CN102167788B - Preparation method of urea formaldehyde resin rubber powder - Google Patents
Preparation method of urea formaldehyde resin rubber powder Download PDFInfo
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Abstract
The invention discloses a preparation method of urea formaldehyde resin rubber powder, which comprises the following steps: firstly adding formalin with the design amount into a three-neck flask with a reflux condensation tube, regulating the pH value to 1.5-2.5, adding a first batch of urea accounting for 50-70% of the total amount into a reaction kettle, when being at the reaction temperature of 90-95 DEG C, immediately rapidly reducing the temperature to 75-80 DEG C when turbidity appears during the reaction, regulating the pH value to 8.0-9.0, adding a second batch of 10-29% urea, then regulating the pH value to 4.5-5.5, and reacting for 30-40 minutes; and further regulating the pH value to 7.0-8.0, adding a modifier, and performing the acid-base-acid-base process so as to synthesize urea formaldehyde resin prepared by the method, and the viscosity of stock solution does not change greatly in comparison with the ordinary process. After the rubber powder obtained by spray drying forms regenerated rubber with water, the free formaldehyde content is reduced, the bonding strength and the dipping and peeling strength are greatly improved, and the formaldehyde releasing amount is lower than 0.5%.
Description
Technical field
The present invention relates to a kind of preparation method, be specifically related to a kind of preparation method of urea formaldehyde resin adhesive powder.
Background technology
Urea-formaldehyde resin is the polymkeric substance that urea and formaldehyde reaction obtain, and claims again urea-formaldehyde resin.Because of the raw materials of this resin be easy to get, with low cost, show again during as sizing agent that curing speed is fast, bonding strength good, do not pollute adherend, the good characteristics of anti-weak electrolyte performance, thereby be widely used as wood-processing industry.But when the timber-work that has used urea-formaldehyde resin adhesive is used for interior decoration, can be to release formaldehyde in room; And formaldehyde has hormesis to people's eye, mucous membrane and respiratory tract, is also potential carinogenicity material simultaneously, long-term inhaled formaldehyde, and HUMAN HEALTH can be subject to great harm.Therefore since the 1950's, developed country namely starts urea-formaldehyde resin goods burst size of methanal is in use strictly limited.In China, formaldehyde while using the urea-formaldehyde resin goods in house decoration discharges and causes that also people pay attention to, and national quality supervision and inspection general bureau has promulgated the mandatory national standards GB/T18580-2001 of " in indoor hardware fitting wood-based plate and goods thereof, formaldehyde discharges and limits the quantity of " in calendar year 2001.
In urea-formaldehyde resin adhesive, the dispose procedure of formaldehyde is very complicated, and is inevitable.Wherein the most direct reason is will use excessive formaldehyde while preparing urea-formaldehyde resin, makes in the urea-formaldehyde resin finished product and has a large amount of free formaldehydes.If the urea-formaldehyde resin glue of liquid state can spray-dried technology be made rubber powder, when rubber powder and water are combined formation regeneration sizing agent again, compare with the free formaldehyde content in former urea-formaldehyde resin glue and will reduce in a large number, this technology is applied at present.
Secondly, methylol in the urea-formaldehyde resin molecule, can with urea-formaldehyde resin in or the chemical reaction that contains a plurality of reactive hydrogens in base material form cross-linked structure, be urea-formaldehyde resin as sizing agent use chemical fundamentals, but inevitably to discharge the formaldehyde small molecules in reaction process; But, due to the defect in the urea-formaldehyde resin microtexture, cause sizing agent in use chemical reaction to occur and discharge a large amount of formaldehyde.For reducing the burst size of methanal in the use procedure of urea-formaldehyde resin goods, correlative study person has carried out a large amount of work.Mainly to be undertaken by adjusting the modes such as UF resin synthesis technology, improvement urea-formaldehyde resin adhesive formula at present.
