CN100408607C - Urea-formaldehyde resin glue produced by making chlorate as catching agent and preparation method thereof - Google Patents
Urea-formaldehyde resin glue produced by making chlorate as catching agent and preparation method thereof Download PDFInfo
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- CN100408607C CN100408607C CNB2005101273967A CN200510127396A CN100408607C CN 100408607 C CN100408607 C CN 100408607C CN B2005101273967 A CNB2005101273967 A CN B2005101273967A CN 200510127396 A CN200510127396 A CN 200510127396A CN 100408607 C CN100408607 C CN 100408607C
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Abstract
The present invention discloses a urea-formaldehyde resin adhesive produced by using chlorate as a capturing agent and a preparation method thereof. The urea-formaldehyde resin adhesive is mainly prepared by the reaction of 162 to 189 parts of formaldehyde, 0.5 to 2.5 parts of ammonia water, 1.0 to 2.0 parts of melamine and 2.0 to 3.0 parts of chlorate on the basis of calculation taking 100 parts by weight of the dosage of urea. The solid content of the urea-formaldehyde resin adhesive is from 52 to 55%, and the content of free formaldehyde is less than 0.25%; the adhesion strength of the urea-formaldehyde resin adhesive is larger than 1.4MPa. In the preparation method, the chlorate is used as the capturing agent for the formaldehyde by utilizing the characteristics of stability property in alkaline media and strong oxidizability in acidic media of the chlorate, and is added under an alkaline condition after a polycondensation reaction of the urea with the formaldehyde is finished. The present invention has the advantages of low prices used raw materials, relatively small dosage of the melamine and low product cost, and the ammonium chloride is added when sheet materials are pressed; under a formed acid condition, formaldehyde and free formaldehyde generated by the breakage of unstable chemical bonds in the urea-formaldehyde resin adhesive are oxidated by the chlorate; therefore, the content of the formaldehyde in the urea-formaldehyde resin adhesive and man-made boards made from the adhesive can not exceed standards.
Description
One, technical field
The present invention relates to a kind of urea-formaldehyde resin adhesive, specifically be a kind of be urea-formaldehyde resin adhesive of producing of trapping agent and preparation method thereof with the oxymuriate.
Two, background technology
Urea-formaldehyde resin adhesive is the polycondensation product of urea and formaldehyde, is most widely used general in the timber industry, the tackiness agent of consumption maximum.Because of its raw materials for production are easy to get, production technique is simple, and is with low cost, and the bonding strength advantages of higher so since nineteen fifty-seven goes into operation in China, used so far always, is that other tackiness agent is irreplaceable.Along with the raising of living standards of the people and falling sharply in a large number of wildwood, wood-based plate is widely used in house decoration and furniture manufacturing, the problem of wood-based plate release formaldehyde is also just more and more outstanding, has become the present important factor that influences domestic environment, and the healthy of people in serious threat.
The formaldehyde that wood-based plate discharges has two main sources, and the one, because the reversibility and the no thoroughness of chemical reaction certainly exist not reacted raw material formaldehyde in the urea-formaldehyde resin adhesive that is synthesized; The 2nd, when addition reaction, unsettled valence bonds such as the methylol of generation and methylene radical, easy fracture when temperature is high and produce formaldehyde.
In order to solve wood-based plate release formaldehyde problem, scientific and technical personnel had developed the urea-formaldehyde resin adhesive of multiple low content of free formaldehyde in recent years.Low-poison urea-formaldehyde resin as developments such as the Zhang Chaojun of Shandong Normal University.(publication is in " Chinese tackiness agent " the 5th phase in 2005).Xiangtan Polytechnical College's chemical industry is the environment protection type urea formaldehyde resin (publication is in " Chinese tackiness agent " the 1st phase in 2004) of Yang Ming equality development.The urea-formaldehyde resin (patent No. CN1621477A) of the low content of free aldehyde of Yu Feng invention.The water-proof lower-aldehyde urea-formaldehyde resin of inventions such as Zhao Ying (patent application publication number is CN1461786A), the environment friendly urea-formaldehyde resin adhesive (patent application publication number is CN1262301A) of Ruan Yukun invention.
