CN102898604B - Preparation method of modified urea-formaldehyde resin with improved storage stability - Google Patents
Preparation method of modified urea-formaldehyde resin with improved storage stability Download PDFInfo
- Publication number
- CN102898604B CN102898604B CN201110216900.6A CN201110216900A CN102898604B CN 102898604 B CN102898604 B CN 102898604B CN 201110216900 A CN201110216900 A CN 201110216900A CN 102898604 B CN102898604 B CN 102898604B
- Authority
- CN
- China
- Prior art keywords
- urea
- formaldehyde
- batch
- properties
- correcting agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
Abstract
A preparation method of a modified urea-formaldehyde resin with improved storage stability. The method comprises the following steps: (1) subjecting a first batch of urea, a modifier and formaldehyde to a first contact reaction until water miscibility reaches 0.4-1.5 times, wherein a molar ratio of the first batch of urea to a total weight of formaldehyde and modifier is 1-1.7:1; (2) subjecting the obtained mixture and a second batch of urea to a second contact reaction at a temperature of 60+/-15 DEG C for 1-30min, wherein a molar ratio of formaldehyde urea to a total weight of the first batch of urea, the second batch of urea and modifier is 0.6-1.25:1; and (3) adjusting the pH value of the mixture obtained in the step (2) to 8.5-10 and cooling to lower than 40 DEG C. The modified urea-formaldehyde resin with improved storage stability prepared by the method provided by the invention has good storage stability and reduced free formaldehyde content, so that a veneer board prepared from the modified urea-formaldehyde resin with improved storage stability has decreased formaldehyde release quantity and free formaldehyde content; and the formaldehyde release quantity further satisfies the regulations in national standard E1 (<=1.5 mg / L).
Description
Technical field
The invention relates to the preparation method of the improved modified urea-formaldehyde resin of a kind of package stability.
Background technology
Urea-formaldehyde resin especially cyanurotriamide modified urea resin (MUF) is widely used in woodenware production, for bonding timber or as adhesive application in the material produce based on timber, for example, for the production of shaving board, glued board and various fiberboards.Urea-formaldehyde resin is the reaction product of urea and formaldehyde.Because water tolerance and the intensity of this urea-formaldehyde resin are poor, therefore the general urea-formaldehyde resin properties-correcting agent that uses carries out modification to the urea-formaldehyde resin of gained, to obtain for example conventional cyanurotriamide modified urea resin (MUF) of urea-formaldehyde resin after modification, the water tolerance of this urea-formaldehyde resin and intensity are all apparently higher than the conventional urea-formaldehyde resin of non-modified.Described urea-formaldehyde resin properties-correcting agent is generally trimeric cyanamide, phenol or Resorcinol, acrylic ester copolymer solution, isocyanic ester, polyvinyl alcohol, xylogen etc.
For example, CN1527853A discloses a kind of preparation method of melamine urea-formaldehyde resin, and the method comprises the following steps: 1) provide formaldehyde first aqueous solution; 2) heat this solution; 3) in one step, add the urea in the first formaldehyde in aqueous solution amount approximately 0.35～0.65 molar equivalent, form formaldehyde-urea (UF) mixture; 4) in said mixture, add acid as formic acid, pH value is adjusted to approximately 4～7, form the UF mixture of acidifying; 5) monitor the viscosity of this acidifying UF mixture, until reach approximately 150～1000 centipoises; 6) the pH value of this acidifying UF mixture is adjusted to approximately 8～10, forms alkaline UF mixture; 7) in this alkalescence UF mixture, add second aqueous solution containing in the first formaldehyde in aqueous solution amount approximately 0.24～1.27 molar equivalent formaldehyde; 8) the pH value of this alkalescence UF mixture is adjusted to approximately 8～10; 9) trimeric cyanamide in the first formaldehyde in aqueous solution amount approximately 0.15～0.55 molar equivalent is added to above-mentioned alkaline UF mixture in one step, form MUF mixture; 10) monitor the viscosity of this MUF mixture, until reach approximately 150～1000 centipoises; With 11) the pH value of this MUF mixture is adjusted to approximately 9～10, be formed in the melamine urea-formaldehyde resin that is less than approximately 1500 centipoises at least about viscosity in 14 days.
Aforesaid method improves the bond strength of cyanurotriamide modified urea resin product by the formaldehyde by high level and accelerates the preparation speed of melamine urea-formaldehyde resin product, improves water tolerance and the further intensity that improves melamine urea-formaldehyde resin product of melamine urea-formaldehyde resin product by the trimeric cyanamide by high level simultaneously.Gained melamine urea-formaldehyde resin product is made dry shearing resistance after tackiness agent all higher than 2000 pounds/square inch.
