CN101191043A - Method for preparing urea-formaldehyde resin adhesive - Google Patents
Method for preparing urea-formaldehyde resin adhesive Download PDFInfo
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- CN101191043A CN101191043A CNA2006101049769A CN200610104976A CN101191043A CN 101191043 A CN101191043 A CN 101191043A CN A2006101049769 A CNA2006101049769 A CN A2006101049769A CN 200610104976 A CN200610104976 A CN 200610104976A CN 101191043 A CN101191043 A CN 101191043A
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Abstract
The invention discloses a preparation method for urea-formaldehyde resin adhesive, which is an adhesive produced by adopting ethylene urea, melamine or polyvinyl alcohol as formaldehyde catching agent and added with urea, potato starch residue and urea-formaldehyde resin to react. The invention has low formaldehyde content, can meet the requirement of low cost for composite sheet adhesive and has all excellent performances of urea-formaldehyde resin adhesive and the production cost is reduced; therefore, a practical adhesive that can be afforded entirely by each composite plate processing enterprises is obtained.
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 and add ammonium chloride solution 0.01-0.1 part of 20% after 30 minutes, continuation remains on 80 ℃～85 ℃ reactions 60 minutes with the degree of solution temperature, when the pH value of solution is 5～6, adds sodium hydroxide solution 0.01-0.1 part of 30%, the degree of solution temperature 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 of potato starchy residue, 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 dimethylolurea, to increasing cross-linkage of resin bigger effect is arranged, 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, participate in reaction-methylolurea and free urea are many, cause degree of crosslinking to descend, and therefore influence 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, touches the top condition that element has gone out 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 dimethylolurea, 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 potato starchy residue, 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 potato starchy residue or the potato starchy residue 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.Trimeric cyanamide and formaldehyde reaction with ring texture become formaldehyde-trapping 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 degree of solution temperature, when the pH value of solution is 5, adds 30% sodium hydroxide solution 1g, the degree of solution temperature 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 12g 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, potato starchy residue 25g, and add 20% ammonium chloride 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 degree of solution temperature, when the pH value of solution is 6, adds 30% sodium hydroxide solution 1g, the degree of solution temperature 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, potato starchy residue 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 degree of solution temperature, when the pH value of solution is 5, adds 30% sodium hydroxide solution 1g, the degree of solution temperature 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, react after 30 minutes, solution is cooled to 80 ℃, kept this thermotonus 30 minutes, react adding polyvinyl alcohol 18g and water 60g 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, potato starchy residue 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 (4)
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 and add ammonium chloride solution 0.01-0.1 part of 20% after 30 minutes, continuation remains on 80 ℃～85 ℃ reactions 60 minutes with the degree of solution temperature, when the pH value of solution is 5～6, adds sodium hydroxide solution 0.01-0.1 part of 30%, the degree of solution temperature 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 of potato starchy residue, 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.
2. the preparation method of a kind of urea-formaldehyde resin adhesive according to claim 1, it is characterized in that: above-mentioned formaldehyde-trapping agent is the ethylene group urea.
3. the preparation method of a kind of urea-formaldehyde resin adhesive according to claim 1, it is characterized in that: above-mentioned formaldehyde-trapping agent is a trimeric cyanamide.
4. the preparation method of a kind of urea-formaldehyde resin adhesive according to claim 1, it is characterized in that: above-mentioned formaldehyde-trapping agent is a polyvinyl alcohol.
