CN101121774A - Method for preparing oxidization starch modified urea-formaldehyde resin - Google Patents
Method for preparing oxidization starch modified urea-formaldehyde resin Download PDFInfo
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Abstract
The invention relates to a preparation technology of the modified urea-formaldehyde resin; with the strong agitation and the presence of the catalyst, the urea, formaldehyde, water and oxidized starch are added at a time according to the stoichiometric ratio; or first the urea and formaldehyde are used to make the urea-formaldehyde resin with the presence of the catalyst, and then the oxidized starch is used to do the cross-linking step-by-step polymerization; after mixing well, the temperature is raised to be 45 to 110 Celsius system; the acid of a certain amount in the return process is added; the reaction is kept for 40 minutes to 3 hours at a constant temperature; the pH value of the solution is maintained between 3.0 and 6.5. Then the alkaline substance is used to adjust the pH value to be between 7.2 and 9.8; the method is to continue to stir for 15 minutes and stop heating; after the reaction, the modified urea-formaldehyde resin product can be made with a certain solid content. The invention has the advantages of the reduction of the cost and at the same time, the increase of the cross-linking reaction, which further lowers the free-formaldehyde content in the resin, lengthens the time for storage, and reduces the environmental pollution. The product produced in the invention has the advantages of a good stability, a high solid content, the saving of energy and so on.
Description
Technical field
The present invention relates to a kind of modification technology of preparing of urea-formaldehyde resin, especially a kind of preparation method who adopts oxidization starch modified urea-formaldehyde resin.Character such as described modified urea-formaldehyde resin has shelf-stable, excellent heat resistance, and free formaldehyde content is low, methylol group content is low, bond strength is good.
Background technology
Urea-formaldehyde resin (UF) glue is in bamboo, wood processing, paper is bonding, a kind of widely tackiness agent of sector applications such as toughened paint, in recent years, people are increasing to the demand of environmental-protection type adhesive, and mostly commercially available UF resin binder is to contain phenyl ring, the high molecular polymer of formaldehyde monomers structure, these oxious components are the meeting toxic gas that discharges strong impulse slowly in production and actual application, stimulate the gentle pipe of eyes, wherein formaldehyde is not only to nasal mucosa, looking the mucous membrane and the upper respiratory tract all has hormesis, but also can cause dermatitis, hepatic disease, multiple diseases such as carcinogenic and mutagenesis.Free formaldehyde content is up to 3～7% in the urea-formaldehyde resin adhesive of at present domestic medium and small sized enterprises' productions and use, and this has a strong impact on producers and consumers's physical and mental health, has also limited its use range.Although the study on the modification about urea-formaldehyde resin makes rapid progress at present, and on certain degree, obtained considerable progress, but the structure of the height of production cost and modified material is the first element that influences the urea-formaldehyde resin modification, also is the bottleneck that this type of material mechanical performance of restriction improves.Therefore in order to overcome these shortcomings, had more about utilizing properties-correcting agent such as phenol, polyvinyl alcohol, trimeric cyanamide, thiocarbamide urea-formaldehyde resin adhesive to be carried out the research report of modification.
Forest product industry, 2003,30 (I): 11-14 have reported that a kind of indoor wood-based plate and low formaldehyde discharge the exploitation and the application of urea-formaldehyde resin adhesive, use that the performance to urea-formaldehyde resin has greatly improved behind the properties-correcting agent though the result shows, but expensive raw material price increases considerably production cost.
Summary of the invention
For overcoming these shortcomings of aforesaid method, the invention provides a kind of modification method for preparing of oxidization starch modified urea-formaldehyde resin.Because the C in the Sumstar 190 structure in the part glucose unit
6Last hydroxyl is converted into aldehyde radical, and aldehyde radical can form hemiacetal and acetal with the hydroxyl in formaldehyde, the urea-formaldehyde resin under solidifying agent (acid) and heating condition, have the Sumstar 190 chain and participate in crosslinked three dimensional structure thereby when solidifying, form, and under condition of cure, can form acetal between the hydroformylation starch molecule and crosslinked.Because ethylidene ether structure has water-fast, alkaline-resisting, antioxidant, thereby has improved bonding strength and the water tolerance and the ageing-resistant performance of urea-formaldehyde resin adhesive.After the simultaneous oxidation cross-linking starch adds urea-formaldehyde resin, thereby, increased storage period, reduced environmental pollution owing to contain poly-hydroxy in its structure and can form acetal with free formaldehyde and reduced the content of free aldehyde in the resin.