Yet the free formaldehyde content of the melamine urea-formaldehyde resin that use aforesaid method makes is higher, all higher than 0.5%.The melamine urea-formaldehyde resin that uses this higher free formaldehyde content is during as wood adhesive main ingredient, the higher burst size of methanal that can cause undoubtedly timber, for example, use above-mentioned free formaldehyde content be the burst size of methanal of three layers of glued board of 0.51% melamine urea-formaldehyde resin compacting up to 9.8 mg/litre, far exceed minimum E2 (≤5.0 mg/litre) regulation of environmental requirement in GB.
CN101134835A also discloses a kind of preparation method of modified urea-formaldehyde resin, the method is by described urea-formaldehyde resin properties-correcting agent is added at least at twice the free formaldehyde content of urea-formaldehyde resin obtained by this method is reduced greatly, thereby is applied to can greatly reduce in timber manufacturing processed the burst size of methanal of wood-based panel product.Although adopt aforesaid method can greatly reduce the free formaldehyde content of the urea-formaldehyde resin making, yet the burst size of methanal of the urea-formaldehyde resin that aforesaid method makes is still higher, generally need on-the-spotly to re-use after mixing with urea, and the package stability of the urea-formaldehyde resin that makes of aforesaid method has much room for improvement.
Summary of the invention
The object of the invention is, in order to overcome the above-mentioned shortcoming of prior art, provides the preparation method of the improved modified urea-formaldehyde resin of a kind of package stability.
The invention provides the preparation method of the improved modified urea-formaldehyde resin of a kind of package stability, the method comprises: (1) carries out the first contact reacts by first urea, properties-correcting agent and formaldehyde, to water Combination be 0.4～1.5 times, formaldehyde: the mol ratio of the total amount of first urea and properties-correcting agent is 1～1.7: 1; (2) by gained mixture and second batch urea, in temperature, be at 60 ± 15 ℃, to carry out second contact reacts 1～30min, formaldehyde: the mol ratio of the total amount of first urea, second batch urea and properties-correcting agent is 0.6～1.25: 1; (3) the pH value of step (2) gained mixture is adjusted to 8.5～10 and be cooled to below 40 ℃.
The package stability of the improved modified urea-formaldehyde resin of package stability that preparation method provided by the invention makes is very good, can be at room temperature in 10～20 ℃ of airtight storages of lucifuge 90 days, and free formaldehyde content reduces greatly compared with the free formaldehyde content of the modified urea-formaldehyde resin of CN101134835A, thereby make to use the burst size of methanal of glued board prepared by this modified urea-formaldehyde resin to reduce, further meet E1 (≤1.5 mg/litre) regulation in GB.
Embodiment
According to the preparation method of the improved modified urea-formaldehyde resin of a kind of package stability provided by the invention, the method comprises:
(1) first urea, properties-correcting agent and formaldehyde are carried out to the first contact reacts, to water Combination be 0.4～1.5 times, formaldehyde: the mol ratio of the total amount of first urea and properties-correcting agent is 1～1.7: 1;
(2) by gained mixture and second batch urea, in temperature, be at 60 ± 10 ℃, to carry out second contact reacts 1～30min, formaldehyde: the mol ratio of the total amount of first urea, second batch urea and properties-correcting agent is 0.6～1.25: 1;
(3) the pH value of step (2) gained mixture is adjusted to 8.5～10 and be cooled to below 40 ℃.
According to the present invention, described first urea: the weight ratio of second batch urea is 0.5～10: 1, is preferably 0.5～5: 1, more preferably 0.56: 1.First urea, properties-correcting agent and formaldehyde carry out the first contact reacts gained mixture and second batch urea carry out the second catalytic condition temperature can be for 60 ± 15 ℃ at, be preferably 65 ± 5 ℃; Can be 1～30min duration of contact, is preferably 5～20min.
According to the present invention, first urea, properties-correcting agent and formaldehyde are carried out to the first contact reacts, and the mode that to react to water Combination be 0.4～1.5 times can comprise the following step of carrying out successively:
(1-1) by first properties-correcting agent, in temperature, be at 90 ± 5 ℃, to carry out first minute contact reacts 15～20min with first urea and first formalin, the pH value of wherein said first formalin is 7.5～9.0, temperature is 50 ± 5 ℃, in first properties-correcting agent and first formalin, the mol ratio of formaldehyde is 0.001～0.1: 1, and the formaldehyde in first formalin and the mol ratio of first urea are 2.5～1.8: 1;
(1-2) step (1-1) gained mixture being carried out to second minute contact reacts to water Combination under temperature is 80 ± 5 ℃, the condition of pH value to 4.4～7.0 is 0.8～9 times;
(1-3) the pH value of step (1-2) gained mixture is adjusted to after 8.0～9.5 and second batch formalin, second batch properties-correcting agent at 90 ± 5 ℃, to carry out the 3rd minute contact reacts to water Combination be 0.8～6 times, the total amount of the formaldehyde in the formaldehyde in first formalin and second batch formalin: the mol ratio of the total amount of first urea, first properties-correcting agent and second batch properties-correcting agent is 1.9～1.1: 1;
(1-4) step (1-3) gained mixture and the 3rd batch of properties-correcting agent being carried out to the 4th minute contact reacts to water Combination at 90 ± 5 ℃ is 0.4～1.5 times, the total amount of the formaldehyde in the formaldehyde in first formalin and second batch formalin: the mol ratio of the total amount of first urea, first properties-correcting agent, second batch properties-correcting agent and the 3rd batch of properties-correcting agent is 1.7～1.0: 1.