The synthesis mechanism of urea-formaldehyde resin is namely that excess formaldehyde and urea obtain the process of superpolymer by the dimethylolurea that addition reaction generates through polycondensation at acidic conditions.Generally, addition reaction is that weak basic condition carries out, and under acidic conditions, addition reaction and condensation reaction can occur simultaneously.The method of present more use is to adopt the technique of " weak base-weak acid-weak base " to synthesize urea-formaldehyde resin, concrete steps are namely: first with part urea and formaldehyde, carry out addition reaction under weak basic condition, then carry out polycondensation under mild acid conditions, obtain again the superpolymer as tackiness agent finally through series reaction under the weak base condition.According to the synthetic urea-formaldehyde resin of this technique, the reaction times is longer, and the product Free-formaldehyde content that obtains is more, poor stability while as sizing agent, using, and cohesive strength is not high, can discharge a large amount of formaldehyde again.
To sum up, when utilizing the burst size of methanal of prior art in reducing the urea-formaldehyde resin use procedure, irrationality due to urea-formaldehyde resin synthetic technology or drying process with atomizing design, can make the degradation of the aspect such as cohesive strength, water tolerance, ageing resistance of sizing agent, cause timber-work second-rate.
Summary of the invention
The objective of the invention is for solving when utilizing the burst size of methanal of prior art in reducing the urea-formaldehyde resin use procedure, irrationality due to urea-formaldehyde resin synthetic technology or drying process with atomizing design, can make the degradation of the aspect such as cohesive strength, water tolerance, ageing resistance of sizing agent, cause the second-rate problem of timber-work, and then a kind of preparation method of urea formaldehyde resin adhesive powder is provided.
Its technical scheme of the preparation method of urea formaldehyde resin adhesive powder of the present invention is as follows: at first to the formalin that adds design flow in the there-necked flask with reflux condensing tube, then reactor is warmed up to 45～60 ℃, regulate pH value to 1.5～2.5, add first urea that accounts for total amount 50～70% in reactor, continue to heat up, during temperature of reaction to 90～95 ℃, reacted 20～30 minutes; When reaction occurs when muddy, be cooled to rapidly immediately 75～80 ℃ and the pH value is adjusted to 8.0～9.0, add the urea of second batch 10～29%, reacted 30～40 minutes; Then the pH value is adjusted to 4.5～5.5, reacted 30～40 minutes; Again the pH value is transferred to 7.0～8.0, urea-formaldehyde resin properties-correcting agent and remaining urea are joined in reactant, react after 30～40 minutes, product is down to room temperature, discharging is standby; The processing condition that powder is made in spraying are: the atomizing wheel rotating speed is 200～500r/min, and the drying tower inlet temperature is 100～140 ℃, and the drying tower temperature out is 80～100 ℃, and input speed is 30～80mLmin
-1Spray-drying tower is furnished with the suction pressure device, rubber powder forms and separates by cyclonic separator, collect powder in the tower exit with stainless steel storage tank, after 180～220 mesh filter screens filter, be placed in loft drier with the bag sealing and preserve, described properties-correcting agent has trimeric cyanamide, polyvinyl alcohol, phenol, Sumstar 190 or thiocarbamide.
The present invention adopts the synthetic technology of " strong acid-weak base-weak acid-weak base " to prepare urea-formaldehyde resin.At first carry out the polyaddition reaction of urea and formaldehyde under the condition of pH value＜3, the methylene bridge of the water-tolerant that can generate and Uron ring, strengthen stability in use and the water tolerance of urea-formaldehyde resin, extend the work-ing life of sizing agent, also can reduce the burst size of methanal in use procedure.For reducing the reaction times, and increase the stability structure in the urea-formaldehyde resin molecule, in this step, temperature of reaction will be controlled at 90～95 ℃.But urea-formaldehyde resin easily forms three dimensional structure under this strong acid hot conditions, and gel reaction occurs, and it is particularly important that the control of this reaction time seems.In the present invention whether muddiness to occur as boundary, the reaction times should be less than 30 minutes the reaction times of urea-formaldehyde resin under strong acidic condition.
