehyde mole ratio are 1: 2.45, be warmed up to 80 ℃ of stirring reactions 60 minutes again, when being 6.5, the pH value of solution adds urea 19g again, urea and formaldehyde mole ratio are 1: 1.84, the temperature of solution is remained on 80 ℃ of reactions 30 minutes, react the ammonium chloride solution 1g of adding 20% after 30 minutes, continuation remains on 80 ℃ of reactions 60 minutes with the temperature of solution, when the pH value of solution is 5, adds 30% sodium hydroxide solution 1g, the temperature of solution is remained on 80 ℃ of reactions 30 minutes, and the pH value that makes solution is 7 to make virgin rubber;
Two, in the virgin rubber that step 1 makes, under agitation add 23g urea, urea and formaldehyde mole ratio are 1: 1.5～1.40, solution is warmed up to 90 ℃, kept this thermotonus 30 minutes, solution is cooled to 80 ℃, kept this thermotonus 30 minutes, and added polyvinyl alcohol 18g and water 60g, solution temperature is remained on 80 ℃ of reactions 30 minutes;
Three, add urea-formaldehyde resin adhesive 250g in the jelly that step 2 is made, flour 30g, and add 20% ammonium chloride solution 1g, stirring reaction is 30 minutes under the room temperature, makes urea-formaldehyde resin adhesive.
The urea-formaldehyde resin adhesive analytical results:
Claims (1)
1. the preparation method of a urea-formaldehyde resin adhesive, it is characterized in that: it is to be made by following steps,
One, in the container of 500ml, add content and be 1.90 parts in 36% formaldehyde, stir and add sodium hydroxide solution 0.01-0.1 part of 30% down, be warmed up to 40 ℃～60 ℃ then, add 0.56 part in urea, urea and formaldehyde mole ratio are 1: 2.45, be warmed up to 80 ℃～90 ℃ stirring reactions 60 minutes again, when being 6.5～7.5, the pH value of solution adds 0.19 part in urea again, urea and formaldehyde mole ratio are 1: 1.84, the temperature of solution is remained on 80 ℃～85 ℃ reactions 30 minutes, react the chlorination of adding 20% after 30 minutes and press solution 0.01-0.1 part, continuation remains on 80 ℃～85 ℃ reactions 60 minutes with the temperature of solution, when the pH value of solution is 5～6, adds sodium hydroxide solution 0.01-0.1 part of 30%, the temperature of solution is remained on 80 ℃～85 ℃ reactions 30 minutes, and the pH value that makes solution is 7 to make virgin rubber;
Two, in the virgin rubber that step 1 makes, under agitation add 0.17 part～0.23 part urea, urea and formaldehyde mole ratio are 1: 1.5～1.40, solution is warmed up to 90 ℃～96 ℃, kept this thermotonus 30 minutes, react after 30 minutes, solution is cooled to 80 ℃～85 ℃, kept this thermotonus 30 minutes, react after 30 minutes and to add 0.40 part～0.60 part in 0.12 part～0.18 part of formaldehyde-trapping agent and water, solution temperature is remained on 80 ℃～85 ℃ reactions 30 minutes;
Three, add 2.50 parts of urea-formaldehyde resin adhesives in the jelly that step 2 is made, 0.25 part～0.30 part in flour, and add ammonium chloride solution 0.01-0.1 part of 20%, stirring reaction is 30 minutes under the room temperature, makes urea-formaldehyde resin adhesive.
Described formaldehyde-trapping agent is ethylene group urea, trimeric cyanamide or polyvinyl alcohol.
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| CN200610104974XA CN101191042B (en) | 2006-11-20 | 2006-11-20 | Method for preparing urea-formaldehyde resin adhesive |
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| CN101191042B true CN101191042B (en) | 2011-03-23 |
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| CN102555009B (en) * | 2012-02-20 | 2014-02-12 | 张国华 | High-strength environment-friendly shaving board |
| CN102528861A (en) * | 2012-03-05 | 2012-07-04 | 辽宁久久木业有限责任公司 | Production method and manufacturing process for environmentally-friendly decorative board |
| CN104031221B (en) * | 2012-07-27 | 2016-04-20 | 大亚木业(江西)有限公司 | A kind of manufacture method of cyanurotriamide modified urea resin glue |
| CN102898987A (en) * | 2012-09-25 | 2013-01-30 | 苏州汾湖电梯有限公司 | Esterified-starch modified urea formaldehyde adhesive |
| CN104559848A (en) * | 2013-10-11 | 2015-04-29 | 闫军杰 | Production method of pasty modified urea-formaldehyde resin adhesive |
| CN104559863A (en) * | 2013-10-22 | 2015-04-29 | 寿光市东宇鸿翔木业有限公司 | Urea-formaldehyde glue and preparation method thereof |
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| CN106589275B (en) * | 2016-12-30 | 2018-10-30 | 广西玉林利而安化工有限公司 | A kind of phenol-formaldehyde resin modified and preparation method thereof for producing outdoor Recombined bamboo |
| CN107805479A (en) * | 2017-11-29 | 2018-03-16 | 柳州市鸿联木业有限公司 | Timber processing adhesive and preparation method thereof |
| CN113480965A (en) * | 2021-07-22 | 2021-10-08 | 长泰化学工业(惠州)有限公司 | High-toughness polyurethane amine-aldehyde resin glue |
| CN114456340A (en) * | 2021-10-28 | 2022-05-10 | 广州市长安粘胶制造有限公司 | Environment-friendly modified urea-formaldehyde resin and preparation method and application thereof |
| CN114855504A (en) * | 2022-05-16 | 2022-08-05 | 广东轻工职业技术学院 | Glue applying combination for fluorine-free food paper and preparation method and application thereof |
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| CN1621477A (en) * | 2004-10-18 | 2005-06-01 | 俞锋 | Urea-formaldehyde glue with low content of free aldehyde and its preparing method |
| CN1834186A (en) * | 2006-03-15 | 2006-09-20 | 北京林业大学 | Cyanurotriamide modified urea resin and prepn. process |
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| EP0990687A2 (en) * | 1998-10-01 | 2000-04-05 | Südzucker Aktiengesellschaft Mannheim/Ochsenfurt | Adhesive and adhesive preproduct |
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