According to the present invention, described formaldehyde add total amount, by mol, can be: formaldehyde add integral molar quantity: urea integral molar quantity=0.1～2: 1, be preferably 0.8～2: 1, more preferably 0.89: 1.
According to the present invention, for regulating the alkaline pH conditioning agent of pH value, can be one or more of sodium hydroxide, trolamine, diethanolamine, Monoethanolamine MEA BASF, ammoniacal liquor, sodium carbonate, Ammonium bicarbonate food grade.Under preferable case, in step (1-1), first use NaOH that the Initial pH of described first formalin is adjusted into 7.5～9.0, in first minute contact reaction process, re-use trolamine and maintain pH in above-mentioned scope; In step (1-3) by obtaining as pH adjusting agent with sodium hydroxide; Step (3) is used the pH of NaOH and Monoethanolamine MEA BASF set-up procedure (2) gained mixture respectively to A and B successively, wherein B-A=0.3～0.5, and B=8.5～10.Adopt the package stability that can further improve in this way gained modified urea-formaldehyde resin.
According to the present invention, the water Combination of described products therefrom is the mode that the another kind that is similar to viscosity represents resin condensation degree of dissolved, the mode of its measurement and expression is by the temperature adjustment to 25 ℃ of gained modified urea-formaldehyde resin, the distilled water that adds gradually constant temperature to 25 in advance ℃, vibration mixes, while occurring that in mixed solution fine insolubles or bottle are attached with insolubles on wall, the water yield adding and the weight ratio of modified urea-formaldehyde resin are the water Combination of this modified urea-formaldehyde resin.Use this method representation level of response, both directly perceived, accurate again, and can also save expensive viscometer and loaded down with trivial details viscosity measurement step, thereby the method is widely used in the art.
According to the present invention, described properties-correcting agent is urea-formaldehyde resin properties-correcting agent, urea-formaldehyde resin properties-correcting agent can be this area conventional use for improving all ingredients of On The Water Resistance of Urea-formaldehyde Resin and intensity, can be for example at least one in trimeric cyanamide, phenol or Resorcinol, isocyanic ester, polyvinyl alcohol, xylogen.The present inventor finds, by using trimeric cyanamide and polyvinyl alcohol, using weight ratio 35～50: the mixture of 1 ratio is as urea-formaldehyde resin properties-correcting agent, can further improve the tack of prepared modified urea-formaldehyde resin, thereby make to use this modified urea-formaldehyde resin further to improve as the bonding strength of the wood-based plate of tackiness agent.Therefore, the mixture that the preferred described urea-formaldehyde resin properties-correcting agent of the present invention is trimeric cyanamide and polyvinyl alcohol, the weight ratio of described trimeric cyanamide and polyvinyl alcohol is 35～50: 1.
According to a kind of preferred implementation of the present invention, the preparation method of the improved modified urea-formaldehyde resin of package stability provided by the invention comprises the steps: a part of formaldehyde solution to regulate pH to 7.5～9.0, and be heated to 50 ± 5 ℃, then under agitation condition, add the urea of first batch and the urea-formaldehyde resin properties-correcting agent of first batch, after reinforced, temperature is elevated to 95 ± 5 ℃, and at this temperature stirring reaction 15～20 minutes, then temperature is adjusted to and is no more than 85 ± 5 ℃, pH value is adjusted to 4.4～7.0, continuation stirring reaction to the water Combination of products therefrom is 0.8～9 times, then be cooled to 40～60 ℃, after again pH being adjusted to 8.0～9.5, add another part formaldehyde or its solution, and under this temperature and pH value condition, add the urea-formaldehyde resin properties-correcting agent of second batch, adjust temperature of reaction to 95 ± 5 ℃, stirring reaction to the water Combination of products therefrom is 0.8～6 times, and then be cooled to 65 ± 5 ℃, behind adjustment pH to 8.0～9.5, add the urea-formaldehyde resin properties-correcting agent of the 3rd batch, at 75～90 ℃, contact reacts to the water Combination of products therefrom is 0.4～1.5 times, product being adjusted to pH value is 8.5～10 again, again be cooled to 65 ± 5 ℃, add second section urea, react 10 minutes, with alkali by pH regulator to 8.5～10, be cooled to below 40 ℃, obtain required modified urea-formaldehyde resin product.Can be by adding acid or alkali to regulate the pH value of reaction system, for example can be by adding one or more in sodium hydroxide or its solution, potassium hydroxide, ammoniacal liquor, formic acid, acetic acid, propionic acid, hydrochloric acid, sulfuric acid to regulate the pH value of reaction system.
