CN1834184A - Environment protection, low cost urea resin gel - Google Patents

Environment protection, low cost urea resin gel Download PDF

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Publication number
CN1834184A
CN1834184A CN 200610075047 CN200610075047A CN1834184A CN 1834184 A CN1834184 A CN 1834184A CN 200610075047 CN200610075047 CN 200610075047 CN 200610075047 A CN200610075047 A CN 200610075047A CN 1834184 A CN1834184 A CN 1834184A
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China
Prior art keywords
urea
add
raw materials
formaldehyde
glue
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Granted
Application number
CN 200610075047
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Chinese (zh)
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CN100344720C (en
Inventor
于红卫
刘志坤
槐敏
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Zhejiang A&F University ZAFU
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Zhejiang Forestry College
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Priority to CNB200610075047XA priority Critical patent/CN100344720C/en
Publication of CN1834184A publication Critical patent/CN1834184A/en
Application granted granted Critical
Publication of CN100344720C publication Critical patent/CN100344720C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

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Abstract

This invention discloses a method for manufacturing a low-cost environment-friendly urea-formaldehyde resin glue, which is composed of the following raw materials (by weight parts): formaldehyde 90-110, urea 50-70 and modifier 20-30. The urea-formaldehyde resin is manufactured by adding total formaldehyde and 2/5 of urea in a kettle and stirring, adjusting the pH value to 8.5 with NaOH, increasing the temperature to 90 deg.C, adding 1/3 of urea, keeping the temperature for 60 min, decreasing the temperature to 70 deg.C, adjusting the pH value to 2.5 with HCl, reacting until the formation of glue, adjusting the pH value to 7.5 with NaOH, adding the modifier, decreasing the temperature to 65 deg.C, adding the reat of urea, reacting until the temperature is naturally decreased to 45 deg.C, and then adjusting the pH value to 7.0. The manufactured glue can be used for gluing bamboo, wood and paper products, and has such advantages as low content of free formaldehyde, low cost, high gluing strength, high water resistance, high prepressing capacity and long storage period.