Within pH value in reaction under described the 3rd step mild acid conditions also needs to be controlled at suitable scope.When pH value＞6, the time of carrying out condensation reaction is longer, and easily generates the structure of dimethylene ether bridge, contains the sizing agent of more this structure, in use can discharge a large amount of formaldehyde; The existence of this structure can make the water tolerance of sizing agent descend in addition.Thereby guaranteeing that under the prerequisite that reaction can steadily be carried out, the pH value in suitable reduction condensation reaction stage, be conducive to generate performance urea-formaldehyde resin preferably, during this goes on foot, the pH value is chosen in 4.5～5.5 scope.Reaction times is related to the height of the resin degree of polycondensation and solids content in addition, and affects the performance such as bonding strength, water tolerance of resin.Reaction times is too short, and polycondensation is incomplete, solid content is low, viscosity is little, and free formaldehyde content is high, the glue-line physical strength is low; On the contrary, the polycondensation time lengthening, relative molecular mass is large, and viscosity is too high, and the resin period of storage is short, thereby bonding quality is reduced.This process reaction time is controlled at 30～40 minutes.
The reactions in described second, four steps will be carried out in the pH value is 7～9 weak alkaline medium.Formaldehyde and urea generation addition reaction generate stable methylolurea, and alkalescence is stronger, and addition reaction is faster.But pH greater than 9 strongly basic medium in, disproportionation reaction easily occurs and generates formic acid and methyl alcohol in formaldehyde, so the present invention is controlled at 8.0～9.0 with the pH value of alkaline condition.Reaction times under alkaline condition is controlled at 30～40 minutes in addition.
The alkaline pH conditioning agent that uses in described urea-formaldehyde resin polyaddition reaction process comprises wherein a kind of in NaOH solution or ammoniacal liquor trolamine.
The acidic ph modifier that uses in described urea-formaldehyde resin polyaddition reaction process comprise in the hydrochloric acid of aqueous ammonium chloride solution, ammonium sulfate solution, oxalic acid or lower concentration wherein one or more.
Described formaldehyde is 35～40% the mass concentration aqueous solution, and the present invention will design by 37% mass concentration the consumption of formaldehyde.
The mol ratio of described formaldehyde and urea is also wanted suitably.Mol ratio increases the dimethylolpropionic urea that produces in the resin that generates while being the raising of formaldehyde consumption, three Oxymethureas increase, and after resin solidification, cross-linking density is high, so viscosity is large, and the methylol that generates is also many, when the effect of further heating or solidifying agent is also shortened lower set time.If but after the excessive curing of mol ratio, unreacted methylol quantity increases, free formaldehyde is also high, and the water tolerance of resin is descended.And mol ratio is too low, and the free formaldehyde in resin can reduce, poor adhesion, so the mol ratio of formaldehyde described in the preparation process of urea-formaldehyde resin of the present invention and urea is controlled at 1.4～1.8.
Be bond strength, the water resistance that improves urea-formaldehyde resin adhesive in the present invention, and reduce the free formaldehyde content in resin,, except by controlling reaction conditions, can also add the mode of properties-correcting agent to realize in reaction process.Described properties-correcting agent has trimeric cyanamide, polyvinyl alcohol, phenol, Sumstar 190 or thiocarbamide etc.Three amino in its melamine molecule, the hydroxyl in polyvinyl alcohol molecule, the phenolic hydroxyl group in phenol etc. all can generate methylol with formaldehyde, these contain intermediates when heating and the urea-formaldehyde resin molecular reaction of a large amount of methylols, the crosslinked macromole that becomes, can improve the quality of urea-formaldehyde glue.
Wherein contain triazine ring structure in the molecule of trimeric cyanamide, 3 amino that reactive behavior is very high are arranged, easily crosslinked with urea-formaldehyde resin, the formation tridimensional network, sealed simultaneously many water-absorbent groups, thereby greatly improved the water resistance of urea-formaldehyde resin.Phenol is introduced urea aldehyde condensation polymerization system, increased reactive site on the one hand, reduced the methylol number in the molecule; , by the condensation with phenolic hydroxyl group, form flexible larger ehter bond on the other hand, improved water tolerance and the fragility of product, simultaneously, increased more phenyl ring adjacency pair position stiff chain after adhesive curing, improved the mechanical strength of product.Polyvinyl alcohol can generate polyvinyl formal with formaldehyde reaction, the latter is chain macromolecule compound, has good toughness and elasticity, it is embedded in the macromole of urea-formaldehyde resin, can improve resin structure, resin viscosity is descended, improve the snappiness of urea-formaldehyde resin molecular chain, improve ageing-resistant performance.But the polyvinyl alcohol add-on can not be too much, otherwise, will affect the water resistance of resin.The add-on of described properties-correcting agent is no more than 8% of formaldehyde and urea total amount.
