CN102675574B - Copolycondensation resin type formaldehyde catching agent and preparation method thereof - Google Patents
Copolycondensation resin type formaldehyde catching agent and preparation method thereof Download PDFInfo
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- CN102675574B CN102675574B CN201210106439.3A CN201210106439A CN102675574B CN 102675574 B CN102675574 B CN 102675574B CN 201210106439 A CN201210106439 A CN 201210106439A CN 102675574 B CN102675574 B CN 102675574B
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Abstract
The invention provides a melamine-urea-formaldehyde copolycondensation resin type formaldehyde catching agent which is made of urea, melamine and formaldehyde by means of copolycondensation reaction, wherein the final molar ratio F/U of the formaldehyde to the urea is 1:2.4-4.0, the formaldehyde is added once, the urea is added twice, the reaction temperature ranges from 85 DEG C to 95 DEG C, and the reaction time is 2-3 hours. The formaldehyde catching agent can be mixed and used with various urea resin adhesives and especially applicable to urea resins prepared with low molar ratio of the formaldehyde to the urea. Strength of main adhesives of urea resins is unaffected within a certain weight addition proportional range. The melamine-urea-formaldehyde copolycondensation resin type formaldehyde catching agent has the advantages of flexibility in use, high comprehensive performances and the like and is applicable to production of various indoor artificial boards.
Description
Technical field
The present invention relates to formaldehyde-trapping agent of a kind of urea-formaldehyde resin for artificial board tackiness agent and preparation method thereof, belong to Wood-based Panel Production technical field in wood working.
Background technology
Urea-formaldehyde resin is a class tackiness agent of current wood-based panel industry usage quantity maximum, but along with the continuous enhancing of people's environmental consciousness and constantly perfecting of national environmental protection regulation, the formaldehyde release And Spread of Solute of urea-formaldehyde resin also more and more causes people's concern.As one of principal reaction raw material of urea-formaldehyde resin, formaldehyde has material impact to the health of human body, is classified as suspect carcinogen matter by international cancer institute.Due to UF resin Free-formaldehyde excessive concentration, not only the Working environment of wood working is polluted, and it is unfavorable to bring to human consumer's health for a long time.The method that reduces artificial board burst size of methanal is a lot, wherein, the mol ratio F/U that reduces reaction raw materials formaldehyde and urea is a kind of the most common method, but in most situation, when burst size of methanal reduces, resin property is also corresponding deteriorated, in order to take into account the requirement of burst size of methanal and bonding property two aspects, the method that does not reduce burst size of methanal by other, mol ratio F/U generally can be down to 1:1.4 ~ 1.2.In the urea-formaldehyde resin of preparing with this mol ratio, still there is certain free formaldehyde, the middle E1 level burst size of methanal requirement that is difficult to be up to state standards of corresponding timber products, the burst size of methanal of urea-formaldehyde resin still has larger reduction space.In addition, by controlling the preparation technology of urea-formaldehyde resin, also can PARA FORMALDEHYDE PRILLS(91,95) burst size produce material impact.
Compare with above-mentioned two kinds of methods, in urea-formaldehyde resin, add the method that formaldehyde-trapping agent is the reduction burst size of methanal that a kind of operation is more easy, effect is more obvious, industrial application is more easily promoted.Composition formaldehyde-trapping agent composition can be a kind of can with the monomeric substance of formaldehyde reaction or solution, can be referring to patent as DE2917159, EP13372, CN1298911, CN1425725 etc., also can be the mixture of many kinds of substance, can, referring to patent as CN1062541, CN101100587, CN1799636, CN1104657 etc., wherein contain the material of multiple seizure formaldehyde.But in general, be often used as formaldehyde-trapping agent and mainly contain ammonia or aminoderivative class material, urea, thiocarbamide mixture, sodium bisulfite, melamine resin, Resorcinol, ammonium lignin sulfonate, Sumstar 190 etc.
See theoretically, every formaldehyde-trapping agent that can all can be used as with the material of formaldehyde reaction urea-formaldehyde resin, therefore, the urea-formaldehyde resin of the active sites of Shang Youneng and formaldehyde reaction itself can be used as formaldehyde-trapping agent and uses.Resin type formaldehyde-trapping agent is taking condensation copolymerization resin as basis, on the one hand, free urea wherein and low-molecular-weight adduct can effectively be removed the free formaldehyde in main gel stick, on the other hand, the impact of the reduction that the existence of resin type methylol polycondensation product can reduce urea and formaldehyde mole ratio to a certain extent on main gel stick strength property, thus realize the balance between mechanical strength of resin performance and burst size of methanal.Therefore, resin type formaldehyde-trapping agent is more excellent than other formaldehyde-trapping agent over-all properties.