The common ground of foregoing invention is it all is to start with from the urea-formaldehyde glue synthesis technique, the polyvinyl alcohol that adds easy and formaldehyde reaction, trimeric cyanamide, raw materials such as thiocarbamide, the chemical reaction that takes place when making urea-formaldehyde resin synthetic is more complete, thereby the free formaldehyde content in the glue is reduced, these methods are effective to the free formaldehyde content that reduces in the urea-formaldehyde resin adhesive, but these methods have only solved first source of above-mentioned wood-based plate release formaldehyde, the problem that the urea-formaldehyde resin adhesive of use foregoing invention may occur is that urea-formaldehyde resin adhesive is qualified, and the wood-based plate that uses this urea-formaldehyde resin adhesive to make is defective.Have again because of in urea-formaldehyde resin adhesive, adding the high raw material of more price, cause environment protection type urea formaldehyde resin adhesive cost height, be not easy to promote the use of.
Three, summary of the invention
The present invention seeks to propose a kind of at the problems referred to above is that trapping agent is produced urea-formaldehyde resin adhesive and preparation method thereof with the oxymuriate, provides the urea-formaldehyde resin adhesive that a kind of production technique is simple, cost is low for producing the wood-based plate industry; Reduce the formaldehyde content in the wood-based plate that uses urea-formaldehyde resin adhesive production.
The technical scheme of being taked is for achieving the above object: in the condensation reaction of urea and formaldehyde, adjust the mol ratio of urea and formaldehyde, reduce the consumption of trimeric cyanamide and adjust joining day of trimeric cyanamide, after allowing formaldehyde and urea fully react, react with the trimeric cyanamide of relative capacity again, be used for reducing the free formaldehyde of urea-formaldehyde resin adhesive, so that the free formaldehyde content in the synthetic urea-formaldehyde resin adhesive is low as far as possible; Utilize oxymuriate in alkaline medium stable in properties, in acidic medium, show the characteristics of strong oxidisability, after polycondensation was finished, alkaline condition added oxymuriate down; During pressed sheet, because the adding of ammonia chloride has formed acidic conditions, formaldehyde and free formaldehyde and the oxymuriate generation oxidizing reaction that fracture produces takes place in the unstable chemical bond in the urea-formaldehyde resin adhesive, and its chemical equation is:
2KClO
3+3HCHO＝2KCl+3CO
2↑+3H
2O
65℃
Produce the raw material feed ratio of urea-formaldehyde resin adhesive: with amount of urea be 100 weight parts as calculating benchmark, mainly make by 100 parts of urea, 162-189 part 37%wt formaldehyde, 0.5-2.5 part 30%wt ammoniacal liquor, 1.0-2.0 part trimeric cyanamide, the reaction of 2.0-3.0 part oxymuriate.
Oxymuriate in the scheme is a formaldehyde-trapping agent, is specially: sodium chlorate, Potcrate.
The preparation method of urea-formaldehyde resin adhesive: urea adds in entire reaction course in batches.Earlier 162-189 part formaldehyde is dropped in the reactor, transferring pH value with 0.5-2.5 part ammoniacal liquor and caustic soda soln is 8, stirs when being warming up to 50 ℃, adds 62.1 parts of urea; Continue to rise to 90 ℃, be incubated 30 minutes, add 6.9 parts of urea; Be incubated 30 minutes again, transferring pH value with acetic acid solution is 4-5, continue reaction, 92 ℃ when being coated with 4 glasss of viscosimetrics and being 14s, transferring pH value with alkali lye is 8 to stop polycondensations, adds 1.0-2.0 trimeric cyanamide and 17.2 parts of urea, feed water coolant in the reacting kettle jacketing, after 30 minutes, add 13.8 parts of urea and 2.0-3.0 part oxymuriate, be cooled to 40 ℃ of blowings.
The urea-formaldehyde resin adhesive product solid content that such scheme makes is 52-55%, and content of free aldehyde is less than 0.25%, and bonding strength meets this product state quality standard greater than 1.4Mpa.
The present invention has the following advantages and positively effect:
1, do not use polyvinyl alcohol and the higher raw material of thiocarbamide price in the invention, reduced the consumption of trimeric cyanamide accordingly, make formaldehyde fully and behind the urea reaction, react with the trimeric cyanamide of relative capacity, product cost is low.