Also comprise following auxiliary agent in preparation method of the present invention: protective colloid, inorganic anti-agglomerating agent and defoamer etc.
Protective colloid of the present invention be alcoholysis degree more than 90%, the polymerization degree is 300～1200 polyvinyl alcohol (PVA).Before using, PVA is mixed with 20% the aqueous solution, its consumption is controlled at 4～10% of urea-formaldehyde resin polymkeric substance total amount.
Inorganic anti-agglomerating agent of the present invention comprises calcium carbonate, clay, silicon-dioxide, pure aluminium silicate, talcum powder, wherein a kind of in kaolin, consumption urea-formaldehyde resin polymkeric substance total amount 5%～20% between.
Being used for explanation is undertaken by following standard through the method for the prepared urea-formaldehyde resin adhesive performance of method of the present invention:
Measure the viscosity of synthetic urea-formaldehyde resin stoste according to GB/T14074.3-93;
Measure the content of urea-formaldehyde resin reclaimed rubber Free-formaldehyde according to GB/T14074.16-93;
Measure the bonding strength of urea-formaldehyde resin reclaimed rubber according to GB/T9846-2004;
Measure the dipping stripping strength of urea-formaldehyde resin reclaimed rubber according to GB/T18103-2000;
Measure the burst size of methanal of urea-formaldehyde resin adhesive reclaimed rubber according to GB/T18580-2001.
Beneficial effect of the present invention: after the rubber powder of spraying drying gained and water formed reclaimed rubber, free formaldehyde content wherein reduced, and cohesive strength, dipping stripping strength all are improved largely, and burst size of methanal is lower than 0.5%.
Embodiment
The better technical scheme of the preparation method of the urea formaldehyde resin adhesive powder that the specific embodiment of the invention provides is as follows: at first to the formalin that adds design flow in the there-necked flask with reflux condensing tube, then reactor is warmed up to 45～60 ℃, regulate pH value to 1.5～2.5, add first urea that accounts for total amount 50～70% in reactor, continue to heat up, during temperature of reaction to 90～95 ℃, reacted 20～30 minutes; When reaction occurs when muddy, be cooled to rapidly immediately 75～80 ℃ and the pH value is adjusted to 8.0～9.0, add the urea of second batch 10～29%, reacted 30～40 minutes; Then the pH value is adjusted to 4.5～5.5, reacted 30～40 minutes; Again the pH value is transferred to 7.0～8.0, urea-formaldehyde resin properties-correcting agent and remaining urea are joined in reactant, react after 30～40 minutes, product is down to room temperature, discharging is standby; The processing condition that powder is made in spraying are: the atomizing wheel rotating speed is 200～500r/min, and the drying tower inlet temperature is 100～140 ℃, and the drying tower temperature out is 80～100 ℃, and input speed is 30～80mLmin
-1Spray-drying tower is furnished with the suction pressure device, and latex powder forms by cyclonic separator separates, and in the tower exit, with stainless steel storage tank, collects powder, after 180～220 mesh filter screens filter, is placed in loft drier with the bag sealing and preserves.
The alkaline pH conditioning agent that uses in described urea-formaldehyde resin polyaddition reaction process comprises wherein a kind of in NaOH solution or ammoniacal liquor trolamine.
The acidic ph modifier that uses in described urea-formaldehyde resin polyaddition reaction process comprise in the hydrochloric acid of aqueous ammonium chloride solution, ammonium sulfate solution, oxalic acid or lower concentration wherein one or more.
Described formaldehyde is 35～40% the mass concentration aqueous solution.