The improved modified urea-formaldehyde resin of package stability that adopts method provided by the invention to make is directly used, without the extra urea that adds, the significantly reduction of load is prepared in realization at the preparation of place to use, and can improve stability and the burst size of methanal of modified urea-formaldehyde resin.
The invention will be further described for the following examples.
Embodiment 1
This embodiment is for illustrating the preparation method of the improved modified urea-formaldehyde resin of package stability provided by the invention.
The formalin that is 36 % by weight by 416.67 grams of concentration (formaldehyde is 5 moles) joins in 1000 milliliters of reactors, the aqueous sodium hydroxide solution that by concentration is 20 % by weight is adjusted into 8.2 by the Initial pH of formalin, and be heated to 50 ℃, then under agitation condition, add 151.67 grams of urea and 61.25 grams of trimeric cyanamides and 1.75 grams of polyvinyl alcohol, temperature is elevated to 90 ℃ and at this temperature, stir 15 minutes, and working concentration is that the trolamine aqueous solution of 30 % by weight makes the pH of reaction system maintain 8.2 in whipping process.
Then temperature of reaction being down to 85 ℃, is that the aqueous formic acid of 10 % by weight is adjusted to 5.0 by the pH value of reaction system by concentration, and continuing stirring reaction to the water Combination of products therefrom in reactor is 2.5 times, is then cooled to 60 ℃.
With the aqueous sodium hydroxide solution that concentration is 20 % by weight, the pH value of reaction system is adjusted to and after 8.8, adds the formalin that 104.69 grams of concentration are 36% again, keeping the pH value of solution is 8.8, add subsequently 124.36 grams of trimeric cyanamides, temperature is risen to 85 ℃, and at this temperature, react to the water Combination of products therefrom in reactor be 1.5 times, be again cooled to 60 ℃.
In pH value, be to add 30.86 grams of trimeric cyanamides for 8.8 times, at 85 ℃, react to the water Combination of products therefrom in reactor be 1.0 times, again be cooled to 60 ℃, add 269.64 grams of urea, react 10 minutes, then, by the pH value that the aqueous sodium hydroxide solution that concentration is 20 % by weight is adjusted the product in reactor, be first 9.0, by the pH value of the product in the Monoethanolamine MEA BASF aqueous solution adjustment reactor of 15 % by weight, be 9.5 again, be cooled to below 40 ℃, obtain cyanurotriamide modified modified urea-formaldehyde resin S1.
Comparative example 1
This comparative example is for illustrating the preparation method of existing modified urea-formaldehyde resin.
The formalin that is 36 % by weight by 416.67 grams of concentration (formaldehyde is 5 moles) joins in 1000 milliliters of reactors, the aqueous sodium hydroxide solution that by concentration is 20 % by weight is adjusted into 8.2 by the Initial pH of formalin, and be heated to 50 ℃, then under agitation condition, add 151.67 grams of urea and 61.25 grams of trimeric cyanamides and 1.75 grams of polyvinyl alcohol, temperature is elevated to 90 ℃ and at this temperature, stir 15 minutes, and working concentration is that the trolamine aqueous solution of 30 % by weight makes the pH of reaction system maintain 8.2 in whipping process.
Then temperature of reaction being down to 85 ℃, is that the aqueous formic acid of 10 % by weight is adjusted to 5.0 by the pH value of reaction system by concentration, and continuing stirring reaction to the water Combination of products therefrom in reactor is 2.5 times, is then cooled to 60 ℃.
With the aqueous sodium hydroxide solution that concentration is 20 % by weight, the pH value of reaction system is adjusted to and after 8.8, adds the formalin that 104.69 grams of concentration are 36% again, keeping the pH value of solution is 8.8, add subsequently 124.36 grams of trimeric cyanamides, temperature is risen to 85 ℃, and at this temperature, react to the water Combination of products therefrom in reactor be 1.5 times, be again cooled to 60 ℃.