2, introduce oxymuriate as formaldehyde-trapping agent, in the urea-formaldehyde resin adhesive for preparing, under the alkaline condition, add oxymuriate, during with the urea-formaldehyde resin adhesive pressed sheet, urea-formaldehyde resin adhesive adds solidifying agent ammonium chloride, the pH value of urea-formaldehyde resin adhesive becomes acidity, and under the acidic conditions that forms, unstable chemical bond rupture produces in the urea-formaldehyde resin adhesive formaldehyde and free formaldehyde are melted by chlorate oxygen, very effective to the formaldehyde content that reduces in the wood-based plate, the contained formaldehyde of the wood-based plate of production does not exceed standard.
Four, embodiment
Embodiment 1: the preparation of urea-formaldehyde resin adhesive
Raw material is formed and content: 37%wt formaldehyde 162 parts of (940kg), urea 100 parts of (580kg), 30%wt ammoniacal liquor 1.79 parts of (10.4kg), trimeric cyanamide 1.79 parts of (10.4kg), 2.68 parts of oxymuriates (15.5kg), urea divides 4 batches of addings in entire reaction course.
At first, in reactor, add 940Kg formaldehyde solution, 10.4kg ammoniacal liquor, adding 30%wt sodium hydroxide (NaOH) solution accent pH value is 8, stirs when being warming up to 50 ℃, add 360Kg urea, continue to be warming up to 90 ℃, be incubated adding 40Kg urea after 30 minutes, continue insulation 30 minutes, transferring PH with 95%wt acetate is 4, continue to react to viscosity be 1 4s (be coated with 4 glasss of surveys, 92 ℃), transferring PH with 30%wt sodium hydroxide (NaOH) solution is 8, stops polycondensation; Add 10.4Kg trimeric cyanamide and 100Kg urea, feed water quench in the reacting kettle jacketing, add 15.5Kg sodium chlorate and 80Kg urea after 30 minutes, be cooled to 40 ℃ of blowings, the products obtained therefrom detected result is as follows:
Viscosity (20 ℃) 120mPa.s
PH value 8
Solid content 54.6%
30 days storage periods
Content of free aldehyde 0.18%
Bonding strength 1.52Mpa.
Use this urea-formaldehyde resin adhesive to produce core-board with known method, during pressed sheet, add ammonium chloride, urea-formaldehyde resin adhesive and timber are heated simultaneously, along with the rising of temperature, urea-formaldehyde resin adhesive is under the effect of ammonium chloride, and pH value becomes acidity, formaldehyde and free formaldehyde and the sodium chlorate generation oxidizing reaction that fracture produces takes place in the unstable chemical bond in the Resin adhesive, produces carbonic acid gas CO
2With water H
2O, thus the formaldehyde content in the artificial board reduced.The core-board of producing is after testing: formaldehyde content is 1.41mg/L, meets the GB18580-2001 national standard.
Embodiment 2: the preparation of urea-formaldehyde resin adhesive
Raw material is formed and content: 37%wt formaldehyde 178 parts of (2060kg), urea 100 parts of (1160kg), 30%wt ammoniacal liquor 2.5 parts of (29kg), trimeric cyanamide 1 part of (11.6kg), 3 parts in Potcrate (35kg), urea add in entire reaction course in batches.
In reactor, add 2060Kg formaldehyde, 29Kg ammoniacal liquor, transferring pH value with 30%wt sodium hydroxide (NaOH) solution is 8, be warming up to 50 ℃, add 720Kg urea, continue to be warming up to 90 ℃ of insulations, add 80Kg urea after 30 minutes, continue insulation 30 minutes, transferring PH with 95%wt acetate is 5, carries out polycondensation, when viscosity reaches 14s (with being coated with 4 glasss of surveys, 92 ℃) time, transferring PH with 30%wt sodium hydroxide (NaOH) solution is 8, stops polycondensation, adds 11.6Kg trimeric cyanamide and 200Kg urea, feed water quench in the reacting kettle jacketing, add 35Kg Potcrate and 160Kg urea after 30 minutes, be cooled to 40 ℃ of blowings, the products obtained therefrom detected result is as follows:
Viscosity (20 ℃) 115mPa.s
PH value 8
Solid content 54.1%
30 days storage periods
Content of free aldehyde 0.22%
Bonding strength 1.68Mpa
The method of producing sheet material with this glue is with embodiment 1, and with the core-board of this glue production after testing, formaldehyde content is 1.45mg/L, meets the GB18580-2001 national standard.