The mol ratio of described formaldehyde and urea is controlled at 1.4～1.8.
Described properties-correcting agent has trimeric cyanamide, polyvinyl alcohol, phenol, Sumstar 190 or thiocarbamide.
The add-on of described properties-correcting agent (weight) equals less than 8% of formaldehyde and urea total amount (weight).
Also comprise following auxiliary agent in the preparation method: protective colloid, inorganic anti-agglomerating agent and defoamer.
Described protective colloid be alcoholysis degree more than 90%, the polymerization degree is 300～1200 polyvinyl alcohol (PVA); Before using, polyvinyl alcohol is mixed with 20% the aqueous solution, the consumption of polyvinyl alcohol (weight) is controlled at 4～10% of urea-formaldehyde resin polymkeric substance total amount (weight).
Inorganic anti-agglomerating agent of the present invention comprises wherein a kind of in calcium carbonate, clay, silicon-dioxide, pure aluminium silicate, talcum powder or kaolin, consumption (weight) urea-formaldehyde resin polymkeric substance total amount (weight) 5%～20% between.
After rubber powder and water formation reclaimed rubber that the technical solution of the present invention gained is described, free formaldehyde content wherein reduces, and cohesive strength, dipping stripping strength all are improved largely, and provide following examples and Comparative Examples to be further described.
One, urea-formaldehyde resin stoste is synthetic
Embodiment 1
Add formalin 145.95 grams in the there-necked flask with reflux condensing tube, then reactor is warmed up to 60 ℃, with the aqueous solution of 10%HCl, regulate pH value to 2.0, add 42 gram urea, continue to heat up, during temperature of reaction to 90 ℃, reacted approximately 20 minutes; When reaction occurs when muddy, be cooled to rapidly immediately 75 ℃ and the pH value is adjusted to 8.5, add 12 gram urea, reacted 30 minutes; Then use NH
4The Cl aqueous solution is adjusted to 5.5 with the pH value, reacts 30 minutes; Again the pH value is transferred to 8.0, remaining 6 gram urea are joined in reactant, react after 30 minutes, product is down to room temperature, discharging is standby.
Embodiment 2
Add formalin 145.95 grams in the there-necked flask with reflux condensing tube, then reactor is warmed up to 60 ℃, with the aqueous solution of 10% formic acid, regulate pH value to 2.0, add 42 gram urea, continue to heat up, during temperature of reaction to 90 ℃, reacted approximately 20 minutes; When reaction occurs when muddy, be cooled to rapidly immediately 80 ℃ and the pH value is adjusted to 8.5, add 12 gram urea and 3 gram trimerization ammonia amine, reacted 30 minutes; Then use NH
4The Cl aqueous solution is adjusted to 5.5 with the pH value, reacts 30 minutes; Again the pH value is transferred to 8.0, remaining 6 gram urea and 2.7 gram ultrapas are joined in reactant, react after 30 minutes, product is down to room temperature, discharging is standby.
Embodiment 3
Add formalin 137.84 grams in the there-necked flask with reflux condensing tube, then reactor is warmed up to 60 ℃, with the aqueous solution of 10% formic acid, regulate pH value to 2.0 left and right, add 42 gram urea, continue to heat up, during temperature of reaction to 90 ℃, reaction approximately 20 minutes; When reaction occurs when muddy, be cooled to rapidly immediately 80 ℃ and the pH value is adjusted to 8.5, add 12 gram urea, reacted 30 minutes; Then use NH
4The Cl aqueous solution is adjusted to 5.5 with the pH value, reacts 30 minutes; Again the pH value is transferred to 8.0, the polyvinyl alcohol water solution that is 20% with remaining 6 gram urea and 33.3 gram concentration joins in reactant, reacts after 30 minutes, and product is down to room temperature, and discharging is standby.