In conjunction with literature search, there is not yet the direct report using through certain polycondensation, the resinification resin of part is urea-formaldehyde resin adhesive formaldehyde-trapping agent.
Summary of the invention
Technical problem to be solved by this invention be to provide a kind of be applicable to urea-formaldehyde resin, there is certain molecular weight and there is the resin base formaldehyde-trapping agent of certain formaldehyde catching ability, the double standards of mixing to realize wood adhesive intensity and burst size of methanal by this trapping agent with urea-formaldehyde resin main gel stick.
In the present invention, " alkali-acid-alkali " technique is selected in the preparation of formaldehyde-trapping agent, and the final mol ratio F/U of formaldehyde and urea is 1:2.41 ~ 4.0, and formaldehyde is disposable to add, and urea adds at twice, 85 ~ 95 DEG C of temperature of reaction, 2 ~ 3 hours reaction times.
Preparation method's step of melamine-urea-methyl aldehyde copolycondensation formaldehyde-trapping agent of the present invention is as follows:
1. the reaction initial stage once adds the formaldehyde of metering, adjust pH value between 8.0-8.5, under stirring, add urea, trimeric cyanamide and suitable quantity of water for the first time, control the mol ratio F/U of formaldehyde and urea at 1:2.0-2.4, the mol ratio F/M of formaldehyde and trimeric cyanamide is between 1:0.05-0.5;
2. after stirring reaction 10-30 minute, be warmed up to gradually 90 ~ 99 DEG C, under 90 ~ 99 DEG C of conditions, after insulation reaction 30-60 minute, adjust pH value between 4.5-5.5, insulation reaction 30-120 minute;
3. adjust pH value between 8.5-9.5, control temperature under 85 ~ 95 DEG C of conditions, add urea and ten water Sodium Tetraboratees for the second time, and add suitable quantity of water control solids content, control final formaldehyde and urea mol ratio F/U between 1:2.41-4.01, insulation reaction is cooling blowing after 15 ~ 45 minutes.
In step 1, be reaction raw materials except selecting urea, formaldehyde monomers, also can select the preshrunk aggressiveness of urea and formaldehyde.The aqueous sodium hydroxide solution that the adjusting of pH value can operating weight concentration is 20 ~ 30% and 10% aqueous formic acid.
The invention has the advantages that:
1) interpolation of resin type formaldehyde-trapping agent has further reduced the mol ratio of urea-formaldehyde resin main gel stick urea and formaldehyde, the free urea remaining in system and the methylol compound with reactive behavior can with main gel stick in formaldehyde reaction, effectively reduce the burst size of methanal of final artificial board;
2) because resin base formaldehyde-trapping agent performance is similar to urea-formaldehyde resin main body Adhensive performance, its interpolation can not impact urea-formaldehyde resin adhesive preparation and operating procedure, can mix with various different performance urea-formaldehyde resins to use and on the impact such as curing performance, sizability of urea-formaldehyde resin adhesive not quite;
3) adding proportion of resin type formaldehyde-trapping agent can be done corresponding adjustment according to the performance requriements of final wood-based panel product, and flexible operation is easy;
4) preparation of resin type formaldehyde-trapping agent is without increasing relevant equipment investment, and raw materials and method are all similar with urea-formaldehyde resin, and cost increases not obvious.
The present invention has obtained a kind of resin type formaldehyde-trapping agent, and its feature is that trapping agent is taking melamine-urea-methyl aldehyde copolycondensation as basis, and in system, free urea, methylol compound and polycondensation product thereof exist simultaneously, and without free formaldehyde.It can mix use with urea-formaldehyde resin main gel stick, obviously reduce the burst size of methanal of tackiness agent, and within the scope of certain weight adding proportion, can not cause obvious impact to the strength property of urea-formaldehyde resin main gel stick, preferably adding proportion is total resin added 10 ~ 20%.This formaldehyde-trapping agent is applicable to various urea-formaldehyde resins, is especially applicable to the urea-formaldehyde resin being prepared by lower urea and formaldehyde mole ratio.Their mixed system is applicable to the production of various indoor level wood-based plates.
Embodiment
Every part of embodiment 1:(is parts by weight, gram or kilogram)
1) get 102 parts of urea, 302 parts of formalin solutions and 225 parts of water, the NaOH aqueous solution that is 20% by weight concentration regulates pH value to 8.0;
2) be warming up to 90 ° of C, and at this temperature, react 45 minutes;
3) aqueous formic acid that is 10% by weight concentration regulates pH value to 4.5, continues reaction 60 minutes;
4) regulate pH value to 8.0, add 457 parts of urea and ten water Sodium Tetraboratees and 54 parts of water, insulation reaction is after 20 minutes, cooling, adjusts pH to 8.0 ~ 8.5, blowing.