Embodiment 3: the preparation of urea-formaldehyde resin adhesive
Raw material is formed and content: 37%wt formaldehyde 189 parts of (2194kg), urea 100 parts of (1160kg), 30%wt ammoniacal liquor 0.5 part of (5.8kg), trimeric cyanamide 2 parts of (23.2kg), 2 parts of sodium chlorate (23.2kg), urea add in entire reaction course in batches.
In reactor, add 2194Kg formaldehyde, 5.8Kg ammoniacal liquor, transferring pH value with 30%wt sodium hydroxide (NaOH) solution is 8, be warming up to 50 ℃, add 720Kg urea, continue to be warming up to 90 ℃ of insulations, add 80Kg urea after 30 minutes, continue insulation 30 minutes, transferring PH with 95%wt acetate is 4, carries out polycondensation, when viscosity reaches 14s (with being coated with 4 glasss of surveys, 92 ℃) time, transferring PH with 30%wt sodium hydroxide (NaOH) solution is 8, stops polycondensation, adds 23.2Kg trimeric cyanamide and 200Kg urea, feed water quench in the reacting kettle jacketing, add 23.2Kg sodium chlorate and 160Kg urea after 30 minutes, be cooled to 40 ℃ of blowings, the products obtained therefrom detected result is as follows:
Viscosity (20 ℃) 123mPa.s
PH value 8
Solid content 52.9%
30 days storage periods
Content of free aldehyde 0.23%
Bonding strength 1.71Mpa
The method of producing sheet material with this urea-formaldehyde resin adhesive is with embodiment 1, and with the core-board of this urea-formaldehyde resin adhesive production after testing, formaldehyde content is 1.42mg/L, meets the GB18580-2001 national standard.
Embodiment 4: the preparation of urea-formaldehyde resin adhesive
Raw material is formed and content: 37%wt formaldehyde 170 parts of (1972kg), urea 100 parts of (1160kg), 30%wt ammoniacal liquor 2 parts of (23.2kg), trimeric cyanamide 1.9 parts of (22kg), 2 parts in Potcrate (23.2kg), urea add in entire reaction course in batches.
In reactor, add 1972Kg formaldehyde, 23.2Kg ammoniacal liquor, transferring pH value with 30%wt sodium hydroxide (NaOH) solution is 8, be warming up to 50 ℃, add 720Kg urea, continue to be warming up to 90 ℃ of insulations, add 80Kg urea after 30 minutes, continue insulation 30 minutes, transferring PH with 95%wt acetate is 5, carries out polycondensation, when viscosity reaches 14s (with being coated with 4 glasss of surveys, 92 ℃) time, transferring PH with 30%wt sodium hydroxide (NaOH) solution is 8, stops polycondensation, adds 22Kg trimeric cyanamide and 200Kg urea, feed water quench in the reacting kettle jacketing, add 23.2Kg Potcrate and 160Kg urea after 30 minutes, be cooled to 40 ℃ of blowings, the products obtained therefrom detected result is as follows:
Viscosity (20 ℃) 121mPa.s
PH value 8
Solid content 53.4%
30 days storage periods
Content of free aldehyde 0.22%
Bonding strength 1.61Mpa
The method of producing sheet material with this urea-formaldehyde resin adhesive is with embodiment 1, and with the core-board of this urea-formaldehyde resin adhesive production after testing, formaldehyde content is 1.45mg/L, meets the GB18580-2001 national standard.