Preparation method of the present invention is:
Under brute force stirs, according to stoichiometric ratio, in the presence of catalyzer, disposable adding urea, formaldehyde, water and Sumstar 190; Perhaps in the presence of catalyzer, form urea-formaldehyde resin earlier, use the crosslinked step-by-step polymerization of Sumstar 190 again by urea and formaldehyde; Be warming up to 45～110 ℃ after mixing, add the acid of certain mass in the reflux course, continue isothermal reaction 40 minutes～3 hours, the pH value of solution value is maintained between 3.0～6.5.Regulate between pH value to 7.2～9.8 with alkaline matter then, continue stirring and stop heating after 15 minutes, reaction finishes, and obtains having the modified urea-formaldehyde resin product of certain solid content.
The present invention's used Sumstar 190 in preparation process can be a hydrogen peroxide oxidation starch, and perchloric acid oxidation's starch also can be potassium permanganate oxidation starch, preferably hydrogen peroxide oxidation starch.Its consumption can be urea-formaldehyde resin total amount 1～80%, preferably 5～20%.
The present invention's mass ratio of formaldehyde and urea in the preparation process of water-based urea-formaldehyde resin can be 2.5: 1～0.65: 1, is preferably 1.2: 1～1.5: 1.
Used catalyzer can be an ammoniacal liquor in the preparation process of water-based urea-formaldehyde resin, trolamine, diethanolamine, ammonium chloride, vulkacit H etc., preferably vulkacit H.Wherein catalyst consumption can be 0.001%～0.6% of formaldehyde solution content, preferably 0.01%～0.05%.
The present invention is in the preparation process of oxidization starch modified urea-formaldehyde resin, being used for regulation system, to be the tart acidic substance can be formic acid, acetate, hydrochloric acid, also can be phenylformic acid, preferably formic acid, its consumption is 0.005%～0.2% of a formaldehyde solution content, preferably 0.01%～0.05%.Regulation system is tart pH value and can be preferably between 4.0～5.0 between 3.0～6.5.
The present invention is in the preparation process of oxidization starch modified urea-formaldehyde resin, and being used for regulation system, to be weakly alkaline alkaline matter can be sodium hydroxide, sodium bicarbonate, and ammonium chloride also can be bicarbonate of ammonia, preferably sodium hydroxide.Its consumption is 0.005%～0.2% of a formaldehyde solution content, preferably 0.01%～0.05%.Regulation system is weakly alkaline pH value and can be preferably between 7.3～8.5 between 7.2～9.8.
The isothermal reaction time of water-based urea-formaldehyde resin can be 40 minutes～3 hours, preferably 1～1.5 hour.Temperature of reaction can be preferably in 80～100 ℃ between 45～110 ℃.
The present invention uses the benefit of oxidization starch modified urea-formaldehyde resin, is that it has reduced cost, has increased both crosslinking reactions simultaneously, thereby has reduced the content of free aldehyde in the resin, has increased storage period, has reduced environmental pollution.Prepared product has good stability when room temperature, and high solids content makes it have advantages such as energy-conservation.The existence of crosslinking structure makes it have stronger adhesive property, has been widely used at adhesive area.
Embodiment: the present invention is described in detail below in conjunction with example, but the present invention is not limited to following example.
Embodiment 1
Under brute force stirs, take by weighing 37% formalin 405g and catalyst ammonia water 0.004g, be added in the there-necked flask and mix.Mix the back and add 60g urea, 1653g water and 2.1g perchloric acid oxidation starch are warming up to 45 ℃, add the acetate of 0.02g in the reflux course, continue reaction 40 minutes, keep the pH value of solution value about 6.5.Regulate about pH value to 7.2 with the 0.02g sodium bicarbonate then, continue to stir and stop heating after 15 minutes, reaction finishes, and obtains solid content and be 10% modified urea-formaldehyde resin product UF1.
Embodiment 2
Under brute force stirs, take by weighing 37% formalin 243g and catalyzer ammonium chloride 0.04g, be added in the there-necked flask and mix.Mix the back and add 60g urea, 10g water and 7.5g hydrogen peroxide oxidation starch are warming up to 85 ℃, add the formic acid of 0.1g in the reflux course, continue reaction 1.5 hours, keep the pH value of solution value about 4.8.Regulate about pH value to 8.2 with 0.1g ammonium chloride then, continue to stir and stop heating after 15 minutes, reaction finishes, and obtains solid content and be 49% modified urea-formaldehyde resin product UF2.