Embodiment 4
Add formalin 121.62 grams in the there-necked flask with reflux condensing tube, then reactor is warmed up to 60 ℃, with the aqueous solution of 10% formic acid, regulate pH value to 2.0 left and right, add 42 gram urea, continue to heat up, during temperature of reaction to 90 ℃, reaction approximately 20 minutes; When reaction occurs when muddy, be cooled to rapidly immediately 80 ℃ and the pH value is adjusted to 8.5, add 12 gram urea, reacted 30 minutes; Then use NH
4The Cl aqueous solution is adjusted to 5.5 with the pH value, reacts 30 minutes; Again the pH value is transferred to 8.0, remaining 6 gram urea and 5.7 gram phenol are joined in reactant, react after 30 minutes, product is down to room temperature, discharging is standby.
Comparative Examples 1
Add formalin 162.26 grams in the there-necked flask with reflux condensing tube, then reactor is warmed up to 60 ℃, the pH value is adjusted to 8.5, add 50 gram urea, continue to heat up, reaction approximately 30 minutes; Add subsequently 10 gram urea, reacted 30 minutes; Then use NH
4The Cl aqueous solution is adjusted to 5.5 with the pH value, reacts 30 minutes; Again the pH value is transferred to 8.0, add in remaining 10 gram urea, react after 30 minutes, product is down to room temperature, discharging is standby.
Comparative Examples 2
Add formalin 105.41 grams in the there-necked flask with reflux condensing tube, then reactor is warmed up to 60 ℃, add 50 gram urea, the pH value is adjusted to 8.5 and continue to be warming up to 80 ℃, reacted 30 minutes; Then use NH
4The Cl aqueous solution is adjusted to 5.5 with the pH value, reacts 30 minutes; Again the pH value is transferred to 8.0, add in remaining 10 gram urea, react after 30 minutes, product is down to room temperature, discharging is standby.
Two, the preparation of urea formaldehyde resin adhesive powder
At first the glue of gained in above each example is diluted to 50% stoste standby.
Choose prepared stoste 100 grams, with the NaOH dilute solution of 0.2 gram 5%, regulate pH value to 8.5.Add in feed liquid that molecular weight is 800, saponification deg is 93%, concentration is 20% the PVA aqueous solution 20 grams, calcium carbonate 3 grams, and 0.05 gram defoamer, disperse to be formed for spray-dired feed liquid under the violent stirring effect.
Setting the atomizer rotating is 300rmin
-1, inlet temperature is 130 ℃, temperature out is 90 ℃, input speed 50mlmin
-1Carry out spraying drying under condition.Spray-drying tower is furnished with the suction pressure device, and rubber powder forms by cyclonic separator and separates, and in the tower exit, with stainless steel storage tank, collects powder, after 200 mesh filter screens filter, is placed in loft drier with the bag sealing and preserves.
Gained sizing agent performance comparison in (table one) each example
As seen from the above table, add properties-correcting agent and the prepared urea-formaldehyde resin of warp " strong acid-weak base-weak acid-weak base " synthesis technique, former fluid viscosity does not have larger variation than ordinary process.After the rubber powder of spraying drying gained and water formed reclaimed rubber, free formaldehyde content wherein reduced, and cohesive strength, dipping stripping strength all are improved largely, and burst size of methanal is lower than 0.5%.
Claims (6)
1. the preparation method of a urea formaldehyde resin adhesive powder, it is characterized in that, at first to the formalin that adds design flow in the there-necked flask with reflux condensing tube, then reactor is warmed up to 45～60 ℃, regulate pH value to 1.5～2.5, add first urea that accounts for total amount 50～70% in reactor, continue to heat up, during temperature of reaction to 90～95 ℃, reacted 20～30 minutes; When reaction occurs when muddy, be cooled to rapidly immediately 75～80 ℃ and the pH value is adjusted to 8.0～9.0, add the urea of second batch 10～29%, reacted 30～40 minutes; Then the pH value is adjusted to 4.5～5.5, reacted 30～40 minutes; Again the pH value is transferred to 7.0～8.0, urea-formaldehyde resin properties-correcting agent and remaining urea are joined in reactant, react after 30～40 minutes, product is down to room temperature, discharging is standby; The processing condition that powder is made in spraying are: the atomizing wheel rotating speed is 200～500r/min, and the drying tower inlet temperature is 100～140 ℃, and the drying tower temperature out is 80～100 ℃, and input speed is 30～80mLmin
-1Spray-drying tower is furnished with the suction pressure device, latex powder forms separates by cyclonic separator, collect powder in the tower exit with stainless steel storage tank, after 180～220 mesh filter screens filter, be placed in loft drier with the bag sealing and preserve, described properties-correcting agent has trimeric cyanamide, polyvinyl alcohol, phenol, Sumstar 190 or thiocarbamide.