Description

Environment protection, low cost urea resin gel
Technical field
The present invention relates to a kind of urea resin gel.
Background technology
Urea-formaldehyde resin adhesive is the tackiness agent of bamboo and woods such as artificial bamboo board, glued board, shaving board, fiberboard, paper product, but the free formaldehyde content is still higher in the at present general urea-formaldehyde resin adhesive, to the operator and the healthy unfavorable of room resident family of decorateing.The people of numerous strong-willed improvement free formaldehyde releases disguises powder etc. and sets about carrying out development by all kinds of means from improving synthesis technique, substance, glue, reaches effect preferably, but these improvedly close the raising that weak point is a production cost altogether.CN02121076.4 discloses Wang Zhenghong's " making method of environment protection type urea formaldehyde resin adhesive " technology, adopt the traditional technology of weak base---weak acid---weak base and higher temperature of reaction, add trimeric cyanamide and make properties-correcting agent and toughener, make the glue water tolerance and the ageing resistance that make undesirable, production cost is higher.
Summary of the invention
At the above-mentioned deficiency of prior art, the purpose of this invention is to provide a kind of strong acid and strong base and in, low temperature synthetic novel process, can effectively reduce free formaldehyde content and the environment protection, low cost urea resin gel that reduces production costs.
Purpose of the present invention can realize by following measure:
This glue is made up of following raw materials according and weight part thereof: 90-110 part formaldehyde, 50-70 part urea, 20-40 part properties-correcting agent; Production technique is the whole formaldehyde that will get the raw materials ready by above-mentioned weight part earlier and accounts for 2/5 amount of getting the raw materials ready urea and add in the reactor, stir, PH=8.0-8.5 with the NaoH regulator solution, carry out addition reaction, be warming up to 90 ± 2 ℃, add the urea that accounts for the amount of getting the raw materials ready 1/30 to reactor again, be incubated 60 minutes, be cooled to 70-75 ℃, add HCI and transfer PH=2.0-2.5, carry out polycondensation, extract reaction solution and splash into when being white in color floss in the beaker that 25 ℃ of water are housed, add NaoH and transfer PH=7.5, add properties-correcting agent, be cooled to 65 ℃ again, add the urea of surplus for the third time, react when solution temperature is 45 ℃, transfer PH=7.0.
Purpose of the present invention can also be come perfect by following measure:
In the production technique of this glue, urea divides and joins for four times in the anti-still, and preceding twice add-on and condition add after adding for the second time urea and transferring PH=7.5 with NaoH as hereinbefore for the third time, add-on is the urea that accounts for 1/3 amount of getting the raw materials ready, heat up 90 ± 2 ℃ again, react after 60 minutes, add properties-correcting agent again, be cooled to 65 ℃ again, add surplus urea the 4th time and react, when cooling to 45 ℃ naturally, accent PH=7.0.
Said properties-correcting agent is thickening material, is at least a in starch paste, carboxymethyl cellulose paste, the sodium alginate paste.
Embodiment
The present invention is described in further detail below in conjunction with embodiment:
The people is known be the formaldehyde and the urea of urea-formaldehyde resin adhesive mol ratio (hereinafter to be referred as UF than) high more, the free formaldehyde content in the glue is just high more, product toxicity is big more, but UF mol ratio<1.05: 1, the gluing intensity that connects reduces greatly.Under the constant situation of mol ratio, urea is divided into 3-4 time and feeds intake, help reaction, more abundant, make free formaldehyde content low, under highly basic-strong acid-highly basic and lesser temps, carry out polycondensation and help improving bonding strength, so the present invention adopts NaoH, hydrochloric acid or other highly basic, strong acid to regulate pH value, and under 70-75 ℃ of temperature condition, carry out polycondensation.In order to reduce production costs and to reduce free formaldehyde content, the present invention does the material modified of glue with the thickening material of pasty state and is added.Urea divides and adds for three times fashionablely, and the UF mol ratio of each time is respectively: U: F=31: 1,28: 1,124: 1, divide add for four times fashionable, U: F=3: 1,28: 1,16: 1,124: 1, adopt technical pure formaldehyde and urea.Easy to operate for producing, now each raw material is listed as follows by corresponding weight part and gradation add-on:
Consult nine kinds of listed embodiment of table, now illustrate with embodiment 1 and 6.
Embodiment 1:
Earlier with the formaldehyde of 95 weight parts with get the raw materials ready in i.e. 22 weight parts of about 2/5 amount of 55 weight part urea, as the initial dose that adds reactor, stir, PH=8.0-8.5 with the NaoH regulator solution, carry out addition reaction, be warming up to 90 ± 2 ℃, add the urea of the 55 weight part amounts of getting the raw materials ready 1/30 that account for for the second time, promptly about 2 weight part urea react, and are incubated 60 minutes, be cooled to 70-75 ℃, add HCI and transfer PH=2.0-2.5, carry out polycondensation, extract reaction solution and splash into when being white in color floss in the beaker that 25 ℃ of water are housed, add 27 weight part sodium alginate pastes, stir, be cooled to 65 ℃, add for the third time surplus promptly the urea of 31 weight parts react again, naturally be cooled to 45 ℃, accent PH=7.0.
Embodiment 6:
Different with embodiment 1 have 2 points, and the one, the weight part difference of the material that adds, the 2nd, urea changes four addings of branchs into.
Earlier 100 weight parts (hereinafter to be referred as part) formaldehyde and 25 parts of urea are added reactor, stir, PH=8.0-8.5 with the NaoH regulator solution, be warming up to 90 ± 2 ℃, 2 parts of urea are added in the still, be incubated 60 minutes, be cooled to 70-75 ℃, add hydrochloric acid and transfer PH=2.0-2.5, extract reaction solution and splash into when presenting white wadding dress thing in the beaker that 25 ℃ of water are housed, add NaoH and transfer PH=7.5, add 20 parts of urea more for the third time, heat up 90 ± 2 ℃, reacted 60 minutes, add 30 parts of flour pastes, be cooled to 65 ℃ again, add 13 parts of urea the 4th time and react, when being cooled to 45 ℃ naturally, transfer PH=7.0 to get final product the plastic emitting barreled.
All the other embodiment 2-5,7-9, the same procedure by embodiment 1,6 makes this glue respectively.Among nine embodiment, preferred with embodiment 2,5,6,8.
With the glue that this law makes, outward appearance is pale brown look transparent or oyster white colloid, solid content 40 ± 2%, PH=7.0-7.5, free formaldehyde≤0.1%, viscosity 18-22 second (20 ℃ are coated with-4 glasss of mensuration), storage period (25 ℃)>1 month.
Test shows, the reaction that urea and formaldehyde generate methylolurea is thermopositive reaction, the complete more content of free aldehyde of methylolation is low more, under strong acid condition, reducing temperature (promptly reducing reaction activity) helps hydroxymethylation and reduces content of free aldehyde, add the thickening material of flour paste and so on, not only reduce production costs, and to reduce free cresols content, improve resistance to deterioration, improve bonding strength and water tolerance, the precompressed effect is very remarkable.
The present invention compares the glue that traditional urea resin gel makes, and has the advantage that content of free aldehyde is low, production cost is low, bonding strength is high, storage period is long and the precompressed performance is good.

Claims (3)