In pH value, be to add 30.86 grams of trimeric cyanamides for 8.8 times, at 85 ℃, react to the water Combination of products therefrom in reactor be 1.0 times, again be cooled to 60 ℃ of reactions 10 minutes, then, by the pH value that the aqueous sodium hydroxide solution that concentration is 20 % by weight is adjusted the product in reactor, be first 9.0, by the pH value of the product in the Monoethanolamine MEA BASF aqueous solution adjustment reactor of 15 % by weight, be 9.5 again, be cooled to below 40 ℃, obtain cyanurotriamide modified modified urea-formaldehyde resin CS1.
Embodiment 2
This embodiment is for illustrating the preparation method of the improved modified urea-formaldehyde resin of package stability provided by the invention.
The formalin that is 36 % by weight by 416.67 grams of concentration (formaldehyde is 5 moles) joins in 1000 milliliters of reactors, the aqueous sodium hydroxide solution that by concentration is 20 % by weight is adjusted into 7.5 and be heated to 45 ℃ by the Initial pH of formalin (formaldehyde) solution, then under agitation condition, add 151.67 grams of urea and 61.46 grams of trimeric cyanamides and 1.54 grams of polyvinyl alcohol, temperature is elevated to 90 ℃ and at this temperature, stir 15 minutes, and working concentration is that the trolamine aqueous solution adjustment of 30 % by weight makes pH be maintained 7.5 in whipping process.
Then temperature of reaction being down to 80 ℃, is that the aqueous formic acid of 10 % by weight is adjusted to 4.4 by the pH value of reaction system by concentration, and continuing stirring reaction to the water Combination of products therefrom in reactor is 9.0 times, is then cooled to 60 ℃.
With the aqueous sodium hydroxide solution that concentration is 20 % by weight, the pH value of reaction system is adjusted to and after 9.0, adds the formalin that 104.69 grams of concentration are 36% again, keeping the pH value of solution is 9.0, add subsequently 124.79 grams of trimeric cyanamides, temperature is risen to 85 ℃, and at this temperature, react to the water Combination of products therefrom in reactor be 0.8 times, be again cooled to 60 ℃.
In pH value, be to add 30.97 grams of trimeric cyanamides for 9.0 times, at 85 ℃, react to the water Combination of products therefrom in reactor be 0.4) doubly, again be cooled to 60 ℃, add 269.64 grams of urea, react 10 minutes, then, by the pH value that the aqueous sodium hydroxide solution that concentration is 20 % by weight is adjusted the product in reactor, be first 8.1, by the pH value of the product in the Monoethanolamine MEA BASF aqueous solution adjustment reactor of 15 % by weight, be 8.5 again, be cooled to below 40 ℃, obtain cyanurotriamide modified modified urea-formaldehyde resin S2.
Embodiment 3
This embodiment is for illustrating the preparation method of the improved modified urea-formaldehyde resin of package stability provided by the invention.
The formalin that is 36 % by weight by 416.67 grams of concentration (formaldehyde is 5 moles) joins in 1000 milliliters of reactors, the aqueous sodium hydroxide solution that by concentration is 20 % by weight is adjusted into 9.0 and be heated to 55 ℃ by the Initial pH of formalin (formaldehyde) solution, then under agitation condition, add 151.67 grams of urea and 61.76 grams of trimeric cyanamides and 1.24 grams of polyvinyl alcohol, temperature is elevated to 100 ℃ and at this temperature, stir 15 minutes, and working concentration is that the trolamine aqueous solution adjustment of 30 % by weight makes reaction system pH be maintained 9.0 in whipping process.
Then temperature of reaction being down to 90 ℃, is that the aqueous formic acid of 10 % by weight is adjusted to 7.0 by the pH value of reaction system by concentration, and continuing stirring reaction to the water Combination of products therefrom in reactor is 9 times, is then cooled to 60 ℃.
With the aqueous sodium hydroxide solution that concentration is 20 % by weight, the pH value of reaction system is adjusted to and after 9.5, adds the formalin that 104.69 grams of concentration are 36% again, keeping the pH value of solution is 9.5, add subsequently 125.4 grams of trimeric cyanamides, temperature is risen to 85 ℃, and at this temperature, react to the water Combination of products therefrom in reactor be 6 times, be again cooled to 60 ℃.
In pH value, be to add 31.22 grams of trimeric cyanamides for 9.5 times, at 85 ℃, react to the water Combination of products therefrom in reactor be 1.5 times, again be cooled to 60 ℃, add 269.64 grams of urea, react 10 minutes, then, by the pH value that the aqueous sodium hydroxide solution that concentration is 20 % by weight is adjusted the product in reactor, be first 9.7, by the pH value of the product in the Monoethanolamine MEA BASF aqueous solution adjustment reactor of 15 % by weight, be 10.0 again, be cooled to below 40 ℃, obtain cyanurotriamide modified modified urea-formaldehyde resin S3.