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Cited By (14)
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| CN102250572A (en) * | 2011-06-17 | 2011-11-23 | 江苏赛奥生化有限公司 | Preparation method of oxidized pueraria starch adhesive |
| CN102277114A (en) * | 2011-06-17 | 2011-12-14 | 江苏赛奥生化有限公司 | Preparation method of bacterial protein urea formaldehyde adhesive |
| CN101955745B (en) * | 2009-12-25 | 2011-12-21 | 湖北康欣木制品有限公司 | Quaternary resin adhesive for manufacturing plywood board for bottom board of container |
| CN102311531A (en) * | 2010-07-09 | 2012-01-11 | 湖北银昌科技有限公司 | Foundry resin with low formaldehyde residue and preparation thereof |
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| CN101760149B (en) * | 2009-12-29 | 2014-07-23 | 莫元烈 | Environmental-friendly amylopectin composite adhesive for paper products and production method thereof |
| CN104474660A (en) * | 2014-11-25 | 2015-04-01 | 成都顺发消洗科技有限公司 | Formaldehyde scavenging agent for urea-formaldehyde glue artificial board |
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| AT412784B (en) * | 1998-10-01 | 2005-07-25 | Tulln Zuckerforschung Gmbh | ADHESIVE BZW. KLEBSTOFFVORPRODUKT |
| CN1621477A (en) * | 2004-10-18 | 2005-06-01 | 俞锋 | Urea-formaldehyde glue with low content of free aldehyde and its preparing method |
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| CN101760149B (en) * | 2009-12-29 | 2014-07-23 | 莫元烈 | Environmental-friendly amylopectin composite adhesive for paper products and production method thereof |
| CN102311531A (en) * | 2010-07-09 | 2012-01-11 | 湖北银昌科技有限公司 | Foundry resin with low formaldehyde residue and preparation thereof |
| CN102311531B (en) * | 2010-07-09 | 2012-11-28 | 湖北银昌科技有限公司 | Foundry resin with low formaldehyde residue and preparation thereof |
| CN102277114A (en) * | 2011-06-17 | 2011-12-14 | 江苏赛奥生化有限公司 | Preparation method of bacterial protein urea formaldehyde adhesive |
| CN102277114B (en) * | 2011-06-17 | 2013-03-13 | 江苏赛奥生化有限公司 | Preparation method of bacterial protein urea formaldehyde adhesive |
| CN102250572A (en) * | 2011-06-17 | 2011-11-23 | 江苏赛奥生化有限公司 | Preparation method of oxidized pueraria starch adhesive |
| CN102516711A (en) * | 2011-12-09 | 2012-06-27 | 江苏省农业科学院 | Halogen seepage-free adhesive and its preparation method and use |
| CN102848447A (en) * | 2012-09-25 | 2013-01-02 | 普洱市卫国林业局 | Manufacture method of intermediate-density fiber plate |
| CN102848447B (en) * | 2012-09-25 | 2015-09-30 | 普洱市卫国林业局 | The preparation method of medium density fibre board (MDF) |
| CN103304339A (en) * | 2013-06-29 | 2013-09-18 | 贵州省五谷惠生态农业科技有限公司 | Special fruit tree long-acting compound fertilizer production method of tree long-acting compound fertilizer special for fruit trees |
| CN103304339B (en) * | 2013-06-29 | 2015-01-07 | 贵州省五谷惠生态农业科技有限公司 | Special fruit tree long-acting compound fertilizer production method of tree long-acting compound fertilizer special for fruit trees |
| CN103725233B (en) * | 2013-11-26 | 2015-03-11 | 张新艳 | Preparation method of lignin-based urea-formaldehyde resin adhesive with low formaldehyde release |
| CN103725233A (en) * | 2013-11-26 | 2014-04-16 | 沃太能源南通有限公司 | Preparation method of lignin-based urea-formaldehyde resin adhesive with low formaldehyde release |
| CN104474660A (en) * | 2014-11-25 | 2015-04-01 | 成都顺发消洗科技有限公司 | Formaldehyde scavenging agent for urea-formaldehyde glue artificial board |
| CN104987479A (en) * | 2015-05-27 | 2015-10-21 | 合肥卓元科技服务有限公司 | Technological design of urea-formaldehyde resin adhesive for wood industry |
| CN106349642A (en) * | 2016-08-29 | 2017-01-25 | 南宁市林润木业有限公司 | Flame-retardant composite urea resin and production method thereof |
| CN109400964A (en) * | 2018-10-17 | 2019-03-01 | 广西京西化工科技有限公司 | A kind of wood-based plate efficient activator and preparation method thereof |
| CN109589779A (en) * | 2018-12-19 | 2019-04-09 | 山东农业大学 | A kind of multifunctional bio base formaldehyde catching agent and preparation method thereof |
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