Embodiment 3
Under brute force stirs, take by weighing 37% formalin 105g and catalyzer diethanolamine 0.03g, be added in the there-necked flask and mix.Mix the back and add 60g urea, 7g water is warming up to 90 ℃, adds the formic acid of 0.2g in the reflux course, continues reaction 2 hours, keeps the pH value of solution value about 3.0.Regulate about pH value to 9.8 with the 0.2g sodium bicarbonate then, add 9.9g potassium permanganate oxidation starch, continue to stir and stop heating after 15 minutes, reaction finishes, and obtains solid content and be 60% modified urea-formaldehyde resin product UF3.
Embodiment 4
Under brute force stirs, take by weighing 37% formalin 162g and catalyzer ammonium chloride 0.04g, be added in the there-necked flask and mix.Mix the back and add 60g urea, 18g water and 14.4g potassium permanganate oxidation starch are warming up to 88 ℃, add the acetate of 0.05g in the reflux course, continue reaction 1 hour, keep the pH value of solution value about 5.4.Regulate about pH value to 7.9 with 0.05g bicarbonate of ammonia then, continue to stir and stop heating after 15 minutes, reaction finishes, and obtains solid content and be 53% modified urea-formaldehyde resin product UF4.
Embodiment 5
Under brute force stirs, take by weighing 37% formalin 219g and catalyzer vulkacit H 0.02g, be added in the there-necked flask and mix.Add 60g urea after vulkacit H all dissolves, 15g water and 16.9g hydrogen peroxide oxidation starch are warming up to 95 ℃, add the formic acid of 0.1g in the reflux course, continue reaction 1.5h, keep the pH value of solution value about 5.1.Regulate about pH value to 7.7 with the sodium hydroxide of 0.1g then, continue to stir and stop heating after 15 minutes, reaction finishes, and obtains solid content and be 61% modified urea-formaldehyde resin product UF5.
Embodiment 6
Under brute force stirs, take by weighing 37% formalin 162g and catalyzer vulkacit H 0.04g, be added in the there-necked flask and mix.Add 60g urea after vulkacit H all dissolves, 20g water is warming up to 100 ℃, adds the formic acid of 0.1g in the reflux course, continues reaction 1.5 hours, keeps the pH value of solution value about 4.4.Regulate about pH value to 7.8 with the sodium hydroxide of 0.05g then, add 24g hydrogen peroxide oxidation starch, continue to stir and stop heating after 15 minutes, reaction finishes, and obtains solid content and be 54% modified urea-formaldehyde resin product UF6.
Embodiment 7
Under brute force stirs, take by weighing 37% formalin 219g and catalyzer vulkacit H 0.02g, be added in the there-necked flask and mix.Add 60g urea after vulkacit H all dissolves, 73g water and 70.5g hydrogen peroxide oxidation starch are warming up to 96 ℃, add the formic acid of 0.1g in the reflux course, continue reaction 1.5h, keep the pH value of solution value about 5.3.Regulate about pH value to 7.6 with 0.1 sodium hydroxide then, continue to stir and stop heating after 15 minutes, reaction finishes, and obtains solid content and be 50% modified urea-formaldehyde resin product UF7.
Embodiment 8
Under brute force stirs, take by weighing 37% formalin 130g and catalyzer trolamine 0.81g, be added in the there-necked flask and mix.Mix the back and add 60g urea and 86g potassium permanganate oxidation starch, be warming up to 110 ℃, add the phenylformic acid of 0.26g in the reflux course, continue reaction 3 hours, keep the pH value of solution value about 3.0.Regulate about pH value to 8.5 with 0.20g ammonium chloride then, continue to stir and stop heating after 15 minutes, reaction finishes, and obtains solid content and be 70% modified urea-formaldehyde resin product UF8.
Experimental technique
Measure free formaldehyde content and the methylol group content and the stability thereof of part oxidization starch modified urea-formaldehyde resin aqueous dispersions sample, the result is as shown in following table.