Embodiment 4
This embodiment is for illustrating the preparation method of the improved modified urea-formaldehyde resin of package stability provided by the invention.
Method according to embodiment 1 is prepared modified urea-formaldehyde resin, different, and concentration is that the trolamine aqueous solution of 30 % by weight is replaced by the ammonia soln of 10 % by weight, obtains cyanurotriamide modified modified urea-formaldehyde resin S4.
Embodiment 5-8
Following embodiment is for illustrating the performance of modified urea-formaldehyde resin prepared by employing preparation method provided by the invention.
According to GB/T 14074-2006, measure respectively content and the viscosity of the modified urea-formaldehyde resin S1-S4 Free-formaldehyde being made by above-described embodiment 1-4, result is as shown in table 1.
The modified urea-formaldehyde resin S1-S4 that 100 grams of above-described embodiment 1-4 are made mixes with 20 grams of flour and 1 gram of ammonium chloride respectively, obtains timber tackiness agent.
Gained tackiness agent is respectively used to prepare three layers of glued board, 1.2 millimeters of board using poplar board thickness, resin added is 160 ± 10 grams/m (two-sided), in room temperature precompressed 20 minutes under 10 ± 1 kilogram force/square centimeters, then 125 ± 3 ℃ of hot pressing 2 minutes under 8 ± 1 kilogram forces/cm2 pressure.Then respectively according in 4.15.4.2 in GB/T 17657-1999 a) I class glued board standard and 4.12 regulation measure bonding strength and the burst size of methanal of glued board, result is as shown in table 1.
Gained tackiness agent is respectively used to prepare three-layer wood composite flooring, surface layer: the Cortex Fraxini mandshuricae veneer of 3 millimeters, sandwich layer: the China fir bar of 10 mm thick, bottom: the board using poplar board of 3 millimeters, Amount of spread: 250 grams/m (two-sided), hot pressing temperature: 130 ℃, hot pressing time: 5 minutes, hot pressing pressure: 1.5 MPas.Then according to burst size of methanal and the dipping of the regulation mensuration solid wooden compound floor of GB/T 17657-1999 and GB/T 18103-2000, peel off respectively, result is as shown in table 1.
Gained tackiness agent is respectively used to prepare structure assembly material, 300 millimeters * 150 millimeters * 7 millimeters of Cortex Fraxini mandshuricae sheet materials, 125 grams/m of Amount of spread (two-sided), hot pressing temperature: 140 ℃, hot pressing time: 8 minutes, hot pressing pressure: 2.5 MPas.With reference to Japanese structure assembly material standard JAS SE-9, measure burst size of methanal and the dipping of test specimen and peel off (1 circulation), result is as shown in table 1.
In the present invention, the number of days that package stability adopts seal-packed modified urea-formaldehyde resin to store while being no more than 1500 centipoise to viscosity in room temperature (10～20 ℃) lucifuge represents, result is as shown in table 1.Number of days is larger, represents that package stability is better, and number of days is less, represents that package stability is poorer.
Comparative example 2
The performance of measuring the modified urea-formaldehyde resin being made by comparative example 1 according to the method described in embodiment 5-8, result is as shown in table 1.
Table 1
From the result of upper table 1, can find out, the improved modified urea-formaldehyde resin package stability of package stability that adopts preparation method provided by the invention to prepare is very good, be used as Wood products as glued board, composite floor board, during the adhesive substrate composition of integrated timber product, burst size of methanal compared with the modified urea-formaldehyde resin of CN101134835A reduces greatly, and free formaldehyde content also decreases, thereby make to use burst size of methanal and the free formaldehyde content of glued board prepared by this modified urea-formaldehyde resin all can reduce, further meet E1 (≤1.5 mg/litre) regulation in GB.Adopt the water-tolerant of the improved modified urea-formaldehyde resin of package stability prepared by preparation method provided by the invention, three layers of glued board of preparation, solid wooden compound floor, the bonding strength of integrated timber product and dipping are peeled off and are met respectively GB/T 9846.3-2004 < < glued board > > I class glued board standard, GB/T 18103-2000 < < solid wooden compound floor > > standard, the requirement of environment for use 2 in Japan structure assembly material standard JAS SE-9.