1, a kind of environment protection, low cost urea resin gel is characterized in that this glue is made up of following raw materials according and weight part thereof: 90-110 part formaldehyde, 50-70 part urea, 20-40 part properties-correcting agent; Production technique is that the whole formaldehyde that will get the raw materials ready by above-mentioned weight part earlier and the urea that accounts for 2/5 amount of getting the raw materials ready add in the reactor, stir, PH=8.0-8.5 with the NaoH regulator solution, carry out addition reaction, be warming up to 90 ± 2 ℃, add the urea that accounts for the amount of getting the raw materials ready 1/30 to reactor again, be incubated 60 minutes, be cooled to 70-75 ℃, add HCI and transfer PH=2.0-2.5, carry out polycondensation, extract reaction solution and splash into when being white in color floss in the beaker that 25 ℃ of water are housed, add NaoH and transfer PH=7.5, add properties-correcting agent, be cooled to 65 ℃ again, add the urea of surplus for the third time, react when solution temperature is 45 ℃, transfer PH=7.0.
2, environment protection, low cost urea resin gel as claimed in claim 1, it is characterized in that in the production technique of this glue, urea divides and joins for four times in the anti-still, preceding twice add-on and condition are as hereinbefore, after adding for the second time urea and transferring PH=7.5, add for the third time with NaoH, add-on is the urea that accounts for 1/3 amount of getting the raw materials ready, heat up 90 ± 2 ℃ again, react after 60 minutes, add properties-correcting agent again, be cooled to 65 ℃ again, the 4th time adding surplus urea reacts, when cooling to 45 ℃ naturally, accent PH=7.0.
3, the environment protection, low cost urea resin gel described in claim 1 or 2 is characterized in that said properties-correcting agent is thickening material, is at least a in starch paste, carboxymethyl cellulose paste, the sodium alginate paste.
CNB200610075047XA 2006-03-30 2006-03-30 Environment protection, low cost urea resin gel Expired - Fee Related CN100344720C (en)

Priority Applications (1)

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Application Number Priority Date Filing Date Title
CNB200610075047XA CN100344720C (en) 2006-03-30 2006-03-30 Environment protection, low cost urea resin gel

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CN1834184A true CN1834184A (en) 2006-09-20
CN100344720C CN100344720C (en) 2007-10-24

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101260284B (en) * 2007-03-17 2011-08-31 广西大学 On-line control multi-still continuous production method for wood adhesive
CN103030462A (en) * 2012-12-12 2013-04-10 四川好时吉化工有限公司 Water-soluble urea-formaldehyde glue and preparation method thereof as well as method for improving strength of water-soluble compound fertilizer granule by water-soluble urea-formaldehyde glue
CN103613925A (en) * 2013-11-29 2014-03-05 江门市奇德工程塑料科技有限公司 Halogen-free flame-retardant PA6 nanocomposite material and preparation method thereof
CN105602500A (en) * 2016-02-19 2016-05-25 武秀英 Biology base urea formaldehyde composite for artificial board
CN105647451A (en) * 2016-01-15 2016-06-08 上海齐驭实业有限公司 Novel waterproof wood material adhesive and preparation method thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2150939B (en) * 1983-12-09 1987-02-04 Enigma Nv A process for preparing urea-formaldehyde resins
GB2192005B (en) * 1986-06-27 1989-12-13 Ciba Geigy Ag Process for the preparation of urea-formaldehyde resins
CN1121084A (en) * 1994-10-21 1996-04-24 遵化市钟馗实业公司 Low-poison synthetic urea-formaldehyde resin glue and its production method
CN1621477A (en) * 2004-10-18 2005-06-01 俞锋 Urea-formaldehyde glue with low content of free aldehyde and its preparing method

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101260284B (en) * 2007-03-17 2011-08-31 广西大学 On-line control multi-still continuous production method for wood adhesive
CN103030462A (en) * 2012-12-12 2013-04-10 四川好时吉化工有限公司 Water-soluble urea-formaldehyde glue and preparation method thereof as well as method for improving strength of water-soluble compound fertilizer granule by water-soluble urea-formaldehyde glue
CN103030462B (en) * 2012-12-12 2015-03-11 四川好时吉化工有限公司 Water-soluble urea-formaldehyde glue and preparation method thereof as well as method for improving strength of water-soluble compound fertilizer granule by water-soluble urea-formaldehyde glue
CN103613925A (en) * 2013-11-29 2014-03-05 江门市奇德工程塑料科技有限公司 Halogen-free flame-retardant PA6 nanocomposite material and preparation method thereof
CN103613925B (en) * 2013-11-29 2016-02-03 广东奇德新材料股份有限公司 A kind of halogen-free flameproof PA6 nano composite material and preparation method thereof
CN105647451A (en) * 2016-01-15 2016-06-08 上海齐驭实业有限公司 Novel waterproof wood material adhesive and preparation method thereof
CN105647451B (en) * 2016-01-15 2018-12-07 上海齐驭实业有限公司 The application of sodium carboxymethylcellulose or carboxymethyl cellulose or carboxymethyl starch in terms of improving based Wood Adhesives waterproofness
CN105602500A (en) * 2016-02-19 2016-05-25 武秀英 Biology base urea formaldehyde composite for artificial board
CN105602500B (en) * 2016-02-19 2018-11-13 武秀英 A kind of wood-based plate biology base ureaformaldehyde composite material

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Effective date of registration: 20111221

Address after: 311300 No. 63 East Road, Zhejiang, Ling'an

Patentee after: Zhejiang A & F University

Address before: 311300 School of engineering, Zhejiang Forestry University, No. 88 Ring North Road, Jincheng Town, Zhejiang, Ling'an

Patentee before: Zhejiang Forestry University

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Granted publication date: 20071024

Termination date: 20120330