The partial properties index of UF sample
| Sample | Starch accounts for the mass percent (%) of urea-formaldehyde resin | Content of free aldehyde (%) | Methylol group content (%) | The storage period/moon |
| UF | 0 | 6.13 | 16.44 | ＞7 |
| UF1 UF2 UF3 UF4 UF5 UF6 UF7 UF8 | 1.0 5.0 10.0 12.0 15.0 20.0 50.0 80.0 | 6.01 4.12 4.07 3.68 1.24 2.16 3.58 / | 14.33 7.97 7.09 5.71 4.08 6.71 7.69 / | ＞6＞6＞6＞6＞6＞6 produce gel produces gel |
"/" expression system viscosity can't be measured too greatly.
The result shows that product oxidization starch modified urea-formaldehyde resin of the present invention has package stability preferably when the Sumstar 190 consumption is little.The adding of Sumstar 190 has significantly reduced the free formaldehyde content in the urea-formaldehyde resin, has increased storage period, has reduced environmental pollution, has reduced production cost simultaneously, will have been widely used in adhesive area.
Claims (7)
1. the preparation method of oxidization starch modified urea-formaldehyde resin is characterized in that under brute force stirs, according to stoichiometric ratio, and in the presence of catalyzer, disposable adding urea, formaldehyde, water and Sumstar 190; Perhaps in the presence of catalyzer, form urea-formaldehyde resin earlier, use the crosslinked step-by-step polymerization of Sumstar 190 again by urea and formaldehyde; Be warming up to 45～110 ℃ after mixing, add acid in the reflux course, continue isothermal reaction 40 minutes～3 hours, the pH value of solution value is maintained between 3.0～6.5; Regulate between pH value to 7.2～9.8 with alkaline matter then, continue stirring and stop heating after 15 minutes, reaction finishes, and obtains having the modified urea-formaldehyde resin product of certain solid content;
Used Sumstar 190 is a hydrogen peroxide oxidation starch, perchloric acid oxidation's starch or potassium permanganate oxidation starch, and its consumption can be urea-formaldehyde resin total amount 1～80%;
The mass ratio of formaldehyde and urea is 2.5: 1～0.65: 1;
Used catalyzer is an ammoniacal liquor, trolamine, and diethanolamine, ammonium chloride or vulkacit H, wherein catalyst consumption is 0.001%～0.6% of a formaldehyde solution content;
The acid that adds is formic acid, acetate, hydrochloric acid, or phenylformic acid, and its consumption is 0.005%～0.2% of a formaldehyde solution content, and the pH value of solution value is between 3.0～6.5;
Being used for regulation system, to be weakly alkaline alkaline matter be sodium hydroxide, sodium bicarbonate, and ammonium chloride, or bicarbonate of ammonia, its consumption are 0.005%～0.2% of formaldehyde solution content; The pH value of solution value is between 7.2～9.8;
Wherein the isothermal reaction time of water-based urea-formaldehyde resin is 40 minutes～3 hours; Temperature of reaction is between 45～110 ℃.
2. the preparation method of oxidization starch modified urea-formaldehyde resin according to claim 1 is characterized in that used Sumstar 190 is a hydrogen peroxide oxidation starch; Its consumption is 5～20% of a urea-formaldehyde resin total amount.
3. the preparation method of oxidization starch modified urea-formaldehyde resin according to claim 1, the mass ratio that it is characterized in that formaldehyde and urea is 1.2: 1～1.5: 1.
4. the preparation method of oxidization starch modified urea-formaldehyde resin according to claim 1 is characterized in that used catalyzer is a vulkacit H, and catalyst consumption is 0.01%～0.05% of a formaldehyde solution content.
5. the preparation method of oxidization starch modified urea-formaldehyde resin according to claim 1 is characterized in that the acid that adds is formic acid, and its consumption is 0.01%～0.05% of a formaldehyde solution content, and the pH value of solution value is between 4.0～5.0.
6. the preparation method of oxidization starch modified urea-formaldehyde resin according to claim 1, it is characterized in that being used for regulation system, to be weakly alkaline alkaline matter be sodium hydroxide, its consumption is 0.01%～0.05% of a formaldehyde solution content; The pH value of solution value is between 7.3～8.5.
7. the preparation method of oxidization starch modified urea-formaldehyde resin according to claim 1, the isothermal reaction time that it is characterized in that the water-based urea-formaldehyde resin is 1～1.5 hour, temperature of reaction is at 80～100 ℃.
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