2. the preparation method of urea formaldehyde resin adhesive powder according to claim 1, is characterized in that, the alkaline pH conditioning agent that uses in described urea-formaldehyde resin polyaddition reaction process comprises wherein a kind of in NaOH solution or ammoniacal liquor trolamine.
3. the preparation method of urea formaldehyde resin adhesive powder according to claim 1, it is characterized in that, the acidic ph modifier that uses in described urea-formaldehyde resin polyaddition reaction process comprises wherein one or more the mixing in the hydrochloric acid of aqueous ammonium chloride solution, ammonium sulfate solution, oxalic acid or lower concentration.
4. the preparation method of urea formaldehyde resin adhesive powder according to claim 1, is characterized in that, also comprises following auxiliary agent in the preparation method: protective colloid, inorganic anti-agglomerating agent and defoamer.
5. the preparation method of urea formaldehyde resin adhesive powder according to claim 4, is characterized in that, described protective colloid be alcoholysis degree more than 90%, the polymerization degree is 300～1200 polyvinyl alcohol; Before using, polyvinyl alcohol is mixed with 20% the aqueous solution, the consumption of polyvinyl alcohol is controlled at 4～10% of urea-formaldehyde resin polymkeric substance total amount.
6. the preparation method of urea formaldehyde resin adhesive powder according to claim 4, it is characterized in that, described inorganic anti-agglomerating agent comprises wherein a kind of in calcium carbonate, clay, silicon-dioxide, pure aluminium silicate, talcum powder and kaolin, consumption urea-formaldehyde resin polymkeric substance total amount 5%～20% between.
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| CN102516710B (en) * | 2011-12-09 | 2015-01-28 | 王喆 | Anti-flaming thermal-insulation environmentally-friendly polymeric foaming material and method for producing the same |
| CN103254860B (en) * | 2013-05-27 | 2014-06-11 | 新凯骅实业发展有限公司 | UFIM adhesive and preparation method thereof and UFIM glued ecological plant fiber board and particle board |
| CN103709601B (en) * | 2013-12-09 | 2016-04-20 | 辽宁盖亚科技开发有限责任公司 | Sheet material containing modified urea-formaldehyde foamed glue and the application of sheet material and preparation method thereof |
| CN104927728B (en) * | 2014-10-16 | 2017-08-15 | 洋浦久聚台木材科技有限公司 | A kind of preparation method of the Lauxite for the low content of free formaldehyde of resistance to boiling water |
| CN106147675A (en) * | 2015-03-27 | 2016-11-23 | 秦瑛 | A kind of melamine modified urea-formaldehyde glue and production method thereof |
| CN104926444A (en) * | 2015-06-05 | 2015-09-23 | 宁夏共享生物化工有限公司 | Method for preparing slow/controlled release fertilizer by use of modified urea resin coating material |
| CN106827771A (en) * | 2016-12-20 | 2017-06-13 | 湖南柳鑫电子新材料有限公司 | A kind of high rigidity melamine sheeting caps and preparation method thereof |
| CN109530184A (en) * | 2018-09-28 | 2019-03-29 | 东北大学秦皇岛分校 | A kind of preparation method and spraying process of phase-change thermal storage-reflective insulation double thermal insulation coating |
| CN113492447A (en) * | 2020-04-05 | 2021-10-12 | 唐晓宇 | Poplar wood modifying liquid containing dialdehyde starch |
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| CN1966541A (en) * | 2006-11-10 | 2007-05-23 | 北京联合大学生物化学工程学院 | Low formaldehyde release volume urea formaldehyde resin preparation method |
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