Claims (4)
1. a preparation method for the improved modified urea-formaldehyde resin of package stability, the method comprises: (1) carries out the first contact reacts by first urea, properties-correcting agent and formaldehyde, to water Combination be 0.4～1.5 times; (2) by gained mixture and second batch urea, in temperature, be at 60 ± 15 ℃, to carry out second contact reacts 1～30min; (3) the pH value of step (2) gained mixture is adjusted to 8.5～10 and be cooled to below 40 ℃;
Wherein, first urea, properties-correcting agent and formaldehyde are carried out to the first contact reacts, the mode that is 0.4～1.5 times to water Combination comprises carry out successively step by step following:
(1-1) by first properties-correcting agent, in temperature, be at 90 ± 5 ℃, to carry out first minute contact reacts 15～20min with first urea and first formalin, the pH value of wherein said first formalin is 7.5～9.0, temperature is 50 ± 5 ℃, in first properties-correcting agent and first formalin, the mol ratio of formaldehyde is 0.001～0.1:1, and the formaldehyde in first formalin and the mol ratio of first urea are 2.5～1.8:1;
(1-2) step (1-1) gained mixture being carried out to second minute contact reacts to water Combination under temperature is 80 ± 5 ℃, the condition of pH value to 4.4～7.0 is 0.8～9 times;
(1-3) the pH value of step (1-2) gained mixture is adjusted to after 8.0～9.5 and second batch formalin, second batch properties-correcting agent at 90 ± 5 ℃, to carry out the 3rd minute contact reacts to water Combination be 0.8～6 times, the total amount of the formaldehyde in the formaldehyde in first formalin and second batch formalin: the mol ratio of the total amount of first urea, first properties-correcting agent and second batch properties-correcting agent is 1.9～1.1:1;
(1-4) step (1-3) gained mixture and the 3rd batch of properties-correcting agent being carried out to the 4th minute contact reacts to water Combination at 90 ± 5 ℃ is 0.4～1.5 times, the total amount of the formaldehyde in the formaldehyde in first formalin and second batch formalin: the mol ratio of the total amount of first urea, first properties-correcting agent, second batch properties-correcting agent and the 3rd batch of properties-correcting agent is 1.7～1.0:1;
Wherein, first urea: the weight ratio of second batch urea is 0.5～10:1; And 0.8～2 times of mole total amount that the add-on of described formaldehyde is urea;
Wherein, described properties-correcting agent is at least one in trimeric cyanamide, phenol, Resorcinol, isocyanic ester, polyvinyl alcohol, xylogen.
2. method according to claim 1, wherein, gained mixture and second batch urea are at 65 ± 5 ℃, to carry out second contact reacts 5～20min in temperature.
3. method according to claim 1, wherein, is first used NaOH that the Initial pH of described first formalin is adjusted into 7.5～9.0 in step (1-1), re-uses trolamine and maintain pH in above-mentioned scope in first minute contact reaction process; In step (1-3) by obtaining as pH adjusting agent with sodium hydroxide; Step (3) is used the pH of NaOH and Monoethanolamine MEA BASF set-up procedure (2) gained mixture respectively to A and B successively, wherein B-A=0.3～0.5, and B=8.5～10.
4. method according to claim 1, wherein, described properties-correcting agent is the mixture of trimeric cyanamide and polyvinyl alcohol, the weight ratio of trimeric cyanamide and polyvinyl alcohol is 35～50:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110216900.6A CN102898604B (en) | 2011-07-29 | 2011-07-29 | Preparation method of modified urea-formaldehyde resin with improved storage stability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110216900.6A CN102898604B (en) | 2011-07-29 | 2011-07-29 | Preparation method of modified urea-formaldehyde resin with improved storage stability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102898604A CN102898604A (en) | 2013-01-30 |
| CN102898604B true CN102898604B (en) | 2014-04-02 |
Family
ID=47571117
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110216900.6A Active CN102898604B (en) | 2011-07-29 | 2011-07-29 | Preparation method of modified urea-formaldehyde resin with improved storage stability |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102898604B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104531017A (en) * | 2014-12-20 | 2015-04-22 | 李成功 | Environment-friendly composite urea-formaldehyde resin adhesive |
| CN106008869B (en) * | 2016-06-28 | 2018-09-11 | 泸州金山林木业有限公司 | A kind of formula and production method of woodwork plate adhesive glue |
| CN107099268A (en) * | 2017-05-05 | 2017-08-29 | 江苏苏林木业有限公司 | A kind of fibre board use adhesive and preparation method thereof |
| CN107556952A (en) * | 2017-10-11 | 2018-01-09 | 大亚(江苏)地板有限公司 | A kind of floor Low Temperature Thermal moulding and its application |