Every part of embodiment 2:(is parts by weight, gram or kilogram)
1) get 207 parts of urea formaldehyde performed polymers (wherein the weight percent of each material is respectively formaldehyde: urea: water=54:23:23), 76 parts of urea and 177 parts of water, the NaOH aqueous solution that is 20% by weight concentration regulates pH value to 8.0;
2) be warming up to 90 ° of C, and at this temperature, react 30 minutes;
3) aqueous formic acid that is 10% by weight concentration regulates pH value to 5.0, continues reaction 60 minutes;
4) regulate pH value to 8.0, add 323 parts of urea and ten water Sodium Tetraboratees, 50 parts of sodium-chlor and 54 parts of water, insulation reaction is after 20 minutes, cooling, adjusts pH to 8.0 ~ 8.5, blowing.
It is 650 ~ 700g/cm that formaldehyde-trapping agent prepared in accordance with the present invention and urea-formaldehyde resin (urea and formaldehyde mole ratio F/U=1) are mixed with to density
3shaving board, tackiness agent resin added is 10% of over dry wood shavings weight, hot pressing time is 5 minutes.When the addition of formaldehyde-trapping agent is total resin added 10 ~ 20% time, the burst size of methanal of shaving board is 0.44 ~ 0.73mg/L, reduce by 20 ~ 50% when not adding formaldehyde-trapping agent, and it is little on the strength property impact of shaving board, the internal bond strength value of shaving board is 0.5 ~ 0.8MPa, meets indoor level wood-based plate performance requriements.
Claims (1)
1. a melamine-urea-methyl aldehyde copolycondensation resin type formaldehyde-trapping agent preparation method, is characterized in that:
A. reacting the initial stage once adds the formaldehyde of metering, adjust pH value between 8.0-8.5, under stirring, add urea, trimeric cyanamide and suitable quantity of water for the first time, control the mol ratio F/U of formaldehyde and urea at 1:2.0-2.4, the mol ratio F/M of formaldehyde and trimeric cyanamide is between 1:0.05-0.5;
B. after stirring reaction 10-30 minute, be warmed up to gradually 90 ~ 99 DEG C, under 90 ~ 99 DEG C of conditions, after insulation reaction 30-60 minute, adjust pH value between 4.5-5.5, insulation reaction 30-120 minute;
C. adjust pH value between 8.5-9.5, control temperature under 85 ~ 95 DEG C of conditions, add urea and ten water Sodium Tetraboratees for the second time, and add suitable quantity of water control solids content, control final formaldehyde and urea mol ratio F/U between 1:2.41-4.01, insulation reaction is cooling blowing after 15 ~ 45 minutes;
Melamine-urea-methyl aldehyde copolycondensation resin type formaldehyde-trapping agent outward appearance is milky white liquid or paste, is made up of free urea, methylol compound, resin initial stage polymkeric substance and water, and wherein free urea content is 5 ~ 40%; Methylol compound content is 10 ~ 50%, and wherein dihydroxymethyl compounds content accounts for 40 ~ 90% of total amount; Resin initial stage polymer content is 10 ~ 40%, and molecular-weight average is 100 ~ 500, comprises 1-6 structural unit in molecular chain.
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| CN102675574B true CN102675574B (en) | 2014-06-11 |
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| CN102961955B (en) * | 2012-11-26 | 2015-09-23 | 山东泰德新能源有限公司 | A kind of formaldehyde scavenger and preparation method thereof |
| CN104530339B (en) * | 2014-12-19 | 2016-06-29 | 宜昌山山林业有限责任公司 | A kind of preparation method of low-poison urea-formaldehyde resin adhesive |
| CN105348464B (en) * | 2015-12-20 | 2017-10-31 | 江西绿洲环保新材料股份有限公司 | The preparation method of environment-friendly modified urea-formaldehyde resin adhesive |
| CN110054710A (en) * | 2019-04-30 | 2019-07-26 | 江苏迅驰新能源科技股份有限公司 | A kind of based Wood Adhesives additive and preparation method thereof except formaldehyde |
| CN110026167A (en) * | 2019-04-30 | 2019-07-19 | 江苏迅驰新能源科技股份有限公司 | A kind of particulate adsorbent material and preparation method thereof for removing formaldehyde |
| CN113461888B (en) * | 2021-08-05 | 2023-06-06 | 西南林业大学 | Hyperbranched urea-polyamine-formaldehyde copolycondensation resin and preparation method thereof |
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| US8088881B2 (en) * | 2008-06-25 | 2012-01-03 | Momentive Specialty Chemicals Inc. | Storage stable melamine-urea-formaldehyde resins and applications thereof |
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Non-Patent Citations (4)
| Title |
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| 三聚氰胺脲醛树脂胶粘剂的改性;闫文涛等;《精细石油化工进展》;20080630;第9卷(第6期);第29-32页 * |
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