Claims (4)
1. one kind is the urea-formaldehyde resin adhesive that trapping agent is produced with the oxymuriate, it is characterized in that: with amount of urea is that 100 weight parts serve as to calculate benchmark, is mainly made by 100 parts of urea, 162-189 part 37%wt formaldehyde, 0.5-2.5 part 30%wt ammoniacal liquor, 1.0-2.0 part trimeric cyanamide, the reaction of 2.0-3.0 part oxymuriate; Earlier 162-189 part 37%wt formaldehyde solution is dropped in the reactor, transferring pH value with 0.5-2.5 part ammoniacal liquor and caustic soda soln is 8, when stirring is warming up to 50 ℃, add 62.1 parts of urea, continue to rise to 90 ℃, be incubated 30 minutes, add 6.9 parts of urea, be incubated 30 minutes again, transferring pH value with acetic acid solution is 4-5, continue reaction extremely with being coated with 4 glasss, when 92 ℃ of viscosimetrics were 14s, transferring pH value with alkali lye was 8 termination polycondensations, adds 1.0-2.0 part trimeric cyanamide and 17.2 parts of urea, feed water coolant in the reacting kettle jacketing, after 30 minutes, add 13.8 parts of urea and 2.0-3.0 part oxymuriate, be cooled to 40 ℃ of blowings; The urea-formaldehyde resin adhesive solid content that makes is 52-55%, and content of free aldehyde is less than 0.25%, and bonding strength is greater than 1.4Mpa.
2. according to claim 1 is the urea-formaldehyde resin adhesive that trapping agent is produced with the oxymuriate, and it is characterized in that: described oxymuriate is the trapping agent of formaldehyde, is specially sodium chlorate or Potcrate.
3. a claim 1 is described is the preparation method that trapping agent is produced urea-formaldehyde resin adhesive with the oxymuriate, make urea-formaldehyde resin adhesive by urea and formaldehyde condensation polymer, its urea is for add in batches, it is characterized in that: earlier 162-189 part 37%wt formaldehyde solution is dropped in the reactor, transferring pH value with 0.5-2.5 part ammoniacal liquor and caustic soda soln is 8, when stirring is warming up to 50 ℃, add 62.1 parts of urea; Continue to rise to 90 ℃, be incubated 30 minutes, add 6.9 parts of urea; Be incubated 30 minutes again, transferring pH value with acetic acid solution is 4-5, continue reaction to when being coated with 4 glasss, 92 ℃ viscosimetrics and being 14s, transferring pH value with alkali lye is 8 termination polycondensations, add 1.0-2.0 part trimeric cyanamide and 17.2 parts of urea, feed water coolant in the reacting kettle jacketing, after 30 minutes, add 13.8 parts of urea and 2.0-3.0 part oxymuriate, be cooled to 40 ℃ of blowings.
4. according to claim 3 is the preparation method that trapping agent is produced urea-formaldehyde resin adhesive with the oxymuriate, it is characterized in that: after polycondensation was finished, pH value was 8 o'clock adding oxymuriates.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101273967A CN100408607C (en) | 2005-12-25 | 2005-12-25 | Urea-formaldehyde resin glue produced by making chlorate as catching agent and preparation method thereof |
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| CNB2005101273967A CN100408607C (en) | 2005-12-25 | 2005-12-25 | Urea-formaldehyde resin glue produced by making chlorate as catching agent and preparation method thereof |
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| CN100408607C true CN100408607C (en) | 2008-08-06 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001038416A1 (en) * | 1999-11-29 | 2001-05-31 | Dynochem Nz Limited | Binders for composite panels |
| CN1111180C (en) * | 2000-05-12 | 2003-06-11 | 中国石油天然气股份有限公司兰州石化分公司 | Water-proof lower-aldehyde urea-formaldehyde resin and its preparing process |
| CN1621477A (en) * | 2004-10-18 | 2005-06-01 | 俞锋 | Urea-formaldehyde glue with low content of free aldehyde and its preparing method |
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2005
- 2005-12-25 CN CNB2005101273967A patent/CN100408607C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001038416A1 (en) * | 1999-11-29 | 2001-05-31 | Dynochem Nz Limited | Binders for composite panels |
| CN1111180C (en) * | 2000-05-12 | 2003-06-11 | 中国石油天然气股份有限公司兰州石化分公司 | Water-proof lower-aldehyde urea-formaldehyde resin and its preparing process |
| CN1621477A (en) * | 2004-10-18 | 2005-06-01 | 俞锋 | Urea-formaldehyde glue with low content of free aldehyde and its preparing method |
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| CN1803875A (en) | 2006-07-19 |
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