| CN108659759A (en) * | 2018-03-28 | 2018-10-16 | 大亚(江苏)地板有限公司 | A kind of low aldehyde adhesive and its application in solid wooden compound floor production |
| CN109082251B (en) * | 2018-07-11 | 2020-11-10 | 吉林大学 | Preparation method of environment-friendly urea-formaldehyde resin adhesive |
| CN109251290A (en) * | 2018-08-29 | 2019-01-22 | 吉林森工露水河刨花板有限责任公司 | A kind of dipping preparation method of Lauxite |
| CN109868101B (en) * | 2019-03-18 | 2021-12-03 | 广西高林林业股份有限公司 | Lignin modified urea-formaldehyde resin adhesive and preparation method and application thereof |
| CN110894273A (en) * | 2019-12-05 | 2020-03-20 | 江苏长顺高分子材料研究院有限公司 | Melamine aldehyde-based adhesive resin with good storage stability and preparation method thereof |
| CN113249069A (en) * | 2021-03-25 | 2021-08-13 | 广西贺州恒达板业股份有限公司 | Anti-corrosion adhesive for finger-jointed board wood and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884332A (en) * | 2006-06-08 | 2006-12-27 | 崔万发 | Urea-formaldehyde resin and its preparation method |
| CN101134835A (en) * | 2007-09-17 | 2008-03-05 | 中国林业科学研究院木材工业研究所 | Method for preparing modified urea-formaldehyde resin |
| CN101200549A (en) * | 2007-12-04 | 2008-06-18 | 中国林业科学研究院木材工业研究所 | Method for preparing modified urea-formaldehyde resin powder material |
-
2011
- 2011-07-29 CN CN201110216900.6A patent/CN102898604B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884332A (en) * | 2006-06-08 | 2006-12-27 | 崔万发 | Urea-formaldehyde resin and its preparation method |
| CN101134835A (en) * | 2007-09-17 | 2008-03-05 | 中国林业科学研究院木材工业研究所 | Method for preparing modified urea-formaldehyde resin |
| CN101200549A (en) * | 2007-12-04 | 2008-06-18 | 中国林业科学研究院木材工业研究所 | Method for preparing modified urea-formaldehyde resin powder material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102898604A (en) | 2013-01-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102898604B (en) | Preparation method of modified urea-formaldehyde resin with improved storage stability | |
| CN100572445C (en) | A kind of preparation method of modified urea-formaldehyde resin | |
| CN101200549B (en) | Method for preparing modified urea-formaldehyde resin powder material | |
| CN101892023B (en) | Aldehyde-free adhesive and preparation method thereof | |
| CN1670104A (en) | Low-release aldehyde adhesive and its preparation method and use | |
| CN102391805B (en) | Modified urea-formaldehyde resin adhesive for concrete formwork and production method of adhesive | |
| CN102604573A (en) | E0-grade melamine modified urea-formaldehyde resin adhesive, and preparation method and application thereof | |
| RU2011153872A (en) | METHOD FOR PRODUCING CARBAMIDOMELAMINO-FORMALDEHYDE RESIN | |
| CN104311767B (en) | A kind of modified urea-formaldehyde resin adhesive and preparation method thereof | |
| US4603191A (en) | Process for preparing a urea-formaldehyde resin having a very low mole ratio of formaldehyde to urea | |
| CN102443369B (en) | Timber adhesive and preparation method thereof | |
| CN102838955A (en) | Urea-formaldehyde adhesive for particleboards and preparation method | |
| CN104629662B9 (en) | The urea-formaldehyde resin adhesive of a kind of ultra-low formaldehyde release and preparation technology thereof | |
| CN103665288A (en) | Method for preparing wood adhesive using cassava starch hydrolyzed sugar | |
| CN102675574A (en) | Copolycondensation resin type formaldehyde catching agent and preparation method thereof | |
| CN103965425A (en) | Preparation method for water-glass modified amino resin | |
| CN104910842B (en) | Preparation method of resorcinol modified urea-formaldehyde resin adhesive | |
| CN110003829A (en) | A kind of preparation method of environment-friendly modified urea-formaldehyde resin adhesive | |
| CN1962800A (en) | Production process of soybean protein adhesive | |
| CN112063343A (en) | High-performance resin-based adhesive and preparation method thereof | |
| FI87363B (en) | Method for production of plant-fibre-based boards, especially of particle boards or fibre boards | |
| CN102555009A (en) | High-strength environment-friendly shaving board | |
| CN103666350B (en) | Maltose-carbamide condensation copolymerization resin wood adhesive and preparation method thereof | |
| EP0001501B1 (en) | Method of bonding lignocellulosic material | |
| CN114133913A (en) | Waste molasses-based high-strength environment-friendly formaldehyde-free adhesive and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180717 Address after: 210000 242, room A, 606 Ning six road, Jiangbei new district, Nanjing, Jiangsu. Patentee after: Nanjing snow Chemical Technology Co., Ltd. Address before: 100091 Beijing city Haidian District Xiangshan Road East small house No. 2 hospital Patentee before: Lumber Industry Inst., Chinese Forestry Scientific Inst. |
|
| TR01 | Transfer of patent right |